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Sample records for chlorophyll micelles models

  1. Small-angle neutron scattering studies of chlorophyll micelles: Models for bacterial antenna chlorophyll

    PubMed Central

    Worcester, D. L.; Michalski, T. J.; Katz, J. J.

    1986-01-01

    Micelles of hydrated chlorophyll a (P740), bacteriochlorophyll a (P865), bacteriochlorophyll c (P750), and pheophytin a prepared in organic media have been studied by small-angle neutron scattering to determine their shape, size, and mass per unit length. All of the micelles are hollow cylinders of well-defined size. The P740 and P750 cylinders are essentially monolayers of macrocycles crosslinked by water, probably in an arrangement similar to that of crystals of chlorophyll derivatives. The P865 micelle is more nearly a bilayer of macrocycles. We show that the curvature necessary to form cylinders probably results from intrinsic curvature of the five-coordinated chlorophyll macrocycle. Studies of P740 micelle formation and the disaggregating effects of another nucleophile (pyridine) are described. As the P750 micelles are nearly identical in size and optical spectra to the rod-shaped structures observed in chlorosomes, and the P865 micelles have optical properties very similar to the in vivo properties of the long-wavelength antenna of purple photosynthetic bacteria, we propose that features of the hydrated cylindrical micelles of these chlorophylls provide good models for antenna chlorophyll in photosynthetic bacteria. Images PMID:16593703

  2. Peroxide decoloration of CI Acid Orange 7 catalyzed by manganese chlorophyll derivatives at the surfaces of micelles and lipid bilayers.

    PubMed

    Ishigure, Shuichi; Mitsui, Tatsuro; Ito, Shingo; Kondo, Yuji; Kawabe, Shigeki; Kondo, Masaharu; Dewa, Takehisa; Mino, Hiroyuki; Itoh, Shigeru; Nango, Mamoru

    2010-06-01

    Manganese-substituted chlorophyll a derivatives (MnChls) were synthesized. We first report peroxidative oxidation of an azo dye, CI Acid Orange 7, catalyzed by MnChls at the surfaces of micelles and lipid bilayers with hydrogen peroxide (H(2)O(2)) under mild conditions (pH 8.0, 25 degrees C). Peroxide decoloration depended upon the structures of MnChls, surfactants, lipids, and the presence of imidazole. Surprisingly, a largest decoloration rate was observed for MnChls dimer, MnPChlide a-K(MnPChlide a)-His 5 in cetyltrimethylammonium bromide (CTAB) micellar solution, especially when imidazole was present: this observation is analogous to the decoloration using horseradish peroxidase (HRP). Interestingly, the dimer complexes showed enhanced decoloration in comparison to the corresponding MnChls monomer in the micellar solution. In contrast, the MnChls monomer showed enhanced decoloration in comparison with the MnChls dimer in liposomal suspensions. Further, the imidazole residue covalently linked to the MnChls plays an important role in increasing the decoloration in both micellar and liposomal suspensions as well as in addition of imidazole into the solutions. It is interesting that the electron paramagnetic resonance (EPR) spectra of MnPChlide a ME 2, MnPChlide a-His 3, and MnMPMME-His 7 have 16 peaks around g = 2 in Egg PC or DMPC liposomal suspension with H(2)O(2), which is typical of a mixed-valence Mn(III)-Mn(IV) complex with coupling between two ions. The higher decoloration performance obtained by the monomer porphyrin compounds at the surface of the lipid bilayers appears to be related to the stability of this mixed-valence Mn(III)-Mn(IV) species formed in the lipid bilayers. This finding should provide useful information to note that MnChls, which are easily found in a number of biological systems, are involved in functions such as hydrogen peroxide decomposition in bacteria and the oxidation of water during photosynthesis as well as the peroxidases

  3. Modeling of estuarne chlorophyll a from an airborne scanner

    USGS Publications Warehouse

    Khorram, Siamak; Catts, Glenn P.; Cloern, James E.; Knight, Allen W.

    1987-01-01

    Near simultaneous collection of 34 surface water samples and airborne multispectral scanner data provided input for regression models developed to predict surface concentrations of estuarine chlorophyll a. Two wavelength ratios were employed in model development. The ratios werechosen to capitalize on the spectral characteristics of chlorophyll a, while minimizing atmospheric influences. Models were then applied to data previously acquired over the study area thre years earlier. Results are in the form of color-coded displays of predicted chlorophyll a concentrations and comparisons of the agreement among measured surface samples and predictions basedon coincident remotely sensed data. The influence of large variations in fresh-water inflow to the estuary are clearly apparent in the results. The synoptic view provided by remote sensing is another method of examining important estuarine dynamics difficult to observe from in situ sampling alone.

  4. [Hyperspectral estimation models of chlorophyll content in apple leaves].

    PubMed

    Liang, Shuang; Zhao, Geng-xing; Zhu, Xi-cun

    2012-05-01

    The present study chose the apple orchard of Shandong Agricultural University as the study area to explore the method of apple leaf chlorophyll content estimation by hyperspectral analysis technology. Through analyzing the characteristics of apple leaves' hyperspectral curve, transforming the original spectral into first derivative, red edge position and leaf chlorophyll index (LCI) respectively, and making the correlation analysis and regression analysis of these variables with the chlorophyll content to establish the estimation models and test to select the high fitting precision models. Results showed that the fitting precision of the estimation model with variable of LCI and the estimation model with variable of the first derivative in the band of 521 and 523 nm was the highest. The coefficients of determination R2 were 0.845 and 0.839, the root mean square errors RMSE were 2.961 and 2.719, and the relative errors RE% were 4.71% and 4.70%, respectively. Therefore LCI and the first derivative are the important index for apple leaf chlorophyll content estimation. The models have positive significance to guide the production of apple cultivation.

  5. Further investigation of the mechanism of Doxorubicin release from P105 micelles using kinetic models

    PubMed Central

    Stevenson-Abouelnasr, Dana; Husseini, Ghaleb A.; Pitt, William G.

    2007-01-01

    The kinetics of the release of Doxorubicin from Pluronic P105 micelles during ultrasonication and its subsequent re-encapsulation upon cessation of insonation were investigated. Four mechanisms are proposed to explain the acoustically-triggered Doxorubicin (Dox) release and re-encapsulation from Pluronic P105 micelles. The four mechanisms are: micelle destruction; destruction of cavitating nuclei; reassembly of micelles, and the re-encapsulation of Dox. The first mechanism, the destruction of micelles during insonation, causes the release of Dox into solution. The micelles are destroyed because of cavitation events produced by collapsing nuclei, or bubbles in the insonated solution. The second mechanism, the slow destruction of cavitating nuclei, results in a slow partial recovery phase, when a small amount of Dox is re-encapsulated. The third and fourth mechanisms, the reassembly of micelles and the re-encapsulatin of Dox, are independent of ultrasound. These two mechanism are responsible for maintaining the drug release at a partial level, and for recovery after insonation ceases. A normal distribution was used to describe micellar size. Parameters for the model were determined based upon the best observed fit to experimental data. The resulting model provides a good approximation to experimental data for the release of Dox from Pluronic P105 micelles. PMID:17207611

  6. Temperature Effect on Micelle Formation: Molecular Thermodynamic Model Revisited.

    PubMed

    Khoshnood, Atefeh; Lukanov, Boris; Firoozabadi, Abbas

    2016-03-01

    Temperature affects the aggregation of macromolecules such as surfactants, polymers, and proteins in aqueous solutions. The effect on the critical micelle concentration (CMC) is often nonmonotonic. In this work, the effect of temperature on the micellization of ionic and nonionic surfactants in aqueous solutions is studied using a molecular thermodynamic model. Previous studies based on this technique have predicted monotonic behavior for ionic surfactants. Our investigation shows that the choice of tail transfer energy to describe the hydrophobic effect between the surfactant tails and the polar solvent molecules plays a key role in the predicted CMC. We modify the tail transfer energy by taking into account the effect of the surfactant head on the neighboring methylene group. The modification improves the description of the CMC and the predicted micellar size for aqueous solutions of sodium n-alkyl sulfate, dodecyl trimethylammonium bromide (DTAB), and n-alkyl polyoxyethylene. The new tail transfer energy describes the nonmonotonic behavior of CMC versus temperature. In the DTAB-water system, we redefine the head size by including the methylene group, next to the nitrogen, in the head. The change in the head size along with our modified tail transfer energy improves the CMC and aggregation size prediction significantly. Tail transfer is a dominant energy contribution in micellar and microemulsion systems. It also promotes the adsorption of surfactants at fluid-fluid interfaces and affects the formation of adsorbed layer at fluid-solid interfaces. Our proposed modifications have direct applications in the thermodynamic modeling of the effect of temperature on molecular aggregation, both in the bulk and at the interfaces.

  7. Biodegradable polymeric micelle-encapsulated quercetin suppresses tumor growth and metastasis in both transgenic zebrafish and mouse models

    NASA Astrophysics Data System (ADS)

    Wu, Qinjie; Deng, Senyi; Li, Ling; Sun, Lu; Yang, Xi; Liu, Xinyu; Liu, Lei; Qian, Zhiyong; Wei, Yuquan; Gong, Changyang

    2013-11-01

    Quercetin (Que) loaded polymeric micelles were prepared to obtain an aqueous formulation of Que with enhanced anti-tumor and anti-metastasis activities. A simple solid dispersion method was used, and the obtained Que micelles had a small particle size (about 31 nm), high drug loading, and high encapsulation efficiency. Que micelles showed improved cellular uptake, an enhanced apoptosis induction effect, and stronger inhibitory effects on proliferation, migration, and invasion of 4T1 cells than free Que. The enhanced in vitro antiangiogenesis effects of Que micelles were proved by the results that Que micelles significantly suppressed proliferation, migration, invasion, and tube formation of human umbilical vein endothelial cells (HUVECs). Subsequently, transgenic zebrafish models were employed to investigate anti-tumor and anti-metastasis effects of Que micelles, in which stronger inhibitory effects of Que micelles were observed on embryonic angiogenesis, tumor-induced angiogenesis, tumor growth, and tumor metastasis. Furthermore, in a subcutaneous 4T1 tumor model, Que micelles were more effective in suppressing tumor growth and spontaneous pulmonary metastasis, and prolonging the survival of tumor-bearing mice. Besides, immunohistochemical and immunofluorescent assays suggested that tumors in the Que micelle-treated group showed more apoptosis, fewer microvessels, and fewer proliferation-positive cells. In conclusion, Que micelles, which are synthesized as an aqueous formulation of Que, possess enhanced anti-tumor and anti-metastasis activity, which can serve as potential candidates for cancer therapy.

  8. [Estimation of forest canopy chlorophyll content based on PROSPECT and SAIL models].

    PubMed

    Yang, Xi-guang; Fan, Wen-yi; Yu, Ying

    2010-11-01

    The forest canopy chlorophyll content directly reflects the health and stress of forest. The accurate estimation of the forest canopy chlorophyll content is a significant foundation for researching forest ecosystem cycle models. In the present paper, the inversion of the forest canopy chlorophyll content was based on PROSPECT and SAIL models from the physical mechanism angle. First, leaf spectrum and canopy spectrum were simulated by PROSPECT and SAIL models respectively. And leaf chlorophyll content look-up-table was established for leaf chlorophyll content retrieval. Then leaf chlorophyll content was converted into canopy chlorophyll content by Leaf Area Index (LAD). Finally, canopy chlorophyll content was estimated from Hyperion image. The results indicated that the main effect bands of chlorophyll content were 400-900 nm, the simulation of leaf and canopy spectrum by PROSPECT and SAIL models fit better with the measured spectrum with 7.06% and 16.49% relative error respectively, the RMSE of LAI inversion was 0. 542 6 and the forest canopy chlorophyll content was estimated better by PROSPECT and SAIL models with precision = 77.02%.

  9. Surface tension model for surfactant solutions at the critical micelle concentration.

    PubMed

    Burlatsky, Sergei F; Atrazhev, Vadim V; Dmitriev, Dmitry V; Sultanov, Vadim I; Timokhina, Elena N; Ugolkova, Elena A; Tulyani, Sonia; Vincitore, Antonio

    2013-03-01

    A model for the limiting surface tension of surfactant solutions (surface tension at and above the critical micelle concentration, cmc) was developed. This model takes advantage of the equilibrium between the surfactant molecules on the liquid/vacuum surface and in micelles in the bulk at the cmc. An approximate analytical equation for the surface tension at the cmc was obtained. The derived equation contains two parameters, which characterize the intermolecular interactions in the micelles, and the third parameter, which is the surface area per surfactant molecule at the interface. These parameters were calculated using a new atomistic modeling approach. The performed calculations of the limiting surface tension for four simple surfactants show good agreement with experimental data (~30% accuracy). The developed model provides the guidance for design of surfactants with low surface tension values.

  10. Titration of fatty acids solubilized in cationic and anionic micelles. Calorimetry and thermodynamic modeling.

    PubMed

    Söderman, Olle; Jönsson, Bengt; Olofsson, Gerd

    2006-02-23

    The electrostatic properties of charged surfactant micelles are investigated through titrations of fatty acid probes solubilized in the micelles. The titration process is followed by means of calorimetric measurements and by determining the pH values as a function of added base. This approach yields a complete thermodynamic description of the titration process. In particular, we find that the process is endothermic at 298 K. This is contrary to the titration of carboxylic acids in water, where DeltaH is approximately 0. To identify the main effect underlying the difference in DeltaH between titration in a micelle and water, a thermodynamic model has been developed which focuses on the transfer properties of charged and uncharged species from bulk water to the surface of a micelle and which incorporates a dielectric discontinuity at the micellar surface. The model relies on the use of the Poisson-Boltzmann equation which is solved using a finite element method. Experimental results and the model calculations imply that the dielectric discontinuity at (or near) the micellar surface plays a major role and hence must be included when analyzing the titration behavior of an acid functionality at the surface of a charged micelle.

  11. Modeling chlorophyll a fluorescence transient: relation to photosynthesis.

    PubMed

    Stirbet, A; Riznichenko, G Yu; Rubin, A B; Govindjee

    2014-04-01

    To honor Academician Alexander Abramovitch Krasnovsky, we present here an educational review on the relation of chlorophyll a fluorescence transient to various processes in photosynthesis. The initial event in oxygenic photosynthesis is light absorption by chlorophylls (Chls), carotenoids, and, in some cases, phycobilins; these pigments form the antenna. Most of the energy is transferred to reaction centers where it is used for charge separation. The small part of energy that is not used in photochemistry is dissipated as heat or re-emitted as fluorescence. When a photosynthetic sample is transferred from dark to light, Chl a fluorescence (ChlF) intensity shows characteristic changes in time called fluorescence transient, the OJIPSMT transient, where O (the origin) is for the first measured minimum fluorescence level; J and I for intermediate inflections; P for peak; S for semi-steady state level; M for maximum; and T for terminal steady state level. This transient is a real signature of photosynthesis, since diverse events can be related to it, such as: changes in redox states of components of the linear electron transport flow, involvement of alternative electron routes, the build-up of a transmembrane pH gradient and membrane potential, activation of different nonphotochemical quenching processes, activation of the Calvin-Benson cycle, and other processes. In this review, we present our views on how different segments of the OJIPSMT transient are influenced by various photosynthetic processes, and discuss a number of studies involving mathematical modeling and simulation of the ChlF transient. A special emphasis is given to the slower PSMT phase, for which many studies have been recently published, but they are less known than on the faster OJIP phase.

  12. Thermosensitive hydrogel containing dexamethasone micelles for preventing postsurgical adhesion in a repeated-injury model.

    PubMed

    Wu, Qinjie; Wang, Ning; He, Tao; Shang, Jinfeng; Li, Ling; Song, Linjiang; Yang, Xi; Li, Xia; Luo, Na; Zhang, Wenli; Gong, Changyang

    2015-09-01

    Tissue adhesion is a common complication after surgery. In this work, a dexamethasone loaded polymeric micelles in thermosensitive hydrogel composite (Dex hydrogel) was prepared, which combined the anti-adhesion barrier with controlled release of anti-adhesion drug. Dexamethasone (Dex) was encapsulated in polymeric micelles (Dex micelles), and then the Dex micelles were loaded into biodegradable and thermosensitive hydrogel. The obtained Dex hydrogel showed a temperature-dependent sol-gel-sol phase transition behavior. The Dex hydrogel could form a non-flowing gel in situ upon subcutaneous injection and gradually degrade in about 20 days. In addition, Dex hydrogel was assigned for anti-adhesion studies in a more rigorous recurrent adhesion animal model. Compared with normal saline (NS) and Dex micelles group, tissue adhesions in hydrogel and Dex hydrogel group were significantly alleviated. In Dex hydrogel group, the media adhesion score is 0, which was dramatically lower than that in blank hydrogel group (2.50, P < 0.001). In histopathological examination and scanning electron microscopy (SEM) analysis, an integral neo-mesothelial cell layer with microvilli on their surface was observed, which revealed that the injured parietal and visceral peritoneum were fully recovered without the concerns of adhesion formation. Our results suggested that Dex hydrogel may serve as a potential anti-adhesion candidate.

  13. Thermosensitive hydrogel containing dexamethasone micelles for preventing postsurgical adhesion in a repeated-injury model

    PubMed Central

    Wu, Qinjie; Wang, Ning; He, Tao; Shang, Jinfeng; Li, Ling; Song, Linjiang; Yang, Xi; Li, Xia; Luo, Na; Zhang, Wenli; Gong, Changyang

    2015-01-01

    Tissue adhesion is a common complication after surgery. In this work, a dexamethasone loaded polymeric micelles in thermosensitive hydrogel composite (Dex hydrogel) was prepared, which combined the anti-adhesion barrier with controlled release of anti-adhesion drug. Dexamethasone (Dex) was encapsulated in polymeric micelles (Dex micelles), and then the Dex micelles were loaded into biodegradable and thermosensitive hydrogel. The obtained Dex hydrogel showed a temperature-dependent sol-gel-sol phase transition behavior. The Dex hydrogel could form a non-flowing gel in situ upon subcutaneous injection and gradually degrade in about 20 days. In addition, Dex hydrogel was assigned for anti-adhesion studies in a more rigorous recurrent adhesion animal model. Compared with normal saline (NS) and Dex micelles group, tissue adhesions in hydrogel and Dex hydrogel group were significantly alleviated. In Dex hydrogel group, the media adhesion score is 0, which was dramatically lower than that in blank hydrogel group (2.50, P < 0.001). In histopathological examination and scanning electron microscopy (SEM) analysis, an integral neo-mesothelial cell layer with microvilli on their surface was observed, which revealed that the injured parietal and visceral peritoneum were fully recovered without the concerns of adhesion formation. Our results suggested that Dex hydrogel may serve as a potential anti-adhesion candidate. PMID:26324090

  14. [Research on Modeling Method for Chlorophyll Content Fine Measurement Based on Neural Network].

    PubMed

    Zhou, Chun-yan; Hua, Deng-xin; Le, Jing; Wan, Wen-bo; Jiang, Peng; Mao, Jian-dong

    2015-09-01

    Aiming at SPAD values of living plant leaf chlorophyll content affected easily by the blade thickness, water content, etc, a fine retrieval method of chlorophyll content based on multiple parameters of neural network model is presented. The SPAD values and water index (WI) of leaves were obtained by the leaf transmittance under the irradiation of light central wavelength in 650 nm, 940 nm, 1450 nm respectively. Meanwhile, the corresponding blade thickness is got by micrometer and the chlorophyll content is measured by spectrophotometric method. To modeling samples, the single parameter model between SPAD values and chlorophyll content was built and the nonlinear model between WI, thickness, SPAD values and chlorophyll content was established based on BP neural network. The predicted value of chlorophyll content of test samples were calculated separately by two models, and the correlation and relative errors were analyzed between predicted values and actual values. 340 samples of three different plant leaves were tested by the method described above in experiment. The results showed that compared with single parameter model, the prediction accuracy of three different plant samples were improved in different degrees, the average absolute relative error of chlorophyll content of all pooled samples predicted by BP neural network model reduced from 7.55% to 5.22%. The fitting determination coefficient is increased from 0.83 to 0.93. The feasibility were verified in this paper that the prediction accuracy of living plant chlorophyll content can improved effectively using multiple parameter BP neural network model.

  15. Quantitative Structure-Property Relationship (QSPR) Modeling of Drug-Loaded Polymeric Micelles via Genetic Function Approximation

    PubMed Central

    Lin, Wenjing; Chen, Quan; Guo, Xindong; Qian, Yu; Zhang, Lijuan

    2015-01-01

    Self-assembled nano-micelles of amphiphilic polymers represent a novel anticancer drug delivery system. However, their full clinical utilization remains challenging because the quantitative structure-property relationship (QSPR) between the polymer structure and the efficacy of micelles as a drug carrier is poorly understood. Here, we developed a series of QSPR models to account for the drug loading capacity of polymeric micelles using the genetic function approximation (GFA) algorithm. These models were further evaluated by internal and external validation and a Y-randomization test in terms of stability and generalization, yielding an optimization model that is applicable to an expanded materials regime. As confirmed by experimental data, the relationship between microstructure and drug loading capacity can be well-simulated, suggesting that our models are readily applicable to the quantitative evaluation of the drug-loading capacity of polymeric micelles. Our work may offer a pathway to the design of formulation experiments. PMID:25780923

  16. Remote sensing of oligotrophic waters: model divergence at low chlorophyll concentrations.

    PubMed

    Mehrtens, Hela; Martin, Thomas

    2002-11-20

    The performance of the OC2 Sea-viewing Wide Field-of-view Sensor (SeaWiFS) algorithm based on 490- and 555-nm water-leaving radiances at low chlorophyll contents is compared with those of semianalytical models and a Monte Carlo radiative transfer model. We introduce our model, which uses two particle phase functions and scattering coefficient parameterizations to achieve a backscattering ratio that varies with chlorophyll concentration. We discuss the various parameterizations and compare them with existent measurements. The SeaWiFS algorithm could be confirmed within an accuracy of 35% over a chlorophyll range from 0.1 to 1 mg m(-3), whereas for lower chlorophyll concentrations we found a significant overestimation of the OC2 algorithm.

  17. Regional models for phytoplankton absorption as a function of chlorophyll a concentration

    NASA Astrophysics Data System (ADS)

    Cleveland, Joan S.

    1995-07-01

    Empirical relationships for predicting phytoplanktonic absorption at 676 and 436 nm from water column chlorophyll a concentration are presented for distinct geographic regions defined by latitude. The forms of the predictive equations are controlled by underlying biological mechanisms and lend insight into these mechanisms. These region-specific models allow prediction of phytoplanktonic absorption from more easily measured parameters such as chlorophyll a concentration or in situ fluorescence and increase accuracy in modeling optical properties or primary production rates from specific absorption coefficients. Phytoplanktonic absorption can be predicted from chlorophyll a concentrations estimated from satellite-based ocean color measurements. Temperate and tropical regions exhibited statistically indistinguishable relationships at low chlorophyll so these regions were combined and treated as one. Nonlinear relationships between phytoplanktonic absorption at both 436 and 676 nm and chlorophyll a concentration for the combined temperate/tropical region suggested that pigment packaging effects were important and variable. Higher slopes between absorption and chlorophyll a at low chlorophyll supported the concept of low pigment packaging effects (thus higher specific absorption) in oligotrophic, low chlorophyll a waters. Subpolar waters displayed a distinct pattern and were defined as a separate region. Near-linear and linear relationships between phytoplanktonic absorption at 436 and 676 nm and chlorophyll a concentration indicated that influences of pigment packaging on phytoplankton specific absorption coefficients were relatively constant and uncoupled from water column chlorophyll a concentration in the subpolar region. Optical depth correlated inversely with specific absorption at 436 nm in the subpolar region, illustrating the role of photoadaptation in determining specific absorption and predictive relationships. Differences between predictive quadratic

  18. Molecular Thermodynamic Modeling of Reverse Micelles and Water-in-Oil Microemulsions.

    PubMed

    Lukanov, Boris; Firoozabadi, Abbas

    2016-04-01

    Surfactant aggregation plays an important role in a variety of chemical and biological nanoscale processes. On a larger scale, using small amounts of amphiphiles compared to large volumes of bulk-phase modifiers can improve the efficiency and reduce the environmental impact of many chemical and industrial processes. To model ternary mixtures of polar, nonpolar, and amphiphilic molecules, we develop a molecular thermodynamic theory for polydisperse water-in-oil (W/O) droplet-type microemulsions and reverse micelles based on global minimization of the Gibbs free energy of the system. The incorporation of size polydispersity into the theoretical formulation has a significant effect on the Gibbs free energy landscape and allows us to accurately predict micelle size distributions and micelle size variation with composition. Results are presented for two sample ionic surfactant/water/oil systems and compared with experimental data. By predicting the structural and compositional characteristics of w/o microemulsions, the molecular thermodynamic approach provides an important bridge between the modeling of ternary systems at the molecular and the macroscopic level. PMID:26919199

  19. Reflectance model for quantifying chlorophyll a in the presence of productivity degradation products

    NASA Technical Reports Server (NTRS)

    Carder, K. L.; Hawes, S. K.; Steward, R. G.; Baker, K. A.; Smith, R. C.; Mitchell, B. G.

    1991-01-01

    A reflectance model developed to estimate chlorophyll a concentrations in the presence of marine colored dissolved organic matter, pheopigments, detritus, and bacteria is presented. Nomograms and lookup tables are generated to describe the effects of different mixtures of chlorophyll a and these degradation products on the R(412):R(443) and R(443):R(565) remote-sensing reflectance or irradiance reflectance ratios. These are used to simulate the accuracy of potential ocean color satellite algorithms, assuming that atmospheric effects have been removed. For the California Current upwelling and offshore regions, with chlorophyll a not greater than 1.3 mg/cu m, the average error for chlorophyll a retrievals derived from irradiance reflectance data for degradation product-rich areas was reduced from +/-61 percent to +/-23 percent by application of an algorithm using two reflectance ratios rather than the commonly used algorithm applying a single reflectance ratio.

  20. Modelling canopy scale solar induced chlorophyll fluorescence simulated by the three dimensional radiative transfer model

    NASA Astrophysics Data System (ADS)

    Kobayashi, H.; Nagai, S.; Inoue, T.; Yang, W.; Ichii, K.

    2014-12-01

    Recent studies show that the vegetation canopy scale sun-induced chlorophyll fluorescence (SIF) can be observed from satellite. To understand how the canopy scale bidirectional fluorescence observations are related to three-dimensional fluorescence distribution within a plant canopy, it is necessary to evaluate canopy scale fluorescence emission using a detailed plant canopy radiative transfer model. In this study, we developed a three-dimensional plant canopy radiative transfer model that can simulate the bidirectional chlorophyll fluorescence radiance and show several preliminary results of fluorescence distribution at the tree level. To simulate the three dimensional variations in chlorophyll fluorescence from trees, we measured tree structures using a terrestrial LiDAR instrument. The measurements were conducted in Yokohama, Japan (35°22'49" N 139°37'29" E). Three Japanese cherry trees (Cerasus Speciosa) were chosen for our study (Figure 1). Leaf-level sun-induced chlorophyll fluorescence (SIF) is also necessary as an input of radiative transfer model. To measure the leaf-level SIF, we used high spectral resolution spectroradiometer (HR 4000, Ocean Optics Inc. USA). The spectral resolution of this instrument is 0.05 nm (full width half maximum). The spectral range measured was 720 to 780 nm. From the spectral radiance measurements, we estimated SIF using the three band Fraunhofer Line Depth (3FLD) method. The effect of solar and view zenith angles, multiple scattering depends on many factors such as back ground reflectance, leaf reflectance transmittance and landscape structures. To understand how the SIF from both sparse and dense forest stands vary with sun and view angles and optical variables, it is necessary to conduct further sensitivity analysis. Radiative transfer simulation will help understand SIF emission at variety of forest canopy cases.

  1. MRI-detectable polymeric micelles incorporating platinum anticancer drugs enhance survival in an advanced hepatocellular carcinoma model

    PubMed Central

    Vinh, Nguyen Quoc; Naka, Shigeyuki; Cabral, Horacio; Murayama, Hiroyuki; Kaida, Sachiko; Kataoka, Kazunori; Morikawa, Shigehiro; Tani, Tohru

    2015-01-01

    Hepatocellular carcinoma (HCC) is one of the most intractable and lethal cancers; most cases are diagnosed at advanced stages with underlying liver dysfunction and are frequently resistant to conventional chemotherapy and radiotherapy. The development of tumor-targeting systems may improve treatment outcomes. Nanomedicine platforms are of particular interest for enhancing chemotherapeutic efficiency, and they include polymeric micelles, which enable targeting of multiple drugs to solid tumors, including imaging and therapeutic agents. This allows concurrent diagnosis, targeting strategy validation, and efficacy assessment. We used polymeric micelles containing the T1-weighted magnetic resonance imaging contrast agent gadolinium-diethylenetriaminpentaacetic acid (Gd-DTPA) and the parent complex of the anticancer drug oxaliplatin [(1,2-diaminocyclohexane)platinum(II) (DACHPt)] for simultaneous imaging and therapy in an orthotopic rat model of HCC. The Gd-DTPA/DACHPt-loaded micelles were injected into the hepatic artery, and magnetic resonance imaging performance and antitumor activity against HCC, as well as adverse drug reactions were assessed. After a single administration, the micelles achieved strong and specific tumor contrast enhancement, induced high levels of tumor apoptosis, and significantly suppressed tumor size and growth. Moreover, the micelles did not induce severe adverse reactions and significantly improved survival outcomes in comparison to oxaliplatin or saline controls. Our results suggest that Gd-DTPA/DACHPt-loaded micelles are a promising approach for effective diagnosis and treatment of advanced HCC. PMID:26203241

  2. Models of fluorescence and photosynthesis for interpreting measurements of solar-induced chlorophyll fluorescence

    PubMed Central

    van der Tol, C; Berry, J A; Campbell, P K E; Rascher, U

    2014-01-01

    We have extended a conventional photosynthesis model to simulate field and laboratory measurements of chlorophyll fluorescence at the leaf scale. The fluorescence paramaterization is based on a close nonlinear relationship between the relative light saturation of photosynthesis and nonradiative energy dissipation in plants of different species. This relationship diverged only among examined data sets under stressed (strongly light saturated) conditions, possibly caused by differences in xanthophyll pigment concentrations. The relationship was quantified after analyzing data sets of pulse amplitude modulated measurements of chlorophyll fluorescence and gas exchange of leaves of different species exposed to different levels of light, CO2, temperature, nitrogen fertilization treatments, and drought. We used this relationship in a photosynthesis model. The coupled model enabled us to quantify the relationships between steady state chlorophyll fluorescence yield, electron transport rate, and photosynthesis in leaves under different environmental conditions. Key Points Light saturation of photosynthesis determines quenching of leaf fluorescence We incorporated steady state leaf fluorescence in a photosynthesis model PMID:27398266

  3. Micelle-monomer equilibria in solutions of ionic surfactants and in ionic-nonionic mixtures: a generalized phase separation model.

    PubMed

    Danov, Krassimir D; Kralchevsky, Peter A; Ananthapadmanabhan, Kavssery P

    2014-04-01

    On the basis of a detailed physicochemical model, a complete system of equations is formulated that describes the equilibrium between micelles and monomers in solutions of ionic surfactants and their mixtures with nonionic surfactants. The equations of the system express mass balances, chemical and mechanical equilibria. Each nonionic surfactant is characterized by a single thermodynamic parameter--its micellization constant. Each ionic surfactant is characterized by three parameters, including the Stern constant that quantifies the counterion binding. In the case of mixed micelles, each pair of surfactants is characterized with an interaction parameter, β, in terms of the regular solution theory. The comparison of the model with experimental data for surfactant binary mixtures shows that β is constant--independent of the micelle composition and electrolyte concentration. The solution of the system of equations gives the concentrations of all monomeric species, the micelle composition, ionization degree, surface potential and mean area per head group. Upon additional assumptions for the micelle shape, the mean aggregation number can be also estimated. The model gives quantitative theoretical interpretation of the dependence of the critical micellization concentration (CMC) of ionic surfactants on the ionic strength; of the CMC of mixed surfactant solutions, and of the electrolytic conductivity of micellar solutions. It turns out, that in the absence of added salt the conductivity is completely dominated by the contribution of the small ions: monomers and counterions. The theoretical predictions are in good agreement with experimental data.

  4. Patterns and Variability in Global Ocean Chlorophyll: Satellite Observations and Modeling

    NASA Technical Reports Server (NTRS)

    Gregg, Watson

    2004-01-01

    Recent analyses of SeaWiFS data have shown that global ocean chlorophyll has increased more than 4% since 1998. The North Pacific ocean basin has increased nearly 19%. These trend analyses follow earlier results showing decadal declines in global ocean chlorophyll and primary production. To understand the causes of these changes and trends we have applied the newly developed NASA Ocean Biogeochemical Assimilation Model (OBAM), which is driven in mechanistic fashion by surface winds, sea surface temperature, atmospheric iron deposition, sea ice, and surface irradiance. The model utilizes chlorophyll from SeaWiFS in a daily assimilation. The model has in place many of the climatic variables that can be expected to produce the changes observed in SeaWiFS data. This enables us to diagnose the model performance, the assimilation performance, and possible causes for the increase in chlorophyll. A full discussion of the changes and trends, possible causes, modeling approaches, and data assimilation will be the focus of the seminar.

  5. [A Three Band Chlorophyll-a Concentration Estimation Model Based on GOCI Imagery].

    PubMed

    Guo, Yu-long; Li, Yun-mei; Li, Yuan; Lü, Heng; Liu, Ge; Wang, Xu-dong; Zhang, Si-min

    2015-09-01

    A GOCI-based three band model is proposed for chlorophyll-a concentration estimation based on the classical three band model. The model was built based on 289 in-situ measured chlorophyll-a concentration and hyperspectral spectrums-simulated GOCI spectrums, and was compared with MERIS-based three band model and GOCI band ratio model. At last, the model was validated using several GOCI images and an independent in-situ sampling dataset. The results showed that: (1) For the current dataset, the ratio of aph (680) and aph (660) was relatively stable. (2) The GOCI-based three band algorithm had a similar performance with MERIS-based three band algorithm in the modeling dataset. The R2 value of the GOCI-based three band model was 0. 809, which was a little lower than that of the MERIS-based three band model (R2 = 0. 820), but was obviously higher than that of GOCI band ratio model (R2 = 0. 450). (3) The performance of GOCI-based three band model in the validation dataset was similar with that in the modeling dataset, which was close to that of the MERIS-based three band model, and significantly better than that of GOCI band ratio model. (4) The GOCI image data validation indicated that GOCI band ratio model would clearly underestimate chlorophyll-a concentration in Taihu Lake. The spatial difference of chlorophyll-a concentration that yielded by the band ratio model was not clear. Compared with the widely used band ratio algorithm, the GOCI-based three band algorithm has higher stability, better accuracy, and stronger potential in application.

  6. [A Three Band Chlorophyll-a Concentration Estimation Model Based on GOCI Imagery].

    PubMed

    Guo, Yu-long; Li, Yun-mei; Li, Yuan; Lü, Heng; Liu, Ge; Wang, Xu-dong; Zhang, Si-min

    2015-09-01

    A GOCI-based three band model is proposed for chlorophyll-a concentration estimation based on the classical three band model. The model was built based on 289 in-situ measured chlorophyll-a concentration and hyperspectral spectrums-simulated GOCI spectrums, and was compared with MERIS-based three band model and GOCI band ratio model. At last, the model was validated using several GOCI images and an independent in-situ sampling dataset. The results showed that: (1) For the current dataset, the ratio of aph (680) and aph (660) was relatively stable. (2) The GOCI-based three band algorithm had a similar performance with MERIS-based three band algorithm in the modeling dataset. The R2 value of the GOCI-based three band model was 0. 809, which was a little lower than that of the MERIS-based three band model (R2 = 0. 820), but was obviously higher than that of GOCI band ratio model (R2 = 0. 450). (3) The performance of GOCI-based three band model in the validation dataset was similar with that in the modeling dataset, which was close to that of the MERIS-based three band model, and significantly better than that of GOCI band ratio model. (4) The GOCI image data validation indicated that GOCI band ratio model would clearly underestimate chlorophyll-a concentration in Taihu Lake. The spatial difference of chlorophyll-a concentration that yielded by the band ratio model was not clear. Compared with the widely used band ratio algorithm, the GOCI-based three band algorithm has higher stability, better accuracy, and stronger potential in application. PMID:26717676

  7. Accumulation and toxicity of antibody-targeted doxorubicin-loaded PEG-PE micelles in ovarian cancer cell spheroid model.

    PubMed

    Perche, Federico; Patel, Niravkumar R; Torchilin, Vladimir P

    2012-11-28

    We describe the evaluation of doxorubicin-loaded PEG-PE micelles targeting using an ovarian cancer cell spheroid model. Most ovarian cancer patients present at an advanced clinical stage and develop resistance to standard of care platinum/taxane therapy. Doxorubicin is also approved for ovarian cancer but had limited benefits in refractory patients. In this study, we used drug-resistant spheroid cultures of ovarian carcinoma to evaluate the uptake and cytotoxicity of an antibody-targeted doxorubicin formulation. Doxorubicin was encapsulated in polyethylene glycol-phosphatidyl ethanolamine (PEG-PE) conjugated micelles. The doxorubicin-loaded PEG-PE micelles (MDOX) were further decorated with a cancer cell-specific monoclonal 2C5 antibody to obtain doxorubicin-loaded immunomicelles (2C5-MDOX). Targeting and resulting toxicity of doxorubicin-loaded PEG-PE micelles were evaluated in three dimensional cancer cell spheroids. Superior accumulation of 2C5-MDOX compared to free doxorubicin or untargeted MDOX in spheroids was evidenced both by flow cytometry, fluorescence and confocal microscopy. Interestingly, even higher toxicity was measured by lactate dehydrogenase release and terminal deoxynucleotidyl transferase dUTP nick end labeling of targeted doxorubicin micelles in Bcl-2 overexpressing adriamycin-resistant spheroids. Overall, these results support use of spheroids to evaluate tumor targeted drug delivery. PMID:22974689

  8. Accumulation and toxicity of antibody-targeted doxorubicin-loaded PEG-PE micelles in ovarian cancer cell spheroid model

    PubMed Central

    Perche, Federico; Torchilin, Vladimir P.

    2012-01-01

    We describe the evaluation of doxorubicin-loaded PEG-PE micelles targeting using an ovarian cancer cell spheroid model. Most ovarian cancer patients present at an advanced clinical stage and develop resistance to standard of care platinum/taxane therapy. Doxorubicin is also approved for ovarian cancer but had limited benefits in refractory patients. In this study, we used drug-resistant spheroid cultures of ovarian carcinoma to evaluate the uptake and cytotoxicity of an antibody-targeted doxorubicin formulation. Doxorubicin was encapsulated in polyethylene glycol-phosphatidyl ethanolamine (PEG-PE) conjugated micelles. The doxorubicin-loaded PEG-PE micelles (MDOX) were further decorated with a cancer cell-specific monoclonal 2C5 antibody to obtain doxorubicin-loaded immunomicelles (2C5-MDOX). Targeting and resulting toxicity of doxorubicin-loaded PEG-PE micelles were evaluated in three dimensional cancer cell spheroids. Superior accumulation of 2C5-MDOX compared to free doxorubicin or untargeted MDOX in spheroids was evidenced both by flow cytometry, fluorescence and confocal microscopy. Interestingly, even higher toxicity was measured by lactate dehydrogenase release and terminal deoxynucleotidyl transferase dUTP nick end labeling of targeted doxorubicin micelles in Bcl-2 overexpressing adriamycin-resistant spheroids. Overall, these results support use of spheroids to evaluate tumor targeted drug delivery. PMID:22974689

  9. Complex coacervate core micelles.

    PubMed

    Voets, Ilja K; de Keizer, Arie; Cohen Stuart, Martien A

    2009-01-01

    In this review we present an overview of the literature on the co-assembly of neutral-ionic block, graft, and random copolymers with oppositely charged species in aqueous solution. Oppositely charged species include synthetic (co)polymers of various architectures, biopolymers - such as proteins, enzymes and DNA - multivalent ions, metallic nanoparticles, low molecular weight surfactants, polyelectrolyte block copolymer micelles, metallo-supramolecular polymers, equilibrium polymers, etcetera. The resultant structures are termed complex coacervate core/polyion complex/block ionomer complex/interpolyelectrolyte complex micelles (or vesicles); i.e., in short C3Ms (or C3Vs) and PIC, BIC or IPEC micelles (and vesicles). Formation, structure, dynamics, properties, and function will be discussed. We focus on experimental work; theory and modelling will not be discussed. Recent developments in applications and micelles with heterogeneous coronas are emphasized.

  10. Molecular Modeling of Triton X Micelles: Force Field Parameters, Self-Assembly, and Partition Equilibria.

    PubMed

    Yordanova, D; Smirnova, I; Jakobtorweihen, S

    2015-05-12

    Nonionic surfactants of the Triton X-series find various applications in extraction processes and as solubilizing agents for the purification of membrane proteins. However, so far no optimized parameters are available to perform molecular simulations with a biomolecular force field. Therefore, we have determined the first optimized set of CHARMM parameters for the Triton X-series, enabling all-atom molecular dynamics (MD) simulations. In order to validate the new parameters, micellar sizes (aggregation numbers) of Triton X-114 and Triton X-100 have been investigated as a function of temperature and surfactant concentration. These results are comparable with experimental results. Furthermore, we have introduced a new algorithm to obtain micelle structures from self-assembly MD simulations for the COSMOmic method. This model allows efficient partition behavior predictions once a representative micelle structure is available. The predicted partition coefficients for the systems Triton X-114/water and Triton X-100/water are in excellent agreement with experimental results. Therefore, this method can be applied as a screening tool to find optimal solute-surfactant combinations or suitable surfactant systems for a specific application.

  11. Molecular-dynamics simulation of amphiphilic bilayer membranes and wormlike micelles: a multi-scale modelling approach to the design of viscoelastic surfactant solutions.

    PubMed

    Boek, E S; Den Otter, W K; Briels, W J; Iakovlev, D

    2004-08-15

    Bilayer membranes and wormlike micelles have been studied using molecular-dynamics simulations. The structure of the worm is analysed in terms of radial density distribution functions, and mechanical properties such as the elastic modulus are calculated. From an analysis of the fluctuation spectra of the tensionless states, we have calculated bending rigidities. Micelles consisting of coarse-grained (CG) model surfactants are studied in order to map the properties of the atomistic micelle. We optimize the CG model with respect to the structure factor of the atomistic micelle. The mechanical properties thus obtained will be used as input for a mesoscopic model of wormlike micelles where the persistence length is the smallest length-scale.

  12. Dynamic laser light scattering studies of the micelle to vesicle transition in model and native bile.

    PubMed

    Schurtenberger, P; Mazer, N A; Känzig, W

    1984-01-01

    Using quasielastic light scattering, we investigated the formation of vesicles produced spontaneously by diluting a mixed micellar solution of bile salt and lecithin beyond the micellar phase boundary. The vesicles were nearly monodisperse, and their size varied between 120 to 500 A depending upon the dilution conditions. A systematic study of the dependence of the vesicle size upon the bile salt and lecithin concentration was made and interpreted in terms of a simple equilibrium model. Likewise, the particle size distribution in native bile obtained from the dog was studied. A comparison of the dilution effect on native bile and on model bile of identical biliary lipid composition provides unambiguous evidence for micellar aggregates and the occurrence of a micelle to vesicle transition in native bile.

  13. Evaluation of drug penetration with cationic micelles and their penetration mechanism using an in vitro tumor model.

    PubMed

    Suzuki, Hidenori; Bae, You Han

    2016-08-01

    Elevated interstitial fluid pressure (IFP) and abnormal extracellular matrix (ECM) are major factors causing significant barriers to penetration of nanomedicines in solid tumors. To better understand the barriers, various in vitro tumor models including multicellular spheroids and multilayered cell cultures (MCCs) have been developing. Recently, we have established a unique in vitro tumor model composed of a MCC and an Ussing chamber system which is modified to add a hydraulic pressure gradient through the MCC. In this study, we evaluated the drug penetration ability of cationic micelles using the unique in vitro tumor model. The doxorubicin (DOX)-loaded cationic micelles, which are formed from a triblock copolymer of poly(d,l-lactide-co-glycolide)-block-branched polyethyleneimine-block-poly(d,l-lactide-co-glycolide), deeply penetrated and released the DOX throughout the MCC against convectional flow caused by a hydraulic pressure gradient. The studies using endocytosis markers and inhibitors showed that the micelles utilized mainly macropinocytosis as an internalization pathway. Furthermore, the penetration was apparently inhibited by treatment with exocytosis inhibitor Exo1. These results suggest that the active penetration of the cationic micelles is induced by iterative transcytosis via macropinocytosis and exocytosis. Our findings could be beneficial information to improve intratumoral penetration in new nanomedicines for solid tumors. PMID:27182814

  14. A predictive model of reverse micelles solubilizing water for solvent extraction.

    PubMed

    Bley, Michael; Siboulet, Bertrand; Karmakar, Anwesa; Zemb, Thomas; Dufrêche, Jean-François

    2016-10-01

    Herein, a minimal model for the common case of W/O solubilization of badly soluble compounds present in an excess phase by reverse micellar aggregates in chemical equilibrium with its single compounds is introduced. A simple model of such liquid-liquid extractions is crucial for obtaining predictive parameter for the modelling of nuclear waste management and hydrometallurgic recycling strategies. The standard Gibbs free energy of aggregation and the concentration of the corresponding aggregate is calculated within a multiple-equilibria approach for a set of aggregate compositions of solute and amphiphilic extractant molecules. This minimal model provides potential surfaces estimating the stability of different aggregate compositions with 6.2kJmol(-1) as a generalized bending constant. The complete concentrations of free and aggregated extractant species as well as the favored aggregation numbers, the polydispersity, the activity of the organic solvent, and the critical concentrations are captured by this thermodynamic model. An increase of the apparent critical micelle concentration for an increasing solute content in the aqueous phase is detected by this method. PMID:27376975

  15. Assessment of predictive models for chlorophyll-a concentration of a tropical lake

    PubMed Central

    2011-01-01

    Background This study assesses four predictive ecological models; Fuzzy Logic (FL), Recurrent Artificial Neural Network (RANN), Hybrid Evolutionary Algorithm (HEA) and multiple linear regressions (MLR) to forecast chlorophyll- a concentration using limnological data from 2001 through 2004 of unstratified shallow, oligotrophic to mesotrophic tropical Putrajaya Lake (Malaysia). Performances of the models are assessed using Root Mean Square Error (RMSE), correlation coefficient (r), and Area under the Receiving Operating Characteristic (ROC) curve (AUC). Chlorophyll-a have been used to estimate algal biomass in aquatic ecosystem as it is common in most algae. Algal biomass indicates of the trophic status of a water body. Chlorophyll- a therefore, is an effective indicator for monitoring eutrophication which is a common problem of lakes and reservoirs all over the world. Assessments of these predictive models are necessary towards developing a reliable algorithm to estimate chlorophyll- a concentration for eutrophication management of tropical lakes. Results Same data set was used for models development and the data was divided into two sets; training and testing to avoid biasness in results. FL and RANN models were developed using parameters selected through sensitivity analysis. The selected variables were water temperature, pH, dissolved oxygen, ammonia nitrogen, nitrate nitrogen and Secchi depth. Dissolved oxygen, selected through stepwise procedure, was used to develop the MLR model. HEA model used parameters selected using genetic algorithm (GA). The selected parameters were pH, Secchi depth, dissolved oxygen and nitrate nitrogen. RMSE, r, and AUC values for MLR model were (4.60, 0.5, and 0.76), FL model were (4.49, 0.6, and 0.84), RANN model were (4.28, 0.7, and 0.79) and HEA model were (4.27, 0.7, and 0.82) respectively. Performance inconsistencies between four models in terms of performance criteria in this study resulted from the methodology used in measuring

  16. Revisiting the chlorophyll biosynthesis pathway using genome scale metabolic model of Oryza sativa japonica.

    PubMed

    Chatterjee, Ankita; Kundu, Sudip

    2015-01-01

    Chlorophyll is one of the most important pigments present in green plants and rice is one of the major food crops consumed worldwide. We curated the existing genome scale metabolic model (GSM) of rice leaf by incorporating new compartment, reactions and transporters. We used this modified GSM to elucidate how the chlorophyll is synthesized in a leaf through a series of bio-chemical reactions spanned over different organelles using inorganic macronutrients and light energy. We predicted the essential reactions and the associated genes of chlorophyll synthesis and validated against the existing experimental evidences. Further, ammonia is known to be the preferred source of nitrogen in rice paddy fields. The ammonia entering into the plant is assimilated in the root and leaf. The focus of the present work is centered on rice leaf metabolism. We studied the relative importance of ammonia transporters through the chloroplast and the cytosol and their interlink with other intracellular transporters. Ammonia assimilation in the leaves takes place by the enzyme glutamine synthetase (GS) which is present in the cytosol (GS1) and chloroplast (GS2). Our results provided possible explanation why GS2 mutants show normal growth under minimum photorespiration and appear chlorotic when exposed to air. PMID:26443104

  17. Revisiting the chlorophyll biosynthesis pathway using genome scale metabolic model of Oryza sativa japonica

    PubMed Central

    Chatterjee, Ankita; Kundu, Sudip

    2015-01-01

    Chlorophyll is one of the most important pigments present in green plants and rice is one of the major food crops consumed worldwide. We curated the existing genome scale metabolic model (GSM) of rice leaf by incorporating new compartment, reactions and transporters. We used this modified GSM to elucidate how the chlorophyll is synthesized in a leaf through a series of bio-chemical reactions spanned over different organelles using inorganic macronutrients and light energy. We predicted the essential reactions and the associated genes of chlorophyll synthesis and validated against the existing experimental evidences. Further, ammonia is known to be the preferred source of nitrogen in rice paddy fields. The ammonia entering into the plant is assimilated in the root and leaf. The focus of the present work is centered on rice leaf metabolism. We studied the relative importance of ammonia transporters through the chloroplast and the cytosol and their interlink with other intracellular transporters. Ammonia assimilation in the leaves takes place by the enzyme glutamine synthetase (GS) which is present in the cytosol (GS1) and chloroplast (GS2). Our results provided possible explanation why GS2 mutants show normal growth under minimum photorespiration and appear chlorotic when exposed to air. PMID:26443104

  18. Revisiting the chlorophyll biosynthesis pathway using genome scale metabolic model of Oryza sativa japonica.

    PubMed

    Chatterjee, Ankita; Kundu, Sudip

    2015-10-07

    Chlorophyll is one of the most important pigments present in green plants and rice is one of the major food crops consumed worldwide. We curated the existing genome scale metabolic model (GSM) of rice leaf by incorporating new compartment, reactions and transporters. We used this modified GSM to elucidate how the chlorophyll is synthesized in a leaf through a series of bio-chemical reactions spanned over different organelles using inorganic macronutrients and light energy. We predicted the essential reactions and the associated genes of chlorophyll synthesis and validated against the existing experimental evidences. Further, ammonia is known to be the preferred source of nitrogen in rice paddy fields. The ammonia entering into the plant is assimilated in the root and leaf. The focus of the present work is centered on rice leaf metabolism. We studied the relative importance of ammonia transporters through the chloroplast and the cytosol and their interlink with other intracellular transporters. Ammonia assimilation in the leaves takes place by the enzyme glutamine synthetase (GS) which is present in the cytosol (GS1) and chloroplast (GS2). Our results provided possible explanation why GS2 mutants show normal growth under minimum photorespiration and appear chlorotic when exposed to air.

  19. A Graphical User Interface for Parameterizing Biochemical Models of Photosynthesis and Chlorophyll Fluorescence

    NASA Astrophysics Data System (ADS)

    Kornfeld, A.; Van der Tol, C.; Berry, J. A.

    2015-12-01

    Recent advances in optical remote sensing of photosynthesis offer great promise for estimating gross primary productivity (GPP) at leaf, canopy and even global scale. These methods -including solar-induced chlorophyll fluorescence (SIF) emission, fluorescence spectra, and hyperspectral features such as the red edge and the photochemical reflectance index (PRI) - can be used to greatly enhance the predictive power of global circulation models (GCMs) by providing better constraints on GPP. The way to use measured optical data to parameterize existing models such as SCOPE (Soil Canopy Observation, Photochemistry and Energy fluxes) is not trivial, however. We have therefore extended a biochemical model to include fluorescence and other parameters in a coupled treatment. To help parameterize the model, we then use nonlinear curve-fitting routines to determine the parameter set that enables model results to best fit leaf-level gas exchange and optical data measurements. To make the tool more accessible to all practitioners, we have further designed a graphical user interface (GUI) based front-end to allow researchers to analyze data with a minimum of effort while, at the same time, allowing them to change parameters interactively to visualize how variation in model parameters affect predicted outcomes such as photosynthetic rates, electron transport, and chlorophyll fluorescence. Here we discuss the tool and its effectiveness, using recently-gathered leaf-level data.

  20. Analysis of Seasonal Chlorophyll-a Using An Adjoint Three-Dimensional Ocean Carbon Cycle Model

    NASA Astrophysics Data System (ADS)

    Tjiputra, J.; Winguth, A.; Polzin, D.

    2004-12-01

    The misfit between numerical ocean model and observations can be reduced using data assimilation. This can be achieved by optimizing the model parameter values using adjoint model. The adjoint model minimizes the model-data misfit by estimating the sensitivity or gradient of the cost function with respect to initial condition, boundary condition, or parameters. The adjoint technique was used to assimilate seasonal chlorophyll-a data from the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) satellite to a marine biogeochemical model HAMOCC5.1. An Identical Twin Experiment (ITE) was conducted to test the robustness of the model and the non-linearity level of the forward model. The ITE experiment successfully recovered most of the perturbed parameter to their initial values, and identified the most sensitive ecosystem parameters, which contribute significantly to model-data bias. The regional assimilations of SeaWiFS chlorophyll-a data into the model were able to reduce the model-data misfit (i.e. the cost function) significantly. The cost function reduction mostly occurred in the high latitudes (e.g. the model-data misfit in the northern region during summer season was reduced by 54%). On the other hand, the equatorial regions appear to be relatively stable with no strong reduction in cost function. The optimized parameter set is used to forecast the carbon fluxes between marine ecosystem compartments (e.g. Phytoplankton, Zooplankton, Nutrients, Particulate Organic Carbon, and Dissolved Organic Carbon). The a posteriori model run using the regional best-fit parameterization yields approximately 36 PgC/yr of global net primary productions in the euphotic zone.

  1. Equilibrium and Kinetics of Block Copolymers Micelles

    NASA Astrophysics Data System (ADS)

    Mysona, Joshua; Morse, David

    Both equilibrium properties of micelles, such as the critical micelle concentration (CMC), and dynamical properties such as the micelle lifetime are difficult to study in simulations because of the slow dynamics of the processes by which micelles are created and destroyed. We first discuss a method of precisely identifying the CMC in a simple model of block copolymer micelles in a homopolymer matrix, which makes use of thermodynamic integration to compute the free energy of formation. We then examine the free energy barriers to competing mechanisms for creating and destroying micelles, which could occur predominantly either by a step-wise process involving insertion and extraction of single molecules or by fission and fusion of entire micelles.

  2. A novel reflectance-based model for evaluating chlorophyll concentrations of fresh and water-stressed leaves

    NASA Astrophysics Data System (ADS)

    Lin, C.; Popescu, S. C.; Huang, S. C.; Chang, P. T.; Wen, H. L.

    2015-01-01

    Water deficits can cause chlorophyll degradation which decreases the total concentration of chlorophyll a and b (Chls). Few studies have investigated the effectiveness of spectral indices under water-stressed conditions. Chlorophyll meters have been extensively used for a wide variety of leaf chlorophyll and nitrogen estimations. Since a chlorophyll meter works by sensing leaves absorptance and transmittance, the reading of chlorophyll concentration will be affected by changes in transmittance as if there were a water deficit in the leaves. The overall objective of this paper was to develop a novel and reliable reflectance-based model for estimating Chls of fresh and water-stressed leaves using the reflectance at the absorption bands of chlorophyll a and b and the red edge spectrum. Three independent experiments were designed to collect data from three leaf sample sets for the construction and validation of Chls estimation models. First, a reflectance experiment was conducted to collect foliar Chls and reflectance of leaves with varying water stress using the ASD FieldSpec spectroradiometer. Second, a chlorophyll meter (SPAD-502) experiment was carried out to collect foliar Chls and meter readings. These two data sets were separately used for developing reflectance-based or absorptance-based Chls estimation models using linear and nonlinear regression analysis. Suitable models were suggested mainly based on the coefficient of determination (R2). Finally, an experiment was conducted to collect the third data set for the validation of Chls models using the root mean squared error (RMSE) and the mean absolute error (MAE). In all of the experiments, the observations (real values) of the foliar Chls were extracted from acetone solution and determined by using a Hitachi U-2000 spectrophotometer. The spectral indices in the form of reflectance ratio/difference/slope derived from the Chl b absorption bands (ρ645 and ρ455) provided Chls estimates with RMSE around 0

  3. Effectiveness of Losartan-Loaded Hyaluronic Acid (HA) Micelles for the Reduction of Advanced Hepatic Fibrosis in C3H/HeN Mice Model

    PubMed Central

    Thomas, Reju George; Moon, Myeong Ju; Kim, Jo Heon; Lee, Jae Hyuk; Jeong, Yong Yeon

    2015-01-01

    Advanced hepatic fibrosis therapy using drug-delivering nanoparticles is a relatively unexplored area. Angiotensin type 1 (AT1) receptor blockers such as losartan can be delivered to hepatic stellate cells (HSC), blocking their activation and thereby reducing fibrosis progression in the liver. In our study, we analyzed the possibility of utilizing drug-loaded vehicles such as hyaluronic acid (HA) micelles carrying losartan to attenuate HSC activation. Losartan, which exhibits inherent lipophilicity, was loaded into the hydrophobic core of HA micelles with a 19.5% drug loading efficiency. An advanced liver fibrosis model was developed using C3H/HeN mice subjected to 20 weeks of prolonged TAA/ethanol weight-adapted treatment. The cytocompatibility and cell uptake profile of losartan-HA micelles were studied in murine fibroblast cells (NIH3T3), human hepatic stellate cells (hHSC) and FL83B cells (hepatocyte cell line). The ability of these nanoparticles to attenuate HSC activation was studied in activated HSC cells based on alpha smooth muscle actin (α-sma) expression. Mice treated with oral losartan or losartan-HA micelles were analyzed for serum enzyme levels (ALT/AST, CK and LDH) and collagen deposition (hydroxyproline levels) in the liver. The accumulation of HA micelles was observed in fibrotic livers, which suggests increased delivery of losartan compared to normal livers and specific uptake by HSC. Active reduction of α-sma was observed in hHSC and the liver sections of losartan-HA micelle-treated mice. The serum enzyme levels and collagen deposition of losartan-HA micelle-treated mice was reduced significantly compared to the oral losartan group. Losartan-HA micelles demonstrated significant attenuation of hepatic fibrosis via an HSC-targeting mechanism in our in vitro and in vivo studies. These nanoparticles can be considered as an alternative therapy for liver fibrosis. PMID:26714035

  4. Effectiveness of Losartan-Loaded Hyaluronic Acid (HA) Micelles for the Reduction of Advanced Hepatic Fibrosis in C3H/HeN Mice Model.

    PubMed

    Thomas, Reju George; Moon, Myeong Ju; Kim, Jo Heon; Lee, Jae Hyuk; Jeong, Yong Yeon

    2015-01-01

    Advanced hepatic fibrosis therapy using drug-delivering nanoparticles is a relatively unexplored area. Angiotensin type 1 (AT1) receptor blockers such as losartan can be delivered to hepatic stellate cells (HSC), blocking their activation and thereby reducing fibrosis progression in the liver. In our study, we analyzed the possibility of utilizing drug-loaded vehicles such as hyaluronic acid (HA) micelles carrying losartan to attenuate HSC activation. Losartan, which exhibits inherent lipophilicity, was loaded into the hydrophobic core of HA micelles with a 19.5% drug loading efficiency. An advanced liver fibrosis model was developed using C3H/HeN mice subjected to 20 weeks of prolonged TAA/ethanol weight-adapted treatment. The cytocompatibility and cell uptake profile of losartan-HA micelles were studied in murine fibroblast cells (NIH3T3), human hepatic stellate cells (hHSC) and FL83B cells (hepatocyte cell line). The ability of these nanoparticles to attenuate HSC activation was studied in activated HSC cells based on alpha smooth muscle actin (α-sma) expression. Mice treated with oral losartan or losartan-HA micelles were analyzed for serum enzyme levels (ALT/AST, CK and LDH) and collagen deposition (hydroxyproline levels) in the liver. The accumulation of HA micelles was observed in fibrotic livers, which suggests increased delivery of losartan compared to normal livers and specific uptake by HSC. Active reduction of α-sma was observed in hHSC and the liver sections of losartan-HA micelle-treated mice. The serum enzyme levels and collagen deposition of losartan-HA micelle-treated mice was reduced significantly compared to the oral losartan group. Losartan-HA micelles demonstrated significant attenuation of hepatic fibrosis via an HSC-targeting mechanism in our in vitro and in vivo studies. These nanoparticles can be considered as an alternative therapy for liver fibrosis.

  5. A Coupled Ocean General Circulation, Biogeochemical, and Radiative Model of the Global Oceans: Seasonal Distributions of Ocean Chlorophyll and Nutrients

    NASA Technical Reports Server (NTRS)

    Gregg, Watson W.; Busalacchi, Antonio (Technical Monitor)

    2000-01-01

    A coupled ocean general circulation, biogeochemical, and radiative model was constructed to evaluate and understand the nature of seasonal variability of chlorophyll and nutrients in the global oceans. Biogeochemical processes in the model are determined from the influences of circulation and turbulence dynamics, irradiance availability. and the interactions among three functional phytoplankton groups (diatoms. chlorophytes, and picoplankton) and three nutrients (nitrate, ammonium, and silicate). Basin scale (greater than 1000 km) model chlorophyll results are in overall agreement with CZCS pigments in many global regions. Seasonal variability observed in the CZCS is also represented in the model. Synoptic scale (100-1000 km) comparisons of imagery are generally in conformance although occasional departures are apparent. Model nitrate distributions agree with in situ data, including seasonal dynamics, except for the equatorial Atlantic. The overall agreement of the model with satellite and in situ data sources indicates that the model dynamics offer a reasonably realistic simulation of phytoplankton and nutrient dynamics on synoptic scales. This is especially true given that initial conditions are homogenous chlorophyll fields. The success of the model in producing a reasonable representation of chlorophyll and nutrient distributions and seasonal variability in the global oceans is attributed to the application of a generalized, processes-driven approach as opposed to regional parameterization and the existence of multiple phytoplankton groups with different physiological and physical properties. These factors enable the model to simultaneously represent many aspects of the great diversity of physical, biological, chemical, and radiative environments encountered in the global oceans.

  6. Hyperspectral remote sensing of crop leaf chlorophyll content using reflectance simulation model and field data in open canopies

    NASA Astrophysics Data System (ADS)

    Jiao, Quanjun; Wu, Yanhong; Liu, Liangyun; Zhang, Bing

    2015-04-01

    Leaf chlorophyll content -a and -b content (Cab) is an indicator for crop nutrition status and photosynthetic capacity. Remote sensing of Cab plays an important role in crop growth monitoring, pest and disease diagnosis, and crop yield assessment, yet the feasibility and stability of such estimation has not been assessed thoroughly for mixed pixels when crop canopies are not closed. This study analyzes the influence of spectral mixing on leaf chlorophyll content estimation using canopy spectra simulated by the PROSAIL reflectance model and the spectral linear mixture concept. It is observed that the accuracy of leaf chlorophyll content estimation would be degraded for mixed pixels using the well accepted approach of the combination of TCARI and OSAVI. A two-step method was thus developed for winter wheat chlorophyll content estimation by taking into consideration the fractional vegetation cover using a look-up table approach. The two methods were validated using ground spectra, airborne hyperspectral data and leaf chlorophyll content measured the same time over experimental winter wheat fields. Using the two-step method, the leaf chlorophyll content of the open canopy was estimated from the airborne hyperspectral imagery with a root mean square error of 5.18 μg cm-2, which is an improvement of about 8.9% relative to the accuracy obtained using the TCARI/OSAVI ratio directly. This implies that the method proposed in this study has great potential for hyperspectral applications in agricultural management, particularly for applications before crop canopy closure. This study, therefore, offers a feasible technique that might be applied to crop chlorophyll content estimation using large-scale remote sensing data.

  7. Evaluating leaf chlorophyll content prediction from multispectral remote sensing data within a physically-based modelling framework

    NASA Astrophysics Data System (ADS)

    Croft, H.; Chen, J. M.; Zhang, Y.; Simic, A.; Noland, T. L.; Nesbitt, N.; Arabian, J.

    2015-04-01

    Accurate modelling of leaf chlorophyll content over a range of spatial and temporal scales is central to monitoring vegetation stress and physiological condition, and vegetation response to different ecological, climatic and anthropogenic drivers. A process-based modelling approach can account for variation in other factors affecting canopy reflectance, providing a more accurate estimate of chlorophyll content across different vegetation species, time-frames, and broader spatial extents. However, physically-based modelling studies usually use hyperspectral data, neglecting a wealth of data from broadband and multispectral sources. In this study, we assessed the potential for using canopy (4-Scale) and leaf radiative transfer (PROSPECT4/5) models to estimate leaf chlorophyll content using canopy Landsat satellite data and simulated Landsat bands from leaf level hyperspectral reflectance data. Over 600 leaf samples were used to test the performance of PROSPECT for different vegetation species, including black spruce (Picea mariana), sugar maple (Acer saccharum), trembling aspen (Populus tremuloides) and jack pine (Pinus banksiana). At the leaf level, hyperspectral and simulated Landsat bands showed very similar results to laboratory measured chlorophyll (R2 = 0.77 and R2 = 0.75, respectively). Comparisons between PROSPECT4 modelled chlorophyll from simulated Landsat and hyperspectral spectra showed a very close correspondence (R2 = 0.97, root mean square error (RMSE) = 3.01 μg/cm2), as did simulated reflectance bands from other broadband and narrowband sensors (MODIS: R2 = 0.99, RMSE = 1.80 μg/cm2; MERIS: R2 = 0.97, RMSE = 2.50 μg/cm2 and SPOT5 HRG: R2 = 0.96, RMSE = 5.38 μg/cm2). Modelled leaf chlorophyll content from Landsat 5 TM canopy reflectance data, acquired from over 40 ground validation sites, demonstrated a strong relationship with measured leaf chlorophyll content (R2 = 0.78, RMSE = 8.73 μg/cm2, p < 0.001), and a high linearity with negligible

  8. Enhanced antitumor activity and mechanism of biodegradable polymeric micelles-encapsulated chetomin in both transgenic zebrafish and mouse models

    NASA Astrophysics Data System (ADS)

    Wu, Qinjie; Li, Guoyou; Deng, Senyi; Ouyang, Liang; Li, Ling; Liu, Lei; Luo, Na; Song, Xiangrong; He, Gu; Gong, Changyang; Wei, Yuquan

    2014-09-01

    Chetomin is a promising molecule with anti-tumor activities in the epipolythiodioxopiperazine family of fungal secondary metabolites; however, strong hydrophobicity has limited its further applications. In this work, chetomin was encapsulated into polymeric micelles to obtain an aqueous formulation, and the chetomin loaded micelles (Che-M) exhibited small particle size and high encapsulation efficiency. When the concentration of copolymer was higher than the critical gelation concentration, the Che-M could form a thermosensitive hydrogel (Che-H), which was free-flowing sol at ambient temperature and converted into a non-flowing gel at body temperature. The molecular modeling study has indicated that chetomin interacted with PCL as a core, which was embraced by PEG as a shell. Che-M showed equal cytotoxicity with free chetomin, but the apoptosis inducing effects of Che-M were more significant. Besides, Che-M could increase the GSSG level, decrease the GSH level, and increase the ROS in CT26 cells. Furthermore, stronger inhibitory effects of Che-M were observed on embryonic angiogenesis, tumor-induced angiogenesis and tumor growth in transgenic zebrafish models. In addition, Che-M was effective in inhibiting tumor growth and prolonging survival in a subcutaneous CT26 tumor model. In a colorectal peritoneal carcinomatosis model, both Che-M and Che-H showed excellent therapeutic effects, but Che-H was more effective. In conclusion, Che-M and Che-H may serve as candidates for cancer therapy.

  9. Determination of thermodynamic potentials and the aggregation number for micelles with the mass-action model by isothermal titration calorimetry: A case study on bile salts.

    PubMed

    Olesen, Niels Erik; Westh, Peter; Holm, René

    2015-09-01

    The aggregation number (n), thermodynamic potentials (ΔG, ΔH, ΔS) and critical micelle concentration (CMC) for 6 natural bile salts were determined on the basis of both original and previously published isothermal titration calorimetry (ITC) data. Different procedures to estimate parameters of micelles with ITC were compared to a mass-action model (MAM) of reaction type: n⋅S⇌Mn. This analysis can provide guidelines for future ITC studies of systems behaving in accordance with this model such as micelles and proteins that undergo self-association to oligomers. Micelles with small aggregation numbers, as those of bile salts, are interesting because such small aggregates cannot be characterized as a separate macroscopic phase and the widely applied pseudo-phase model (PPM) is inaccurate. In the present work it was demonstrated that the aggregation number of micelles was constant at low concentrations enabling determination of the thermodynamic potentials by the MAM. A correlation between the aggregation number and the heat capacity was found, which implies that the dehydrated surface area of bile salts increases with the aggregation number. This is in accordance with Tanford's principles of opposing forces where neighbouring molecules in the aggregate are better able to shield from the surrounding hydrophilic environment when the aggregation number increases.

  10. Simulations of chlorophyll fluorescence incorporated into the Community Land Model version 4.

    PubMed

    Lee, Jung-Eun; Berry, Joseph A; van der Tol, Christiaan; Yang, Xi; Guanter, Luis; Damm, Alexander; Baker, Ian; Frankenberg, Christian

    2015-09-01

    Several studies have shown that satellite retrievals of solar-induced chlorophyll fluorescence (SIF) provide useful information on terrestrial photosynthesis or gross primary production (GPP). Here, we have incorporated equations coupling SIF to photosynthesis in a land surface model, the National Center for Atmospheric Research Community Land Model version 4 (NCAR CLM4), and have demonstrated its use as a diagnostic tool for evaluating the calculation of photosynthesis, a key process in a land surface model that strongly influences the carbon, water, and energy cycles. By comparing forward simulations of SIF, essentially as a byproduct of photosynthesis, in CLM4 with observations of actual SIF, it is possible to check whether the model is accurately representing photosynthesis and the processes coupled to it. We provide some background on how SIF is coupled to photosynthesis, describe how SIF was incorporated into CLM4, and demonstrate that our simulated relationship between SIF and GPP values are reasonable when compared with satellite (Greenhouse gases Observing SATellite; GOSAT) and in situ flux-tower measurements. CLM4 overestimates SIF in tropical forests, and we show that this error can be corrected by adjusting the maximum carboxylation rate (Vmax ) specified for tropical forests in CLM4. Our study confirms that SIF has the potential to improve photosynthesis simulation and thereby can play a critical role in improving land surface and carbon cycle models. PMID:25881891

  11. Prevention of Metastasis in a 4T1 Murine Breast Cancer Model by Doxorubicin Carried by Folate Conjugated pH Sensitive Polymeric Micelles

    PubMed Central

    Gao, Zhong-Gao; Tian, Li; Hu, Jun; Park, In-Suh; Bae, You Han

    2011-01-01

    This study primarily focused on the anti-metastatic activity of doxorubicin (DOX) loaded in a pH-sensitive mixed polymeric micelle formed from two block polymers: poly(L-lactide) (PLLA) (Mn 3000)-b-poly(ethylene glycol) (PEG) (Mn 2000)-folate and poly(L-histidine) (PHis) (Mn 4700)-b-PEG (Mn 2000). Tumor formation and metastasis in mice were examined using a murine mammary carcinoma cell of 4T1 which is one of the most aggressive metastatic cancer cell lines. The efficacy was evaluated by tumor size, body weight change, survival rate, dorsal skin fold window chamber model, and histological observation of the lung, heart, liver and spleen after treatment with various DOX formulations. When the tumor reached 50–100 mm3 in size, the mice were treated by 4 times at a 3-day interval at a dose of 10 mg DOX/kg. The mixed micelle formulation resulted in retarded tumor growth, no weight loss, and no death for 4–5 weeks. In another set of the in vivo test for histological evaluation of the organs, the mice were similarly treated but the formulations were injected one day after 4T1 cell inoculation. The treatment by DOX loaded mixed micelle showed no apparent metastasis till 28 days. However, significant metastasis to the lung and heart was observed on Day 28 when the mice were treated with DOX carried by PBS, PLLA-b-PEG micelle and PHis-b-PEG micelle. PMID:21295088

  12. The Effects of Chlorophyll Assimilation on Carbon Fluxes in a Global Biogeochemical Model. [Technical Report Series on Global Modeling and Data Assimilation

    NASA Technical Reports Server (NTRS)

    Koster, Randal D. (Editor); Rousseaux, Cecile Severine; Gregg, Watson W.

    2014-01-01

    In this paper, we investigated whether the assimilation of remotely-sensed chlorophyll data can improve the estimates of air-sea carbon dioxide fluxes (FCO2). Using a global, established biogeochemical model (NASA Ocean Biogeochemical Model, NOBM) for the period 2003-2010, we found that the global FCO2 values produced in the free-run and after assimilation were within -0.6 mol C m(sup -2) y(sup -1) of the observations. The effect of satellite chlorophyll assimilation was assessed in 12 major oceanographic regions. The region with the highest bias was the North Atlantic. Here the model underestimated the fluxes by 1.4 mol C m(sup -2) y(sup -1) whereas all the other regions were within 1 mol C m(sup -2) y(sup -1) of the data. The FCO2 values were not strongly impacted by the assimilation, and the uncertainty in FCO2 was not decreased, despite the decrease in the uncertainty in chlorophyll concentration. Chlorophyll concentrations were within approximately 25% of the database in 7 out of the 12 regions, and the assimilation improved the chlorophyll concentration in the regions with the highest bias by 10-20%. These results suggest that the assimilation of chlorophyll data does not considerably improve FCO2 estimates and that other components of the carbon cycle play a role that could further improve our FCO2 estimates.

  13. Filamentous, mixed micelles of triblock copolymers enhance tumor localization of indocyanine green in a murine xenograft model

    PubMed Central

    Kim, Tae Hee; Mount, Christopher W; Dulken, Benjamin W; Ramos, Jenelyn; Fu, Caroline J; Khant, Htet A; Chiu, Wah; Gombotz, Wayne R; Pun, Suzie H

    2012-01-01

    Polymeric micelles formed by the self-assembly of amphiphilic block copolymers can be used to encapsulate hydrophobic drugs for tumor-delivery applications. Filamentous carriers with high aspect ratios offer potential advantages over spherical carriers, including prolonged circulation times. In this work, mixed micelles comprised of poly (ethylene oxide)-poly-[(R)-3-hydroxybutyrate]-poly (ethylene oxide) (PEO-PHB-PEO) and Pluronic F-127 (PF-127) were used to encapsulate a near-infrared fluorophore. The micelle formulations were assessed for tumor accumulation after tail vein injection to xenograft tumor-bearing mice by non-invasive optical imaging. The mixed micelle formulation that facilitated the highest tumor accumulation was shown by cryo-electron microscopy to be filamentous in structure compared to spherical structures of pure PF-127 micelles. In addition, increased dye loading efficiency and dye stability was attained in this mixed micelle formulation compared to pure PEO-PHB-PEO micelles. Therefore, the optimized PEO-PHB-PEO/PF-127 mixed micelle formulation offers advantages for cancer delivery over micelles formed from the individual copolymer components. PMID:22118658

  14. Filamentous, mixed micelles of triblock copolymers enhance tumor localization of indocyanine green in a murine xenograft model.

    PubMed

    Kim, Tae Hee; Mount, Christopher W; Dulken, Benjamin W; Ramos, Jenelyn; Fu, Caroline J; Khant, Htet A; Chiu, Wah; Gombotz, Wayne R; Pun, Suzie H

    2012-01-01

    Polymeric micelles formed by the self-assembly of amphiphilic block copolymers can be used to encapsulate hydrophobic drugs for tumor-delivery applications. Filamentous carriers with high aspect ratios offer potential advantages over spherical carriers, including prolonged circulation times. In this work, mixed micelles composed of poly(ethylene oxide)-poly[(R)-3-hydroxybutyrate]-poly(ethylene oxide) (PEO-PHB-PEO) and Pluronic F-127 (PF-127) were used to encapsulate a near-infrared fluorophore. The micelle formulations were assessed for tumor accumulation after tail vein injection to xenograft tumor-bearing mice by noninvasive optical imaging. The mixed micelle formulation that facilitated the highest tumor accumulation was shown by cryo-electron microscopy to be filamentous in structure compared to spherical structures of pure PF-127 micelles. In addition, increased dye loading efficiency and dye stability were attained in this mixed micelle formulation compared to pure PEO-PHB-PEO micelles. Therefore, the optimized PEO-PHB-PEO/PF-127 mixed micelle formulation offers advantages for cancer delivery over micelles formed from the individual copolymer components.

  15. Seasonal Distributions of Global Ocean Chlorophyll and Nutrients: Analysis with a Coupled Ocean General Circulation Biogeochemical, and Radiative Model

    NASA Technical Reports Server (NTRS)

    Gregg, Watson W.

    1999-01-01

    A coupled general ocean circulation, biogeochemical, and radiative model was constructed to evaluate and understand the nature of seasonal variability of chlorophyll and nutrients in the global oceans. The model is driven by climatological meteorological conditions, cloud cover, and sea surface temperature. Biogeochemical processes in the model are determined from the influences of circulation and turbulence dynamics, irradiance availability, and the interactions among three functional phytoplankton groups (diatoms, chorophytes, and picoplankton) and three nutrient groups (nitrate, ammonium, and silicate). Phytoplankton groups are initialized as homogeneous fields horizontally and vertically, and allowed to distribute themselves according to the prevailing conditions. Basin-scale model chlorophyll results are in very good agreement with CZCS pigments in virtually every global region. Seasonal variability observed in the CZCS is also well represented in the model. Synoptic scale (100-1000 km) comparisons of imagery are also in good conformance, although occasional departures are apparent. Agreement of nitrate distributions with in situ data is even better, including seasonal dynamics, except for the equatorial Atlantic. The good agreement of the model with satellite and in situ data sources indicates that the model dynamics realistically simulate phytoplankton and nutrient dynamics on synoptic scales. This is especially true given that initial conditions are homogenous chlorophyll fields. The success of the model in producing a reasonable representation of chlorophyll and nutrient distributions and seasonal variability in the global oceans is attributed to the application of a generalized, processes-driven approach as opposed to regional parameterization, and the existence of multiple phytoplankton groups with different physiological and physical properties. These factors enable the model to simultaneously represent the great diversity of physical, biological

  16. Assimilation of SeaWiFS Ocean Chlorophyll Data into a Three-Dimensional Global Ocean Model

    NASA Technical Reports Server (NTRS)

    Gregg, Watson W.

    2005-01-01

    Assimilation of satellite ocean color data is a relatively new phenomenon in ocean sciences. However, with routine observations from the Sea-viewing Wide Field-of-view Sensor (SeaWiFS), launched in late 1997, and now with new data from the Moderate Resolution Imaging Spectroradometer (MODIS) Aqua, there is increasing interest in ocean color data assimilation. Here SeaWiFS chlorophyll data were assimilated with an established thre-dimentional global ocean model. The assimilation improved estimates of hlorophyll and primary production relative to a free-run (no assimilation) model. This represents the first attempt at ocean color data assimilation using NASA satellites in a global model. The results suggest the potential of assimilation of satellite ocean chlorophyll data for improving models.

  17. Assimilation of remotely sensed chlorophyll fluorescence data into the land surface model CLM4

    NASA Astrophysics Data System (ADS)

    Wieneke, S.; Ahrends, H. E.; Rascher, U.; Schween, J.; Schickling, A.; Crewell, S.

    2013-12-01

    Photosynthesis is the most important exchange process of CO2 between the atmosphere and the land-surface. Therefore, the prediction of vegetation response to environmental conditions like increasing CO2 concentrations or plant stress is crucial for a reliable prediction of climate change. Photosynthesis is a complex physiological process that consists of numerous bio-physical sub-processes and chemical reactions. Spatial and temporal patterns of photosynthesis depend on dynamic plant-specific adaptation strategies to highly variable environmental conditions. Photosynthesis can be estimated using land-surface models, but, while state-of-the-art models often rely on Plant Functional Type (PFT) specific constants, they poorly simulate the dynamic adaptation of the physiological status of plant canopies in space and time. Remotely sensed sun-induced chlorophyll fluorescence (SICF) gives us now the possibility to estimate the diurnal dynamic vitality of the photosynthetic apparatus at both, the leaf and canopy levels. We installed within the framework of the Transregio32 project (www.tr32.de) automated hyperspectral fluorescence sensors at an agricultural site (winter wheat) in the Rur catchment area in West Germany at the end of July 2012. End of August, additional measurements of SIFC on nearby temperate grassland site (riparian meadow) and on a sugar beet field were performed. Spatial covering SICF data of the region were obtained during a measurement campaign using the newly developed air-borne hyperspectral sensor HyPlant on the 23 and 27 August 2012. SIFC data and data provided by eddy covariance measurements will be used to update certain model parameters that are normally set as constants. First model results demonstrate that the assimilation of SIFC into the Community Land Model 4 (CLM4) will result in a more realistic simulation of plant-specific adaptation strategies and therefore in a more realistic simulation of photosynthesis in space and time.

  18. Leaf chlorophyll constraint on model simulated gross primary productivity in agricultural systems

    NASA Astrophysics Data System (ADS)

    Houborg, Rasmus; F. McCabe, Matthew; Cescatti, Alessandro; A. Gitelson, Anatoly

    2015-12-01

    Leaf chlorophyll content (Chll) may serve as an observational proxy for the maximum rate of carboxylation (Vmax), which describes leaf photosynthetic capacity and represents the single most important control on modeled leaf photosynthesis within most Terrestrial Biosphere Models (TBMs). The parameterization of Vmax is associated with great uncertainty as it can vary significantly between plants and in response to changes in leaf nitrogen (N) availability, plant phenology and environmental conditions. Houborg et al. (2013) outlined a semi-mechanistic relationship between Vmax25 (Vmax normalized to 25 °C) and Chll based on inter-linkages between Vmax25, Rubisco enzyme kinetics, N and Chll. Here, these relationships are parameterized for a wider range of important agricultural crops and embedded within the leaf photosynthesis-conductance scheme of the Community Land Model (CLM), bypassing the questionable use of temporally invariant and broadly defined plant functional type (PFT) specific Vmax25 values. In this study, the new Chll constrained version of CLM is refined with an updated parameterization scheme for specific application to soybean and maize. The benefit of using in-situ measured and satellite retrieved Chll for constraining model simulations of Gross Primary Productivity (GPP) is evaluated over fields in central Nebraska, U.S.A between 2001 and 2005. Landsat-based Chll time-series records derived from the Regularized Canopy Reflectance model (REGFLEC) are used as forcing to the CLM. Validation of simulated GPP against 15 site-years of flux tower observations demonstrate the utility of Chll as a model constraint, with the coefficient of efficiency increasing from 0.91 to 0.94 and from 0.87 to 0.91 for maize and soybean, respectively. Model performances particularly improve during the late reproductive and senescence stage, where the largest temporal variations in Chll (averaging 35-55 μg cm-2 for maize and 20-35 μg cm-2 for soybean) are observed. While

  19. Three-band model for noninvasive estimation of chlorophyll, carotenoids, and anthocyanin contents in higher plant leaves

    NASA Astrophysics Data System (ADS)

    Gitelson, Anatoly A.; Keydan, Galina P.; Merzlyak, Mark N.

    2006-06-01

    Leaf pigment content and composition provide important information about plant physiological status. Reflectance measurements offer a rapid, nondestructive technique to estimate pigment content. This paper describes a recently developed three-band conceptual model capable of remotely estimating total of chlorophylls, carotenoids and anthocyanins contents in leaves from many tree and crop species. We tuned the spectral regions used in the model in accord with pigment of interest and the optical characteristics of the leaves studied, and showed that the developed technique allowed accurate estimation of total chlorophylls, carotenoids and anthocyanins, explaining more than 91%, 70% and 93% of pigment variation, respectively. This new technique shows a great potential for noninvasive tracking of the physiological status of vegetation and the impact of environmental changes.

  20. Improving the modeling of the seasonal carbon cycle of the boreal forest with chlorophyll fluorescence measurements

    NASA Astrophysics Data System (ADS)

    Thum, Tea; Aalto, Tuula; Aurela, Mika; Laurila, Tuomas; Zaehle, Sönke

    2014-05-01

    The boreal ecosystems are characterized a very strong seasonal cycle and they are very sensitive to the climatic variables. The vegetation's deep wintertime dormancy requires a long recovery time during spring before the plants reach their full photosynthetic capacity. During this recovery time the plants are highly susceptible the night frosts. The transition period is different during spring and autumn for the evergreen plants. During spring there is plenty of light, but cold air temperatures inhibit the photosynthesis. The plants therefore experience to high stress levels, as they need to protect their photosynthetic apparatus from intense light. In autumn the air temperature and light level decrease more concurrently. To have a realistic presentation of the carbon cycle in boreal forests it is important to have these characteristics properly modeled, so that also the implications of changing seasonality under climate change can be more reliably predicted. In this study, we focus on the CO2 exchange of a Scots pine forest Sodankylä located in Finnish Lapland, 100 km north from the Arctic Circle. Micrometeorological flux measurements provide information about the exchanges of carbon, energy and water between atmosphere and vegetation. To complement these fluxes, we use dark-adapted chlorophyll fluorescence (CF) measurements, which is an optical measurement and tracks the development of the photosynthetic capacity. These two approaches combined together are very useful when we want to improve the modeling of the forest's CO2 exchange. We used two models that describe the photosynthesis with the biochemical model of Farquhar et al. The FMI-CANOPY is a canopy level model that is feasible to use in parameter estimation. We used the CF measurements of Fv/Fm, that is a measure of the maximum photosynthetic capacity, to include a seasonal development in the base rate of the maximum carboxylation rate (Vc(max)) in FMI-CANOPY. The simulation results matched the

  1. "Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

    PubMed

    Nagarajan, Ramanathan

    2015-07-01

    Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to

  2. Systemic siRNA delivery to a spontaneous pancreatic tumor model in transgenic mice by PEGylated calcium phosphate hybrid micelles.

    PubMed

    Pittella, Frederico; Cabral, Horacio; Maeda, Yoshinori; Mi, Peng; Watanabe, Sumiyo; Takemoto, Hiroyasu; Kim, Hyun Jin; Nishiyama, Nobuhiro; Miyata, Kanjiro; Kataoka, Kazunori

    2014-03-28

    Efficient systems for delivery of small interfering RNA (siRNA) are required for clinical application of RNA interference (RNAi) in cancer therapy. Herein, we developed a safe and efficient nanocarrier comprising poly(ethylene glycol)-block-charge-conversional polymer (PEG-CCP)/calcium phosphate (CaP) hybrid micelles for systemic delivery of siRNA and studied their efficacy in spontaneous bioluminescent pancreatic tumors from transgenic mice. PEG-CCP was engineered to provide the siRNA-loaded hybrid micelles with enhanced colloidal stability and biocompatibility due to the PEG capsule and with endosome-disrupting functionality due to the acidic pH-responsive CCP segment where the polyanionic structure could be converted to polycationic structure at acidic pH through cis-aconitic amide cleavage. The resulting hybrid micelles were confirmed to have a diameter of <50nm, with a narrow size distribution. Intravenously injected hybrid micelles significantly reduced the luciferase-based luminescent signal from the spontaneous pancreatic tumors in an siRNA sequence-specific manner. The gene silencing activity of the hybrid micelles correlated with their preferential tumor accumulation, as indicated by fluorescence imaging and histological analysis. Moreover, there were no significant changes in hematological parameters in mice treated with the hybrid micelles. These results demonstrate the great potential of the hybrid micelles as siRNA carriers for RNAi-based cancer therapy. PMID:24440662

  3. The distribution of bioluminescence and chlorophyll during the late summer in the North Atlantic: Maps and a predictive model

    NASA Astrophysics Data System (ADS)

    Ondercin, Daniel G.; Atkinson, Charles A.; Kiefer, Dale A.

    1995-04-01

    During August 1991 an instrument array (the Paravane) was towed continuously for several days over long distances in the North Atlantic and around the Marine Light-Mixed Layer (MLML) mooring (60°N, 21°W). Among other sensors, the Paravane carried a thermistor, a fluorometer that measured the fluorescence emitted by chlorophyll a, a bathyphotometer that measured stimulable bioluminescence, and a beam transmissometer that measured the volume attenuation coefficient at 490 nm. The record of these biooptical measurements provides a detailed description of the upper 150 m of the water column as well as of diel variability. An examination of the transects, which covered a latitudinal range from 43°N to 60°N and a longitudinal range from 13°W to 54°W, indicates that in the colder and more northerly waters most of the chlorophyll a, attenuation, and bioluminescence were found within the surface mixed layer. In the warmer waters to the south, there were subsurface maxima for all three parameters. We have used the Paravane records to test a model that provides predictions of the vertical distribution of chlorophyll a, bioluminescence, and beam attenuation from oceanographie parameters that characterize the surface mixed layer: temperature, chlorophyll a concentration, irradiance incident to the sea surface, mixed layer depth, and nitrate concentration. The first three parameters can be measured from sensors aboard satellites while the last two parameters can be obtained from oceanographie databases. The model is based upon a description of the acclimation of the phytoplankton, an assumption about the vertical distribution of phytoplankton within the euphotic zone, and an empirical description of the relationship between bioluminescence, light intensity, and phytoplankton concentration.

  4. Rheology of giant micelles

    NASA Astrophysics Data System (ADS)

    Cates, M. E.; Fielding, S. M.

    2006-12-01

    Giant micelles are elongated, polymer-like objects created by the self-assembly of amphiphilic molecules (such as detergents) in solution. Giant micelles are typically flexible, and can become highly entangled even at modest concentrations. The resulting viscoelastic solutions show fascinating flow behaviour (rheology) which we address theoretically in this article at two levels. First, we summarize advances in understanding linear viscoelastic spectra and steady-state nonlinear flows, based on microscopic constitutive models that combine the physics of polymer entanglement with the reversible kinetics of self-assembly. Such models were first introduced two decades ago, and since then have been shown to explain robustly several distinctive features of the rheology in the strongly entangled regime, including extreme shear thinning. We then turn to more complex rheological phenomena, particularly involving spatial heterogeneity, spontaneous oscillation, instability and chaos. Recent understanding of these complex flows is based largely on grossly simplified models which capture in outline just a few pertinent microscopic features, such as coupling between stresses and other order parameters such as concentration. The role of ‘structural memory’ (the dependence of structural parameters such as the micellar length distribution on the flow history) in explaining these highly nonlinear phenomena is addressed. Structural memory also plays an intriguing role in the little-understood shear thickening regime, which occurs in a concentration regime close to but below the onset of strong entanglement, and which is marked by a shear-induced transformation from an inviscid to a gelatinous state.

  5. Improving Global Models of Remotely Sensed Ocean Chlorophyll Content Using Partial Least Squares and Geographically Weighted Regression

    NASA Astrophysics Data System (ADS)

    Gholizadeh, H.; Robeson, S. M.

    2015-12-01

    Empirical models have been widely used to estimate global chlorophyll content from remotely sensed data. Here, we focus on the standard NASA empirical models that use blue-green band ratios. These band ratio ocean color (OC) algorithms are in the form of fourth-order polynomials and the parameters of these polynomials (i.e. coefficients) are estimated from the NASA bio-Optical Marine Algorithm Data set (NOMAD). Most of the points in this data set have been sampled from tropical and temperate regions. However, polynomial coefficients obtained from this data set are used to estimate chlorophyll content in all ocean regions with different properties such as sea-surface temperature, salinity, and downwelling/upwelling patterns. Further, the polynomial terms in these models are highly correlated. In sum, the limitations of these empirical models are as follows: 1) the independent variables within the empirical models, in their current form, are correlated (multicollinear), and 2) current algorithms are global approaches and are based on the spatial stationarity assumption, so they are independent of location. Multicollinearity problem is resolved by using partial least squares (PLS). PLS, which transforms the data into a set of independent components, can be considered as a combined form of principal component regression (PCR) and multiple regression. Geographically weighted regression (GWR) is also used to investigate the validity of spatial stationarity assumption. GWR solves a regression model over each sample point by using the observations within its neighbourhood. PLS results show that the empirical method underestimates chlorophyll content in high latitudes, including the Southern Ocean region, when compared to PLS (see Figure 1). Cluster analysis of GWR coefficients also shows that the spatial stationarity assumption in empirical models is not likely a valid assumption.

  6. Membrane-micelle model for humus in soils and sediments and its relation to humification

    USGS Publications Warehouse

    Wershaw, Robert L.

    1994-01-01

    Humification, the process whereby biomass consisting of dead plant and animal remains is converted into soil organic matter (humus), is one of the basic processes of the carbon cycle. The organic compounds that make up plant and animal tissue are thermodynamically unstable in the oxidizing atmosphere at the surface of the Earth. After the organisms in which they are incorporated die, the compounds are converted back to carbon dioxide and water by degradation reactions catalyzed by enzymes secreted by micro-organisms. However, not all the organic compounds in the dead biomass are immediately converted; some of the material is only partially oxidized. The residue left after partial oxidative degradation of the dead biomass is the source of the organic compounds that accumulate in soils and sediments as humus. Previously, humification was thought to involve a conversion of degradation products by a series of polymerization reactions into new types of polymeric species that are different from the precursor molecular species in the original biomass. However, it is proposed here that the depolymerization and oxidation reactions that take place during the enzymatic degradation of biopolymers produce amphiphiles--molecules that have a polar (hydrophilic) part and a nonpolar (hydrophobic) part. These amphiphiles that result from the partial oxidative degradation of dead biomass assemble spontaneously into ordered aggregates in which the hydrophobic parts of the molecules form the interiors and the hydrophilic parts of the molecules make up the exterior surfaces of the aggregates. These ordered aggregates constitute the humus in soils and sediments. Humus ordered aggregates most likely exist as bilayer membranes coating mineral grains and as micelles in solution.

  7. Musk Oxen and Micelles

    NASA Astrophysics Data System (ADS)

    Hill, John W.

    1996-09-01

    Musk oxen behavior provides an analogy to micelle formation by amphipathic substances. Mature male musk oxen protect their young and females from wolves by forming a protective circle around them. The males stand with their tails to the inside and their heads facing outward. Amphipathic substances such as soap form micelles. The hydrophobic hydrocarbon tails of the soap are turned to the inside of the micelle and the hydrophilic carboxylate heads are on the outside at the interface with the polar water molecules.

  8. Charged Diblock Copolymers at Interfaces: Micelle Dissociation Upon Compression

    SciTech Connect

    Checco, A.; Theodoly, O.; Muller, P.

    2010-05-20

    We use grazing incidence X-ray scattering to study the surface micellization of charged amphiphilic diblock copolymers poly(styrene-block-acrylic acid) at the air-water interface. Scattering interference peaks are consistent with the formation of hexagonally packed micelles. The remarkable increase of inter-micelle distance upon compression is explained by a dissociation of micelles into a brush. Hence, surface micelles reorganize, whereas micelles of the same copolymers in solutions are 'frozen'. We show indeed that the energetic cost of unimer extraction from micelles is much lower for surface than for solution. Finally, a model combining electrostatic interactions and micelle/brush equilibrium explains surface pressure vs. area without free parameters. keywords - soft matter, liquids and polymers, biological physics, chemical physics and physical chemistry.

  9. Charged Diblock Copolymers at Interfaces: Micelle Dissociation Upon Compression

    SciTech Connect

    Theodoly, O.; Checco, A; Muller, P

    2010-01-01

    We use grazing incidence X-ray scattering to study the surface micellization of charged amphiphilic diblock copolymers poly(styrene-block-acrylic acid) at the air-water interface. Scattering interference peaks are consistent with the formation of hexagonally packed micelles. The remarkable increase of inter-micelle distance upon compression is explained by a dissociation of micelles into a brush. Hence, surface micelles reorganize, whereas micelles of the same copolymers in solutions are 'frozen'. We show indeed that the energetic cost of unimer extraction from micelles is much lower for surface than for solution. Finally, a model combining electrostatic interactions and micelle/brush equilibrium explains surface pressure vs. area without free parameters.

  10. Temperature Effect on the Nanostructure of SDS Micelles in Water

    PubMed Central

    Hammouda, Boualem

    2013-01-01

    Sodium dodecyl sulfate (SDS) surfactants form micelles when dissolved in water. These are formed of a hydrocarbon core and hydrophilic ionic surface. The small-angle neutron scattering (SANS) technique was used with deuterated water (D2O) in order to characterize the micelle structure. Micelles were found to be slightly compressed (oblate ellipsoids) and their sizes shrink with increasing temperature. Fits of SANS data to the Mean Spherical Approximation (MSA) model yielded a calculated micelle volume fraction which was lower than the SDS surfactant (sample mixing) volume fraction; this suggests that part of the SDS molecules do not participate in micelle formation and remain homogeneously mixed in the solvent. A set of material balance equations allowed the estimation of the SDS fraction in the micelles. This fraction was found to be high (close to one) except for samples around 1 % SDS fraction. The micelle aggregation number was found to decrease with increasing temperature and/or decreasing SDS fraction. PMID:26401428

  11. In situ hyperspectral data analysis for canopy chlorophyll content estimation of an invasive species spartina alterniflora based on PROSAIL canopy radiative transfer model

    NASA Astrophysics Data System (ADS)

    Ai, Jinquan; Gao, Wei; Shi, Runhe; Zhang, Chao; Sun, Zhibin; Chen, Wenhui; Liu, Chaoshun; Zeng, Yuyan

    2015-09-01

    Spartina alterniflora is one of the most serious invasive species in the coastal saltmarshes of China. An accurate quantitative estimation of its canopy leaf chlorophyll content is of great importance for monitoring plant physiological state and vegetation productivity. Hyperspectral reflectance data representing a range of canopy chlorophyll content were simulated by using the PROSAIL radiative transfer model at a 1nm sampling interval, which was based on prior knowledge of S.alterniflora. A set of indices was tested for estimating canopy chlorophyll content. Subsequently, validation were performed for testing the performance of indices, based on the PROSAIL model using in situ data measured by a Spectroradiometer with spectral range of 350-2500nm in a late autumn in a sub-tropical estuarine marsh. PROSAIL simulations showed that the most readily available indices were not good to be directly used in canopy chlorophyll estimation of S.alterniflora. The modified Chlorophyll Absorption in Reflectance Index MCARI[705,750] was linear related to the canopy chlorophyll content (R2=0.94) , but did not achieve a satisfactory estimation results with a high RMSE (RMSE=0.95 g.m-2). We optimized the index MCARI[705,750] by introducing a scale conversion coefficient to the formula to solve data units inconsistent, which is between the practical application unit and the unit used in the process of establishing the index, and balance scale transformation through radiative transfer models and examing corresponding canopy reflectance index values. We proposed index Optimized modified Chlorophyll Absorption in Reflectance Index OMCARI[705, 750]. The results showed that the index OMCARI[705, 750] had higher precision of prediction of chlorophyll for S.alterniflora (R2=0.94,RMSE=0.41 g.m-2 ).

  12. Derivation of coarse-grained simulation models of chlorophyll molecules in lipid bilayers for applications in light harvesting systems.

    PubMed

    Debnath, Ananya; Wiegand, Sabine; Paulsen, Harald; Kremer, Kurt; Peter, Christine

    2015-09-14

    The correct interplay of interactions between protein, pigment and lipid molecules is highly relevant for our understanding of the association behavior of the light harvesting complex (LHCII) of green plants. To cover the relevant time and length scales in this multicomponent system, a multi-scale simulation ansatz is employed that subsequently uses a classical all atomistic (AA) model to derive a suitable coarse grained (CG) model which can be backmapped into the AA resolution, aiming for a seamless conversion between two scales. Such an approach requires a faithful description of not only the protein and lipid components, but also the interaction functions for the indispensable pigment molecules, chlorophyll b and chlorophyll a (referred to as chl b/chl a). In this paper we develop a CG model for chl b and chl a in a dipalmitoylphosphatidyl choline (DPPC) bilayer system. The structural properties and the distribution behavior of chl within the lipid bilayer in the CG simulations are consistent with those of AA reference simulations. The non-bonded potentials are parameterized such that they fit to the thermodynamics based MARTINI force-field for the lipid bilayer and the protein. The CG simulation shows chl aggregation in the lipid bilayer which is supported by fluorescence quenching experiments. It is shown that the derived chl model is well suited for CG simulations of stable, structurally consistent, trimeric LHCII and can in the future be used to study their large scale aggregation behavior.

  13. Micelle Formation of n-Decyltrimethylammonium Perfluorocarboxylates

    PubMed

    Yoshida; Matsuoka; Moroi

    1997-03-15

    Critical micelle concentrations (CMCs) of three ionic surfactants that contain n-decyltrimethylammonium ion as a surfactant cation and bromide, perfluoroacetate, and perfluoropropionate anions as a counterion, respectively, were determined by electrical conductivity at several temperatures. The degrees of counterion binding to micelle were obtained at the same temperatures as the change in CMC with total counterion concentration. Molecular weights of micelles were determined by static light scattering. The change in monomeric surfactant ion concentration with total surfactant concentration was determined by membrane potential measurement. The mass-action model was applied to micelle formation to calculate the three micellization parameters: micellization constant, micelle aggregation number, and number of counterions per micelle. Thermodynamic parameters (DeltaG0, DeltaH0, DeltaS0) of the micelle formations were calculated from the temperature dependence of these parameters. At lower temperatures micellization has been found to be entropy driven, whereas it is enthalpy driven at higher temperatures. For n-decyltrimethylammonium perfluoropropionate, however, the tendency is quite different from those of other surfactants. The micellization parameters also made it possible to evaluate the concentration change of monomeric surfactant ion with total surfactant concentration. The evaluated concentration explains the results from the membrane potential measurement.

  14. Assimilation of SeaWiFS chlorophyll data into a 3D-coupled physical-biogeochemical model applied to a freshwater-influenced coastal zone

    NASA Astrophysics Data System (ADS)

    Fontana, Clément; Grenz, Christian; Pinazo, Christel; Marsaleix, Patrick; Diaz, Frédéric

    2009-06-01

    In order to predict eutrophication events in coastal areas we tested an assimilation scheme based on sequential data assimilation of SeaWiFS chlorophyll data into a coupled 3D physical-biogeochemical model. The area investigated is a semi-enclosed estuarine system (Gulf of Fos-North-western Mediterranean Sea) closely linked to the Rhone River delta. This system is subjected to episodic eutrophication caused by certain hydrodynamic conditions and intermittent nutrient inputs. The 3D hydrodynamic model Symphonie was coupled to the biogeochemical modelling platform Eco3M. Surface chlorophyll concentrations were derived from SeaWiFS data using the OC5 algorithm and were sequentially assimilated using a singular evolutive extended Kalman filter. Assimilation efficiency was evaluated through an independent in situ data set collected during a field survey that took place in May 2001 (ModelFos cruise). An original approach was used in constructing the state vector and the observation vector. By assimilating pseudo-salinity extracted from the model biogeochemical dynamics in both open sea and plume region were respected. We proved that substantial improvements were made in short-term forecasts by integrating such satellite-estimated chlorophyll maps. We showed that missing freshwater inputs could be corrected to a certain extent by the assimilation process. Simulated concentrations of surface chlorophyll and other basic components of the pelagic ecosystem such as nitrates were improved by assimilating surface chlorophyll maps. Finally we showed the coherent spatial behaviour of the filter over the whole modelled domain.

  15. Assimilation of surface data in a one-dimensional physical-biogeochemical model of the surface ocean: 2. Adjusting a simple trophic model to chlorophyll, temperature, nitrate, and pCO{sub 2} data

    SciTech Connect

    Prunet, P.; Minster, J.F.; Echevin, V.

    1996-03-01

    This paper builds on a previous work which produced a constrained physical-biogeochemical model of the carbon cycle in the surface ocean. Three issues are addressed: (1) the results of chlorophyll assimilation using a simpler trophic model, (2) adjustment of parameters using the simpler model and data other than surface chlorophyll concentrations, and (3) consistency of the main carbon fluxes derived by the simplified model with values from the more complex model. A one-dimensional vertical model coupling the physics of the ocean mixed layer and a description of biogeochemical processes with a simple trophic model was used to address these issues. Chlorophyll concentration, nitrate concentration, and temperature were used to constrain the model. The surface chlorophyll information was shown to be sufficient to constrain primary production within the photic layer. The simultaneous assimilation of chlorophyll, nitrate, and temperature resulted in a significant improvement of model simulation for the data used. Of the nine biological and physical parameters which resulted in significant variations of the simulated chlorophyll concentration, seven linear combinations of the mode parameters were constrained. The model fit was an improvement on independent surface chlorophyll and nitrate data. This work indicates that a relatively simple biological model is sufficient to describe carbon fluxes. Assimilation of satellite or climatological data coulc be used to adjust the parameters of the model for three-dimensional models. It also suggests that the main carbon fluxes driving the carbon cycle within surface waters could be derived regionally from surface information. 38 refs., 16 figs., 7 tabs.

  16. Simultaneous determination of interfacial molarities of amide bonds, carboxylate groups, and water by chemical trapping in micelles of amphiphiles containing peptide bond models.

    PubMed

    Zhang, Yongliang; Romsted, Laurence S; Zhuang, Lanzhen; de Jong, Sander

    2013-01-15

    Chemical trapping is a powerful approach for obtaining experimental estimates of interfacial molarities of weakly basic nucleophiles in the interfacial regions of amphiphile aggregates. Here, we demonstrate that the chemical probe 4-hexadecyl-2,6-dimethylbenzenediazonium ion (16-ArN(2)(+)) reacts competitively with interfacial water, with the amide carbonyl followed by cleavage of the headgroups from the tail at the amide oxygen, and with the terminal carboxylate groups in micelles of two N-acyl amino-acid amphiphiles, sodium N-lauroylsarcosinate (SLS) and sodium N-lauroylglycinate (SLG), simple peptide bond model amphiphiles. Interfacial molarities (in moles per liter of interfacial volume) of these three groups were obtained from product yields, assuming that selectivity toward a particular nucleophile compared to water is the same in an aqueous reference solution and in the interfacial region. Interfacial carboxylate group molarities are ~1.5 M in both SLS and SLG micelles, but the concentration of the amide carbonyl for SLS micelles is ~4.6-5 times less (ca. 0.7 M) than that of SLG micelles (~3 M). The proton on the secondary N of SLG helps solubilize the amide bond in the aqueous region, but the methyl on the tertiary N of SLS helps solubilize the amide bond in the micellar core, reducing its reaction with 16-ArN(2)(+). Application of chemical trapping to proteins in membrane mimetic interfaces should provide insight into the topology of the protein within the interface because trapping of the amide carbonyl and cleavage at the C-N bond occurs only within the interface, and fragment characterization marks those peptide bonds located within the interface.

  17. Styrene maleic acid-encapsulated paclitaxel micelles: antitumor activity and toxicity studies following oral administration in a murine orthotopic colon cancer model.

    PubMed

    Parayath, Neha N; Nehoff, Hayley; Norton, Samuel E; Highton, Andrew J; Taurin, Sebastien; Kemp, Roslyn A; Greish, Khaled

    2016-01-01

    Oral administration of paclitaxel (PTX), a broad spectrum anticancer agent, is challenged by its low uptake due to its poor bioavailability, efflux through P-glycoprotein, and gastrointestinal toxicity. We synthesized PTX nanomicelles using poly(styrene-co-maleic acid) (SMA). Oral administration of SMA-PTX micelles doubled the maximum tolerated dose (60 mg/kg vs 30 mg/kg) compared to the commercially available PTX formulation (PTX [Ebewe]). In a murine orthotopic colon cancer model, oral administration of SMA-PTX micelles at doses 30 mg/kg and 60 mg/kg reduced tumor weight by 54% and 69%, respectively, as compared to the control group, while no significant reduction in tumor weight was observed with 30 mg/kg of PTX (Ebewe). In addition, toxicity of PTX was largely reduced by its encapsulation into SMA. Furthermore, examination of the tumors demonstrated a decrease in the number of blood vessels. Thus, oral delivery of SMA-PTX micelles may provide a safe and effective strategy for the treatment of colon cancer. PMID:27574427

  18. Styrene maleic acid-encapsulated paclitaxel micelles: antitumor activity and toxicity studies following oral administration in a murine orthotopic colon cancer model

    PubMed Central

    Parayath, Neha N; Nehoff, Hayley; Norton, Samuel E; Highton, Andrew J; Taurin, Sebastien; Kemp, Roslyn A; Greish, Khaled

    2016-01-01

    Oral administration of paclitaxel (PTX), a broad spectrum anticancer agent, is challenged by its low uptake due to its poor bioavailability, efflux through P-glycoprotein, and gastrointestinal toxicity. We synthesized PTX nanomicelles using poly(styrene-co-maleic acid) (SMA). Oral administration of SMA-PTX micelles doubled the maximum tolerated dose (60 mg/kg vs 30 mg/kg) compared to the commercially available PTX formulation (PTX [Ebewe]). In a murine orthotopic colon cancer model, oral administration of SMA-PTX micelles at doses 30 mg/kg and 60 mg/kg reduced tumor weight by 54% and 69%, respectively, as compared to the control group, while no significant reduction in tumor weight was observed with 30 mg/kg of PTX (Ebewe). In addition, toxicity of PTX was largely reduced by its encapsulation into SMA. Furthermore, examination of the tumors demonstrated a decrease in the number of blood vessels. Thus, oral delivery of SMA-PTX micelles may provide a safe and effective strategy for the treatment of colon cancer. PMID:27574427

  19. Utility of an image-based canopy reflectance modeling tool for remote estimation of LAI and leaf chlorophyll content at the field scale

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A REGularized canopy reFLECtance (REGFLEC) modeling tool that couples leaf optics (PROSPECT), canopy reflectance (ACRM), and atmospheric radiative transfer (6SV1) models is described and the model output of leaf chlorophyll (Cab) and total leaf area index (LAI) is validated against ground measuremen...

  20. Modeling of a violaxanthin-chlorophyll b chromophore pair in its LHCII environment using CAM-B3LYP.

    PubMed

    Kröner, Dominik; Götze, Jan Philipp

    2012-04-01

    Collecting energy for photosystem II is facilitated by several pigments, xanthophylls and chlorophylls, embedded in the light harvesting complex II (LHCII). One xanthophyll, violaxanthin (Vio), is loosely bound at a site close to a chlorophyll b (Chl). No final answer has yet been found for the role of this specific xanthophyll. We study the electronic structure of Vio in the presence of Chl and under the influence of the LHCII environment, represented by a point charge field (PCF). We compare the capability of the long range corrected density functional theory (DFT) functional CAM-B3LYP to B3LYP for the modeling of the UV/vis spectrum of the Vio+Chl pair. CAM-B3LYP was reported to allow for a very realistic reproduction of bond length alternation of linear polyenes, which has considerable impact on the carotenoid structure and spectrum. To account for the influence of the LHCII environment, the chromophore geometries are optimized using an ONIOM(DFT/6-31G(d):PM6) scheme. Our calculations show that the energies of the locally excited states are almost unaffected by the presence of the partner chromophore or the PCF. There are, however, indications for excitonic coupling of the Chl Soret band and Vio. We propose that Vio may accept energy from blue-light excited Chl.

  1. Using Leaf Chlorophyll to Parameterize Light-Use-Efficiency Within a Thermal-Based Carbon, Water and Energy Exchange Model

    NASA Technical Reports Server (NTRS)

    Houlborg, Rasmus; Anderson, Martha C.; Daughtry, C. S. T.; Kustas, W. P.; Rodell, Matthew

    2010-01-01

    Chlorophylls absorb photosynthetically active radiation and thus function as vital pigments for photosynthesis, which makes leaf chlorophyll content (C(sub ab) useful for monitoring vegetation productivity and an important indicator of the overall plant physiological condition. This study investigates the utility of integrating remotely sensed estimates of C(sub ab) into a thermal-based Two-Source Energy Balance (TSEB) model that estimates land-surface CO2 and energy fluxes using an analytical, light-use-efficiency (LUE) based model of canopy resistance. The LUE model component computes canopy-scale carbon assimilation and transpiration fluxes and incorporates LUE modifications from a nominal (species-dependent) value (LUE(sub n)) in response to short term variations in environmental conditions, However LUE(sub n) may need adjustment on a daily timescale to accommodate changes in plant phenology, physiological condition and nutrient status. Day to day variations in LUE(sub n) were assessed for a heterogeneous corn crop field in Maryland, U,S.A. through model calibration with eddy covariance CO2 flux tower observations. The optimized daily LUE(sub n) values were then compared to estimates of C(sub ab) integrated from gridded maps of chlorophyll content weighted over the tower flux source area. The time continuous maps of daily C(sub ab) over the study field were generated by focusing in-situ measurements with retrievals generated with an integrated radiative transfer modeling tool (accurate to within +/-10%) using at-sensor radiances in green, red and near-infrared wavelengths acquired with an aircraft imaging system. The resultant daily changes in C(sub ab) within the tower flux source area generally correlated well with corresponding changes in daily calibrated LUE(sub n) derived from the tower flux data, and hourly water, energy and carbon flux estimation accuracies from TSEB were significantly improved when using C(sub ab) for delineating spatio

  2. Effect of anthocyanins, carotenoids, and flavonols on chlorophyll fluorescence excitation spectra in apple fruit: signature analysis, assessment, modelling, and relevance to photoprotection.

    PubMed

    Merzlyak, Mark N; Melø, Thor Bernt; Naqvi, K Razi

    2008-01-01

    Whole apple fruit (Malus domestica Borkh.) widely differing in pigment content and composition has been examined by recording its chlorophyll fluorescence excitation and diffuse reflection spectra in the visible and near UV regions. Spectral bands sensitive to the pigment concentration have been identified, and linear models for non-destructive assessment of anthocyanins, carotenoids, and flavonols via chlorophyll fluorescence measurements are put forward. The adaptation of apple fruit to high light stress involves accumulation of these protective pigments, which absorb solar radiation in broad spectral ranges extending from UV to the green and, in anthocyanin-containing cultivars, to the red regions of the spectrum. In ripening apples the protective effect in the blue region could be attributed to extrathylakoid carotenoids. A simple model, which allows the simulation of chlorophyll fluorescence excitation spectra in the visible range and a quantitative evaluation of competitive absorption by anthocyanins, carotenoids, and flavonols, is described. Evidence is presented to support the view that anthocyanins, carotenoids, and flavonols play, in fruit with low-to-moderate pigment content, the role of internal traps (insofar as they compete with chlorophylls for the absorption of incident light in specific spectral bands), affecting thereby the shape of the chlorophyll fluorescence excitation spectrum.

  3. Moving toward finer scales in oceanography: Predictive linear functional model of Chlorophyll a profile from light data

    NASA Astrophysics Data System (ADS)

    Bayle, Séverine; Monestiez, Pascal; Guinet, Christophe; Nerini, David

    2015-05-01

    The Southern Ocean plays a key role in ocean-atmosphere carbon dioxide fluxes. Estimation of carbon exchanges between ocean and atmosphere must rely on accurate estimations of primary productivity which require measurements of phytoplankton concentration within the water column. In this paper, we are interested in relationships between primary productivity and light in the Antarctic ocean. The originality of this work is twofold. Starting from physical hypothesis, a statistical model is constructed for the prediction of Chlorophyll a (Chl a) profiles where light profiles are used as a covariate. Taking into account of the functional nature of the data, solutions are proposed to estimate continuous vertical profiles from discrete data sampled by elephant seals equipped with a new generation of oceanographic tags. Bootstrapped prediction intervals show a good quality of prediction of Chl a profiles, giving access to the shape of the profiles along depth and to the submesoscale structure of phytoplankton within the euphotic layer of the Southern Ocean.

  4. Global monthly sea surface nitrate fields estimated from remotely sensed sea surface temperature, chlorophyll, and modeled mixed layer depth

    NASA Astrophysics Data System (ADS)

    Arteaga, Lionel; Pahlow, Markus; Oschlies, Andreas

    2015-02-01

    Information about oceanic nitrate is crucial for making inferences about marine biological production and the efficiency of the biological carbon pump. While there are no optical properties that allow direct estimation of inorganic nitrogen, its correlation with other biogeochemical variables may permit its inference from satellite data. Here we report a new method for estimating monthly mean surface nitrate concentrations employing local multiple linear regressions on a global 1° by 1° resolution grid, using satellite-derived sea surface temperature, chlorophyll, and modeled mixed layer depth. Our method is able to reproduce the interannual variability of independent in situ nitrate observations at the Bermuda Atlantic Time Series, the Hawaii Ocean Time series, the California coast, and the southern New Zealand region. Our new method is shown to be more accurate than previous algorithms and thus can provide improved information on temporal and spatial nutrient variations beyond the climatological mean at regional and global scales.

  5. Correlation of insulin-enhancing properties of vanadium-dipicolinate complexes in model membrane systems: phospholipid langmuir monolayers and AOT reverse micelles.

    PubMed

    Sostarecz, Audra G; Gaidamauskas, Ernestas; Distin, Steve; Bonetti, Sandra J; Levinger, Nancy E; Crans, Debbie C

    2014-04-22

    We explore the interactions of V(III) -, V(IV) -, and V(V) -2,6-pyridinedicarboxylic acid (dipic) complexes with model membrane systems and whether these interactions correlate with the blood-glucose-lowering effects of these compounds on STZ-induced diabetic rats. Two model systems, dipalmitoylphosphatidylcholine (DPPC) Langmuir monolayers and AOT (sodium bis(2-ethylhexyl)sulfosuccinate) reverse micelles present controlled environments for the systematic study of these vanadium complexes interacting with self-assembled lipids. Results from the Langmuir monolayer studies show that vanadium complexes in all three oxidation states interact with the DPPC monolayer; the V(III) -phospholipid interactions result in a slight decrease in DPPC molecular area, whereas V(IV) and V(V) -phospholipid interactions appear to increase the DPPC molecular area, an observation consistent with penetration into the interface of this complex. Investigations also examined the interactions of V(III) - and V(IV) -dipic complexes with polar interfaces in AOT reverse micelles. Electron paramagnetic resonance spectroscopic studies of V(IV) complexes in reverse micelles indicate that the neutral and smaller 1:1 V(IV) -dipic complex penetrates the interface, whereas the larger 1:2 V(IV) complex does not. UV/Vis spectroscopy studies of the anionic V(III) -dipic complex show only minor interactions. These results are in contrast to behavior of the V(V) -dipic complex, [VO2 (dipic)](-) , which penetrates the AOT/isooctane reverse micellar interface. These model membrane studies indicate that V(III) -, V(IV) -, and V(V) -dipic complexes interact with and penetrate the lipid interfaces differently, an effect that agrees with the compounds' efficacy at lowering elevated blood glucose levels in diabetic rats.

  6. Evaluation of model simulated and MODIS-Aqua retrieved sea surface chlorophyll in the eastern Arabian Sea

    NASA Astrophysics Data System (ADS)

    Chakraborty, Kunal; Gupta, Anubhav; Lotliker, Aneesh A.; Tilstone, Gavin

    2016-11-01

    In this study we assess the accuracy of sea surface Chlorophyll-a (Chla) retrieved from satellite (MODIS-Aqua), using standard OC3M algorithm, and from a Regional Ocean Modelling System (ROMS) biophysical model against in situ data, measured in surface waters of the eastern Arabian Sea, from April 2009 to December 2012. MODIS-Aqua OC3M Chla concentrations showed a high correlation with the in situ data with slope close to unity and low root mean square error. In comparison, the ROMS model underestimated Chla, though the correlation was significant indicating that the model is capable of reproducing the trend in in situ Chla. Time Series trends in Chla were examined against wind driven Upwelling Indices (UIW) from April 2009 to December 2012 in north-eastern (Gujarat) and south-eastern (Kochi) coastal waters of the Arabian Sea. The annual peak in Chla along the Kochi coast during the summer monsoon was adequately captured by the model. It is well known that the peak in surface Chla along the Kochi and Gujarat coasts during the summer monsoon is the result of coastal upwelling, which the ROMS model was able to reproduce accurately. The maximum surface Chla along the Gujarat coast during the winter monsoon is due to convective mixing, which was also significantly captured by ROMS biophysical model. There was a lag of approximately one week between the maximum surface Chla and the peak in the Upwelling Index.

  7. Chlorophyll a Simulation in a Lake Ecosystem Using a Model with Wavelet Analysis and Artificial Neural Network

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Wang, Xuan; Chen, Bin; Zhao, Ying; Yang, Zhifeng

    2013-05-01

    Accurate and reliable forecasting is important for the sustainable management of ecosystems. Chlorophyll a (Chl a) simulation and forecasting can provide early warning information and enable managers to make appropriate decisions for protecting lake ecosystems. In this study, we proposed a method for Chl a simulation in a lake that coupled the wavelet analysis and the artificial neural networks (WA-ANN). The proposed method had the advantage of data preprocessing, which reduced noise and managed nonstationary data. Fourteen variables were included in the developed and validated model, relating to hydrologic, ecological and meteorologic time series data from January 2000 to December 2009 at the Lake Baiyangdian study area, North China. The performance of the proposed WA-ANN model for monthly Chl a simulation in the lake ecosystem was compared with a multiple stepwise linear regression (MSLR) model, an autoregressive integrated moving average (ARIMA) model and a regular ANN model. The results showed that the WA-ANN model was suitable for Chl a simulation providing a more accurate performance than the MSLR, ARIMA, and ANN models. We recommend that the proposed method be widely applied to further facilitate the development and implementation of lake ecosystem management.

  8. Chlorophyll a simulation in a lake ecosystem using a model with wavelet analysis and artificial neural network.

    PubMed

    Wang, Fei; Wang, Xuan; Chen, Bin; Zhao, Ying; Yang, Zhifeng

    2013-05-01

    Accurate and reliable forecasting is important for the sustainable management of ecosystems. Chlorophyll a (Chl a) simulation and forecasting can provide early warning information and enable managers to make appropriate decisions for protecting lake ecosystems. In this study, we proposed a method for Chl a simulation in a lake that coupled the wavelet analysis and the artificial neural networks (WA-ANN). The proposed method had the advantage of data preprocessing, which reduced noise and managed nonstationary data. Fourteen variables were included in the developed and validated model, relating to hydrologic, ecological and meteorologic time series data from January 2000 to December 2009 at the Lake Baiyangdian study area, North China. The performance of the proposed WA-ANN model for monthly Chl a simulation in the lake ecosystem was compared with a multiple stepwise linear regression (MSLR) model, an autoregressive integrated moving average (ARIMA) model and a regular ANN model. The results showed that the WA-ANN model was suitable for Chl a simulation providing a more accurate performance than the MSLR, ARIMA, and ANN models. We recommend that the proposed method be widely applied to further facilitate the development and implementation of lake ecosystem management. PMID:23515906

  9. Near infrared-red models for the remote estimation of chlorophyll- a concentration in optically complex turbid productive waters: From in situ measurements to aerial imagery

    NASA Astrophysics Data System (ADS)

    Gurlin, Daniela

    Today the water quality of many inland and coastal waters is compromised by cultural eutrophication in consequence of increased human agricultural and industrial activities and remote sensing is widely applied to monitor the trophic state of these waters. This study explores near infrared-red models for the remote estimation of chlorophyll-a concentration in turbid productive waters and compares several near infrared-red models developed within the last 35 years. Three of these near infrared-red models were calibrated for a dataset with chlorophyll-a concentrations from 2.3 to 81.2 mg m -3 and validated for independent and statistically significantly different datasets with chlorophyll-a concentrations from 4.0 to 95.5 mg m-3 and 4.0 to 24.2 mg m-3 for the spectral bands of the MEdium Resolution Imaging Spectrometer (MERIS) and Moderate-resolution Imaging Spectroradiometer (MODIS). The developed MERIS two-band algorithm estimated chlorophyll-a concentrations from 4.0 to 24.2 mg m-3, which are typical for many inland and coastal waters, very accurately with a mean absolute error 1.2 mg m-3. These results indicate a high potential of the simple MERIS two-band algorithm for the reliable estimation of chlorophyll-a concentration without any reduction in accuracy compared to more complex algorithms, even though more research seems required to analyze the sensitivity of this algorithm to differences in the chlorophyll-a specific absorption coefficient of phytoplankton. Three near infrared-red models were calibrated and validated for a smaller dataset of atmospherically corrected multi-temporal aerial imagery collected by the hyperspectral airborne imaging spectrometer for applications (AisaEAGLE). The developed algorithms successfully captured the spatial and temporal variability of the chlorophyll-a concentrations and estimated chlorophyll- a concentrations from 2.3 to 81.2 mg m-3 with mean absolute errors from 4.4 mg m-3 for the AISA two band algorithm to 5.2 mg m-3

  10. Global simulation of canopy scale sun-induced chlorophyll fluorescence with a 3 dimensional radiative transfer model

    NASA Astrophysics Data System (ADS)

    Kobayashi, H.; Yang, W.; Ichii, K.

    2015-12-01

    Global simulation of canopy scale sun-induced chlorophyll fluorescence with a 3 dimensional radiative transfer modelHideki Kobayashi, Wei Yang, and Kazuhito IchiiDepartment of Environmental Geochemical Cycle Research, Japan Agency for Marine-Earth Science and Technology3173-25, Showa-machi, Kanazawa-ku, Yokohama, Japan.Plant canopy scale sun-induced chlorophyll fluorescence (SIF) can be observed from satellites, such as Greenhouse gases Observation Satellite (GOSAT), Orbiting Carbon Observatory-2 (OCO-2), and Global Ozone Monitoring Experiment-2 (GOME-2), using Fraunhofer lines in the near infrared spectral domain [1]. SIF is used to infer photosynthetic capacity of plant canopy [2]. However, it is not well understoond how the leaf-level SIF emission contributes to the top of canopy directional SIF because SIFs observed by the satellites use the near infrared spectral domain where the multiple scatterings among leaves are not negligible. It is necessary to quantify the fraction of emission for each satellite observation angle. Absorbed photosynthetically active radiation of sunlit leaves are 100 times higher than that of shaded leaves. Thus, contribution of sunlit and shaded leaves to canopy scale directional SIF emission should also be quantified. Here, we show the results of global simulation of SIF using a 3 dimensional radiative transfer simulation with MODIS atmospheric (aerosol optical thickness) and land (land cover and leaf area index) products and a forest landscape data sets prepared for each land cover category. The results are compared with satellite-based SIF (e.g. GOME-2) and the gross primary production empirically estimated by FLUXNET and remote sensing data.

  11. Assessing boreal forest photosynthetic dynamics through space-borne measurements of greenness, chlorophyll fluorescence and model GPP

    NASA Astrophysics Data System (ADS)

    Walther, Sophia; Guanter, Luis; Voigt, Maximilian; Köhler, Philipp; Jung, Martin; Joiner, Joanna

    2015-04-01

    sophia.walther@gfz-potsdam.de The seasonality of photosynthesis of boreal forests is an essential driver of the terrestrial carbon, water and energy cycles. However, current carbon cycle model results only poorly represent interannual variability and predict very different magnitudes and timings of carbon fluxes between the atmosphere and the land surface (e.g. Jung et al. 2011, Richardson et al. 2012). Reflectance-based satellite measurements, which give an indication of the amount of green biomass on the Earth's surface, have so far been used as input to global carbon cycle simulations, but they have limitations as they are not directly linked to instantaneous photosynthesis. As an alternative, space-borne retrievals of sun-induced chlorophyll fluorescence (SIF) boast the potential to provide a direct indication of the seasonality of boreal forest photosynthetic activity and thus to improve carbon model performances. SIF is a small electromagnetic signal that is re-emitted from the photosystems in the chloroplasts, which results in a direct relationship to photosynthetic efficiency. In this contribution we examine the seasonality of the boreal forests with three different vegetation parameters, namely greenness, SIF and model simulations of gross primary production (gross carbon flux into the plants by photosynthesis, GPP). We use the enhanced vegetation index (EVI) to represent green biomass. EVI is calculated from NBAR MODIS reflectance measurements (0.05deg, 16 days temporal resolution) for the time from January 2007-May 2013. SIF data originate from GOME-2 measurements on board the MetOp-A satellite in a spatial resolution of 0.5deg for the time from 2007-2011 (Joiner et al. (2013), Köhler et al. (2014)). As a third data source, data-driven GPP model results are used for the time from 2006-2012 with 0.5deg spatial resolution. The method to quantify phenology developed by Gonsamo et al. (2013) is applied to infer the main phenological phases (greenup/onset of

  12. Multiscale Modeling of Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Copolymer Micelles in Aqueous Solution.

    PubMed

    Bedrov, Dmitry; Ayyagari, Chakravarthy; Smith, Grant D

    2006-05-01

    We present a multiscale modeling approach for simulation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer micelles in aqueous solution. We rely on systematic elimination of computationally expensive degrees of freedom yet retain implicitly their influence on the remaining degrees freedom in a coarser-grained model. Quantum chemistry (QC) calculations, atomistic explicit solvent (AES) molecular dynamics (MD) simulations, and coarse-grained implicit solvent (CGIS) simulations have been applied to investigate physical properties of these important self-assembling triblock copolymers. High-level QC calculations have been used to parametrize classical atomistic force fields that implicitly take into account and reproduce the important energetic and structural features due to correlations of electronic degrees of freedom. AES MD simulations utilizing the QC-based force fields have been used to provide structural and conformational properties of polymers in aqueous solution which were subsequently used for parametrization of the CGIS model using the Inverted Boltzmann method. The CGIS simulations were then employed to investigate structural properties of two PEO-PPO-PEO micelles (EO13-PO30-EO13 and EO99-PO65-EO99 also known as Pluronic L64 and F127, respectively) in aqueous solution.

  13. Validation of the 3D biogeochemical model MIRO&CO with field nutrient and phytoplankton data and MERIS-derived surface chlorophyll a images

    NASA Astrophysics Data System (ADS)

    Lacroix, Geneviève; Ruddick, Kevin; Park, Youngje; Gypens, Nathalie; Lancelot, Christiane

    2007-01-01

    This paper presents results obtained with MIRO&CO-3D, a biogeochemical model dedicated to the study of eutrophication and applied to the Channel and Southern Bight of the North Sea (48.5°N-52.5°N). The model results from coupling of the COHERENS-3D hydrodynamic model and the biogeochemical model MIRO, which was previously calibrated in a multi-box implementation. MIRO&CO-3D is run to simulate the annual cycle of inorganic and organic carbon and nutrients (nitrogen, phosphorus and silica), phytoplankton (diatoms, nanoflagellates and Phaeocystis), bacteria and zooplankton (microzooplankton and copepods) with realistic forcing (meteorological conditions and river loads) for the period 1991-2003. Model validation is first shown by comparing time series of model concentrations of nutrients, chlorophyll a, diatom and Phaeocystis with in situ data from station 330 (51°26.00'N, 2°48.50'E) located in the centre of the Belgian coastal zone. This comparison shows the model's ability to represent the seasonal dynamics of nutrients and phytoplankton in Belgian waters. However the model fails to simulate correctly the dissolved silica cycle, especially during the beginning of spring, due to the late onset (in the model) of the early spring diatom bloom. As a general trend the chlorophyll a spring maximum is underestimated in simulations. A comparison between the seasonal average of surface winter nutrients and spring chlorophyll a concentrations simulated with in situ data for different stations is used to assess the accuracy of the simulated spatial distribution. At a seasonal scale, the spatial distribution of surface winter nutrients is in general well reproduced by the model with nevertheless a small overestimation for a few stations close to the Rhine/Meuse mouth and a tendency to underestimation in the coastal zone from Belgium to France. PO 4 was simulated best; silica was simulated with less success. Spring chlorophyll a concentration is in general underestimated by

  14. Dynamics of Two Picophytoplankton Groups in Mediterranean Sea: Analysis of the Deep Chlorophyll Maximum by a Stochastic Advection-Reaction-Diffusion Model

    PubMed Central

    Denaro, Giovanni; Valenti, Davide; Spagnolo, Bernardo; Basilone, Gualtiero; Mazzola, Salvatore; Zgozi, Salem W.; Aronica, Salvatore; Bonanno, Angelo

    2013-01-01

    A stochastic advection-reaction-diffusion model with terms of multiplicative white Gaussian noise, valid for weakly mixed waters, is studied to obtain the vertical stationary spatial distributions of two groups of picophytoplankton, i.e., picoeukaryotes and Prochlorococcus, which account about for 60% of total chlorophyll on average in Mediterranean Sea. By numerically solving the equations of the model, we analyze the one-dimensional spatio-temporal dynamics of the total picophytoplankton biomass and nutrient concentration along the water column at different depths. In particular, we integrate the equations over a time interval long enough, obtaining the steady spatial distributions for the cell concentrations of the two picophytoplankton groups. The results are converted into chlorophyll a and divinil chlorophyll a concentrations and compared with experimental data collected in two different sites of the Sicily Channel (southern Mediterranean Sea). The comparison shows that real distributions are well reproduced by theoretical profiles. Specifically, position, shape and magnitude of the theoretical deep chlorophyll maximum exhibit a good agreement with the experimental values. PMID:23826130

  15. Targeted antithrombotic protein micelles.

    PubMed

    Kim, Wookhyun; Haller, Carolyn; Dai, Erbin; Wang, Xiowei; Hagemeyer, Christoph E; Liu, David R; Peter, Karlheinz; Chaikof, Elliot L

    2015-01-26

    Activated platelets provide a promising target for imaging inflammatory and thrombotic events along with site-specific delivery of a variety of therapeutic agents. Multifunctional protein micelles bearing targeting and therapeutic proteins were now obtained by one-pot transpeptidation using an evolved sortase A. Conjugation to the corona of a single-chain antibody (scFv), which binds to the ligand-induced binding site (LIBS) of activated GPIIb/IIIa receptors, enabled the efficient detection of thrombi. The inhibition of thrombus formation was subsequently accomplished by incorporating the catalytically active domain of thrombomodulin (TM) onto the micelle corona for the local generation of activated protein C, which inhibits the formation of thrombin. An effective strategy has been developed for the preparation of protein micelles that can be targeted to sites of activated platelets with broad potential for treatment of acute thrombotic events. PMID:25504546

  16. Adiabatic compressibility of AOT [sodium bis(2-ethylhexyl)sulfosuccinate] reverse micelles: Analysis of a simple model based on micellar size and volumetric measurements

    NASA Astrophysics Data System (ADS)

    Amararene, A.; Gindre, M.; Le Huérou, J.-Y.; Urbach, W.; Valdez, D.; Waks, M.

    2000-01-01

    The self-assembly of amphiphilic molecules into supramolecular aggregates involves a number of complex phenomena and forces. Recent developments of highly sensitive, densimetric and acoustic methods on small volume samples have provided novel sensitive probes to explore the physical properties of these complex fluids. We have investigated, by high precision densimetry and ultrasound velocimetry, reverse micelles of [sodium bis(2-ethylhexyl)sulfosuccinate] in oil (isooctane and decane), at increasing water concentration and at variable micellar volume fractions. The size of these spherical micelles has been determined by small angle x-ray scattering. Using these results, in the framework of the effective medium theory, we have developed a simple model of micellar compressibility, allowing the calculation of physical parameters (aggregation number, volume, and compressibility) of the surfactant monomolecular film as well as that of the micellar waters. In particular, we show that the central aqueous core designated as ``free'' water, located at a distance from the oil-water interacting interface, is twice as compressible as ``bulk'' water. One notable feature of this work is the influence of the nature of the oil on the above parameters.

  17. Development of FT-NIR models for the simultaneous estimation of chlorophyll and nitrogen content in fresh apple (Malus domestica) leaves.

    PubMed

    Tamburini, Elena; Ferrari, Giuseppe; Marchetti, Maria Gabriella; Pedrini, Paola; Ferro, Sergio

    2015-01-01

    Agricultural practices determine the level of food production and, to great extent, the state of the global environment. During the last decades, the indiscriminate recourse to fertilizers as well as the nitrogen losses from land application have been recognized as serious issues of modern agriculture, globally contributing to nitrate pollution. The development of a reliable Near-Infra-Red Spectroscopy (NIRS)-based method, for the simultaneous monitoring of nitrogen and chlorophyll in fresh apple (Malus domestica) leaves, was investigated on a set of 133 samples, with the aim of estimating the nutritional and physiological status of trees, in real time, cheaply and non-destructively. By means of a FT (Fourier Transform)-NIR instrument, Partial Least Squares (PLS) regression models were developed, spanning a concentration range of 0.577%-0.817% for the total Kjeldahl nitrogen (TKN) content (R2 = 0.983; SEC = 0.012; SEP = 0.028), and of 1.534-2.372 mg/g for the total chlorophyll content (R2 = 0.941; SEC = 0.132; SEP = 0.162). Chlorophyll-a and chlorophyll-b contents were also evaluated (R2 = 0.913; SEC = 0.076; SEP = 0.101 and R2 = 0.899; SEC = 0.059; SEP = 0.101, respectively). All calibration models were validated by means of 47 independent samples. The NIR approach allows a rapid evaluation of the nitrogen and chlorophyll contents, and may represent a useful tool for determining nutritional and physiological status of plants, in order to allow a correction of nutrition programs during the season. PMID:25629703

  18. Development of FT-NIR Models for the Simultaneous Estimation of Chlorophyll and Nitrogen Content in Fresh Apple (Malus Domestica) Leaves

    PubMed Central

    Tamburini, Elena; Ferrari, Giuseppe; Marchetti, Maria Gabriella; Pedrini, Paola; Ferro, Sergio

    2015-01-01

    Agricultural practices determine the level of food production and, to great extent, the state of the global environment. During the last decades, the indiscriminate recourse to fertilizers as well as the nitrogen losses from land application have been recognized as serious issues of modern agriculture, globally contributing to nitrate pollution. The development of a reliable Near-Infra-Red Spectroscopy (NIRS)-based method, for the simultaneous monitoring of nitrogen and chlorophyll in fresh apple (Malus domestica) leaves, was investigated on a set of 133 samples, with the aim of estimating the nutritional and physiological status of trees, in real time, cheaply and non-destructively. By means of a FT (Fourier Transform)-NIR instrument, Partial Least Squares (PLS) regression models were developed, spanning a concentration range of 0.577%–0.817% for the total Kjeldahl nitrogen (TKN) content (R2 = 0.983; SEC = 0.012; SEP = 0.028), and of 1.534–2.372 mg/g for the total chlorophyll content (R2 = 0.941; SEC = 0.132; SEP = 0.162). Chlorophyll-a and chlorophyll-b contents were also evaluated (R2 = 0.913; SEC = 0.076; SEP = 0.101 and R2 = 0.899; SEC = 0.059; SEP = 0.101, respectively). All calibration models were validated by means of 47 independent samples. The NIR approach allows a rapid evaluation of the nitrogen and chlorophyll contents, and may represent a useful tool for determining nutritional and physiological status of plants, in order to allow a correction of nutrition programs during the season. PMID:25629703

  19. Development of FT-NIR models for the simultaneous estimation of chlorophyll and nitrogen content in fresh apple (Malus domestica) leaves.

    PubMed

    Tamburini, Elena; Ferrari, Giuseppe; Marchetti, Maria Gabriella; Pedrini, Paola; Ferro, Sergio

    2015-01-26

    Agricultural practices determine the level of food production and, to great extent, the state of the global environment. During the last decades, the indiscriminate recourse to fertilizers as well as the nitrogen losses from land application have been recognized as serious issues of modern agriculture, globally contributing to nitrate pollution. The development of a reliable Near-Infra-Red Spectroscopy (NIRS)-based method, for the simultaneous monitoring of nitrogen and chlorophyll in fresh apple (Malus domestica) leaves, was investigated on a set of 133 samples, with the aim of estimating the nutritional and physiological status of trees, in real time, cheaply and non-destructively. By means of a FT (Fourier Transform)-NIR instrument, Partial Least Squares (PLS) regression models were developed, spanning a concentration range of 0.577%-0.817% for the total Kjeldahl nitrogen (TKN) content (R2 = 0.983; SEC = 0.012; SEP = 0.028), and of 1.534-2.372 mg/g for the total chlorophyll content (R2 = 0.941; SEC = 0.132; SEP = 0.162). Chlorophyll-a and chlorophyll-b contents were also evaluated (R2 = 0.913; SEC = 0.076; SEP = 0.101 and R2 = 0.899; SEC = 0.059; SEP = 0.101, respectively). All calibration models were validated by means of 47 independent samples. The NIR approach allows a rapid evaluation of the nitrogen and chlorophyll contents, and may represent a useful tool for determining nutritional and physiological status of plants, in order to allow a correction of nutrition programs during the season.

  20. Significant Findings: Seasonal Distributions of Global Ocean Chlorophyll and Nutrients With a Coupled Ocean General Circulation, Biogeochemical, and Radiative Model. 2; Comparisons With Satellite and In Situ Data

    NASA Technical Reports Server (NTRS)

    Gregg, Watson W.; Busalacchi, Antonio (Technical Monitor)

    2000-01-01

    A coupled ocean general circulation, biogeochemical, and radiative model was constructed to evaluate and understand the nature of seasonal variability of chlorophyll and nutrients in the global oceans. Biogeochemical processes in the model were determined from the influences of circulation and turbulence dynamics, irradiance availability, and the interactions among three functional phytoplankton groups (diatoms, chlorophytes, and picoplankton) and three nutrients (nitrate, ammonium, and silicate). Basin scale (>1000 km) model chlorophyll seasonal distributions were statistically positively correlated with CZCS chlorophyll in 10 of 12 major oceanographic regions, and with SeaWiFS in all 12. Notable disparities in magnitudes occurred, however, in the tropical Pacific, the spring/summer bloom in the Antarctic, autumn in the northern high latitudes, and during the southwest monsoon in the North Indian Ocean. Synoptic scale (100-1000 km) comparisons of satellite and in situ data exhibited broad agreement, although occasional departures were apparent. Model nitrate distributions agreed with in situ data, including seasonal dynamics, except for the equatorial Atlantic. The overall agreement of the model with satellite and in situ data sources indicated that the model dynamics offer a reasonably realistic simulation of phytoplankton and nutrient dynamics on basin and synoptic scales.

  1. Comparison of solar-induced chlorophyll fluorescence, light-use efficiency, and process-based GPP models in maize.

    PubMed

    Wagle, Pradeep; Zhang, Yongguang; Jin, Cui; Xiao, Xiangming

    2016-06-01

    Accurately quantifying cropland gross primary production (GPP) is of great importance to monitor cropland status and carbon budgets. Satellite-based light-use efficiency (LUE) models and process-based terrestrial biosphere models (TBMs) have been widely used to quantify cropland GPP at different scales in past decades. However, model estimates of GPP are still subject to large uncertainties, especially for croplands. More recently, space-borne solar-induced chlorophyll fluorescence (SIF) has shown the ability to monitor photosynthesis from space, providing new insights into actual photosynthesis monitoring. In this study, we examined the potential of SIF data to describe maize phenology and evaluated three GPP modeling approaches (space-borne SIF retrievals, a LUE-based vegetation photosynthesis model [VPM], and a process-based soil canopy observation of photochemistry and energy flux [SCOPE] model constrained by SIF) at a maize (Zea mays L.) site in Mead, Nebraska, USA. The result shows that SIF captured the seasonal variations (particularly during the early and late growing season) of tower-derived GPP (GPP_EC) much better than did satellite-based vegetation indices (enhanced vegetation index [EVI] and land surface water index [LSWI]). Consequently, SIF was strongly correlated with GPP_EC than were EVI and LSWI. Evaluation of GPP estimates against GPP_EC during the growing season demonstrated that all three modeling approaches provided reasonable estimates of maize GPP, with Pearson's correlation coefficients (r) of 0.97, 0.94, and 0.93 for the SCOPE, VPM, and SIF models, respectively. The SCOPE model provided the best simulation of maize GPP when SIF observations were incorporated through optimizing the key parameter of maximum carboxylation capacity (Vcmax). Our results illustrate the potential of SIF data to offer an additional way to investigate the seasonality of photosynthetic activity, to constrain process-based models for improving GPP estimates, and to

  2. Performance evaluation of ocean color satellite models for deriving accurate chlorophyll estimates in the Gulf of Saint Lawrence

    NASA Astrophysics Data System (ADS)

    Montes-Hugo, M.; Bouakba, H.; Arnone, R.

    2014-06-01

    The understanding of phytoplankton dynamics in the Gulf of the Saint Lawrence (GSL) is critical for managing major fisheries off the Canadian East coast. In this study, the accuracy of two atmospheric correction techniques (NASA standard algorithm, SA, and Kuchinke's spectral optimization, KU) and three ocean color inversion models (Carder's empirical for SeaWiFS (Sea-viewing Wide Field-of-View Sensor), EC, Lee's quasi-analytical, QAA, and Garver- Siegel-Maritorena semi-empirical, GSM) for estimating the phytoplankton absorption coefficient at 443 nm (aph(443)) and the chlorophyll concentration (chl) in the GSL is examined. Each model was validated based on SeaWiFS images and shipboard measurements obtained during May of 2000 and April 2001. In general, aph(443) estimates derived from coupling KU and QAA models presented the smallest differences with respect to in situ determinations as measured by High Pressure liquid Chromatography measurements (median absolute bias per cruise up to 0.005, RMSE up to 0.013). A change on the inversion approach used for estimating aph(443) values produced up to 43.4% increase on prediction error as inferred from the median relative bias per cruise. Likewise, the impact of applying different atmospheric correction schemes was secondary and represented an additive error of up to 24.3%. By using SeaDAS (SeaWiFS Data Analysis System) default values for the optical cross section of phytoplankton (i.e., aph(443) = aph(443)/chl = 0.056 m2mg-1), the median relative bias of our chl estimates as derived from the most accurate spaceborne aph(443) retrievals and with respect to in situ determinations increased up to 29%.

  3. Triggered disassembly of hierarchically assembled onion-like micelles into the pristine core-shell micelles via a small change in pH.

    PubMed

    Cai, Guoqiang; Zhang, Haiwen; Liu, Peng; Wang, Liqun; Jiang, Hongliang

    2011-10-01

    The size and surface property of nanomaterial-based delivery systems administered intravenously play important roles in their cell uptake and in vivo distribution. Both of them should be capable of self-evolution in order to achieve efficient targeting performance. A facile strategy was proposed to manipulate both the size and surface property of polymeric micelles. It was found that the hierarchical assembly between trimethylated chitosan-g-poly(ε-caprolactone) (TMC-PCL) micelles and carboxyethyl chitosan-g-poly(ethylene glycol) (CEC-PEG) could produce onion-like micelles with enlarged size and PEGylated surface. The onion-like micelles could withstand the ionic strength of plasma and competitive exchange with BSA, and abruptly disassemble into the pristine TMC-PCL micelles via a small change in pH. By varying the degree of carboxyethylation, the disassembly pH could be modulated to the range of the tumoral microclimate pH. In contrast with TMC-PCL micelles, which displayed high cytotoxicity and endocytic ability towards C6 glioma cells, the onion-like micelles were cell-friendly and internalized by the cells at a very low level. Doxorubicin was used as a model chemotherapeutic agent and incorporated within TMC-PCL micelles. Dox release from both TMC-PCL micelles and the onion-like micelles was very slow under normal physiological conditions and displayed excellent pH sensitivity. Cell viability of Dox-loaded micelles was also investigated.

  4. Polymer Micelles Laden Hydrogel Contact Lenses for Ophthalmic Drug Delivery.

    PubMed

    Hu, Xiaohong; Tan, Huaping; Chen, Pin; Wang, Xin; Pang, Juan

    2016-06-01

    Hydrogel contact lens is an attractive drug carrier for the delivery of ophthalmic drugs. But limited drug loading capacity and burst release restricted its application in this field. Polymer micelle laden hydrogel contact lenses were designed for ophthalmic drug delivery in the work. β-CD/PAA/PEG ternary system was chosen to form polymer micelle. The micelle size could be adjusted by β-CD content and PAA/PEG concentration. The zeta potential of micelle was irrelevant to β-CD content, but influenced by PAA/PEG concentration. The absorbed drug concentration in micelle solution depended on both β-CD content and PAA/PEG concentration. Polymer micelle laden hydrogels were obtained by radical polymerization in situ. The transparency of polymer micelle laden hydrogel declined with PAA/PEG concentration increasing. The equilibrium water content and water loss showed that polymer micelle laden hydrogel with higher PAA/PEG concentration was in a higher swollen state. The dynamic viscoelastic properties howed that all polymer micelle laden hydrogels had some characteristics of crosslinked elastomers. The surface structure of freeze dried composite hydrogels was different from freeze dried pure hydrogel. The drug loading and releasing behaviors were detected to evaluate the drug loading and releasing capacity of hydrogels using orfloxacin and puerarin as model drugs. The results indicated the polymer micelle in hydrogel could hold or help to hold some ophthalmic drugs, and slow down orfloxacin release speed or keep puerarin stably stay for a time in hydrogels. In the end, it was found that the transparency of composite hydrogel became better after the hydrogel had been immersed in PBS for several weeks.

  5. Biodegradable polymeric micelle-encapsulated doxorubicin suppresses tumor metastasis by killing circulating tumor cells

    NASA Astrophysics Data System (ADS)

    Deng, Senyi; Wu, Qinjie; Zhao, Yuwei; Zheng, Xin; Wu, Ni; Pang, Jing; Li, Xuejing; Bi, Cheng; Liu, Xinyu; Yang, Li; Liu, Lei; Su, Weijun; Wei, Yuquan; Gong, Changyang

    2015-03-01

    Circulating tumor cells (CTCs) play a crucial role in tumor metastasis, but it is rare for any chemotherapy regimen to focus on killing CTCs. Herein, we describe doxorubicin (Dox) micelles that showed anti-metastatic activity by killing CTCs. Dox micelles with a small particle size and high encapsulation efficiency were obtained using a pH-induced self-assembly method. Compared with free Dox, Dox micelles exhibited improved cytotoxicity, apoptosis induction, and cellular uptake. In addition, Dox micelles showed a sustained release behavior in vitro, and in a transgenic zebrafish model, Dox micelles exhibited a longer circulation time and lower extravasation from blood vessels into surrounding tissues. Anti-tumor and anti-metastatic activities of Dox micelles were investigated in transgenic zebrafish and mouse models. In transgenic zebrafish, Dox micelles inhibited tumor growth and prolonged the survival of tumor-bearing zebrafish. Furthermore, Dox micelles suppressed tumor metastasis by killing CTCs. In addition, improved anti-tumor and anti-metastatic activities were also confirmed in mouse tumor models, where immunofluorescent staining of tumors indicated that Dox micelles induced more apoptosis and showed fewer proliferation-positive cells. There were decreased side effects in transgenic zebrafish and mice after administration of Dox micelles. In conclusion, Dox micelles showed stronger anti-tumor and anti-metastatic activities and decreased side effects both in vitro and in vivo, which may have potential applications in cancer therapy.

  6. Casein micelles and their internal structure

    SciTech Connect

    De Kruif, Cornelis G; Huppertz, Thom; Urban, Volker S; Petukhov, Andrei V

    2012-01-01

    The internal structure of casein micelles was studied by calculating the small-angle neutron and X-ray scattering and static light scattering spectrum (SANS, SAXS, SLS) as a function of the scattering contrast and composition. We predicted experimental SANS, SAXS, SLS spectra self consistently using independently determined parameters for composition size, polydispersity, density and voluminosity. The internal structure of the casein micelles, i.e. how the various components are distributed within the casein micelle, was modeled according to three different models advocated in the literature; i.e. the classical sub-micelle model, the nanocluster model and the dual binding model. In this paper we present the essential features of these models and combine new and old experimental SANS, SAXS, SLS and DLS scattering data with new calculations that predict the spectra. Further evidence on micellar substructure was obtained by internally cross linking the casein micelles using transglutaminase, which led to casein nanogel particles. In contrast to native casein micelles, the nanogel particles were stable in 6 M urea and after sequestering the calcium using trisodium citrate. The changed scattering properties were again predicted self consistently. An important result is that the radius of gyration is independent of contrast, indicating that the mass distribution within a casein micelle is homogeneous. Experimental contrast is predicted quite well leading to a match point at a D{sub 2}O volume fraction of 0.41 ratio in SANS. Using SANS and SAXS model calculations it is concluded that only the nanocluster model is capable of accounting for the experimental scattering contrast variation data. All features and trends are predicted self consistently, among which the 'famous' shoulder at a wave vector value Q = 0.35 nm{sup -1}. In the nanocluster model, the casein micelle is considered as a (homogeneous) matrix of caseins in which the colloidal calcium phosphate (CCP

  7. Joint Leaf chlorophyll and leaf area index retrieval from Landsat data using a regularized model inversion system

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Leaf area index (LAI) and leaf chlorophyll (Chl) content represent key biophysical and biochemical controls on water, energy and carbon exchange processes in the terrestrial biosphere. In combination, LAI and leaf Chl content provide critical information on vegetation density, vitality and photosynt...

  8. Estimation of vegetation photosynthetic capacity from space-based measurements of chlorophyll fluorescence for terrestrial biosphere models.

    PubMed

    Zhang, Yongguang; Guanter, Luis; Berry, Joseph A; Joiner, Joanna; van der Tol, Christiaan; Huete, Alfredo; Gitelson, Anatoly; Voigt, Maximilian; Köhler, Philipp

    2014-12-01

    Photosynthesis simulations by terrestrial biosphere models are usually based on the Farquhar's model, in which the maximum rate of carboxylation (Vcmax ) is a key control parameter of photosynthetic capacity. Even though Vcmax is known to vary substantially in space and time in response to environmental controls, it is typically parameterized in models with tabulated values associated to plant functional types. Remote sensing can be used to produce a spatially continuous and temporally resolved view on photosynthetic efficiency, but traditional vegetation observations based on spectral reflectance lack a direct link to plant photochemical processes. Alternatively, recent space-borne measurements of sun-induced chlorophyll fluorescence (SIF) can offer an observational constraint on photosynthesis simulations. Here, we show that top-of-canopy SIF measurements from space are sensitive to Vcmax at the ecosystem level, and present an approach to invert Vcmax from SIF data. We use the Soil-Canopy Observation of Photosynthesis and Energy (SCOPE) balance model to derive empirical relationships between seasonal Vcmax and SIF which are used to solve the inverse problem. We evaluate our Vcmax estimation method at six agricultural flux tower sites in the midwestern US using spaced-based SIF retrievals. Our Vcmax estimates agree well with literature values for corn and soybean plants (average values of 37 and 101 μmol m(-2)  s(-1) , respectively) and show plausible seasonal patterns. The effect of the updated seasonally varying Vcmax parameterization on simulated gross primary productivity (GPP) is tested by comparing to simulations with fixed Vcmax values. Validation against flux tower observations demonstrate that simulations of GPP and light use efficiency improve significantly when our time-resolved Vcmax estimates from SIF are used, with R(2) for GPP comparisons increasing from 0.85 to 0.93, and for light use efficiency from 0.44 to 0.83. Our results support the use of

  9. Estimation of vegetation photosynthetic capacity from space-based measurements of chlorophyll fluorescence for terrestrial biosphere models.

    PubMed

    Zhang, Yongguang; Guanter, Luis; Berry, Joseph A; Joiner, Joanna; van der Tol, Christiaan; Huete, Alfredo; Gitelson, Anatoly; Voigt, Maximilian; Köhler, Philipp

    2014-12-01

    Photosynthesis simulations by terrestrial biosphere models are usually based on the Farquhar's model, in which the maximum rate of carboxylation (Vcmax ) is a key control parameter of photosynthetic capacity. Even though Vcmax is known to vary substantially in space and time in response to environmental controls, it is typically parameterized in models with tabulated values associated to plant functional types. Remote sensing can be used to produce a spatially continuous and temporally resolved view on photosynthetic efficiency, but traditional vegetation observations based on spectral reflectance lack a direct link to plant photochemical processes. Alternatively, recent space-borne measurements of sun-induced chlorophyll fluorescence (SIF) can offer an observational constraint on photosynthesis simulations. Here, we show that top-of-canopy SIF measurements from space are sensitive to Vcmax at the ecosystem level, and present an approach to invert Vcmax from SIF data. We use the Soil-Canopy Observation of Photosynthesis and Energy (SCOPE) balance model to derive empirical relationships between seasonal Vcmax and SIF which are used to solve the inverse problem. We evaluate our Vcmax estimation method at six agricultural flux tower sites in the midwestern US using spaced-based SIF retrievals. Our Vcmax estimates agree well with literature values for corn and soybean plants (average values of 37 and 101 μmol m(-2)  s(-1) , respectively) and show plausible seasonal patterns. The effect of the updated seasonally varying Vcmax parameterization on simulated gross primary productivity (GPP) is tested by comparing to simulations with fixed Vcmax values. Validation against flux tower observations demonstrate that simulations of GPP and light use efficiency improve significantly when our time-resolved Vcmax estimates from SIF are used, with R(2) for GPP comparisons increasing from 0.85 to 0.93, and for light use efficiency from 0.44 to 0.83. Our results support the use of

  10. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles.

  11. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  12. Smart wormlike micelles.

    PubMed

    Chu, Zonglin; Dreiss, Cécile A; Feng, Yujun

    2013-09-01

    A major scientific challenge of the past decade pertaining to the field of soft matter has been to craft 'adaptable' materials, inspired by nature, which can dynamically alter their structure and functionality on demand, in response to triggers produced by environmental changes. Amongst these, 'smart' surfactant wormlike micelles, responsive to external stimuli, are a particularly recent area of development, yet highly promising, given the versatility of the materials but simplicity of the design-relying on small amphiphilic molecules and their spontaneous self-assembly. The switching 'on' and 'off' of the micellar assembly structures has been reported using electrical, optical, thermal or pH triggers and is now envisaged for multiple stimuli. The structural changes, in turn, can induce major variations in the macroscopic characteristics, affecting properties such as viscosity and elasticity and sometimes even leading to a spontaneous and effective 'sol-gel' transition. These original smart materials based on wormlike micelles have been successfully used in the oil industry, and offer a significant potential in a wide range of other technological applications, including biomedicine, cleaning processes, drag reduction, template synthesis, to name but a few. This review will report results in this field published over the last few years, describe the potential and practical applications of stimuli-responsive wormlike micelles and point out future challenges.

  13. Evaluating Southern Ocean biological production in two ocean biogeochemical models on daily to seasonal time-scales using satellite surface chlorophyll and O2/Ar observations

    NASA Astrophysics Data System (ADS)

    Jonsson, B. F.; Doney, S.; Dunne, J.; Bender, M. L.

    2014-06-01

    We assess the ability of ocean biogeochemical models to represent seasonal structures in biomass and net community production (NCP) in the Southern Ocean. Two models are compared to observations on daily to seasonal time scales in four different sections of the region. We use daily satellite fields of Chlorophyll (Chl) as a proxy for biomass, and in-situ observations of O2 and Ar supersaturation (ΔO2Ar) to estimate NCP. ΔO2Ar is converted to the flux of biologically generated O2 from sea to air ("O2 bioflux"). All data are aggregated to a climatological year with a daily resolution. To account for potential regional differences within the Southern Ocean, we conduct separate analyses of sections south of South Africa, around the Drake Passage, south of Australia, and south of New Zealand. We find that the models simulate the upper range of Chl concentrations well, underestimate spring levels significantly, and show differences in skill between early and late parts of the growing season. While there is a great deal of scatter in the bioflux observations in general, the four sectors each have distinct patterns that the models pick up. Neither model exhibit a significant distinction between the Australian and New Zealand sectors, and between the Drake Passage and African sectors. South of 60° S, the models fail to predict the observed extent of biological O2 undersaturation. We suggest that this shortcoming may be due either to problems with the ecosystem dynamics or problems with the vertical transport of oxygen. Overall, the bioflux observations are in general agreement with the seasonal structures in satellite chlorophyll, suggesting that this seasonality represent changes in carbon biomass and not Chl : C ratios. This agreement is shared in the models and allows us to interpret the seasonal structure of satellite chlorophyll as qualitatively reflecting the integral of biological production over time for the purposes of model assessment.

  14. Vegetation Red-edge Spectral Modeling for Solar-induced Chlorophyll Fluorescence Retrieval at O2-B Band

    NASA Astrophysics Data System (ADS)

    Huang, C.; Zhang, L.; Qiao, N.; Zhang, X.; Li, Y.

    2015-12-01

    Remotely sensed solar-induced chlorophyll fluorescence (SIF) has been considered an ideal probe in monitoring global vegetation photosynthesis. However, challenges in accurate estimate of faint SIF (less than 5% of the total reflected radiation in near infrared bands) from the observed apparent reflected radiation greatly limit its wide applications. Currently, the telluric O2-B (~688nm) and O2-A (~761nm) have been proved to be capable of SIF retrieval based on Fraunhofer line depth (FLD) principle. They may still work well even using conventional ground-based commercial spectrometers with typical spectral resolutions of 2~5 nm and high enough signal-to-noise ratio (e.g., the ASD spectrometer). Nevertheless, almost all current FLD based algorithms were mainly developed for O2-A, a few concentrating on the other SIF emission peak in O2-B. One of the critical reasons is that it is very difficult to model the sudden varying reflectance around O2-B band located in the red-edge spectral region (about 680-800 nm). This study investigates a new method by combining the established inverted Gaussian reflectance model (IGM) and FLD principle using diurnal canopy spectra with relative low spectral resolutions of 1 nm (FluorMOD simulations) and 3 nm (measured by ASD spectrometer) respectively. The IGM has been reported to be an objective and good method to characterize the entire vegetation red-edge reflectance. Consequently, the proposed SIF retrieval method (hereinafter called IGMFLD) could exploit all the spectral information along the whole red-edge (680-800 nm) to obtain more reasonable reflectance and fluorescence correction coefficients than traditional FLD methods such as the iFLD. Initial results show that the IGMFLD can better capture the spectrally non-linear characterization of the reflectance in 680-800 nm and thereby yields much more accurate SIFs in O2-B than typical FLD methods, including sFLD, 3FLD and iFLD (see figure 1). Finally, uncertainties and prospect

  15. On the stability and morphology of complex coacervate core micelles: from spherical to wormlike micelles.

    PubMed

    van der Kooij, Hanne M; Spruijt, Evan; Voets, Ilja K; Fokkink, Remco; Cohen Stuart, Martien A; van der Gucht, Jasper

    2012-10-01

    We present a systematic study of the stability and morphology of complex coacervate core micelles (C3Ms) formed from poly(acrylic acid) (PAA) and poly(N-methyl-2-vinylpyridinium)-b-poly(ethylene oxide) (PM2VP-b-PEO). We use polarized and depolarized dynamic and static light scattering, combined with small-angle X-ray scattering, to investigate how the polymer chain length and salt concentration affect the stability, size, and shape of these micelles. We show that C3Ms are formed in aqueous solution below a critical salt concentration, which increases considerably with increasing PAA and PM2VP length and levels off for long chains. This trend is in good agreement with a mean-field model of polyelectrolyte complexation based on the Voorn-Overbeek theory. In addition, we find that salt induces morphological changes in C3Ms when the PAA homopolymer is sufficiently short: from spherical micelles with a diameter of several tens of nanometers at low salt concentration to wormlike micelles with a contour length of several hundreds of nanometers just before the critical salt concentration. By contrast, C3Ms of long PAA homopolymers remain spherical upon addition of salt and shrink slightly. A critical review of existing literature on other C3Ms reveals that the transition from spherical to wormlike micelles is probably a general phenomenon, which can be rationalized in terms of a classical packing parameter for amphiphiles.

  16. Improving the Algae Bloom Prediction through the Assimilation of the Remotely Sensed Chlorophyll-A Data in a Generic Ecological Model in the North Sea

    NASA Astrophysics Data System (ADS)

    El Serafy, Ghada

    2010-05-01

    Harmful algae can cause damage to co-existing organisms, tourism and farmers. Accurate predictions of algal future composition and abundance as well as when and where algal blooms may occur could help early warning and mitigating. The Generic Ecological Model, GEM, [Blauw et al 2008] is an instrument that can be applied to any water system (fresh, transitional or coastal) to calculate the primary production, chlorophyll-a concentration and phytoplankton species composition. It consists of physical, chemical and ecological model components which are coupled together to build one generic and flexible modeling tool. For the North Sea, the model has been analyzed to assess sensitivity of the simulated chlorophyll-a concentration to a subset of ecologically significant set of factors. The research led to the definition of the most significant set of parameters to the algae blooming process in the North Sea [Salacinska et al 2009]. In order to improve the prediction of the model, the set of parameters and the chlorophyll-a concentration can be further estimated through the use of data assimilation. In this research, the Ensemble Kalman Filter (EnKF) data assimilation technique is used to assimilate the chlorophyll-a data of the North Sea, retrieved from MEdium Resolution Imaging Sensor (MERIS) spectrometer data [Peters et al 2005], in the GEM model. The chlorophyll-a data includes concentrations and error information that enable their use in data assimilation. For the same purpose, the uncertainty of the ecological generic model, GEM has been quantified by means of Monte Carlo approach. Through a study covering the year of 2003, the research demonstrates that both data and model are sufficiently robust for a successful assimilation. The results show that through the assimilation of the satellite data, a better description of the algae bloom has been achieved and an improvement of the capability of the model to predict the algae bloom for the North Sea has been confirmed

  17. Molecular Exchange Dynamics in Block Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Bates, Frank; Lu, Jie; Choi, Soohyung; Lodge, Timothy

    2012-02-01

    Poly(styrene-b-ethylene propylene) (PS-PEP) diblock copolymers were mixed with squalane (C30H62) at 1% by weight resulting in the formation of spherical micelles. The structure and dynamics of molecular exchange were characterized by synchrotron small-angle x-ray scattering (SAXS) and time resolved small-angle neutron scattering (TR-SANS), respectively, between 100 C and 160 C. TR-SANS measurements were performed with solutions initially containing deuterium labeled micelle cores and normal cores dispersed in a contrast matched squalane. Monitoring the reduction in scattering intensity as a function of time at various temperatures revealed molecular exchange dynamics highly sensitive to the core molecular weight and molecular weight distribution. Time-temperature superposition of data acquired at different temperatures produced a single master curve for all the mixtures. Experiments conducted with isotopically labeled micelle cores, each formed from two different but relatively mondisperse PS blocks, confirmed a simple dynamical model based on first order kinetics and core Rouse single chain relaxation. These findings demonstrate a dramatic transition to nonergodicity with increasing micelle core molecular weight and confirm the origins of the logarithmic exchange kinetics in such systems.

  18. Thermal-based modeling of coupled carbon, water and energy fluxes using nominal light use efficiencies constrained by leaf chlorophyll observations

    NASA Astrophysics Data System (ADS)

    Schull, M. A.; Anderson, M. C.; Houborg, R.; Gitelson, A.; Kustas, W. P.

    2014-10-01

    Recent studies have shown that estimates of leaf chlorophyll content (Chl), defined as the combined mass of chlorophyll a and chlorophyll b per unit leaf area, can be useful for constraining estimates of canopy light-use-efficiency (LUE). Canopy LUE describes the amount of carbon assimilated by a vegetative canopy for a given amount of Absorbed Photosynthetically Active Radiation (APAR) and is a key parameter for modeling land-surface carbon fluxes. A carbon-enabled version of the remote sensing-based Two-Source Energy Balance (TSEB) model simulates coupled canopy transpiration and carbon assimilation using an analytical sub-model of canopy resistance constrained by inputs of nominal LUE (βn), which is modulated within the model in response to varying conditions in light, humidity, ambient CO2 concentration and temperature. Soil moisture constraints on water and carbon exchange are conveyed to the TSEB-LUE indirectly through thermal infrared measurements of land-surface temperature. We investigate the capability of using Chl estimates for capturing seasonal trends in the canopy βn from in situ measurements of Chl acquired in irrigated and rain-fed fields of soybean and maize near Mead, Nebraska. The results show that field-measured Chl is non-linearly related to βn, with variability primarily related to phenological changes during early growth and senescence. Utilizing seasonally varying βn inputs based on an empirical relationship with in-situ measured Chl resulted in improvements in carbon flux estimates from the TSEB model, while adjusting the partitioning of total water loss between plant transpiration and soil evaporation. The observed Chl-βn relationship provides a functional mechanism for integrating remotely sensed Chl into the TSEB model, with the potential for improved mapping of coupled carbon, water, and energy fluxes across vegetated landscapes.

  19. Thermal-based modeling of coupled carbon, water, and energy fluxes using nominal light use efficiencies constrained by leaf chlorophyll observations

    NASA Astrophysics Data System (ADS)

    Schull, M. A.; Anderson, M. C.; Houborg, R.; Gitelson, A.; Kustas, W. P.

    2015-03-01

    Recent studies have shown that estimates of leaf chlorophyll content (Chl), defined as the combined mass of chlorophyll a and chlorophyll b per unit leaf area, can be useful for constraining estimates of canopy light use efficiency (LUE). Canopy LUE describes the amount of carbon assimilated by a vegetative canopy for a given amount of absorbed photosynthetically active radiation (APAR) and is a key parameter for modeling land-surface carbon fluxes. A carbon-enabled version of the remote-sensing-based two-source energy balance (TSEB) model simulates coupled canopy transpiration and carbon assimilation using an analytical sub-model of canopy resistance constrained by inputs of nominal LUE (βn), which is modulated within the model in response to varying conditions in light, humidity, ambient CO2 concentration, and temperature. Soil moisture constraints on water and carbon exchange are conveyed to the TSEB-LUE indirectly through thermal infrared measurements of land-surface temperature. We investigate the capability of using Chl estimates for capturing seasonal trends in the canopy βn from in situ measurements of Chl acquired in irrigated and rain-fed fields of soybean and maize near Mead, Nebraska. The results show that field-measured Chl is nonlinearly related to βn, with variability primarily related to phenological changes during early growth and senescence. Utilizing seasonally varying βn inputs based on an empirical relationship with in situ measured Chl resulted in improvements in carbon flux estimates from the TSEB model, while adjusting the partitioning of total water loss between plant transpiration and soil evaporation. The observed Chl-βn relationship provides a functional mechanism for integrating remotely sensed Chl into the TSEB model, with the potential for improved mapping of coupled carbon, water, and energy fluxes across vegetated landscapes.

  20. Chlorophyll-a variability in the Seychelles-Chagos Thermocline Ridge: Analysis of a coupled biophysical model

    NASA Astrophysics Data System (ADS)

    Dilmahamod, A. F.; Hermes, J. C.; Reason, C. J. C.

    2016-02-01

    The biological variability of the upwelling region of the Seychelles-Chagos Thermocline Ridge (SCTR), both at surface and subsurface levels, is investigated using monthly outputs of a coupled biophysical model from 1958 to 2011. Owing to its large spatial distribution and sensitivity to climate variability, the SCTR is studied as three distinct regions; namely, sub-regions 1 (western; 5°S-12°S, 55°E-65°E), 2 (central; 5°S-12°S, 65°E-75°E) and 3 (eastern; 5°S-12°S, 75°E-90°E). Surface and subsurface chlorophyll-a (Chl-a) exhibit completely different response mechanisms in sub-region 3 compared to sub-regions 1 and 2 during El Niño Southern Oscillation (ENSO) and Indian Ocean Dipole (IOD) events. During the intense 1997/1998 ENSO-IOD event, the high Chl-a tongue observed in the eastern Indian Ocean induces an increase in surface concentration in sub-region 3, whose subsurface variability is also substantially less (more) impacted by downwelling (upwelling) Rossby waves generated by El Niño (La Niña) forcing. After filtering out the annual signal, wavelet analysis of surface Chl-a revealed a significant 6 month periodicity in sub-regions 1 and 2 whereas a 5-year signal dominated in sub-region 3. The latter suggests that sub-region 3 is more prone to different ENSO/IOD influences, due to its proximity to the eastern Indian Ocean. In the unfiltered data, the subsurface Chl-a in sub-region 3 exhibits a strong signal near 1 year, with sub-regions 1 and 2 having a pronounced 6-year and 5-year signals respectively. These analyses show that the SCTR cannot be investigated as a single homogeneous region due to its large spatial distribution and different response mechanisms to climate events. Furthermore, changes in SST, thermocline depth, winds and Chl-a before and after the 1976-1977 climate shift differed across the SCTR, further highlighting the heterogeneity of this sensitive region in the Indian Ocean.

  1. Optical water quality model of Lake Ontario. 2: Determination of chlorophyll a and suspended mineral concentrations of natural waters from submersible and low altitude optical sensors.

    PubMed

    Bukata, R P; Bruton, J E; Jerome, J H; Jain, S C; Zwick, H H

    1981-05-01

    Spectrooptical and water quality data collected from a 1979 coordinated in situ and airborne study of western Lake Ontario are used to devise a five-component model from which subsurface chlorophyll a and suspended solids concentrations may be determined from submersible optical sensors capable of measuring spectral irradiance reflectance just beneath the free-surface layer. A water-air interface model, which incorporates the effects of surface reflection, is also presented in an attempt to extend such water quality estimations to low altitude remote sensors. Special emphasis is given to the spectral wavelength bands of the Coastal Zone Color Scanner aboard Nimbus-7.

  2. Marine chlorophyll a analysis

    NASA Technical Reports Server (NTRS)

    Johnson, R. W.

    1979-01-01

    Quantitative distribution maps of chlorophyll a and other important environmental parameters of coastal zones are prepared by regression analysis of sea-truth data and data collected by aircraft multispectral scanners.

  3. Optofluidic chlorophyll lasers.

    PubMed

    Chen, Yu-Cheng; Chen, Qiushu; Fan, Xudong

    2016-06-21

    Chlorophylls are essential for photosynthesis and also one of the most abundant pigments on earth. Using an optofluidic ring resonator of extremely high Q-factors (>10(7)), we investigated the unique characteristics and underlying mechanism of chlorophyll lasers. Chlorophyll lasers with dual lasing bands at 680 nm and 730 nm were observed for the first time in isolated chlorophyll a (Chla). Particularly, a laser at the 730 nm band was realized in 0.1 mM Chla with a lasing threshold of only 8 μJ mm(-2). Additionally, we observed lasing competition between the two lasing bands. The presence of laser emission at the 680 nm band can lead to quenching or significant reduction of laser emission at the 730 nm band, effectively increasing the lasing threshold for the 730 nm band. Further concentration-dependent studies, along with theoretical analysis, elucidated the mechanism that determines when and why the laser emission band appears at one of the two bands, or concomitantly at both bands. Finally, Chla was exploited as the donor in fluorescence resonance energy transfer to extend the laser emission to the near infrared regime with an unprecedented wavelength shift as large as 380 nm. Our work will open a door to the development of novel biocompatible and biodegradable chlorophyll-based lasers for various applications such as miniaturized tunable coherent light sources and in vitro/in vivo biosensing. It will also provide important insight into the chlorophyll fluorescence and photosynthesis processes inside plants. PMID:27220992

  4. Stressor-response modeling using the 2D water quality model and regression trees to predict chlorophyll-a in a reservoir system

    NASA Astrophysics Data System (ADS)

    Park, Yongeun; Pachepsky, Yakov A.; Cho, Kyung Hwa; Jeon, Dong Jin; Kim, Joon Ha

    2015-10-01

    To control algal blooms, the stressor-response relationships between water quality metrics, environmental variables, and algal growth need to be better understood and modeled. Machine-learning methods have been suggested as means to express the stressor-response relationships that are found when applying mechanistic water quality models. The objective of this work was to evaluate the efficiency of regression trees in the development of a stressor-response model for chlorophyll-a (Chl-a) concentrations, using the results from site-specific mechanistic water quality modeling. The 2-dimensional hydrodynamic and water quality model (CE-QUAL-W2) model was applied to simulate water quality using four-year observational data and additional scenarios of air temperature increases for the Yeongsan Reservoir in South Korea. Regression tree modeling was applied to the results of these simulations. Given the well-expressed seasonality in the simulated Chl-a dynamics, separate regression trees were developed for months from May to September. The regression trees provided a reasonably accurate representation of the stressor-response dependence generated by the CE-QUAL-W2 model. Different stressors were then selected as split variables for different months, and, in most cases, splits by the same stressor variable yielded the same correlation sign between the variable and the Chl-a concentration. Compared to physical variables, nutrient content appeared to better predict Chl-a responses. The highest Chl-a temperature sensitivities were found for May and June. Regression tree splits based on ammonium concentration resulted in a consistent trend of greater sensitivity in the groups of samples with higher ammonium concentrations. Regression tree models provided a transparent visual representation of the stressor-response relationships for Chl-a and its sensitivity. Overall, the representation of relationships using classification and regression tools can be considered a useful

  5. Synthesis of MSnO{sub 3} (M = Ba, Sr) nanoparticles by reverse micelle method and particle size distribution analysis by whole powder pattern modeling

    SciTech Connect

    Ahmed, Jahangeer; Blakely, Colin K.; Bruno, Shaun R.; Poltavets, Viktor V.

    2012-09-15

    Highlights: ► BaSnO{sub 3} and SrSnO{sub 3} nanoparticles synthesized using the reverse micelle method. ► Particle size and size distribution studied by whole powder pattern modeling. ► Nanoparticles are of optimal size for investigation in dye-sensitized solar cells. -- Abstract: Light-to-electricity conversion efficiency in dye-sensitized solar cells critically depends not only on the dye molecule, semiconducting material and redox shuttle selection but also on the particle size and particle size distribution of the semiconducting photoanode. In this study, nanocrystalline BaSnO{sub 3} and SrSnO{sub 3} particles have been synthesized using the microemulsion method. Particle size distribution was studied by whole powder pattern modeling which confirmed narrow particle size distribution with an average size of 18.4 ± 8.3 nm for SrSnO{sub 3} and 15.8 ± 4.2 nm for BaSnO{sub 3}. These values are in close agreement with results of transmission electron microscopy. The prepared materials have optimal microstructure for successive investigation in dye-sensitized solar cells.

  6. Decadal trends in global pelagic ocean chlorophyll: A new assessment integrating multiple satellites, in situ data, and models

    PubMed Central

    Gregg, Watson W; Rousseaux, Cécile S

    2014-01-01

    Quantifying change in ocean biology using satellites is a major scientific objective. We document trends globally for the period 1998–2012 by integrating three diverse methodologies: ocean color data from multiple satellites, bias correction methods based on in situ data, and data assimilation to provide a consistent and complete global representation free of sampling biases. The results indicated no significant trend in global pelagic ocean chlorophyll over the 15 year data record. These results were consistent with previous findings that were based on the first 6 years and first 10 years of the SeaWiFS mission. However, all of the Northern Hemisphere basins (north of 10° latitude), as well as the Equatorial Indian basin, exhibited significant declines in chlorophyll. Trend maps showed the local trends and their change in percent per year. These trend maps were compared with several other previous efforts using only a single sensor (SeaWiFS) and more limited time series, showing remarkable consistency. These results suggested the present effort provides a path forward to quantifying global ocean trends using multiple satellite missions, which is essential if we are to understand the state, variability, and possible changes in the global oceans over longer time scales. PMID:26213675

  7. Supercritical fluid reverse micelle separation

    DOEpatents

    Fulton, John L.; Smith, Richard D.

    1993-01-01

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W.sub.o that determines the maximum size of the reverse micelles. The maximum ratio W.sub.o of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions.

  8. Supercritical fluid reverse micelle separation

    DOEpatents

    Fulton, J.L.; Smith, R.D.

    1993-11-30

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

  9. Eutrophication study at the Panjiakou-Daheiting Reservoir system, northern Hebei Province, People's Republic of China: Chlorophyll-a model and sources of phosphorus and nitrogen

    USGS Publications Warehouse

    Domagalski, J.; Lin, C.; Luo, Y.; Kang, Jie; Wang, Shaoming; Brown, L.R.; Munn, M.D.

    2007-01-01

    Concentrations, loads, and sources of nitrate and total phosphorus were investigated at the Panjiakou and Daheiting Reservoir system in northern Hebei Province, People's Republic of China. The Luan He River is the primary source of water to these reservoirs, and the upstream watershed has a mix of land uses including agriculture, forest, and one large urban center. The reservoirs have a primary use for storage of drinking water and partially supply Tianjin City with its annual needs. Secondary uses include flood control and aqua culture (fish cages). The response of the reservoir system from phosphorus input, with respect to chlorophyll-a production from algae, was fitted to a model of normalized phosphorus loading that regresses the average summer-time chlorophyll-a concentration to the average annual phosphorus concentration of the reservoir. Comparison of the normalized phosphorus loading and chlorophyll-a response of this system to other reservoirs throughout the world indicate a level of eutrophication that will require up to an approximate 5-10-fold decrease in annual phosphorus load to bring the system to a more acceptable level of algal productivity. Isotopes of nitrogen and oxygen in dissolved nitrate were measured from the headwater streams and at various locations along the major rivers that provide the majority of water to these reservoirs. Those isotopic measurements indicate that the sources of nitrate change from natural background in the rivers to animal manure and septic waste upstream of the reservoir. Although the isotopic measurements suggest that animal and septic wastes are a primary source of nutrients, measurements of the molar ratio of nitrogen to phosphorus are more indicative of row-cropping practices. Options for reduction of nutrient loads include changing the management practices of the aqua culture, installation of new sewage treatment systems in the large urbanized area of the upper watershed, and agricultural management practices

  10. Eutrophication study at the Panjiakou-Daheiting Reservoir system, northern Hebei Province, People’s Republic of China: Chlorophyll-a model and sources of phosphorous and nitrogen

    USGS Publications Warehouse

    Domagalski, Joseph L.; Lin, Chao; Luo, Yang; Kang, Jie; Wang, Shaoming; Brown, Larry R.; Munn, Mark D.

    2007-01-01

    Concentrations, loads, and sources of nitrate and total phosphorus were investigated at the Panjiakou and Daheiting Reservoir system in northern Hebei Province, People's Republic of China. The Luan He River is the primary source of water to these reservoirs, and the upstream watershed has a mix of land uses including agriculture, forest, and one large urban center. The reservoirs have a primary use for storage of drinking water and partially supply Tianjin City with its annual needs. Secondary uses include flood control and aqua culture (fish cages). The response of the reservoir system from phosphorus input, with respect to chlorophyll-a production from algae, was fitted to a model of normalized phosphorus loading that regresses the average summer-time chlorophyll-aconcentration to the average annual phosphorus concentration of the reservoir. Comparison of the normalized phosphorus loading and chlorophyll-a response of this system to other reservoirs throughout the world indicate a level of eutrophication that will require up to an approximate 5–10-fold decrease in annual phosphorus load to bring the system to a more acceptable level of algal productivity. Isotopes of nitrogen and oxygen in dissolved nitrate were measured from the headwater streams and at various locations along the major rivers that provide the majority of water to these reservoirs. Those isotopic measurements indicate that the sources of nitrate change from natural background in the rivers to animal manure and septic waste upstream of the reservoir. Although the isotopic measurements suggest that animal and septic wastes are a primary source of nutrients, measurements of the molar ratio of nitrogen to phosphorus are more indicative of row-cropping practices. Options for reduction of nutrient loads include changing the management practices of the aqua culture, installation of new sewage treatment systems in the large urbanized area of the upper watershed, and agricultural management practices

  11. Eutrophication Study at the Panjiakou-Daheiting Reservoir System, Northern Hebei Province, People's Republic of China: Chlorophyll-a Model and Sources of Phosphorus and Nitrogen

    NASA Astrophysics Data System (ADS)

    Domagalski, J.; Lin, C.; Luo, Y.; Kang, J.; Wang, S.; Brown, L.; Munn, M.

    2007-05-01

    Concentrations, loads, and sources of nitrate and total phosphorus were investigated at the Panjiakou and Daheiting Reservoir system in northern Hebei Province, People's Republic of China. The Luan He River is the primary source of water to these reservoirs, and the upstream watershed has a mix of land uses including agriculture, forest, with one large urban center. The reservoirs have a primary use for storage of drinking water and partially supply Tianjin City with its annual needs. Secondary uses include flood control and aqua culture (fish cages). The response of the reservoir system from phosphorus input, with respect to chlorophyll-a production from algae, was fitted to a model of normalized phosphorus loading that regresses the average summer-time chlorophyll-a concentration to the average annual phosphorus concentration of the reservoir. Comparison of the normalized phosphorus loading and chlorophyll-a response of this system to other reservoirs throughout the world indicate a level of eutrophication that will require up to an approximate 10-fold decrease in annual phosphorus load to bring the system to a more acceptable level of algal productivity. Isotopes of nitrogen and oxygen in dissolved nitrate were measured from the headwater streams and at various locations along the major rivers that provide the majority of water to these reservoirs. Those isotopic measurements indicate that the sources of nitrate change from natural background in the rivers to animal manure and septic waste upstream of the reservoir. Although the isotopic measurements suggest that animal and septic wastes are a primary source of nutrients, measurements of the molar ratio of nitrogen to phosphorus are more indicative of row-cropping practices. Options for reduction of nutrient loads include changing the management practices of the aqua culture, installation of new sewage treatment systems, especially in the one major urbanized area of the upper watershed, and agricultural

  12. Applicability of three-band model for estimating chlorophyll-a concentration in two Asian lakes (Lake Kasumigaura, Japan and Lake Dianchi, China)

    NASA Astrophysics Data System (ADS)

    Matsushita, B.; Yang, W.; Chen, J.; Fukushima, T.

    2009-12-01

    Bunkei Matsushita1*, Wei Yang1, 2, Jin Chen2 and Takehiko Fukushima1 1Graduate School of Life and Environmental Sciences, University of Tsukuba 1-1-1 Tennoudai, Tsukuba, Ibaraki, 305-8572, Japan E-mails: mbunkei@sakura.cc.tsukuba.ac.jp, fukusima@sakura.cc.tsukuba.ac.jp 2 State key laboratory of earth surface processes and resource ecology, Beijing Normal University, Beijing 100875, China E-mails: chenjin@ires.cn, yangwei1022@gmail.com Abstract: The remote sensing of chlorophyll-a in case II water has been far less successful than that in case I water, due mainly to the complex interactions among optically active substances (i.e., phytoplankton, tripton, colored dissolved organic matter, and water) in the former. To address this problem, Gitelson et al. (2008) suggested a three-band model, which can minimize the effects of tripton, colored dissolved organic matter (CDOM), and pure water, and thus promised an accurate estimation of chlorophyll-a. In this study, we used three datasets with different phytoplankton species to test the performance of the three-band model developed by Gitelson et al. The major findings of our study were as follows: (1) the mechanism of the three-band model could work very well for each phytoplankton species (R2>0.84, rRMSE<23%); (2) the slope and intercept of the three-band model strongly depended on variation of phytoplankton species; (3) chlorophyll-specific absorption coefficients at 440 nm (a*ph(440)) could be used to predict the slope and intercept of the three-band model for different species of phytoplankton. Compared with the previous three-band model, the RMSEs of the improved three-band model were reduced from 37.2 mg m-3 to 7.3 mg m-3, and from 34.3 mg m-3 to 15.9 mg m-3, for Lake Kasumigaura, and Lake Dianchi, respectively. Keywords: phytoplankton species, field survey, tank experiment, bio-optical model, case II water

  13. Simvastatin Prodrug Micelles Target Fracture and Improve Healing

    PubMed Central

    Dusad, Anand; Yuan, Hongjiang; Ren, Ke; Li, Fei; Fehringer, Edward V.; Purdue, P. Edward; Goldring, Steven R.; Daluiski, Aaron; Wang, Dong

    2014-01-01

    Simvastatin (SIM), a widely used anti-lipidaemic drug, has been identified as a bone anabolic agent. Its poor water solubility and the lack of distribution to the skeleton, however, have limited its application in the treatment of bone metabolic diseases. In this study, an amphiphilic macromolecular prodrug of SIM was designed and synthesized to overcome these limitations. The polyethylene glycol (PEG)-based prodrug can spontaneously self-assemble to form micelles. The use of SIM trimer as the prodrug’s hydrophobic segment allows easy encapsulation of additional free SIM. The in vitro studies showed that SIM/SIM-mPEG micelles were internalized by MC3T3 cells via lysosomal trafficking and consistently induced expression of both BMP2 and DKK1 mRNA, suggesting that the prodrug micelle retains the biological functions of SIM. After systemic administration, optical imaging suggests that the micelles would passively target to bone fracture sites associated with hematoma and inflammation. Furthermore, flow cytometry study revealed that SIM/SIM-mPEG micelles had preferred cellular uptake by inflammatory and resident cells within the fracture callus tissue. The treatment study using a mouse osteotomy model validated the micelles’ therapeutic efficacy in promoting bone fracture healing as demonstrated by micro-CT and histological analyses. Collectively, these data suggest that the macromolecular prodrug-based micelle formulation of SIM may have great potential for clinical management of impaired fracture healing. PMID:25542644

  14. Synthesis and agglomeration of gold nanoparticles in reverse micelles

    NASA Astrophysics Data System (ADS)

    Herrera, Adriana P.; Resto, Oscar; Briano, Julio G.; Rinaldi, Carlos

    2005-07-01

    Reverse micelles prepared in the system water, sodium bis-(2-ethylhexyl) sulfoccinate (AOT), and isooctane were investigated as a templating system for the production of gold nanoparticles from Au(III) and the reducing agent sulfite. A core-shell Mie model was used to describe the optical properties of gold nanoparticles in the reverse micelles. Dynamic light scattering of gold colloids in aqueous media and in reverse micelle solution indicated agglomeration of micelles containing particles. This was verified theoretically with an analysis of the total interaction energy between pairs of particles as a function of particle size. The analysis indicated that particles larger than about 8 nm in diameter should reversibly flocculate. Transmission electron microscopy measurements of gold nanoparticles produced in our reverse micelles showed diameters of 8-10 nm. Evidence of cluster formation was also observed. Time-correlated UV-vis absorption measurements showed a red shift for the peak wavelength. This was interpreted as the result of multiple scattering and plasmon interaction between particles due to agglomeration of micelles with particles larger than 8 nm.

  15. [Estimation of canopy chlorophyll content using hyperspectral data].

    PubMed

    Dong, Jing-Jing; Wang, Li; Niu, Zheng

    2009-11-01

    Many researches have developed models to estimate chlorophyl content at leaf and canopy level, but they were species-specific. The objective of the present paper was to develop a new model. First, canopy reflectance was simulated for different species and different canopy architecture using radiative transfer models. Based on the simulated canopy reflectance, the relationship between canopy reflectance and canopy chlorophyll content was studied, and then a chlorophyll estimation model was built using the method of spectral index. The coefficient of determination (R2) between spectral index based model and canopy chlorophyll content reached 0.75 for simulated data. To investigate the applicability of this chlorophyll model, the authors chose a field sample area in Gansu Province to carry out the measurement of leaf chlorophyll content, canopy reflectance and other parameters. Besides, the authors also ordered the synchronous Hyperion data, a hyperspectral image with a spatial resolution of 30 m. Canopy reflectance from field measurment and reflectance from Hyperion image were respectively used as the input parameter for the chlorophyll estimation model. Both of them got good results, which indicated that the model could be used for accurate canopy chlorophyll estimation using canopy reflectance. However, while using spaceborne hyperspectral data to estimate canopy chlorophyll content, good atmospheric correction is required. PMID:20101973

  16. Micelle Formation in Liquid Ammonia.

    PubMed

    Griffin, Joseph M; Atherton, John H; Page, Michael I

    2015-07-17

    Perfluorinated long chain alkyl amides aggregate in liquid ammonia with increasing concentration which reflects micelle-type formation based on changes in (19)F NMR chemical shifts. The critical micelle concentrations (cmc) decrease with increasing chain length and give Kleven parameters A = 0.18 and B = 0.19. The micelles catalyze the ammonolysis of esters in liquid ammonia. The corresponding perfluorinated long chain alkyl carboxylates form ion pairs in liquid ammonia, but the equilibrium dissociation constants indicate favorable interactions between the chains in addition to the electrostatic forces. These perfluorinated carboxylates form micelles in aqueous solution, and their cmc's generate a Kleven B-value = 0.52 compared with 0.30 for the analogous alkyl carboxylates. The differences in hydrophobicity of CH2 and CF2 units in water and liquid ammonia are discussed, as is the possible relevance to life forms in liquid ammonia.

  17. Effect of water on the local electric potential of simulated ionic micelles

    NASA Astrophysics Data System (ADS)

    Brodskaya, Elena N.; Vanin, Alexander A.

    2015-07-01

    Ionic micelles in an aqueous solution containing single-charged counter-ions have been simulated by molecular dynamics. For both cationic and anionic micelles, it has been demonstrated that explicit description of solvent has strong effect on the micelle's electric field. The sign of the local charge alters in the immediate vicinity of the micellar crown and the electric potential varies nonmonotonically. Two micelle models have been examined: the hybrid model with a rigid hydrocarbon core and the atomistic model. For three molecular models of water (Simple Point Charge model (SPC), Transferable Intermolecular Potential 5- Points (TIP5P) and two-centered S2), the results have been compared with those for the continuum solvent model. The orientational ordering of solvent molecules has strong effect on the local electric field surprisingly far from the micelle surface.

  18. Chain exchange in triblock copolymer micelles

    NASA Astrophysics Data System (ADS)

    Lu, Jie; Lodge, Timothy; Bates, Frank

    2015-03-01

    Block polymer micelles offer a host of technological applications including drug delivery, viscosity modification, toughening of plastics, and colloidal stabilization. Molecular exchange between micelles directly influences the stability, structure and access to an equilibrium state in such systems and this property recently has been shown to be extraordinarily sensitive to the core block molecular weight in diblock copolymers. The dependence of micelle chain exchange dynamics on molecular architecture has not been reported. The present work conclusively addresses this issue using time-resolved small-angle neutron scattering (TR-SANS) applied to complimentary S-EP-S and EP-S-EP triblock copolymers dissolved in squalane, a selective solvent for the EP blocks, where S and EP refer to poly(styrene) and poly(ethylenepropylene), respectively. Following the overall SANS intensity as a function of time from judiciously deuterium labelled polymer and solvent mixtures directly probes the rate of molecular exchange. Remarkably, the two triblocks display exchange rates that differ by approximately ten orders of magnitude, even though the solvophobic S blocks are of comparable size. This discovery is considered in the context of a model that successfully explains S-EP diblock exchange dynamics.

  19. Choline Derivate-Modified Doxorubicin Loaded Micelle for Glioma Therapy.

    PubMed

    Li, Jianfeng; Yang, Huiying; Zhang, Yujie; Jiang, Xutao; Guo, Yubo; An, Sai; Ma, Haojun; He, Xi; Jiang, Chen

    2015-09-30

    Ligand-mediated polymeric micelles have enormous potential for improving the efficacy of glioma therapy. Linear-dendritic drug-polymer conjugates composed of doxorubicin (DOX) and polyethylene glycol (PEG) were synthesized with or without modification of choline derivate (CD). The resulting MeO-PEG-DOX8 and CD-PEG-DOX8 could self-assemble into polymeric micelles with a nanosized diameter around 30 nm and a high drug loading content up to 40.6 and 32.3%, respectively. The optimized formulation 20% CD-PEG-DOX8 micelles had superior cellular uptake and antitumor activity against MeO-PEG-DOX8 micelles. The subcellular distribution using confocal study revealed that 20% CD-PEG-DOX8 micelles preferentially accumulated in the mitochondria. Pharmacokinetic study showed area under the plasma concentration-time curve (AUC0-t) and Cmax for 20% CD-PEG-DOX8 micelles and DOX solution were 1336.58 ± 179.43 mg/L·h, 96.35 ± 3.32 mg/L and 1.40 ± 0.19 mg/L·h, 1.15 ± 0.25 mg/L, respectively. Biodistribution study showed the DOX concentration of 20% CD-PEG-DOX8 micelles treated group at 48 h was 2.37-fold higher than that of MeO-PEG-DOX8 micelles treated group at 48 h and was 24 fold-higher than that of DOX solution treated group at 24 h. CD-PEG-DOX8 micelles (20%) were well tolerated with reduced cardiotoxicity, as evaluated in the body weight change and HE staining studies, while they induced most significant antitumor activity with longest media survival time in an orthotopic mouse model of U87-luci glioblastoma model as displayed in the bioluminescence imaging and survival curve studies. Our findings consequently indicated that 20% CD-PEG-DOX8 micelles are promising drug delivery system for glioma chemotherapy. PMID:26356793

  20. Pulse amplitude modulated chlorophyll fluorometer

    SciTech Connect

    Greenbaum, Elias; Wu, Jie

    2015-12-29

    Chlorophyll fluorometry may be used for detecting toxins in a sample because of changes in micro algae. A portable lab on a chip ("LOAC") based chlorophyll fluorometer may be used for toxin detection and environmental monitoring. In particular, the system may include a microfluidic pulse amplitude modulated ("PAM") chlorophyll fluorometer. The LOAC PAM chlorophyll fluorometer may analyze microalgae and cyanobacteria that grow naturally in source drinking water.

  1. Multifunctional polymeric micelles co-loaded with anti-survivin siRNA and paclitaxel overcome drug resistance in an animal model of ovarian cancer

    PubMed Central

    Salzano, Giuseppina; Navarro, Gemma; Trivedi, Malav S.; De Rosa, Giuseppe; Torchilin, Vladimir P.

    2015-01-01

    Ovarian cancer is a dreadful disease estimated to be the second most common gynecological malignancy worldwide. Its current therapy, based on cytoreductive surgery followed by the combination of platinum and taxanes, is frequently complicated by the onset of multidrug resistance (MDR). The discovery that survivin, a small anti-apoptotic protein, is involved in chemo-resistance, provided a new prospect to overcome MDR in cancer, since siRNA could be used to inhibit the expression of survivin in cancer cells. With this in mind, we have developed self-assembly polymeric micelles (PM) able to efficiently co-load an anti-survivin siRNA and a chemotherapeutic agent, such as Paclitaxel (PXL) (survivin siRNA/PXL PM). Previously, we have successfully demonstrated that the down-regulation of survivin by using siRNA-containing PM strongly sensitizes different cancer cells to PXL. Here, we have evaluated the applicability of the developed multifunctional PM in vivo. Changes in survivin expression, therapeutic efficacy and biological effects of the nanopreparation were investigated in an animal model of PXL-resistant ovarian cancer. The results obtained in mice xenografed with SKOV3-tr revealed a significant down-regulation of survivin expression in tumor tissues together with a potent anticancer activity of survivin siRNA/PXL PM, while the tumors remained unaffected with the same quantity of free PXL alone. These promising results introduce a novel type of non-toxic and easy-to-obtain nano-device for the combined therapy of siRNA and anti-cancer agents in the treatment of chemo-resistant tumors. PMID:25657335

  2. Multifunctional Polymeric Micelles Co-loaded with Anti-Survivin siRNA and Paclitaxel Overcome Drug Resistance in an Animal Model of Ovarian Cancer.

    PubMed

    Salzano, Giuseppina; Navarro, Gemma; Trivedi, Malav S; De Rosa, Giuseppe; Torchilin, Vladimir P

    2015-04-01

    Ovarian cancer is a dreadful disease estimated to be the second most common gynecologic malignancy worldwide. Its current therapy, based on cytoreductive surgery followed by the combination of platinum and taxanes, is frequently complicated by the onset of multidrug resistance (MDR). The discovery that survivin, a small antiapoptotic protein, is involved in chemoresistance provided a new prospect to overcome MDR in cancer, because siRNA could be used to inhibit the expression of survivin in cancer cells. With this in mind, we have developed self-assembly polymeric micelles (PM) able to efficiently co-load an anti-survivin siRNA and a chemotherapeutic agent, such as paclitaxel (PXL; survivin siRNA/PXL PM). Previously, we have successfully demonstrated that the downregulation of survivin by using siRNA-containing PM strongly sensitizes different cancer cells to paclitaxel. Here, we have evaluated the applicability of the developed multifunctional PM in vivo. Changes in survivin expression, therapeutic efficacy, and biologic effects of the nanopreparation were investigated in an animal model of paclitaxel-resistant ovarian cancer. The results obtained in mice xenografed with SKOV3-tr revealed a significant downregulation of survivin expression in tumor tissues together with a potent anticancer activity of survivin siRNA/PXL PM, while the tumors remained unaffected with the same quantity of free paclitaxel. These promising results introduce a novel type of nontoxic and easy-to-obtain nanodevice for the combined therapy of siRNA and anticancer agents in the treatment of chemoresistant tumors. PMID:25657335

  3. The Use of Dodecylphosphocholine Micelles in Solution NMR

    NASA Astrophysics Data System (ADS)

    Kallick, D. A.; Tessmer, M. R.; Watts, C. R.; Li, C. Y.

    Dodecylphosphocholine (DPC) micelles are useful as a model membrane system for solution NMR. Several new observations on dodecylphosphocholine micelles and their interactions with opioid peptides are described. The optimal lipid concentration has been investigated for small peptide NMR studies in DPC micelles for two opioid peptides, a 5-mer and a 17-mer. In contrast to reports in the literature, identical 2D spectra have been observed at low and high lipid concentrations. The chemical shift of resolved peptide proton resonances has been followed as a function of added lipid and indicates that there are changes in the chemical shifts above the critical micelle concentration and up to a ratio of 7:1 (lipid:peptide) for the 17-mer, and 9.6:1 for the 5-mer. These results suggest that conformational changes occur in the peptide significantly above the critical micelle concentration, up to a lipid:peptide ratio which is dependent upon the peptide, here ranging from 7:1 to 9.6:1. To address the stoichiometry more directly, the diffusion coefficients of the lipid alone and the lipid with peptide have been measured using pulsed-field gradient spin-echo NMR experiments. These data have been used to calculate the hydrodynamic radius and the aggregation number of the micelle with and without peptide and show that the aggregation number of the peptide-lipid complex increases at high lipid concentrations without a concomitant change in the peptide conformation. Last, several protonated impurities have been observed in the commercial preparation of DPC which resonate in the amide proton region of the NMR spectrum. These results are significant for researchers using DPC micelles and illustrate that both care in sample preparation and the stoichiometry are important issues with the use of DPC as a model membrane.

  4. Recent Trends in Global Ocean Chlorophyll

    NASA Technical Reports Server (NTRS)

    Gregg, Watson; Casey, Nancy

    2004-01-01

    Recent analyses of SeaWiFS data have shown that global ocean chlorophyll has increased more than 5% since 1998. The North Pacific ocean basin has increased nearly 19%. To understand the causes of these trends we have applied the newly developed NASA Ocean Biogeochemical Assimilation Model (OBAM), which is driven in mechanistic fashion by surface winds, sea surface temperature, atmospheric iron deposition, sea ice, and surface irradiance. The mode1 utilizes chlorophyll from SeaWiFS in a daily assimilation. The model has in place many of the climatic variables that can be expected to produce the changes observed in SeaWiFS data. Ths enables us to diagnose the model performance, the assimilation performance, and possible causes for the increase in chlorophyll.

  5. Self-assembly of star micelle into vesicle in solvents of variable quality: the star micelle retains its core-shell nanostructure in the vesicle.

    PubMed

    Liu, Nijuan; He, Qun; Bu, Weifeng

    2015-03-01

    Intra- and intermolecular interactions of star polymers in dilute solutions are of fundamental importance for both theoretical interest and hierarchical self-assembly into functional nanostructures. Here, star micelles with a polystyrene corona and a small ionic core bearing platinum(II) complexes have been regarded as a model of star polymers to mimic their intra- and interstar interactions and self-assembled behaviors in solvents of weakening quality. In the chloroform/methanol mixture solvents, the star micelles can self-assemble to form vesicles, in which the star micelles shrink significantly and are homogeneously distributed on the vesicle surface. Unlike the morphological evolution of conventional amphiphiles from micellar to vesicular, during which the amphiphilic molecules are commonly reorganized, the star micelles still retain their core-shell nanostructures in the vesicles and the coronal chains of the star micelle between the ionic cores are fully interpenetrated.

  6. Evaluation of the MERIS terrestrial Chlorophyll Index

    NASA Astrophysics Data System (ADS)

    Dash, J.; Curran, P.

    The MEdium Resolution Imaging Spectrometer (MERIS), one of the payloads on Envisat, has fine spectral resolution, moderate spatial resolution and a three day repeat cycle. This makes MERIS a potentially valuable sensor for the measurement and monitoring of terrestrial environments at regional to global scales. The red edge, which results from an abrupt change in reflectance in red and near-infrared wavelengths has a location that is related directly to the chlorophyll content of vegetation. A new index called the MERIS terrestrial chlorophyll index (MTCI) uses data in three red and NIR wavebands centred at 681.25nm, 705nm and 753.75nm (bands 8, 9 and 10 in the MERIS standard band setting). The MTCI is easy to calculate and can be automated. Preliminary indirect evaluation using model, field and MERIS data suggested its sensitivity, notably to high values of chlorophyll content and its limited sensitivity to spatial resolution and atmospheric effects. As a result this index is now a standard level-2 product of the European Space Agency. For direct MTCI evaluation two different approaches were used. First, the MTCI/chlorophyll content relationship were determined using a surrogate of chlorophyll content for sites in southern Vietnam and second, the MTCI/chlorophyll relationship was determined using actual chlorophyll content for sites in the New Forest, UK and for plots in a greenhouse. Forests in southern Vietnam were contaminated heavily with Agent Orange during the Vietnam War. The contamination levels were so high that it led to a long term decrease in chlorophyll content within forests that have long since regained full canopy cover. In this approach the amount of Agent Orange dropped onto the forest between 1965 and 1971 was used as a surrogate for contemporary chlorophyll content and was related to current MTCI at selected forest sites. The resulting relationship was positive. Further per pixel investigation of the MTCI/Agent Orange concentration relationship

  7. Configurations of the amphiphilic molecules in micelles

    SciTech Connect

    Dill, K.A.

    1982-04-29

    Several theoretic models aim to account for the properties of micelles in terms of the configurations of the constituent amphiphilic chain molecules. Recent /sup 13/C NMR measurement of one property of the configuration distribution of the the hydrocarbon chain segments allows critical evaluation of these theories. It is concluded that the interphase and singly-bent chain theories, which fully account for chain continuity and for intermolecular constraints imposed by hydrophobic and steric forces, give a more satisfactory description of micellar molecular organization than models in which chains are ordered and radially aligned, or in which they have the complete disorder characteristic of an amorphous hydrocarbon liquid.

  8. Towards the development of a global land chlorophyll content map

    NASA Astrophysics Data System (ADS)

    Dash, Jadunandan; Vuolo, Francesco; Frampton, Will; Curran, Paul; Lajas, Dulce; Kwiatkowska, Ewa

    -VISAT MERIS imagery, is proposed. Because of the limited number of ground measurements of canopy chlorophyll at appropriate spatial resolution, the parameterization of MTCI-canopy chlorophyll relationships, at global scale, is only possible by using estimation of canopy chloro-phyll and relating these estimations to MTCI from satellite. Thus, the approach is based on an indirect parameterization by using a more complex method based on the inversion of a radiative transfer model. The study will combine the results from field campaigns and model inversion to investigate the possible effect of landcover and seasonality on MTCI -canopy chlorophyll content relationship, these will be then generalised to produce a global land chlorophyll content map.

  9. Bowel perforation detection using metabolic fluorescent chlorophylls

    NASA Astrophysics Data System (ADS)

    Han, Jung Hyun; Jo, Young Goun; Kim, Jung Chul; Choi, Sujeong; Kang, Hoonsoo; Kim, Yong-Chul; Hwang, In-Wook

    2016-03-01

    Thus far, there have been tries of detection of disease using fluorescent materials. We introduce the chlorophyll derivatives from food plants, which have longer-wavelength emissions (at >650 nm) than those of fluorescence of tissues and organs, for detection of bowel perforation. To figure out the possibility of fluorescence spectroscopy as a monitoring sensor of bowel perforation, fluorescence from organs of rodent models, intestinal and peritoneal fluids of rodent models and human were analyzed. In IVIS fluorescence image of rodent abdominal organ, visualization of perforated area only was possible when threshold of image is extremely finely controlled. Generally, both perforated area of bowel and normal bowel which filled with large amount of chlorophyll derivatives were visualized with fluorescence. The fluorescence from chlorophyll derivatives penetrated through the normal bowel wall makes difficult to distinguish perforation area from normal bowel with direct visualization of fluorescence. However, intestinal fluids containing chlorophyll derivatives from food contents can leak from perforation sites in situation of bowel perforation. It may show brighter and longer-wavelength regime emissions of chlorophyll derivatives than those of pure peritoneal fluid or bioorgans. Peritoneal fluid mixed with intestinal fluids show much brighter emissions in longer wavelength (at>650 nm) than those of pure peritoneal fluid. In addition, irrigation fluid, which is used for the cleansing of organ and peritoneal cavity, made of mixed intestinal and peritoneal fluid diluted with physiologic saline also can be monitored bowel perforation during surgery.

  10. The threshold feeding response of microzooplankton within Pacific high-nitrate low-chlorophyll ecosystem models under steady and variable iron input

    NASA Astrophysics Data System (ADS)

    Leising, Andrew W.; Gentleman, Wendy C.; Frost, Bruce W.

    2003-11-01

    The equatorial Pacific is an HNLC (High-Nitrate Low-Chlorophyll) region. Modeling and in-situ process studies have confirmed the importance of microzooplankton grazing in this ecosystem. Unfortunately, both the parameters and functions representing microzooplankton grazing within current ecosystem models are poorly constrained. We used a simple 4-component food web model to test the assumption that a lower grazing threshold, which is common in many models, is necessary to achieve the HNLC condition. Without the grazing threshold, the model did not reproduce the HNLC condition. However, by raising the half-saturation constant within the microzooplankton functional response with no threshold, it was possible to reproduce the critical dynamics of the HNLC condition under both steady and moderate seasonal variability in nutrient input. It was also possible to reproduce the HNLC system using a sigmoidal functional response for the microzooplankton, with results somewhere between the other two forms of the model, although this version had the highest sensitivity to changes in its parameters. The three models predicted similar phytoplankton biomass and primary productivity under steady nutrient input, but diverge in these metrics as the amplitude of nutrient input variability increases. These three functional responses also imply certain important differences in the microzooplankton community. Whereas the threshold model had the least sensitivity to parameter choice, the high half-saturation constant, no-threshold model may actually be a better approximation when modeling a community of grazers. Ecosystem models that predict carbon production and export in HNLC regions can be very sensitive to assumptions concerning microzooplankton grazing; future studies need to concentrate on the functional responses of microzooplankton before these models can be used for predicting fluxes in times or regions where forcing is beyond that used to constrain the original model.

  11. Chlorophyll content retrieval from hyperspectral remote sensing imagery.

    PubMed

    Yang, Xiguang; Yu, Ying; Fan, Wenyi

    2015-07-01

    Chlorophyll content is the essential parameter in the photosynthetic process determining leaf spectral variation in visible bands. Therefore, the accurate estimation of the forest canopy chlorophyll content is a significant foundation in assessing forest growth and stress affected by diseases. Hyperspectral remote sensing with high spatial resolution can be used for estimating chlorophyll content. In this study, the chlorophyll content was retrieved step by step using Hyperion imagery. Firstly, the spectral curve of the leaf was analyzed, 25 spectral characteristic parameters were identified through the correlation coefficient matrix, and a leaf chlorophyll content inversion model was established using a stepwise regression method. Secondly, the pixel reflectance was converted into leaf reflectance by a geometrical-optical model (4-scale). The three most important parameters of reflectance conversion, including the multiple scattering factor (M 0 ), and the probability of viewing the sunlit tree crown (P T ) and the background (P G ), were estimated by leaf area index (LAI), respectively. The results indicated that M 0 , P T , and P G could be described as a logarithmic function of LAI, with all R (2) values above 0.9. Finally, leaf chlorophyll content was retrieved with RMSE = 7.3574 μg/cm(2), and canopy chlorophyll content per unit ground surface area was estimated based on leaf chlorophyll content and LAI. Chlorophyll content mapping can be useful for the assessment of forest growth stage and diseases.

  12. Doxorubicin-loaded alginate-g-poly(N-isopropylacrylamide) micelles for cancer imaging and therapy.

    PubMed

    Ahn, Dong-Gyun; Lee, Jangwook; Park, So-Young; Kwark, Young-Je; Lee, Kuen Yong

    2014-12-24

    Chemotherapy is a widely adopted method for the treatment of cancer. However, its use is often limited due to side effects produced by anti-cancer drugs. Therefore, various drug carriers, including polymeric micelles, have been investigated to find a method to overcome this limitation. In this study, alginate-based, self-assembled polymeric micelles were designed and prepared using alginate-g-poly(N-isopropylacrylamide) (PNIPAAm). Amino-PNIPAAm was chemically introduced to the alginate backbone via carbodiimide chemistry. The resulting polymer was dissolved in distilled water at room temperature and formed self-assembled micelles at 37 °C. Characteristics of alginate-g-PNIPAAm micelles were dependent on the molecular weight of PNIPAAm, the degree of substitution, and the polymer concentration. Doxorubicin (DOX), a model anti-cancer drug, was efficiently encapsulated in alginate-g-PNIPAAm micelles, and sustained release of DOX from the micelles was achieved at 37 °C in vitro. These micelles accumulated at the tumor site of a tumor-bearing mouse model as a result of the enhanced permeability and retention effect. Interestingly, DOX-loaded alginate-g-PNIPAAm micelles showed excellent anti-cancer therapeutic efficacy in a mouse model without any significant side effects. This approach to designing and tailoring natural polymer-based systems to fabricate nanoparticles at human body temperature may provide a useful means for cancer imaging and therapy. PMID:25487046

  13. Peptide micelle-mediated delivery of tissue-specific suicide gene and combined therapy with avastin in a glioblastoma model.

    PubMed

    Oh, Binna; Han, Jaesik; Choi, Eunji; Tan, Xiaonan; Lee, Minhyung

    2015-04-01

    Bevacizumab (Avastin) is an angiogenesis inhibitor used as a treatment for various cancers. In this study, the combination therapy of Avastin and glioblastoma-specific thymidine kinase gene [pEpo-NI2-SV-herpes simplex virus thymidine kinase(HSVtk)] was evaluated in a glioblastoma animal model. The R7L10 peptide was used as a gene carrier of pEpo-NI2-SV-HSVtk. Gel retardation assays confirmed that R7L10 formed stable complexes with pEpo-NI2-SV-HSVtk. R7L10 protected DNA from nuclease digestion. R7L10 had lower transfection efficiency than polyethylenimine (PEI; 25 kDa). However, the in vitro and in vivo toxicity assays showed that R7L10 had lower cytotoxicity than PEI, suggesting that R7L10 is safer than PEI. For the combination therapy, Avastin was injected intravenously and the pEpo-NI2-SV-HSVtk/R7L10 complexes were injected intratumorally in the glioblastoma animal model. Tumor growth was most effectively inhibited by the combination therapy of Avastin and the gene. The immunostaining results confirmed that the HSVtk genes were expressed in the groups with the pEpo-NI2-SV-HSVtk/R7L10 complex. The terminal deoxynucleotidyl transferase dUTP nick end labeling assay showed a higher level of apoptotic cells in the combination group than the pEpo-NI2-SV-HSVtk/R7L10 complex or Avastin group. In conclusion, the combination of Avastin and the glioblastoma-specific HSVtk gene has a higher antitumor effect than single therapy of Avastin or HSVtk after intratumoral administration in glioblastoma animal model.

  14. The 2010 Russian Drought Impact on Satellite Measurements of Solar-Induced Chlorophyll Fluorescence: Insights from Modeling and Comparisons with the Normalized Differential Vegetation Index (NDVI)

    NASA Technical Reports Server (NTRS)

    Yoshida, Y.; Joiner, J.; Tucker, C.; Berry, J.; Lee, J. -E.; Walker, G.; Reichle, R.; Koster, R.; Lyapustin, A.; Wang, Y.

    2015-01-01

    We examine satellite-based measurements of chlorophyll solar-induced fluorescence (SIF) over the region impacted by the Russian drought and heat wave of 2010. Like the popular Normalized Difference Vegetation Index (NDVI) that has been used for decades to measure photosynthetic capacity, SIF measurements are sensitive to the fraction of absorbed photosynthetically-active radiation (fPAR). However, in addition, SIF is sensitive to the fluorescence yield that is related to the photosynthetic yield. Both SIF and NDVI from satellite data show drought-related declines early in the growing season in 2010 as compared to other years between 2007 and 2013 for areas dominated by crops and grasslands. This suggests an early manifestation of the dry conditions on fPAR. We also simulated SIF using a global land surface model driven by observation-based meteorological fields. The model provides a reasonable simulation of the drought and heat impacts on SIF in terms of the timing and spatial extents of anomalies, but there are some differences between modeled and observed SIF. The model may potentially be improved through data assimilation or parameter estimation using satellite observations of SIF (as well as NDVI). The model simulations also offer the opportunity to examine separately the different components of the SIF signal and relationships with Gross Primary Productivity (GPP).

  15. Curcumin-loaded biodegradable polymeric micelles for colon cancer therapy in vitro and in vivo

    NASA Astrophysics Data System (ADS)

    Gou, Maling; Men, Ke; Shi, Huashan; Xiang, Mingli; Zhang, Juan; Song, Jia; Long, Jianlin; Wan, Yang; Luo, Feng; Zhao, Xia; Qian, Zhiyong

    2011-04-01

    Curcumin is an effective and safe anticancer agent, but its hydrophobicity inhibits its clinical application. Nanotechnology provides an effective method to improve the water solubility of hydrophobic drug. In this work, curcumin was encapsulated into monomethoxy poly(ethylene glycol)-poly(ε-caprolactone) (MPEG-PCL) micelles through a single-step nano-precipitation method, creating curcumin-loaded MPEG-PCL (Cur/MPEG-PCL) micelles. These Cur/MPEG-PCL micelles were monodisperse (PDI = 0.097 +/- 0.011) with a mean particle size of 27.3 +/- 1.3 nm, good re-solubility after freeze-drying, an encapsulation efficiency of 99.16 +/- 1.02%, and drug loading of 12.95 +/- 0.15%. Moreover, these micelles were prepared by a simple and reproducible procedure, making them potentially suitable for scale-up. Curcumin was molecularly dispersed in the PCL core of MPEG-PCL micelles, and could be slow-released in vitro. Encapsulation of curcumin in MPEG-PCL micelles improved the t1/2 and AUC of curcuminin vivo. As well as free curcumin, Cur/MPEG-PCL micelles efficiently inhibited the angiogenesis on transgenic zebrafish model. In an alginate-encapsulated cancer cell assay, intravenous application of Cur/MPEG-PCL micelles more efficiently inhibited the tumor cell-induced angiogenesisin vivo than that of free curcumin. MPEG-PCL micelle-encapsulated curcumin maintained the cytotoxicity of curcumin on C-26 colon carcinoma cellsin vitro. Intravenous application of Cur/MPEG-PCL micelle (25 mg kg-1curcumin) inhibited the growth of subcutaneous C-26 colon carcinoma in vivo (p < 0.01), and induced a stronger anticancer effect than that of free curcumin (p < 0.05). In conclusion, Cur/MPEG-PCL micelles are an excellent intravenously injectable aqueous formulation of curcumin; this formulation can inhibit the growth of colon carcinoma through inhibiting angiogenesis and directly killing cancer cells.

  16. Evaluation of Iron Oxide Nanoparticle Micelles for Magnetic Particle Imaging (MPI) of Thrombosis

    PubMed Central

    Aussems-Custers, Erica; Daemen, Mat J. A. P.; Strijkers, Gustav J.; Nicolay, Klaas; Grüll, Holger

    2015-01-01

    Magnetic particle imaging (MPI) is an emerging medical imaging modality that directly visualizes magnetic particles in a hot-spot like fashion. We recently developed an iron oxide nanoparticle-micelle (ION-Micelle) platform that allows highly sensitive MPI. The goal of this study was to assess the potential of the ION-Micelles for MPI-based detection of thrombi. To this aim, an in vivo carotid artery thrombosis mouse model was employed and ex vivo magnetic particle spectrometer (MPS) measurements of the carotid arteries were performed. In addition, we studied the effect of functionalization of the ION-Micelle nanoplatform with fibrin-binding peptides (FibPeps) with respect to nanoparticle thrombus uptake and hence thrombus detection. In vivo quantitative MR imaging pre- and post-ION-Micelle injection was performed as reference for visualization of ION-micelle uptake. ION-Micelles significantly decreased T2 values in the thrombi with respect to pre-injection T2 values (p < 0.01) and significantly increased ex vivo MPS thrombus signal with respect to the noninjured, contralateral carotid (p < 0.01). Functionalization of the ION-Micelles with the FibPep peptides did not result in an increased MPS thrombus signal with respect to the non-fibrin binding ION-Micelles. The lack of a significant increased thrombus uptake for the FibPep-ION-Micelles indicates that (non-fibrin-specific) entrapment of nanoparticles in the mesh-like thrombi is the key contributor to thrombus nanoparticle uptake. Therefore, (nontargeted) ION-Micelles might be of value for noninvasive MPI-based diagnosis, characterization and treatment monitoring of thrombosis. PMID:25746677

  17. Improving anticancer activity and reducing systemic toxicity of doxorubicin by self-assembled polymeric micelles

    NASA Astrophysics Data System (ADS)

    Gou, MaLing; Shi, HuaShan; Guo, Gang; Men, Ke; Zhang, Juan; Zheng, Lan; Li, ZhiYong; Luo, Feng; Qian, ZhiYong; Zhao, Xia; Wei, YuQuan

    2011-03-01

    In an attempt to improve anticancer activity and reduce systemic toxicity of doxorubicin (Dox), we encapsulated Dox in monomethoxy poly(ethylene glycol)-poly(ɛ-caprolactone) (MPEG-PCL) micelles by a novel self-assembly procedure without using surfactants, organic solvents or vigorous stirring. These Dox encapsulated MPEG-PCL (Dox/MPEG-PCL) micelles with drug loading of 4.2% were monodisperse and ~ 20 nm in diameter. The Dox can be released from the Dox/MPEG-PCL micelles; the Dox-release at pH 5.5 was faster than that at pH 7.0. Encapsulation of Dox in MPEG-PCL micelles enhanced the cellular uptake and cytotoxicity of Dox on the C-26 colon carcinoma cell in vitro, and slowed the extravasation of Dox in the transgenic zebrafish model. Compared to free Dox, Dox/MPEG-PCL micelles were more effective in inhibiting tumor growth in the subcutaneous C-26 colon carcinoma and Lewis lung carcinoma models, and prolonging survival of mice bearing these tumors. Dox/MPEG-PCL micelles also induced lower systemic toxicity than free Dox. In conclusion, incorporation of Dox in MPEG-PCL micelles enhanced the anticancer activity and decreased the systemic toxicity of Dox; these Dox/MPEG-PCL micelles are an interesting formulation of Dox and may have potential clinical applications in cancer therapy.

  18. Inherent limitations of nondestructive chlorophyll meters: a comparison of two types of meters

    NASA Technical Reports Server (NTRS)

    Monje, O. A.; Bugbee, B.

    1992-01-01

    Two types of nondestructive chlorophyll meters were compared with a standard, destructive chlorophyll measurement technique. The nondestructive chlorophyll meters were 1) a custom built, single-wavelength meter, and 2) the recently introduced, dual-wavelengh, chlorophyll meter from Minolta (model SPAD-502). Data from both meters were closely correlated with destructive measurements of chlorophyll (r2 = 0.90 and 0.93; respectively) for leaves with chlorophyll concentrations ranging from 100 to 600 mg m-2, but both meters consistently overestimated chlorophyll outside this range. Although the dual-wavelength meter was slightly more accurate than the single-wavelength meter (higher r2), the light-scattering properties of leaf cells and the nonhomogeneous distribution of chlorophyll in leaves appear to limit the ability of all meters to estimate in vivo chlorophyll concentration.

  19. Chlorophyll breakdown and chlorophyll catabolites in leaves and fruit†

    PubMed Central

    Kräutler, Bernhard

    2010-01-01

    Chlorophyll metabolism probably is the most visible manifestation of life. Total annual turnover of chlorophyll has been estimated to involve more than 1000 million tons. Surprisingly, chlorophyll catabolism has remained an enigma until less than twenty years ago, when a colorless chlorophyll catabolite from senescent plant leaves was identified and its structure was elucidated. In the meantime, chlorophyll breakdown products have been identified in a variety of plant leaves and their structural features have been elucidated. Most recently, chlorophyll breakdown products have also been identified in some ripening fruit. Chlorophyll breakdown in vascular plants only fleetingly involves enzyme-bound colored intermediates. The stage of fluorescent catabolites is also passed rapidly, as these isomerize further to colorless nonfluorescent tetrapyrrolic catabolites. The latter accumulate in the vacuoles of de-greened leaves and are considered the final products of controlled chlorophyll breakdown. The same tetrapyrroles are also found in ripening fruit and are effective antioxidants. Chlorophyll breakdown leads to tetrapyrroles that appear to have physiologically beneficial chemical properties, and it may thus not merely be a detoxification process. PMID:18846275

  20. Micelle to trapping solution stacking in micellar electrokinetic chromatography.

    PubMed

    Liu, Lihong; Deng, Xinxian; Chen, Xingguo

    2010-01-01

    An analytical strategy micelle to trapping solution stacking (MSS) was developed in acidic buffer in micellar electrokinetic chromatography (MEKC). The stacking mechanism is based on the transport, release, capturing of molecules bound to micelle carriers that are made to collapse into trapping solution (TS) to serve as the medium to contain and stacking the analytes. Tetrandrine and fangchinoline were selected as model mixture using sodium dodecyl sulfate (SDS) micelles as carrier to demonstrate this stacking method. The experiments by MSS-MEKC were carried out and further compared with those by normal MEKC. The results reveal that 113-123-fold improvements in the detection sensitivity was obtained for the analytes, and separation and determination of tetrandrine and fangchinoline in Stephaniae tetrandrae S. Moore and Fengtongan capsules were finished under optimum conditions using the sample matrix containing 8.0mM SDS and TS containing 50mM H(3)PO(4)-55% (v/v) ethanol. PMID:19945115

  1. Charged micelle depletion attraction and interfacial colloidal phase behavior.

    PubMed

    Iracki, Tara D; Beltran-Villegas, Daniel J; Eichmann, Shannon L; Bevan, Michael A

    2010-12-21

    Ensemble total internal reflection microscopy (TIRM) is used to directly measure the evolution of colloid-surface depletion attraction with increasing sodium dodecyl sulfate (SDS) concentration near the critical micelle concentration (CMC). Measured potentials are well described by a modified Asakura-Oosawa (AO) depletion potential in addition to electrostatic and van der Waals contributions. The modified AO potential includes effects of electrostatic interactions between micelles and surfaces via effective depletant dimensions in an excluded volume term and partitioning in an osmotic pressure term. Directly measured colloid-surface depletion potentials are used in Monte Carlo (MC) simulations to capture video microscopy (VM) measurements of micelle-mediated quasi-two-dimensional phase behavior including fluid, crystal, and gel microstructures. Our findings provide information to develop more rigorous and analytically simple models of depletion attraction in charged micellar systems. PMID:21077612

  2. Tunable depletion potentials driven by shape variation of surfactant micelles

    NASA Astrophysics Data System (ADS)

    Gratale, Matthew D.; Still, Tim; Matyas, Caitlin; Davidson, Zoey S.; Lobel, Samuel; Collings, Peter J.; Yodh, A. G.

    2016-05-01

    Depletion interaction potentials between micron-sized colloidal particles are induced by nanometer-scale surfactant micelles composed of hexaethylene glycol monododecyl ether (C12E6 ), and they are measured by video microscopy. The strength and range of the depletion interaction is revealed to arise from variations in shape anisotropy of the surfactant micelles. This shape anisotropy increases with increasing sample temperature. By fitting the colloidal interaction potentials to theoretical models, we extract micelle length and shape anisotropy as a function of temperature. This work introduces shape anisotropy tuning as a means to control interparticle interactions in colloidal suspensions, and it shows how the interparticle depletion potentials of micron-scale objects can be employed to probe the shape and size of surrounding macromolecules at the nanoscale.

  3. Photoinduced electron transfer between donors and acceptors on micelle surfaces

    NASA Astrophysics Data System (ADS)

    Weidemaier, Kristin; Tavernier, H. L.; Chu, K. T.; Fayer, M. D.

    1997-09-01

    Fluorescence time-dependence and fluorescence yield data are used to examine photoinduced electron transfer between N,N-dimethylaniline and octadecylrhodamine B on the surfaces of dodecyltrimethylammonium bromide (DTAB) and Triton X-100 micelles. The data are analyzed with a detailed theory that includes diffusion of the chromophores over the micelle surface and models the reaction rate by a distance-dependent Marcus form. Good agreement between theory and experiment is obtained for reasonable choices of the transfer parameters for DTAB. However, for Triton X-100, there is reasonable agreement between theory and experiment only for values of the parameters that verge on unphysical. Possible explanations are discussed.

  4. A novel chlorophyll solar cell

    NASA Astrophysics Data System (ADS)

    Ludlow, J. C.

    The photosynthetic process is reviewed in order to produce a design for a chlorophyll solar cell. In a leaf, antenna chlorophyll absorbs light energy and conducts it to an energy trap composed of a protein and two chlorophyll molecules, which perform the oxidation-reduction chemistry. The redox potential of the trap changes from 0.4 to -0.6 V, which is sufficient to reduce nearby molecules with redox potentials in that range. The reduction occurs by transfer of an electron, and a chlorophyll solar cell would direct the transferred electron to a current carrier. Chlorophyll antenna and traps are placed on a metallic support immersed in an electron acceptor solution, and resulting electrons from exposure to light are gathered by a metallic current collector. Spinach chlorophyll extracted, purified, and applied in a cell featuring a Pt collector and an octane water emulsion resulted in intensity independent voltages.

  5. Protein and water confined in nanometer-scale reverse micelles studied by near infrared, terahertz, and ultrafast visible spectroscopies.

    PubMed

    Murakami, Hiroshi

    2013-01-01

    Protein-containing reverse (PCR) micelles are suitable systems to study the properties of proteins and waters in a cell-like environment. A model for determining the structural parameters of PCR micelles, such as the aqueous cavity size and molecule number of water within the reverse micelle, is presented. The model is based on an important hypothesis that the structural parameters of the protein-unfilled reverse micelle do not change after solubilization of protein. I describe a procedure using near infrared spectroscopy of OH stretching vibration band of water to verify the hypothesis. Further, the terahertz (THz) absorption spectrum of myoglobin is derived from THz time-domain spectroscopy of the PCR micellar solution, and the states of waters in reverse micelles with and without protein are discussed on the basis of the structural parameters. The last topic is on internal dynamics of PCR micelles on timescales from femtoseconds to nanoseconds studied by femtosecond time-resolved fluorescence spectroscopy.

  6. Image-guided and tumor-targeted drug delivery with radiolabeled unimolecular micelles.

    PubMed

    Guo, Jintang; Hong, Hao; Chen, Guojun; Shi, Sixiang; Zheng, Qifeng; Zhang, Yin; Theuer, Charles P; Barnhart, Todd E; Cai, Weibo; Gong, Shaoqin

    2013-11-01

    Unimolecular micelles formed by dendritic amphiphilic block copolymers poly(amidoamine)-poly(L-lactide)-b-poly(ethylene glycol) conjugated with anti-CD105 monoclonal antibody (TRC105) and 1,4,7-triazacyclononane-N, N', N-triacetic acid (NOTA, a macrocyclic chelator for (64)Cu) (abbreviated as PAMAM-PLA-b-PEG-TRC105) were synthesized and characterized. Doxorubicin (DOX), a model anti-cancer drug, was loaded into the hydrophobic core of the unimolecular micelles formed by PAMAM and PLA via physical encapsulation. The unimolecular micelles exhibited a uniform size distribution and pH-sensitive drug release behavior. TRC105-conjugated unimolecular micelles showed a CD105-associated cellular uptake in human umbilical vein endothelial cells (HUVEC) compared with non-targeted unimolecular micelles, which was further validated by cellular uptake in CD105-negative MCF-7 cells. In 4T1 murine breast tumor-bearing mice, (64)Cu-labeled targeted micelles exhibited a much higher level of tumor accumulation than (64)Cu-labeled non-targeted micelles, measured by serial non-invasive positron emission tomography (PET) imaging and confirmed by biodistribution studies. These unimolecular micelles formed by dendritic amphiphilic block copolymers that synergistically integrate passive and active tumor-targeting abilities with pH-controlled drug release and PET imaging capabilities provide the basis for future cancer theranostics. PMID:23932288

  7. Image-guided and tumor-targeted drug delivery with radiolabeled unimolecular micelles

    PubMed Central

    Chen, Guojun; Shi, Sixiang; Zheng, Qifeng; Zhang, Yin; Theuer, Charles P.; Barnhart, Todd E.; Cai, Weibo; Gong, Shaoqin

    2013-01-01

    Unimolecular micelles formed by dendritic amphiphilic block copolymers poly(amidoamine)–poly(l-lactide)-b-poly(ethylene glycol) conjugated with anti-CD105 monoclonal antibody (TRC105) and 1,4,7-triazacyclononane-N, N’, N-triacetic acid (NOTA, a macrocyclic chelator for 64Cu) (abbreviated as PAMAM–PLA-b-PEG–TRC105) were synthesized and characterized. Doxorubicin (DOX), a model anti-cancer drug, was loaded into the hydrophobic core of the unimolecular micelles formed by PAMAM and PLA via physical encapsulation. The unimolecular micelles exhibited a uniform size distribution and pH-sensitive drug release behavior. TRC105-conjugated unimolecular micelles showed a CD105-associated cellular uptake in human umbilical vein endothelial cells (HUVEC) compared with non-targeted unimolecular micelles, which was further validated by cellular uptake in CD105-negative MCF-7 cells. In 4T1 murine breast tumor-bearing mice, 64Cu-labeled targeted micelles exhibited a much higher level of tumor accumulation than 64Cu-labeled non-targeted micelles, measured by serial non-invasive positron emission tomography (PET) imaging and confirmed by biodistribution studies. These unimolecular micelles formed by dendritic amphiphilic block copolymers that synergistically integrate passive and active tumor-targeting abilities with pH-controlled drug release and PET imaging capabilities provide the basis for future cancer theranostics. PMID:23932288

  8. Positively charged micelles based on a triblock copolymer demonstrate enhanced corneal penetration

    PubMed Central

    Li, Jingguo; Li, Zhanrong; Zhou, Tianyang; Zhang, Junjie; Xia, Huiyun; Li, Heng; He, Jijun; He, Siyu; Wang, Liya

    2015-01-01

    Purpose The cornea is a main barrier to drug penetration after topical application. The aim of this study was to evaluate the abilities of micelles generated from a positively charged triblock copolymer to penetrate the cornea after topical application. Methods The triblock copolymer poly(ethylene glycol)-poly(ε-caprolactone)-g-polyethyleneimine was synthesized, and the physicochemical properties of the self-assembled polymeric micelles were investigated, including hydrodynamic size, zeta potential, morphology, drug-loading content, drug-loading efficiency, and in vitro drug release. Using fluorescein diacetate as a model drug, the penetration capabilities of the polymeric micelles were monitored in vivo using a two-photon scanning fluorescence microscopy on murine corneas after topical application. Results The polymer was successfully synthesized and confirmed using nuclear magnetic resonance and Fourier transform infrared. The polymeric micelles had an average particle size of 28 nm, a zeta potential of approximately +12 mV, and a spherical morphology. The drug-loading efficiency and drug-loading content were 75.37% and 3.47%, respectively, which indicates that the polymeric micelles possess a high drug-loading capacity. The polymeric micelles also exhibited controlled-release behavior in vitro. Compared to the control, the positively charged polymeric micelles significantly penetrated through the cornea. Conclusion Positively charged micelles generated from a triblock copolymer are a promising vehicle for the topical delivery of hydrophobic agents in ocular applications. PMID:26451109

  9. Evaluating Southern Ocean biological production in two ocean biogeochemical models on daily to seasonal timescales using satellite chlorophyll and O2 / Ar observations

    NASA Astrophysics Data System (ADS)

    Jonsson, B. F.; Doney, S.; Dunne, J.; Bender, M. L.

    2015-02-01

    We assess the ability of ocean biogeochemical models to represent seasonal structures in biomass and net community production (NCP) in the Southern Ocean. Two models are compared to observations on daily to seasonal timescales in four different sections of the region. We use daily satellite fields of chlorophyll (Chl) as a proxy for biomass and in situ observations of O2 and Ar supersaturation (ΔO2 / Ar) to estimate NCP. ΔO2 / Ar is converted to the flux of biologically generated O2 from sea to air (O2 bioflux). All data are aggregated to a climatological year with a daily resolution. To account for potential regional differences within the Southern Ocean, we conduct separate analyses of sections south of South Africa, around the Drake Passage, south of Australia, and south of New Zealand. We find that the models simulate the upper range of Chl concentrations well, underestimate spring levels significantly, and show differences in skill between early and late parts of the growing season. While there is a great deal of scatter in the bioflux observations in general, the four sectors each have distinct patterns that the models pick up. Neither model exhibits a significant distinction between the Australian and New Zealand sectors and between the Drake Passage and African sectors. South of 60° S, the models fail to predict the observed extent of biological O2 undersaturation. We suggest that this shortcoming may be due either to problems with the ecosystem dynamics or problems with the vertical transport of oxygen.

  10. Development of early-warning protocol for predicting chlorophyll-a concentration using machine learning models in freshwater and estuarine reservoirs, Korea.

    PubMed

    Park, Yongeun; Cho, Kyung Hwa; Park, Jihwan; Cha, Sung Min; Kim, Joon Ha

    2015-01-01

    Chlorophyll-a (Chl-a) is a direct indicator used to evaluate the ecological state of a waterbody, such as algal blooms that degrade the water quality in lakes, reservoirs and estuaries. In this study, artificial neural network (ANN) and support vector machine (SVM) were used to predict Chl-a concentration for the early warning in the Juam Reservoir and Yeongsan Reservoir, which are located in an upstream region (freshwater reservoir) and downstream region (estuarine reservoir), respectively. Weekly water quality data and meteorological data for a 7-year period were used to train and validate both the ANN and SVM models. The Latin-hypercube one-factor-at-a-time (LH-OAT) method and a pattern search algorithm were applied to perform sensitivity analyses for the input variables and to optimize the parameters of the two models, respectively. Results revealed that the two models well-reproduced the temporal variation of Chl-a based on the weekly input variables. In particular, the SVM model showed better performance than the ANN model, displaying a higher prediction accuracy in the validation step. The Williams-Kloot test and sensitivity analysis demonstrated that the SVM model was superior for predicting Chl-a in terms of prediction accuracy and description of the cause-and-effect relationship between Chl-a concentration and environmental variables in both the Juam Reservoir and Yeongsan Reservoir. Furthermore, a 7-day interval was determined as an efficient early warning interval in the two reservoirs. As such, this study suggested an effective early-warning prediction method for Chl-a concentration and improved the eutrophication management scheme for reservoirs. PMID:25241206

  11. Small-angle neutron-scattering study of triglyceride solubilization by lecithin micelles: A direct observation of rod-to-sphere transition

    SciTech Connect

    Lin, Tsanglang; Chen, Sowhsin ); Gabriel, N.E.; Roberts, M.F. )

    1990-01-25

    The solubilization of tributyrin by rodlike diheptanoylphosphatidylcholine (diheptanoyl-PC) micelles has been studied by small-angle neutron-scattering techniques. A rod to sphere transition is observed from the measured angular distribution of neutron-scattering intensities. The transition is from the rodlike micelle to a globular mixed micelle which has tributyrin molecules at the core surrounded by an outer shell of diheptanoyl-PC molecules. When the molar ratio of tributyrin to diheptanoyl-PC is increased beyond 0.18, all rodlike diheptanoyl-PC micelles are transformed into globular mixed micelles. The size of these globular mixed micelles increases with increasing tributyrin concentration in the simple micelle region up to the solubility limit. The small-angle neutron scattering data were analyzed to obtain the structural parameters of the mixed micelles. It is found that the growth of the mixed micelles does not follow a constant available surface area model or a constant palisade layer thickness model. If the model is modified to include tributyrin molecules at the surface of the mixed micelle, the growth behavior can be explained. For the tributyrin/diheptanoyl-PC molar ratio less than 0.18, rodlike micelles are found to coexist with globular mixed micelles. By fitting the neutron scattering data in the middle Q range, it is possible to determine the size and number density of the mixed micelles in the coexistence region. The results of analyzing the small-angle neutron scattering data in the coexistence region. The results of analyzing the small-angle neutron scattering data in the coexistence region show that some tributyrin molecules are solubilized by the rodlike dipheptanoyl-PC micelles and only part of the added tributyrin forms globular micelles.

  12. Chlorophyll a + b content and chlorophyll fluorescence in avocado

    Technology Transfer Automated Retrieval System (TEKTRAN)

    One Tonnage (T) and one Simmonds (S) avocado tree and four TxS crosses were evaluated for differences in chlorophyll content and maximal quantum yield of photosystem II in sun and shade-type leaves. Total chlorophyll content by area (Chl a+bar) ranged from 981 mg m-2 in TxS240 to 4339 mg m-2 in Simm...

  13. Bimodal intramolecular excitation energy transfer in a multichromophore photosynthetic model system: hybrid fusion proteins comprising natural phycobilin- and artificial chlorophyll-binding domains.

    PubMed

    Zeng, Xiao-Li; Tang, Kun; Zhou, Nan; Zhou, Ming; Hou, Harvey J M; Scheer, Hugo; Zhao, Kai-Hong; Noy, Dror

    2013-09-11

    The phycobilisomes of cyanobacteria and red-algae are highly efficient peripheral light-harvesting complexes that capture and transfer light energy in a cascade of excitation energy transfer steps through multiple phycobilin chromophores to the chlorophylls of core photosystems. In this work, we focus on the last step of this process by constructing simple functional analogs of natural phycobilisome-photosystem complexes that are based on bichromophoric protein complexes comprising a phycobilin- and a chlorophyll- or porphyrin-binding domain. The former is based on ApcE(1-240), the N-terminal chromophore-binding domain of the phycobilisome's L(CM) core-membrane linker, and the latter on HP7, a de novo designed four-helix bundle protein that was originally planned as a high-affinity heme-binding protein, analogous to b-type cytochromes. We fused a modified HP7 protein sequence to ApcEΔ, a water-soluble fragment of ApcE(1-240) obtained by excising a putative hydrophobic loop sequence of residues 77-153. HP7 was fused either to the N- or the C-terminus of ApcEΔ or inserted between residues 76 and 78, thereby replacing the native hydrophobic loop domain. We describe the assembly, spectral characteristics, and intramolecular excitation energy transfer of two unique systems: in the first, the short-wavelength absorbing zinc-mesoporphyrin is bound to the HP7 domain and serves as an excitation-energy donor to the long-wavelength absorbing phycocyanobilin bound to the ApcE domain; in the second, the short-wavelength absorbing phycoerythrobilin is bound to the ApcE domain and serves as an excitation energy donor to the long-wavelength absorbing zinc-bacteriochlorophyllide bound to the HP7 domain. All the systems that were constructed and tested exhibited significant intramolecular fluorescence resonance energy transfer with yields ranging from 21% to 50%. This confirms that our modular, covalent approach for studying EET between the cyclic and open chain tetrapyrroles is

  14. Effect of water on the local electric potential of simulated ionic micelles

    SciTech Connect

    Brodskaya, Elena N.; Vanin, Alexander A.

    2015-07-28

    Ionic micelles in an aqueous solution containing single-charged counter-ions have been simulated by molecular dynamics. For both cationic and anionic micelles, it has been demonstrated that explicit description of solvent has strong effect on the micelle’s electric field. The sign of the local charge alters in the immediate vicinity of the micellar crown and the electric potential varies nonmonotonically. Two micelle models have been examined: the hybrid model with a rigid hydrocarbon core and the atomistic model. For three molecular models of water (Simple Point Charge model (SPC), Transferable Intermolecular Potential 5- Points (TIP5P) and two-centered S2), the results have been compared with those for the continuum solvent model. The orientational ordering of solvent molecules has strong effect on the local electric field surprisingly far from the micelle surface.

  15. Positron emission tomography based analysis of long-circulating cross-linked triblock polymeric micelles in a U87MG mouse xenograft model and comparison of DOTA and CB-TE2A as chelators of copper-64.

    PubMed

    Jensen, Andreas I; Binderup, Tina; Kumar EK, Pramod; Kjær, Andreas; Rasmussen, Palle H; Andresen, Thomas L

    2014-05-12

    Copolymers of ABC-type (PEG-PHEMA-PCMA) architecture were prepared by atom transfer radical polymerization and formulated as micelles with functionalizable primary alcohols in the shell-region (PHEMA-block) to which the metal-ion chelators DOTA or CB-TE2A were conjugated. Using this micelle system we compared the in vivo stabilities of DOTA and CB-TE2A as chelators of (64)Cu in micelle nanoparticles. The coumarin polymer (PCMA-block) micelle core was cross-linked by UV irradiation at 2 W/cm(2) for 30 min. The cross-linked micelles were labeled with (64)Cu at room temperature for 2 h (DOTA) or 80 °C for 3 h (CB-TE2A), giving labeling efficiencies of 60-76% (DOTA) and 40-47% (CB-TE2A). (64)Cu-micelles were injected into tumor-bearing mice (8 mg/kg) and PET/CT scans were carried out at 1, 22, and 46 h postinjection. The micelles showed good blood stability (T1/2: 20-26 h) and tumor uptake that was comparable with other nanoparticle systems. The DOTA micelles showed a biodistribution similar to the CB-TE2A micelles and the tumor uptake was comparable for both micelle types at 1 h (1.9% ID/g) and 22 h (3.9% ID/g) but diverged at 46 h with 3.6% ID/g (DOTA) and 4.9% ID/g (CB-TE2A). On the basis of our data, we conclude that cross-linked PEG-PHEMA-PCMA micelles have long circulating properties resulting in tumor accumulation and that DOTA and CB-TE2A (64)Cu-chelates show similar in vivo stability for the studied micelle system.

  16. The future of the subsurface chlorophyll-a maximum in the Canada Basin—A model intercomparison

    NASA Astrophysics Data System (ADS)

    Steiner, N. S.; Sou, T.; Deal, C.; Jackson, J. M.; Jin, M.; Popova, E.; Williams, W.; Yool, A.

    2016-01-01

    Six Earth system models and three ocean-ice-ecosystem models are analyzed to evaluate magnitude and depth of the subsurface Chl-a maximum (SCM) in the Canada Basin and ratio of surface to subsurface Chl-a in a future climate scenario. Differences in simulated Chl-a are caused by large intermodel differences in available nitrate in the Arctic Ocean and to some extent by ecosystem complexity. Most models reproduce the observed SCM and nitracline deepening and indicate a continued deepening in the future until the models reach a new state with seasonal ice-free waters. Models not representing a SCM show either too much nitrate and hence no surface limitation or too little nitrate with limited surface growth only. The models suggest that suppression of the nitracline and deepening of the SCM are caused by enhanced stratification, likely driven by enhanced Ekman convergence and freshwater contributions with primarily large-scale atmospheric driving mechanisms. The simulated ratio of near-surface Chl-a to depth-integrated Chl-a is slightly decreasing in most areas of the Arctic Ocean due to enhanced contributions of subsurface Chl-a. Exceptions are some shelf areas and regions where the continued ice thinning leaves winter ice too thin to provide a barrier to momentum fluxes, allowing winter mixing to break up the strong stratification. Results confirm that algorithms determining vertically integrated Chl-a from surface Chl-a need to be tuned to Arctic conditions, but likely require little or no adjustments in the future.

  17. Spatial and temporal variability of chlorophyll in Bay of Bengal.

    NASA Astrophysics Data System (ADS)

    Jutla, A.; Akanda, S.; Islam, S.

    2009-04-01

    The Bay of Bengal (BoB) receives approximately 628 km3/ year of freshwater discharge from the Ganges and Brahmaputra rivers. Freshwater discharge from rivers increases the nutrient load and thereby enhances phytoplankton production in the BoB. Cholera, an infectious water-borne disease caused by bacterium Vibrio cholerae, remains endemic in the BoB region. Phytoplankton provides favorable environment for survival of cholera bacteria. Therefore, for development of any predictive model for cholera, it is important to quantify the spatial and temporal variability of phytoplankton in the BoB. Satellite remote sensing is the most effective way to quantify this variability over a range of space and time scales. Using ten years (1998-2007) of daily, weekly and monthly SeaWiFs chlorophyll, a surrogate variable for measuring phytoplankton, imagery we explore the spatial pattern and dominant temporal variability of chlorophyll over the BoB region. We find that chlorophyll in the coastal waters has more variability, both in temporal and spatial scales, than the offshore waters. Mechanism of production and space-time variability of coastal chlorophyll is different from those of offshore chlorophyll. While coastal chlorophyll is dominated by influx of terrestrial nutrients through river discharge, chlorophyll in the offshore region is primarily controlled by oceanic processes. We will also explore issues related to dominant space and time scales of chlorophyll variations in the entire bay.

  18. Structural transitions of CTAB micelles in the presence of n-octylamine: A small angle neutron scattering study

    SciTech Connect

    Prasad, C.D.; Singh, H.N. ); Goyal, P.S.; Rao, K.S. )

    1993-02-01

    Small angle neutron scattering (SANS) was used to characterize the micelles of cetyltrimethylammonium bromide (CTAB) in D[sub 2]O solutions, with or without added n-octylamine. SANS data have been analyzed using various models. Micellar parameters, such as mean aggregation numbers, micelle dimensions, and fractional charge on the micelles, are reported from the analysis of SANS spectra for the CTAB/n-octylamine system as a function of octylamine concentration and temperature. Results are interpreted in terms of micellar sphere-to-rod transition prompted by amine concentration in CTAB micellar solution. The size of the micelle decreases as the temperature increases.

  19. The alignment of a voltage-sensing peptide in dodecylphosphocholine micelles and in oriented lipid bilayers by nuclear magnetic resonance and molecular modeling.

    PubMed Central

    Mattila, K; Kinder, R; Bechinger, B

    1999-01-01

    The S4 segments of voltage-gated sodium channels are important parts of the voltage-sensing elements of these proteins. Furthermore, the addition of the isolated S4 polypeptide to planar lipid bilayers results in stepwise increases of ion conductivity. In order to gain insight into the mechanisms of pore formation by amphipathic peptides, the structure and orientation of the S4 segment of the first internal repeat of the rat brain II sodium channel was investigated in the presence of DPC micelles by multidimensional solution NMR spectroscopy and solid-state NMR spectroscopy on oriented phospholipid bilayers. Both the anisotropic chemical shift observed by proton-decoupled (15)N solid-state NMR spectroscopy and the attenuating effects of DOXYL-stearates on TOCSY crosspeak intensities of micelle-associated S4 indicate that the central alpha-helical portion of this peptide is oriented approximately parallel to the membrane surface. Simulated annealing and molecular dynamics calculations of the peptide in a biphasic tetrachloromethane-water environment indicate that the peptide alpha-helix extends over approximately 12 residues. A less regular structure further toward the C-terminus allows for the hydrophobic residues of this part of the peptide to be positioned in the tetrachloromethane environment. The implications for possible pore-forming mechanisms are discussed. PMID:10512830

  20. Identifying Efficacious Approaches to Chemoprevention with chlorophyllin, purified chlorophylls and freeze-dried spinach in a Mouse Model of Transplacental Carcinogenesis

    SciTech Connect

    Castro, David J.; Lohr, Christiane V.; Fischer, Kay A.; Waters, Katrina M.; Webb-Robertson, Bobbie-Jo M.; Dashwood, Roderick H.; Bailey, George S.; Williams, David E.

    2009-02-01

    The carcinogenic potential of dibenzo[a,l]pyrene (DBP) has been well characterized in numerous animal models. We have previously documented that a single dose of 15 mg/Kg DBP to pregnant mice late in gestation (GD 17) produces an aggressive T-cell lymphoma as well as lung and liver cancer in offspring. The current study examines the chemopreventative properties of chlorophyllin (CHL) and chlorophyll (Chl) in this transplacental carcinogenesis model. Pregnant B6129SF1 females, bred to 129S1/SvIm males, received purified diets incorporated with either 2000 ppm CHL, 2000 ppm Chl, or 10% freeze-dried spinach beginning at gestation day 9. Lymphoma-dependent mortality was not significantly altered by maternal consumption of any of the diet and little effect on lung tumor burden in mice surviving to 10 months of age was observed. However, co-administration of CHL at 380 mg/Kg with DBP by gavage (molar ratio of 10:1, CHL:DBP) provided significant protection against DBP initiated carcinogenesis. Offspring born to dams receiving CHL co-gavaged with DBP exhibited markedly fewer lymphoma-dependent mortalities (p< 0.001). The degree of protection by CHL, compared to controls dosed with DBP in tricaprylin (TCP) as the vehicle, were less marked, but still significant. Co-administration of CHL (TCP as vehicle) also reduced lung tumor multiplicity in mice by approximately 50% and this was observed throughout the study (p< 0.005). This is the first demonstration that CHL can provide potent chemoprotection in a transplacental carcinogenesis model and supports a mechanism involving complex-mediated reduction of carcinogen uptake.

  1. Study of sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

    PubMed

    Bastiat, Guillaume; Grassl, Bruno; Khoukh, Abdel; François, Jeanne

    2004-07-01

    Sodium dodecyl sulfate (SDS)-poly(propylene oxide) methacrylate (PPOMA) (of molecular weight M(w) = 434 g x mol(-1)) mixtures have been studied using conductimetry, static light scattering, fluorescence spectroscopy, and 1H NMR. It has been shown that SDS and PPOMA form mixed micelles, and SDS and PPOMA aggregation numbers, N(ag SDS) and N(ag PPOMA), have been determined. Total aggregation numbers of the micelles (N(ag SDS) + N(ag PPOMA)) and those of SDS decrease upon increasing the weight ratio R = PPOMA/SDS. Localization of PPOMA inside the mixed micelles is considered (i) using 1H NMR to localize the methacrylate function at the hydrophobic core-water interface and (ii) by studying the SDS-PPO micellar system (whose M(w) = 400 g x mol(-1)). Both methods have indicated that the PPO chain of the macromonomer is localized at the SDS micelle surface. Models based on the theorical prediction of the critical micellar concentration of mixed micelles and structural model of swollen micelles are used to confirm the particular structure proposed for the SDS-PPOMA system, i.e., the micelle hydrophobic core is primarily composed of the C12 chains of the sodium dodecyl sulfate, the hydrophobic core-water interface is made up of the SDS polar heads as well as methacrylate functions of the PPOMA, the PPO chains of the macromonomer are adsorbed preferentially on the surface, i.e., on the polar heads of the SDS.

  2. [Detection of corn chlorophyll content using canopy spectral reflectance].

    PubMed

    Sun, Hong; Li, Min-zan; Zhang, Yan-e; Zhao, Yong; Wang, Hai-hua

    2010-09-01

    The canopy spectral reflectance and chlorophyll content of corn were measured and analyzed under different nitrogen treatments. The correlation between spectral reflectance and chlorophyll content was discussed based on different growth stages and different nitrogen levels. The results showed positive correlations under high and normal nitrogen treatment, while negative correlation under low nitrogen treatment. The relation between reflectance of normal fertilizer region and chlorophyll content was better than others, with r(Normal) > r(High) > r(Low). Normal fertilizer was the best condition to detect the corn chlorophyll content using spectral reflectance. Analysis of the relations at different growth stages showed that on the band of 400-1000 nm the absolute value of correlation coefficient increased and reached the maximum at shooting stage, it decreased until anthesis-silking stage, and then rebounded at milking stage. The positive correlations were found at shooting and milking stage, while negative correlations were found at seedling, trumpet and anthesis-silking stage. It was indicated that the sensitive stages to detect the chlorophyll content were shooting and trumpet stage with high absolute value of correlation coefficient above 0.6 around 550 nm. In order to detect the chlorophyll content of corn, 558, 667, 714 and 912 nm were selected to establish the MLR model and PLSR model. The results showed that PLSR was more capable of building chlorophyll content models reflecting correct relations among multi-variables compared with MLR. In the meanwhile, three wavelengths were selected (558, 667 and 714 nm) to build different vegetation indices such as GDVI, GRVI, GNDVI, DVI, RVI and NDVI. The correlation between DVI and chlorophyll con tent was better than others and DVI was used to establish binomial model and exponential model at shooting stage (R2 = 0.80) and trumpet stage (R2 = 0.66) respectively which was higher than PLSR It also provided a feasible

  3. Ultrasound-Mediated Polymeric Micelle Drug Delivery.

    PubMed

    Xia, Hesheng; Zhao, Yue; Tong, Rui

    2016-01-01

    The synthesis of multi-functional nanocarriers and the design of new stimuli-responsive means are equally important for drug delivery. Ultrasound can be used as a remote, non-invasive and controllable trigger for the stimuli-responsive release of nanocarriers. Polymeric micelles are one kind of potential drug nanocarrier. By combining ultrasound and polymeric micelles, a new modality (i.e., ultrasound-mediated polymeric micelle drug delivery) has been developed and has recently received increasing attention. A major challenge remaining in developing ultrasound-responsive polymeric micelles is the improvement of the sensitivity or responsiveness of polymeric micelles to ultrasound. This chapter reviews the recent advance in this field. In order to understand the interaction mechanism between ultrasound stimulus and polymeric micelles, ultrasound effects, such as thermal effect, cavitation effect, ultrasound sonochemistry (including ultrasonic degradation, ultrasound-initiated polymerization, ultrasonic in-situ polymerization and ultrasound site-specific degradation), as well as basic micellar knowledge are introduced. Ultrasound-mediated polymeric micelle drug delivery has been classified into two main streams based on the different interaction mechanism between ultrasound and polymeric micelles; one is based on the ultrasound-induced physical disruption of the micelle and reversible release of payload. The other is based on micellar ultrasound mechanochemical disruption and irreversible release of payload.

  4. Electrosorption of pectin onto casein micelles.

    PubMed

    Tuinier, R; Rolin, C; de Kruif, C G

    2002-01-01

    Pectin, a polysaccharide derived from plant cells of fruit, is commonly used as stabilizer in acidified milk drinks. To gain a better understanding of the way that pectin stabilizes these drinks, we studied the adsorption and layer thickness of pectin on casein micelles in skim milk dispersions. Dynamic light scattering was used to measure the layer thickness of adsorbed pectin onto casein micelles in situ during acidification. The results indicate that the adsorption of pectin onto casein micelles is multilayered and takes place at and below pH 5.0. Renneting, i.e., cleaving-off kappa-casein from the casein micelles, did not alter the adsorption pH. It did, however, show that pectin arrests the rennet-induced flocculation of casein micelles below pH 5.0. From the findings we concluded the attachment of pectin onto casein micelles is driven by electrosorption. Adsorption measurements confirmed the multilayered nature of the adsorption of pectin onto casein micelles. Both the adsorbed amount and the layer thickness increased with decreasing pH in the relevant range 3.5-5.0. The phase behavior of a casein micelles/pectin mixture was determined and could be explained in terms of thermodynamic incompatibility being relevant above pH 5.0 and adsorption, leading to either stabilization and bridging, being relevant below pH 5.0. The results confirm that electrosorption is the driving force for the adsorption of pectin onto casein micelles.

  5. Identification of the 7-Hydroxymethyl Chlorophyll a Reductase of the Chlorophyll Cycle in Arabidopsis[W

    PubMed Central

    Meguro, Miki; Ito, Hisashi; Takabayashi, Atsushi; Tanaka, Ryouichi; Tanaka, Ayumi

    2011-01-01

    The interconversion of chlorophyll a and chlorophyll b, referred to as the chlorophyll cycle, plays a crucial role in the processes of greening, acclimation to light intensity, and senescence. The chlorophyll cycle consists of three reactions: the conversions of chlorophyll a to chlorophyll b by chlorophyllide a oxygenase, chlorophyll b to 7-hydroxymethyl chlorophyll a by chlorophyll b reductase, and 7-hydroxymethyl chlorophyll a to chlorophyll a by 7-hydroxymethyl chlorophyll a reductase. We identified 7-hydroxymethyl chlorophyll a reductase, which is the last remaining unidentified enzyme of the chlorophyll cycle, from Arabidopsis thaliana by genetic and biochemical methods. Recombinant 7-hydroxymethyl chlorophyll a reductase converted 7-hydroxymethyl chlorophyll a to chlorophyll a using ferredoxin. Both sequence and biochemical analyses showed that 7-hydroxymethyl chlorophyll a reductase contains flavin adenine dinucleotide and an iron-sulfur center. In addition, a phylogenetic analysis elucidated the evolution of 7-hydroxymethyl chlorophyll a reductase from divinyl chlorophyllide vinyl reductase. A mutant lacking 7-hydroxymethyl chlorophyll a reductase was found to accumulate 7-hydroxymethyl chlorophyll a and pheophorbide a. Furthermore, this accumulation of pheophorbide a in the mutant was rescued by the inactivation of the chlorophyll b reductase gene. The downregulation of pheophorbide a oxygenase activity is discussed in relation to 7-hydroxymethyl chlorophyll a accumulation. PMID:21934147

  6. Cationic micelle delivery of Trp2 peptide for efficient lymphatic draining and enhanced cytotoxic T-lymphocyte responses.

    PubMed

    Zeng, Qin; Jiang, Hao; Wang, Ting; Zhang, Zhirong; Gong, Tao; Sun, Xun

    2015-02-28

    Neutral particles 20-45 nm in diameter showed potential as tumor antigen vectors because they targeted the draining lymph nodes after subcutaneous injection. However, they were weakly immune-stimulatory and could also spread throughout the body, raising the risk of systemic toxicity. Here we explored whether incorporating positively charged amphiphilic polymers into micelles improves their site specificity and immunogenicity. Cationic polyethylenimine (2k)-stearic acid (PSA) micelles were loaded with the melanoma antigen peptide Trp2; they showed an average size of 28.7±8.2 nm and an encapsulation efficiency of 99.21±5.38%. Empty PSA micelles acted as a robust adjuvant in vitro, promoting maturation, proliferation and migration of bone marrow-derived dendritic cells in a dose-dependent manner. After subcutaneous injection into mice, Trp2-loaded PSA micelles accumulated preferentially in the medulla and paracortex of the draining lymph nodes and were present at negligible levels in the systemic circulation. Mice immunized with Trp2-loaded PSA micelles showed significantly higher Trp2-specific cytotoxic T lymphocyte activity than mice immunized with free Trp2 or a mixture of Trp2 and empty PSA micelles. In a B16-F10 murine melanoma model, Trp2-loaded PSA micelles inhibited tumor growth significantly more than did free Trp2 and PSA micelles caused less systemic toxicity. These findings suggest that cationic PSA micelles loaded with Trp2 may be a potential approach for melanoma immunotherapy.

  7. pH-Responsive Poly(ethylene glycol)/Poly(L-lactide) Supramolecular Micelles Based on Host-Guest Interaction.

    PubMed

    Zhang, Zhe; Lv, Qiang; Gao, Xiaoye; Chen, Li; Cao, Yue; Yu, Shuangjiang; He, Chaoliang; Chen, Xuesi

    2015-04-29

    pH-responsive supramolecular amphiphilic micelles based on benzimidazole-terminated poly(ethylene glycol) (PEG-BM) and β-cyclodextrin-modified poly(L-lactide) (CD-PLLA) were developed by exploiting the host-guest interaction between benzimidazole (BM) and β-cyclodextrin (β-CD). The dissociation of the supramolecular micelles was triggered in acidic environments. An antineoplastic drug, doxorubicin (DOX), was loaded into the supramolecular micelles as a model drug. The release of DOX from the supramolecular micelles was clearly accelerated as the pH was reduced from 7.4 to 5.5. The DOX-loaded PEG-BM/CD-PLLA supramolecular micelles displayed an enhanced intracellular drug-release rate in HepG2 cells compared to the pH-insensitive DOX-loaded PEG-b-PLLA counterpart. After intravenous injection into nude mice bearing HepG2 xenografts by the tail vein, the DOX-loaded supramolecular micelles exhibited significantly higher tumor inhibition efficacy and reduced systemic toxicity compared to free DOX. Furthermore, the DOX-loaded supramolecular micelles showed a blood clearance rate markedly lower than that of free DOX and comparable to that of the DOX-loaded PEG-b-PLLA micelles after intravenous injection into rats. Therefore, the pH-responsive PEG-BM/CD-PLLA supramolecular micelles hold potential as a smart nanocarrier for anticancer drug delivery. PMID:25856564

  8. A Novel approach to monitor chlorophyll-a concentration using an adaptive model from MODIS data at 250 metres spatial resolution

    NASA Astrophysics Data System (ADS)

    El Alem, A.; Chokmani, K.; Laurion, I.; El Adlouni, S.

    2013-12-01

    Occurrence and extent of Harmful Algal Bloom (HAB) has increased in inland water bodies around the world. The appearance of these blooms reflects the advanced state of eutrophication of several aquatic systems caused by urban, agricultural, and industrial development. Algal blooms, especially those cyanobacterial origins, are capable to produce and release toxins, threatening human and animal health, quality of drinking water, and recreational water bodies. Conventional monitoring networks, based on infrequent sampling in a few fixed monitoring stations, cannot provide the information needed as HABs are spatially and temporally heterogeneous. Remote sensing represents an interesting alternative to provide the required spatial and temporal coverage. The usefulness of air-borne and satellite remote sensing data to detect HABs was demonstrated since three decades ago, and since several empirical and semi-empirical models, using satellite imagery, were developed to estimate chlorophyll-a concentration [Chl-a] as a proxy to detect bloom proliferations. However, most of those models presented several weaknesses that are generally linked to the range of [Chl-a] to be estimated. Indeed, models originally calibrated for high [Chl-a] fail to estimate low concentrations and vice versa. In this study, an adaptive model to estimate [Chl-a], spread over a wide range of concentrations, is developed for optically complex inland water bodies based on combination of water spectral response classification and three developed semi-empirical algorithms using a multivariate regression. Three distinct water types (low, medium, and high [Chl-a]) are first identified using the Classification and Regression Tree (CART) method performed on remote sensing reflectance over a dataset of 44 [Chl-a] samples collected from Lakes over Quebec province. Based on the water classification, a specific multivariate model to each water type is developed using the same dataset and the MODIS data at 250-m

  9. Isothermal titration calorimetric analysis on solubilization of an octane oil-in-water emulsion in surfactant micelles and surfactant-anionic polymer complexes.

    PubMed

    Zhang, Hui; Zeeb, Benjamin; Salminen, Hanna; Weiss, Jochen

    2015-01-15

    Polymers may alter the ability of surfactant micelles to solubilize hydrophobic molecules depending on surfactant-polymer interactions. In this study, isothermal titration calorimetry (ITC) was used to investigate the solubilization thermodynamics of an octane oil-in-water emulsion in anionic sodium dodecylsulphate (SDS), nonionic polyoxyethylene sorbitan monooleate (Tween 80), cationic cetyltrimethylammonium bromide (CTAB) surfactant micelles and respective complexes formed by these micelles and an anionic polymer (carboxymethyl cellulose). Results indicated that the oil solubilization in single ionic micelles was endothermic, while in nonionic micelles or mixed ionic/nonionic micelles it was exothermic. The addition of carboxymethyl cellulose did not influence the solubilization behavior in these micelles, but affected the solubilization capacities of these systems. The solubilization capacity of cationic micelles or mixed cationic/nonionic micelles was enhanced while that of nonionic or anionic micelles was decreased. Based on the phase separation model, a molecular pathway mechanism driven by enthalpy was proposed for octane solubilization in surfactant micelles and surfactant-polymer complexes.

  10. Dynamics of Chain Exchange in Block Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Lodge, Timothy

    Block copolymer micelles are rarely at equilibrium. The primary reason is the large number of repeat units in the insoluble block, Ncore, which makes the thermodynamic penalty for extracting a single chain (``unimer exchange'') substantial. As a consequence, the critical micelle concentration (CMC) is rarely accessed experimentally; however, in the proximity of a critical micelle temperature (CMT), equilibration is possible. We have been using time-resolved small angle neutron scattering (TR-SANS) to obtain a detailed picture of the mechanisms and time scales for chain exchange, at or near equilibrium. Our model system is poly(styrene)-block-poly(ethylene-alt-propylene)) (PS-PEP), in the PEP-selective solvent squalane (C30H62) . Equivalent micelles with either normal (hPS) or perdeuterated (dPS) cores are initially mixed in a blend of isotopically substituted squalane, designed to contrast-match a 50:50 hPS:dPS core. Samples are then annealed at a target temperature, and chain exchange is revealed quantitatively by the temporal decay in scattered intensity. The rate of exchange as function of concentration, temperature, Ncore, Ncorona, and chain architecture (diblock versus triblock) will be discussed.

  11. Spontaneous chlorophyll mutants of Pennisetum americanum: Genetics and chlorophyll quantities.

    PubMed

    Koduru, P R; Rao, M K

    1980-05-01

    Thirteen spontaneously occurring chlorophyll deficient phenotypes have been described and their genetic basis was established. Ten of these - 'white', 'white tipped green', 'patchy white', 'white virescent', 'white striping 1', 'white striping 2', 'white striping 4', 'fine striping', 'chlorina' and 'yellow virescent' showed monogenic recessive inheritance and the remaining three - 'yellow striping', 'yellow green' and 'light green' seedling phenotypes showed digenic recessive inheritance. The genes for (i) 'white tipped green' (wr) and 'yellow virescent' (yv) and (ii) 'patchy white' (pw) and 'white striping 1' (wst 1) showed independent assortment. Further, the genes for 'white' (w), 'white tipped green' (wr) and 'yellow virescent' (yv) were inherited independently of the gene for hairy leaf margin (Hm).In the mutants - 'white tipped green', 'patchy white', 'white striping 1', 'white striping 2', 'fine striping', 'chlorina', 'yellow virescent', 'yellow striping', 'yellow green' and 'light green' phenotypes total quantity of chlorophyll was significantly less than that in the corresponding controls, while in 'white virescent' there was no reduction in the mature stage. For nine of the mutants the quantity of chlorophyll was also estimated in F1's (mutant x control green). In F1's of six of the mutants - 'white tip', 'patchy white', 'chlorina', 'yellow virescent', 'fine striping' and 'yellow striping' the quantity of chlorophyll was almost equal to the wild type. In the F1's of three of the mutants - 'white striping 1', 'white striping 2' and 'light green' an intermediate value between the mutant and wild types was observed. In 'yellow virescent' retarded synthesis of chlorophyll, particularly chlorophyll a was observed in the juvenile stage. Reduced quantity of chlorophyll was associated with defective chloroplasts. In the mutants - 'white tipped green, 'white virescent', 'fine striping', 'chlorina', 'yellow striping', 'yellow green' and 'light green' defective

  12. Plant chlorophyll content meter

    NASA Technical Reports Server (NTRS)

    Spiering, Bruce A. (Inventor); Carter, Gregory A. (Inventor)

    2000-01-01

    A plant chlorophyll content meter is described which collects light reflected from a target plant and separates the collected light into two different wavelength bands. These wavelength bands, or channels, are described as having center wavelengths of 700 nm and 840 nm. The light collected in these two channels are processed using photo detectors and amplifiers. An analog to digital converter is described which provides a digital representation of the level of light collected by the lens and falling within the two channels. A controller provided in the meter device compares the level of light reflected from a target plant with a level of light detected from a light source, such as light reflected by a target having 100% reflectance, or transmitted through a diffusion receptor. The percent of reflection in the two separate wavelength bands from a target plant are compared to provide a ratio which indicates a relative level of plant physiological stress. A method of compensating for electronic drift is described where a sample is taken when a collection lens is covered to prevent light from entering the device. This compensation method allows for a more accurate reading by reducing error contributions due to electronic drift from environmental conditions at the location where a hand-held unit is used.

  13. A comparative study of chlorophyll-a concentration during different tropical cyclones in the Bay of Bengal based on measurements and model simulations

    NASA Astrophysics Data System (ADS)

    Pandey, Suchita; Bhagawati, Chirantan; Patel, Ramkrushnbhai; Chakraborty, Arun; Jayanarayanan, Kuttippurath

    2016-04-01

    Chlorophyll-a (chl-a) pigments derived from ocean color can be used as a tool for estimating phytoplankton distribution in the observed oceanic region. This study aims at providing new insights on the variability of chl-a concentration during the occurrences of different cyclones in the Bay of Bengal (BoB). We consider two tropical cyclones of different intensities observed in the BOB; MALA and NILAM. MALA was a cyclonic storm and was formed on 24 April 2006 and dissipated by 30 April 2006. The wind speed and lowest pressure during the MALA have been recorded as 185‒220 Km/h and 950 hp, respectively. Multi-satellite observations are used for chl-a (SeaWiFS, MODIS, OCM-2), winds (QuickSCAT) and sea surface height (SSH) (TOPEX/POSEIDON) analyses in this study. Argo data taken from CORIOLIS (along the cyclone track) are used for temperature and salinity, from which Mixed Layer Depth (MLD), Isothermal Layer Depth (ILD), Barrier Layer Thickness (BLT) is calculated. A case study for MALA cyclone using daily forcing of winds and surface net heat flux in 'Regional Ocean Modeling System' (ROMS) with NPCHLZD (Nitrate, Phytoplankton, Chlorophyll, Zooplankton and Detritus), five components ecosystem model is used for study the chl-a variability during the cyclone. The results show high chl-a concentration along the track as well as in the right side of the track of the cyclone. The daily variations of MLD, BLT, SSH and wind stress curl (WSC) are compared with the daily time series of chl-a for pre-cyclone, during cyclone and post cyclone period. During and after the passage of cyclone average chl-a values increased from 0.2 mg/l to 0.4 mg/l and greater. It shows good agreement with MLD (30‒40 m), negligible BLT and strong WSC (4*10-6n/m3). It implies the strong winds has initiated upwelling, which subsequently triggered phytoplankton bloom during and after the cyclonic storm. The cyclone NILAM was formed on 28 October 2012 and dissipated by 1 November 2012, which had a

  14. Bone-targeted acid-sensitive doxorubicin conjugate micelles as potential osteosarcoma therapeutics.

    PubMed

    Low, Stewart A; Yang, Jiyuan; Kopeček, Jindřich

    2014-11-19

    Osteosarcoma is a malignancy of the bone that primarily affects adolescents. Current treatments retain mortality rates, which are higher than average cancer mortality rates for the adolescent age group. We designed a micellar delivery system with the aim to increase drug accumulation in the tumor and potentially reduce side effects associated with chemotherapy. The design features are the use of the hydrophilic D-aspartic acid octapeptide as both the effective targeting agent as well as the hydrophilic micelle corona. Micelle stabilization was accomplished by binding of model drug (doxorubicin) via an acid-sensitive hydrazone bond and incorporating one to four 11-aminoundecanoic acid (AUA) moieties to manipulate the hydrophobic/hydrophilic ratio. Four micelle-forming unimers have been synthesized and their self-assembly into micelles was evaluated. Size of the micelles could be modified by changing the architecture of the unimers from linear to branched. The stability of the micelles increased with increasing content of AUA moieties. Adsorption of all micelles to hydroxyapatite occurred rapidly. Doxorubicin release occurred at pH 5.5, whereas no release was detected at pH 7.4. Cytotoxicity toward human osteosarcoma Saos-2 cells correlated with drug release data.

  15. Influence of serum albumin on intracellular delivery of drug-loaded hyaluronan polymeric micelles.

    PubMed

    Nešporová, Kristina; Šógorková, Jana; Šmejkalová, Daniela; Kulhánek, Jaromír; Huerta-Angeles, Gloria; Kubala, Lukáš; Velebný, Vladimír

    2016-09-10

    Polymeric micelles are attractive drug delivery systems for intravenously administered nonpolar drugs. Although physical parameters like size, shape and loading capacity are considered as the most important for their efficiency, here we demonstrate that the effects of serum protein interaction and characteristics of loaded compound cannot be neglected during the micelle development and design of experimental set up. Polymeric micelles prepared from amphiphilic hyaluronic acid grafted with short (hexanoic) and long fatty acids (oleic) were tested after loading with two different hydrophobic models, Nile red and curcumin. The composition of micelles affected mainly the loading capacity. Both encapsulated compounds behaved differently in the in vitro cell uptake, which was also influenced by serum concentration, where serum albumin was found to be the primary destabilizing component. This destabilization was found to be influenced by polymeric micelle concentration. Thus, the chemical structure of micelle, the properties of non-covalently loaded substance and serum albumin/polymeric micelle ratio modulate the in vitro intracellular uptake of drugs loaded in nanocarriers. PMID:27473277

  16. Bone-Targeted Acid-Sensitive Doxorubicin Conjugate Micelles as Potential Osteosarcoma Therapeutics

    PubMed Central

    2015-01-01

    Osteosarcoma is a malignancy of the bone that primarily affects adolescents. Current treatments retain mortality rates, which are higher than average cancer mortality rates for the adolescent age group. We designed a micellar delivery system with the aim to increase drug accumulation in the tumor and potentially reduce side effects associated with chemotherapy. The design features are the use of the hydrophilic d-aspartic acid octapeptide as both the effective targeting agent as well as the hydrophilic micelle corona. Micelle stabilization was accomplished by binding of model drug (doxorubicin) via an acid-sensitive hydrazone bond and incorporating one to four 11-aminoundecanoic acid (AUA) moieties to manipulate the hydrophobic/hydrophilic ratio. Four micelle-forming unimers have been synthesized and their self-assembly into micelles was evaluated. Size of the micelles could be modified by changing the architecture of the unimers from linear to branched. The stability of the micelles increased with increasing content of AUA moieties. Adsorption of all micelles to hydroxyapatite occurred rapidly. Doxorubicin release occurred at pH 5.5, whereas no release was detected at pH 7.4. Cytotoxicity toward human osteosarcoma Saos-2 cells correlated with drug release data. PMID:25291150

  17. Probing the Structure and Dynamics of Confined Water in AOT Reverse Micelles

    PubMed Central

    Martinez, Anna Victoria; Dominguez, Laura; Małolepsza, Edyta; Moser, Adam; Ziegler, Zack; Straub, John E.

    2013-01-01

    Reverse micelles are attractive nanoscale systems used for the confinement of molecules in studies of structure and chemical reactions, including protein folding and aggregation. The simulation of reverse micelles, in which a water “pool” is separated from a non-polar bulk phase by a surfactant layer, poses significant challenges to empirical force fields due to the diversity of interactions between non-polar, polar, and charged groups. We have explored the dependence of system density, reverse micelle structure, and water configurational relaxation times as a function of reverse micelle composition, including water:surfactant ratio, absolute number of water molecules, and force field using molecular dynamics simulations. The resulting structures and dynamics are found to depend more on the force field used than on varying interpretations of the water:surfactant ratio in terms of absolute size of the reverse micelle. Substantial deviations from spherical reverse micelle geometries are observed in all unrestrained simulations. Rotational anisotropy decay times and water residence times show a strong dependence of force field and water model used, but power-law relaxation in time is observed independent of the force field. Our results suggest the need for further experimental study of reverse micelles that can provide insight into the distribution and dynamics of shape fluctuations in these complex systems. PMID:23687916

  18. Probing the structure and dynamics of confined water in AOT reverse micelles.

    PubMed

    Martinez, Anna Victoria; Dominguez, Laura; Małolepsza, Edyta; Moser, Adam; Ziegler, Zack; Straub, John E

    2013-06-20

    Reverse micelles are attractive nanoscale systems used for the confinement of molecules in studies of structure and chemical reactions, including protein folding, and aggregation. The simulation of reverse micelles, in which a water "pool" is separated from a nonpolar bulk phase by a surfactant layer, poses significant challenges to empirical force fields due to the diversity of interactions between nonpolar, polar, and charged groups. We have explored the dependence of system density, reverse micelle structure, and water configurational relaxation times as a function of reverse micelle composition, including water:surfactant ratio, absolute number of water molecules, and force field using molecular dynamics simulations. The resulting structures and dynamics are found to depend more on the force field used than on varying interpretations of the water:surfactant ratio in terms of absolute size of the reverse micelle. Substantial deviations from spherical reverse micelle geometries are observed in all unrestrained simulations. Rotational anisotropy decay times and water residence times show a strong dependence on force field and water model used, but power-law relaxation in time is observed independent of the force field. Our results suggest the need for further experimental study of reverse micelles that can provide insight into the distribution and dynamics of shape fluctuations in these complex systems. PMID:23687916

  19. Therapeutic and scintigraphic applications of polymeric micelles: combination of chemotherapy and radiotherapy in hepatocellular carcinoma.

    PubMed

    Shih, Ying-Hsia; Peng, Cheng-Liang; Chiang, Ping-Fang; Lin, Wuu-Jyh; Luo, Tsai-Yueh; Shieh, Ming-Jium

    2015-01-01

    This study evaluated a multifunctional micelle simultaneously loaded with doxorubicin (Dox) and labeled with radionuclide rhenium-188 ((188)Re) as a combined radiotherapy and chemotherapy treatment for hepatocellular carcinoma. We investigated the single photon emission computed tomography, biodistribution, antitumor efficacy, and pathology of (188)Re-Dox micelles in a murine orthotopic luciferase-transfected BNL tumor cells hepatocellular carcinoma model. The single photon emission computed tomography and computed tomography images showed high radioactivity in the liver and tumor, which was in agreement with the biodistribution measured by γ-counting. In vivo bioluminescence images showed the smallest size tumor (P<0.05) in mice treated with the combined micelles throughout the experimental period. In addition, the combined (188)Re-Dox micelles group had significantly longer survival compared with the control, (188)ReO4 alone (P<0.005), and Dox micelles alone (P<0.01) groups. Pathohistological analysis revealed that tumors treated with (188)Re-Dox micelles had more necrotic features and decreased cell proliferation. Therefore, (188)Re-Dox micelles may enable combined radiotherapy and chemotherapy to maximize the effectiveness of treatment for hepatocellular carcinoma. PMID:26719687

  20. Evaluating bio-optical models to determine chlorophyll a from hyper spectral data in the turbid coastal waters of South Carolina

    NASA Astrophysics Data System (ADS)

    Hames, J. B.; Ali, K.

    2013-12-01

    Millions of people visit the beaches of South Carolina every year and the increasing utilization of the coastal waters is leading to the deterioration of water quality and the marine ecosystem. Ecological stress on these environments is reflected by the increase in the frequency and severity of Harmful Algal Blooms (HABs). This was evident during recent summer seasons particularly in the shallow nearshore waters of Long Bay, South Carolina, an open coast embayment on the South Atlantic Bight. These aspects threaten human and marine life. The early detection of HABs in the coastal waters requires more efficient and accurate monitoring tools. Remote sensing provides synoptic view of the entire Long Bay waters at high temporal coverage and allows resource managers to effectively map and monitor algal bloom development, near real time. Various remote sensing (RS) algorithms have been developed but were mostly calibrated to low resolution global data and or other specific sites. In the summer of 2013, a suite of measurements and water samples were collected from 15 locations along the nearshore waters of Long Bay using the Grice Laboratory R/V. In this study, we evaluate the efficiency of 10 bio-optical blue-green and NIR-red based RS models applied to GER 1500 hyper spectral reflectance data to predict chlorophyll a, a proxy for phytoplankton density, in the Long Bay waters of SC. Efficiency of the algorithms performance in the study site were tested through a least squares regression and residual analysis. Results show that among the selected suite of algorithms the blue green models by Darecki and Stramski (2004) produced R2 of 0.68 with RMSE=0.39μg/l, Oc4v4 model by O'Reilly et al. (2000) gave R2 of 0.62 with RMSE=0.73ug/l, and the Oc2v4 also by O'Reilly et al (2000) gave R2 of 0.69 with RMSE=0.65. Among the NIR-red models, Moses et al (2009) two-band algorithm produced R2 of 0.75 and RMSE=1.79, and the three-band version generated R2 of 0.81 and RMSE=2.25ug

  1. Biodegradable polymeric micelles encapsulated JK184 suppress tumor growth through inhibiting Hedgehog signaling pathway

    NASA Astrophysics Data System (ADS)

    Zhang, Nannan; Liu, Shichang; Wang, Ning; Deng, Senyi; Song, Linjiang; Wu, Qinjie; Liu, Lei; Su, Weijun; Wei, Yuquan; Xie, Yongmei; Gong, Changyang

    2015-01-01

    JK184 can specially inhibit Gli in the Hedgehog (Hh) pathway, which showed great promise for cancer therapeutics. For developing aqueous formulation and improving anti-tumor activity of JK184, we prepared JK184 encapsulated MPEG-PCL micelles by the solid dispersion method without using surfactants or toxic organic solvents. The cytotoxicity and cellular uptake of JK184 micelles were both increased compared with the free drug. JK184 micelles induced more apoptosis and blocked proliferation of Panc-1 and BxPC-3 tumor cells. In addition, JK184 micelles exerted a sustained in vitro release behavior and had a stronger inhibitory effect on proliferation, migration and invasion of HUVECs than free JK184. Furthermore, JK184 micelles had stronger tumor growth inhibiting effects in subcutaneous Panc-1 and BxPC-3 tumor models. Histological analysis showed that JK184 micelles improved anti-tumor activity by inducing more apoptosis, decreasing microvessel density and reducing expression of CD31, Ki67, and VEGF in tumor tissues. JK184 micelles showed a stronger inhibition of Gli expression in Hh signaling, which played an important role in pancreatic carcinoma. Furthermore, circulation time of JK184 in blood was prolonged after entrapment in polymeric micelles. Our results suggested that JK184 micelles are a promising drug candidate for treating pancreatic tumors with a highly inhibitory effect on Hh activity.JK184 can specially inhibit Gli in the Hedgehog (Hh) pathway, which showed great promise for cancer therapeutics. For developing aqueous formulation and improving anti-tumor activity of JK184, we prepared JK184 encapsulated MPEG-PCL micelles by the solid dispersion method without using surfactants or toxic organic solvents. The cytotoxicity and cellular uptake of JK184 micelles were both increased compared with the free drug. JK184 micelles induced more apoptosis and blocked proliferation of Panc-1 and BxPC-3 tumor cells. In addition, JK184 micelles exerted a sustained in

  2. Development and application of a remote sensing-based Chlorophyll-a concentration prediction model for complex coastal waters of Hong Kong

    NASA Astrophysics Data System (ADS)

    Nazeer, Majid; Nichol, Janet E.

    2016-01-01

    Despite recent advances in estimation of water quality parameters using satellite remote sensing, the estimation of Chlorophyll-a (Chl-a) has remained problematic due to optical complexity of coastal waters and imprecise atmospheric correction of imagery. Local environmental agencies require frequent measurement and monitoring of Chl-a over coastal regions at detailed level, for water quality assessment and control. To monitor Chl-a around the complex coastal waters of Hong Kong using remote sensing, 27 Landsat Thematic Mapper (TM) and Enhanced Thematic Mapper Plus (ETM+) images over a 13-year period from January 2000 to December 2012, were used, along with 120 in situ Chl-a samples. Atmospherically corrected Landsat TM/ETM+ bands 1-4 along with in situ Chl-a data were used to develop and validate regression models for a Chl-a concentration range of 0.3-13.0 μg/l. Validation results indicated that the ratio of band 3 (red, 0.63-0.69 μm) and the square of band 1 (blue, 0.45-0.52 μm), with correlation coefficient (R) of 0.89, Root Mean Square Error (RMSE) of 2.53 μg/l and Mean Absolute Error (MAE) of 1.02 μg/l was most capable of representing actual Chl-a concentrations. This is attributed to the differential response of the red and blue wavebands to the Chl-a signal. The study is considered more robust than previous studies of Chl-a retrieval, due to the much larger number of images and in situ samples used for model development and validation, as well as the different times of year, water quality zones, and wide range of Chl-a concentrations which were investigated. The robustness of the developed model was also tested by its application to monitoring an extensive red tide event. The results indicate that the developed model is capable of routine monitoring of such algal blooms which frequently occur from late summer to early autumn in Hong Kong and its adjacent coastal waters.

  3. Simulated laser fluorosensor signals from subsurface chlorophyll distributions

    NASA Technical Reports Server (NTRS)

    Venable, D. D.; Khatun, S.; Punjabi, A.; Poole, L.

    1986-01-01

    A semianalytic Monte Carlo model has been used to simulate laser fluorosensor signals returned from subsurface distributions of chlorophyll. This study assumes the only constituent of the ocean medium is the common coastal zone dinoflagellate Prorocentrum minimum. The concentration is represented by Gaussian distributions in which the location of the distribution maximum and the standard deviation are variable. Most of the qualitative features observed in the fluorescence signal for total chlorophyll concentrations up to 1.0 microg/liter can be accounted for with a simple analytic solution assuming a rectangular chlorophyll distribution function.

  4. The interaction of Co 2+ ions and sodium deoxycholate micelles

    NASA Astrophysics Data System (ADS)

    Sun, Y.; Yang, Z.-L.; Zhang, L.; Zhou, N.-F.; Weng, S.-F.; Wu, J.-G.

    2003-07-01

    To mimic the interaction between divalent metal ions and bile slats in vivo, two groups of coordination complex compounds, crystalline and gel-like, were synthesized in vitro by mixing the aqueous solutions of CoCl 2 with sodium deoxycholate (NaDC) at various concentrations. Structures and compositions of the compounds were investigated using FT-IR, EXAFS, XRD as well as elemental and ICP analysis, respectively. Then the interaction of Co 2+ with deoxycholate in solution was observed by laser light scattering (LLS), Transmission electronic microscope techniques and ICP analysis. Conclusions are (1) the crystalline complexes, Co (DC) 2·3H 2O were obtained by reaction of Co 2+ with mono-molecules of NaDC, and the gel-like complexes, Na nCo m(DC) n+2 m formed by reaction of Co 2+ with NaDC micelles. The gel-like complexes exhibit the non-stoichiometric character; (2) the coordination structures of carboxyl groups with Co 2+ were different between the crystalline and gel-like complexes. In Co(DC) 2·3H 2O complex, the carboxyl groups of deoxycholate coordinated with Co 2+ in chelating and pseudo-chelating modes, but that in bridge mode in the case of Na nCo m(DC) n+2 m complexes. The non-stoichiometric complexes of Na nCo m(DC) n+2 m are formed with a macromolecular structure through the Co 2+ bridges; (3) NaDC can increase the solubility of Co(DC) 2·3H 2O in aqueous solution, and larger micelles (30-80 nm diameter) formed in the supernate. It is a mixed micelle formed by Co 2+ ions bridges connecting with NaDC simple micelles. So these micelles are a new kind of micelle containing two kinds of metal ions; (4) these results are in agreement with those formed under physiological conditions in that the different states such as gel, precipitate, micelles of various structures are present in bile of gallbladder. An ideal model of the interaction between Co 2+ and bile salts in vivo has been proposed.

  5. The Distribution of Solubilized Molecules among Micelles.

    ERIC Educational Resources Information Center

    Miller, Dennis J.

    1978-01-01

    Conflicting views have been put forward on the derivation of the distribution of solubilized molecules among micelles. This stems from failure to consider the arrangement of the solubilized molecules in the micelles. In the treatment presented enthalpy effects are ignored as they are not amenable to a simple general theory. (Author/BB)

  6. Continental shelf fish production estimation from CZCS chlorophyll data

    NASA Technical Reports Server (NTRS)

    Iverson, Richard L.

    1989-01-01

    A method for ocean fish production estimation was proposed for development. The method was to use data acquired with the Coastal Zone Color Scanner, and processed into chlorophyll concentrations by the GSFC ocean Sciences Division, in combination with fish production and primary production data acquired from different ocean areas. A linear relation exits between annual fish production and annual phytoplankton carbon production for a wide range of coastal ocean environments. The uses of several existing algorithms which relate primary production to CZCS chlorophyll data as input to the fish production regression model is proposed. A question relating phytoplankton production to CZCS chlorophyll was obtained by Eppley (1984) using chlorophyll data obtained from field samples, equivalent to chlorophyll data obtained from CZCS imagery, and primary production data obtained from ship-board observations on a wide variety of coastal and open ocean environments. This equation was modified with additional data and was successfully tested using CZCS data and field chlorophyll and phytoplankton production data obtained from northeastern North American continental shelf waters and Atlantic open ocean waters. The modified Eppley (1984) relation also estimated phytoplankton annual carbon production in the Sargasso Sea within the confidence limits of a mean value obtained from the Eppley (1984) equation for oceanic waters that provide about 90 percent of total ocean primary production. The modified Eppley production formula applied to CZCS chlorophyll data obtained from several northeastern North American coastal environments gave phytoplankton annual carbon production values similar to the values used in the fish production regression equation.

  7. Molecular dynamics simulation of self-assembly of n-decyltrimethylammonium bromide micelles.

    PubMed

    Jorge, Miguel

    2008-06-01

    In this paper, a molecular dynamics simulation of surfactant self-assembly using realistic atomistic models is presented. The simulations are long enough to enable the observation of several processes leading to equilibrium, such as monomer addition and detachment, micelle dissolution, and micelle fusion. The self-assembly of DeTAB surfactants takes place in three stages: fast aggregation of monomers to form small disordered oligomers; ripening process by which larger aggregates grow at the expense of smaller ones; slower stage involving collisions between large micelles. The first two stages were described well by a simple kinetic model with a size-independent rate constant estimated from the self-diffusion coefficient and collision radius of an isolated monomer. The average cluster size, area per headgroup, degree of counterion dissociation, and critical micelle concentration estimated from the simulation are in reasonable agreement with experimental values. An all-atom and united-atom surfactant model were compared, and the results were seen to be almost independent of the choice of model. DeTAB micelles are spheroidal, with a hydrophobic core composed of tail atoms surrounded by a hydrophilic corona of head atoms. A Stern layer composed of bromide counterions was also identified. Water molecules solvate the counterions and the head atoms, penetrating into the micelle up to the location of the atom connecting the head to the aliphatic tail, in agreement with recent experimental observations.

  8. Specific tumor delivery of paclitaxel using glycolipid-like polymer micelles containing gold nanospheres.

    PubMed

    You, Jian; Wang, Zuhua; Du, Yongzhong; Yuan, Hong; Zhang, Peizun; Zhou, Jialin; Liu, Fei; Li, Chun; Hu, Fuqiang

    2013-06-01

    It is difficult for most of the drug delivery systems to really display a temporal and spatial release of entrapped drug once the systems are iv administrated. We hypothesized that the photothermal effect, mediated by a near-infrared (NIR) laser and hollow gold nanospheres (HAuNS), can modulate paclitaxel (PTX) release from polymer micelles, and further result in the enhanced antitumor activity of the micelles. We loaded PTX and HAuNS, which display strong plasmon absorption in the NIR region, into glycolipid-like polymer micelles with an excellent cell internalization capability. The surface of the micelles was conjugated successfully with a peptide, which has the specific-binding with EphB4, a member of the Eph family of receptor tyrosine kinases overexpressed on cell membrane of numerous tumors, to increase the delivery of PTX into tumor cells. Rapid and repetitive drug release from our polymer (HP-TCS) micelles could be readily achieved upon NIR laser irradiation. Our data demonstrated the specific delivery of HP-TCS micelles into positive-EphB4 tumors using a duel-tumor model after iv administration during the whole experiment process (1-48 h). Interestingly, significantly higher uptake of the micelles by SKOV3 tumors (positive-EphB4) than A549 tumors (negtive-EphB4) was observed, with increased ratio on experiment time. However, the specific cell uptake was observed only during the short incubation time (1-4 h) in vitro. Our data also indicated the treatment of tumor cells with the micelles followed by NIR laser irradiation showed significantly greater toxicity activity than the treatment with the micelles alone, free PTX and the micelles (without PTX loading) plus NIR laser irradiation. The enhanced toxicity activity to tumor cells should be attributed to the enhanced drug cellular uptake mediated by the glycolipid-like micelles, chemical toxicity of the released drug from the micelles due to the trigger of NIR laser, and the photothermal ablation under NIR

  9. Specific tumor delivery of paclitaxel using glycolipid-like polymer micelles containing gold nanospheres

    PubMed Central

    You, Jian; Wang, Zuhua; Du, Yongzhong; Yuan, Hong; Zhang, Peizun; Zhou, Jialin; Liu, Fei; Li, Chun; Hu, Fuqiang

    2014-01-01

    It is difficult for most of drug delivery system to really display a temporal and spatial release of entrapped drug once the systems are iv administrated. We hypothesized that the photothermal effect, mediated by a near-infrared (NIR) laser and hollow gold nanospheres (HAuNS), can modulate paclitaxel (PTX) release from polymer micelles, and further result in the enhanced antitumor activity of the micelles. We loaded PTX and HAuNS, which display strong plasmon absorption in the NIR region, into glycolipid-like polymer micelles with an excellent cell internalization capability. The surface of the micelles was conjugated successfully with a peptide, which has the specific-binding with EphB4, a member of the Eph family of receptor tyrosine kinases overexpressed on cell membrane of numerous tumors, to increase the delivery of PTX into tumor cells. Rapid and repetitive drug release from our polymer (HP-TCS) micelles could be readily achieved upon NIR laser irradiation. Our data demonstrated the specific-delivery of HPTCS micelles into positive-EphB4 tumors using a duel-tumor model after iv administration during the whole experiment process (1-48h). Interestingly, significantly higher uptake of the micelles by SKOV3 tumors (positive-EphB4) than A549 tumors (negtive-EphB4) was observed, with increased ratio on experiment time. However, the specific cell uptake was observed only during the short incubation time (1-4h) in vitro. Our data also indicated the treatment of tumor cells with the micelles followed by NIR laser irradiation showed significantly greater toxicity activity than the treatment with the micelles alone, free PTX and the micelles (without PTX loading) plus NIR laser irradiation. The enhanced toxicity activity to tumor cells should be attributed to the enhanced drug cellular uptake mediated by the glycolipid-like micelles, chemical toxicity of the released drug from the micelles due to the trigger of NIR laser, and the photothermal ablation under NIR laser

  10. Fractal structures in casting films from chlorophyll

    NASA Astrophysics Data System (ADS)

    Pedro, G. C.; Gorza, F. D. S.; de Souza, N. C.; Silva, J. R.

    2014-04-01

    Chlorophyll (Chl) molecules are important because they can act as natural light-harvesting devices during the photosynthesis. In addition, they have potential for application as component of solar cell. In this work, we have prepared casting films from chlorophyll (Chl) and demonstrated the occurrence of fractal structures when the films were submitted to different concentrations. By using optical microscopy and the box-count method, we have found that the fractal dimension is Df = 1.55. This value is close to predicted by the diffusion-limited aggregation (DLA) model. This suggests that the major mechanism - which determines the growth of the fractal structures from Chl molecules - is the molecular diffusion. Since the efficiencies of solar cells depend on the morphology of their interfaces, these finds can be useful to improve this kind of device.

  11. Biochemical characterization of the interactions between doxorubicin and lipidic GM1 micelles with or without paclitaxel loading

    PubMed Central

    Leonhard, Victoria; Alasino, Roxana V; Bianco, Ismael D; Garro, Ariel G; Heredia, Valeria; Beltramo, Dante M

    2015-01-01

    Doxorubicin (Dox) is an anthracycline anticancer drug with high water solubility, whose use is limited primarily due to significant side effects. In this study it is shown that Dox interacts with monosialoglycosphingolipid (GM1) ganglioside micelles primarily through hydrophobic interactions independent of pH and ionic strength. In addition, Dox can be incorporated even into GM1 micelles already containing highly hydrophobic paclitaxel (Ptx). However, it was not possible to incorporate Ptx into Dox-containing GM1 micelles, suggesting that Dox could be occupying a more external position in the micelles. This result is in agreement with a higher hydrolysis of Dox than of Ptx when micelles were incubated at alkaline pH. The loading of Dox into GM1 micelles was observed over a broad range of temperature (4°C–55°C). Furthermore, Dox-loaded micelles were stable in aqueous solutions exhibiting no aggregation or precipitation for up to 2 months when kept at 4°C–25°C and even after freeze–thawing cycles. Upon exposure to blood components, Dox-containing micelles were observed to interact with human serum albumin. However, the amount of human serum albumin that ended up being associated to the micelles was inversely related to the amount of Dox, suggesting that both could share their binding sites. In vitro studies on Hep2 cells showed that the cellular uptake and cytotoxic activity of Dox and Ptx from the micellar complexes were similar to those of the free form of these drugs, even when the micelle was covered with albumin. These results support the idea of the existence of different nano-domains in a single micelle and the fact that this micellar model could be used as a platform for loading and delivering hydrophobic and hydrophilic active pharmaceutical ingredients. PMID:26005348

  12. Selective intracellular delivery of proteasome inhibitors through pH-sensitive polymeric micelles directed to efficient antitumor therapy.

    PubMed

    Quader, S; Cabral, H; Mochida, Y; Ishii, T; Liu, X; Toh, K; Kinoh, H; Miura, Y; Nishiyama, N; Kataoka, K

    2014-08-28

    The ubiquitin-proteasome system is central in the regulation of cellular proteins controlling cell cycle progression and apoptosis, drawing much interest for developing effective targeted cancer therapies. Herein, we developed a novel pH-responsive polymeric-micelle-based carrier system to effectively deliver the proteasome inhibitor MG132 into cancer cells. MG132 is covalently bound to the block copolymer composed of polyethylene glycol (PEG) and polyaspartate through an acid-labile hydrazone bond. This bond is stable at physiological condition, but hydrolytically degradable in acidic compartments in the cell, such as late-endosomes and lysosomes, and thus, it was used for controlled release of MG132 after EPR-mediated preferential accumulation of the micelles into the tumor. MG132-loaded micelles have monodispersed size distribution with an average diameter of 45nm, and critical micelle concentration is well below 10(-7)M. In vitro studies against several cancer cell lines confirmed that MG132-loaded micelles retained the cytotoxic effect, and this activity was indeed due to the inhibition of proteasome by released MG132 from the micelles. Real-time in vitro confocal-microscopy experiments clearly indicated that MG132-conjugated micelles disintegrated only inside the target cells. By intravital confocal micro-videography, we also confirmed the prolonged circulation of MG132 loaded micelles in the bloodstream, which lead to tumor specific accumulation of micelles, as confirmed by in vivo imaging 24h after injection. These micelles showed significantly lower in vivo toxicity than free MG132, while achieving remarkable antitumor effect against a subcutaneous HeLa-luc tumor model. Our findings create a paradigm for future development of polymeric-micelle-based carrier system for other peptide aldehyde type proteasome inhibitors to make them effective cohort of the existing cancer therapeutic regiments. PMID:24892974

  13. Amphiphilic Copolymeric Micelles for Doxorubicin and Curcumin Co-Delivery to Reverse Multidrug Resistance in Breast Cancer.

    PubMed

    Lv, Li; Qiu, Kaifeng; Yu, Xiaoxia; Chen, Chuxiong; Qin, Fengchao; Shi, Yonghui; Ou, Jiebin; Zhang, Tao; Zhu, Hua; Wu, Junyan; Liu, Chunxia; Li, Guocheng

    2016-05-01

    Development of multidrug resistance against chemotherapeutic drugs is one of the major obstacles to successful cancer therapy in the clinic. Thus far, amphiphilic polymeric micelles and chemosensitizers have been used to overcome multidrug resistance in cancer. The goals of this study were to prepare poly(ethylene glycol)-bock-poly(lactide) (PEG(2k)-PLA(5k)) micelles for co-delivery of the chemotherapeutic drug doxorubicin (DOX) with a chemosensitizer curcumin (CUR), investigate the potential of the dual drug-loaded micelles ((DOX+CUR)-Micelles) to reverse multidrug resistance, and explore the underlying mechanisms. (DOX + CUR)-Micelles were prepared using an emulsion solvent evaporation method. The cellular uptake, drug efflux, down-regulation of P-glycoprotein expression and inhibition of ATP activity of (DOX+ CUR)-Micelles were studied in drug-resistant MCF-7/ADR cells. In vitro analyses demonstrated that (DOX + CUR)-Micelles were superior to free DOX, free drug combination (DOX + CUR), and DOX-loaded micelles in inhibiting proliferation of MCF-7/ADR cells. This effect of (DOX + CUR)-Micelles was partially attributable to their highest cellular uptake, lowest efflux rate of DOX, and strongest effects on down-regulation of P-glycoprotein and inhibition of ATP activity. Additionally, (DOX+CUR)-Micelles showed increased tumor accumulation and strong inhibitory effect on tumor growth in the xenograft model of drug-resistant MCF-7/ADR cells compared to that of other drug formulations. These results indicate that (DOX + CUR)-Micelles display potential for application in the therapy of drug-resistant breast carcinoma. PMID:27305819

  14. Chemical and biosynthetic studies of chlorophylls

    SciTech Connect

    Huster, M.S.

    1988-01-01

    Chlorophyll occurrence, structure, biosynthesis, and degradation are discussed. Degradation and ring cleavage of heme is also discussed. The author examines the formation of dihydrobiliverdins by alkaline hydrolysis of zinc(II) meso-trifluoroacetoxypheophoribides, as a possible model for chlorophyll catabolism. {sup 18}O{sub 2}-labelling experiments show that the dihydrobiliverdin terminal lactam oxygens are derived from two different dioxygen molecules, also analogous to the Two Oxygen Molecular mechanism observed in heme degradation. The initially obtained dihydrobiliverdin readily undergoes an isomeric structural transformation, which is proposed as a model for the P{sub R}-P{sub FR} interconversion of the light sensor pigment phytochrome. The generality of the ring-opening reaction is demonstrated with various chlorophyll-derived zinc(II) trifluoroacetoxychlorins, and side reactions of the isocyclic ring are discussed. The synthesis and properties of a chlorophyll-derived meso-oxochlorin are described. Facile one-electron oxidation, and its inhibition by protonation, is demonstrated by NMR, ESR, and cyclic voltammetry studies. Cyclic voltammetry is also used to measure redox potentials of a range of pheophorbide and meso-trifluoroacetoxypheophorbide metal complexes, including an oxochlorin nickel(II) complex. The results are presented of biosynthetic feeding studies of green sulfur bacteria with {sup 13}C- and {sup 14}C-labelled glutamate, glycine, and methionine. This study examines an unusual oxidation of a bacteriomethylpheophorbide 5-ethyl substituent, and describes attempts to elucidate the mechanism by {sup 18}O-labelling studies. Attempts to similarily derivatize a pyropheophorbide 5-methyl substituent are discussed.

  15. An improved procedure for determination of the mean aggregation number of micelles

    NASA Astrophysics Data System (ADS)

    Wu, Shuangyan; Tachiya, Masanori; Yan, Zhenning

    2015-03-01

    In this paper, a theory of fluorescence quenching in micelles which enables a dynamic approach to the evaluation of the aggregation numbers of micelles is presented. This method is based on a detailed kinetic model of quenching of fluorescent probe developed by Tachiya (1975, 1982) and takes into account that a part of quenchers are associated with micelles but the remaining quenchers are in the aqueous phase. The approach presented is an improvement on a previous fluorescence quenching method (Turro and Yekta, 1978) and is applied to determine the aggregation number of sodium dodecyl sulfonate (SAS) in aqueous dipeptide solution using cetylpyridinium chloride as quencher. The values of aggregation number and association constant for quencher-micelle association are presented.

  16. Ultrasonic relaxation studies of mixed micelles formed from alcohol-decyltrimethylammonium bromide-water

    SciTech Connect

    Jobe, D.J.; Verrall, R.E.; Skalski, B.

    1992-08-06

    This paper discusses how ultrasonic relaxation and conductance studies of alcohol (1-pentanol or 1-butanol)-DTAB-water mixed micelles reveal two relaxation frequencies related to the exchange of monomer surfactant and of alcohol between the micelles and the bulk phase. Conductance and time-resolved fluorescence measurements were used to obtain the alcohol distribution coefficients, micelle ionization, critical micellar concentration, and the alcohol and surfactant mean aggregation numbers. Using two models (Aniansson and Hall & Wyn-Jones), information about the forward and backward rate constants, polydispersity of the mixed micelles and the change in volumes of the two exchange processes are obtained and compared with 1-propanol-DTAB-water. Alcohol chain length influence on thermodynamics and kinetics is also discussed. 16 refs., 12 figs., 6 tabs.

  17. Black Sea spectral bio-optical models based on satellite data and their applications for assessment of spatial and temporal variability in waters transparency, chlorophyll a content and primary production

    NASA Astrophysics Data System (ADS)

    Churilova, T.; Suslin, V.

    2012-04-01

    Satellite observations of ocean color provide a unique opportunity in oceanography to assess productivity of the sea on different spatial and temporal scales. However it has been shown that the standard SeaWiFS algorithm generally overestimates summer chlorophyll concentration and underestimates pigment content during spring phytoplankton bloom in comparison with in situ measurements. It is required to develop regional algorithms which are based on biooptical characteristics typical for the Sea and consequently could be used for correct transformation of spectral features of water-leaving radiance to chlorophyll a concentrations (Chl), light absorption features of suspended and dissolved organic matter (CDM), downwelling light attenuation coefficient/euphotic zone depth (PAR1%) and rate of primary synthesis of organic substances (PP). The numerous measurements of light absorption spectra of phytoplankton, non-algal particles and coloured dissolved organic matter carried out since 1996 in different seasons and regions of the Black Sea allowed to make a parameterization of the light absorption by all optically active components. Taking into account regional peculiarities of the biooptical parameters, their difference between seasons, shallow and deep-waters, their depth-dependent variability within photosynthetic zone regional spectral models for estimation of chlorophyll a concentration (Chl Model), colored dissolved and suspended organic matter absorption (CDM Model), downwelling irradiance (PAR Model) and primary production (PP Model) have been developed based on satellite data. Test of validation of models showed appropriate accuracy of the models. The developed models have been applied for estimation of spatial/temporal variability of chlorophyll a, dissolved organic matter concentrations, waters transparency, euphotic zone depth and primary production based on SeaWiFS data. Two weeks averaged maps of spatial distribution of these parameters have been composed

  18. Chemical reactions in reverse micelle systems

    DOEpatents

    Matson, Dean W.; Fulton, John L.; Smith, Richard D.; Consani, Keith A.

    1993-08-24

    This invention is directed to conducting chemical reactions in reverse micelle or microemulsion systems comprising a substantially discontinuous phase including a polar fluid, typically an aqueous fluid, and a microemulsion promoter, typically a surfactant, for facilitating the formation of reverse micelles in the system. The system further includes a substantially continuous phase including a non-polar or low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and which is generally a water-insoluble fluid in a near critical or supercritical state. Thus, the microemulsion system is maintained at a pressure and temperature such that the density of the non-polar or low-polarity fluid exceeds the critical density thereof. The method of carrying out chemical reactions generally comprises forming a first reverse micelle system including an aqueous fluid including reverse micelles in a water-insoluble fluid in the supercritical state. Then, a first reactant is introduced into the first reverse micelle system, and a chemical reaction is carried out with the first reactant to form a reaction product. In general, the first reactant can be incorporated into, and the product formed in, the reverse micelles. A second reactant can also be incorporated in the first reverse micelle system which is capable of reacting with the first reactant to form a product.

  19. Ocean Chlorophyll Studies from a U-2 Aircraft Platform

    NASA Technical Reports Server (NTRS)

    Kim, H. H.; Mcclain, C. R.; Blaine, L. R.; Hart, W. D.; Atkinson, L. P.; Yoder, J. A.

    1979-01-01

    Chlorophyll gradient maps of large ocean areas were generated from U-2 ocean color scanner data obtained over test sites in the Pacific and Atlantic Oceans. The delineation of oceanic features using the upward radiant intensity relies on an analysis method which presupposes that radiation backscattered from the atmosphere and ocean surface can be properly modeled using a measurement made at 778 nm. An estimation of the chlorophyll concentration was performed by properly ratioing radiances measured at 472 nm and 548 nm after removing the atmospheric effects. The correlation between the remotely sensed data and in-situ surface chlorophyll measurements was validated in two sets of data. The results show that the correlation between the in-situ measured chlorophyll and the derived quantity is a negative exponential function and the correlation coefficient was calculated to be -0.965.

  20. Chlorophyll 'A' in the Northern Canary box. Retrieving of Total Chlorophyll Content From Sewifs Data.

    NASA Astrophysics Data System (ADS)

    Perez-Marrero, J.; Maroto, L.; Godoy, J. M.; Cianca, A.; Villagarcia, M.; Rueda, M. J.; Llinas, O.

    2001-12-01

    We have studied the performance of several empirical algorithms for the determination of chlorophyll 'a' from satellites by comparing their results to the fluorometric measuremens made during four cruises carried out during CANIGO project. These campaigns encopassed all seasons to the north of the Canarian Archipelago. The in situ data set was complemented by ESTOC monthly measurements for the same period. The comparison of satellite derived information with the surface measurements allows for the selection of the most suitable algorithm for this area, It has been also posible to stablish a model for the seasonal behavoir of the chlorophyll 'a' profiles and the total amount of this pigment. We have also studied the relationships between surface concentration and total columnar amount of chlorophyll 'a' and also between seawifs data and total chlorophyll content. In view of the results of the analisys performed we established a locally enhanced method for estimating total phytoplanktonic biomass from seawifs data, together with the accuracy level and aplicabilty conditions of such estimation. The biomass obtained from satellite together with light conditions were used to estimate the primary productivity of these oligotrophic waters.

  1. Rheological properties of polyoxyethylene cholesteryl ether wormlike micelles in aqueous system.

    PubMed

    Shrestha, Rekha Goswami; Sakai, Kenichi; Sakai, Hideki; Abe, Masahiko

    2011-03-31

    Polyoxyethylene cholesteryl ether (ChEO(20)) nonionic surfactant self-assembles into spherical micelles above the critical micelle concentration in water. An ordering of micelles takes place with an increase in surfactant concentration and forms a micellar cubic phase with the space group Pm3n at ∼30%. Cocamid methyl MEA (designated as C-11S) cosurfactant is soluble at the palisade layer of the ChEO(20) micelle as a result; the curvature of the aggregates tends to decrease and favors sphere-to-rod transition. The axial length of the rod increases with C-11S concentration, and after a certain concentration, elongated micelles entangle with each other, forming a transient network of wormlike micelles. Viscosity increases by 5 orders of magnitude. The zero-shear viscosity (η(0)) versus C-11S concentration curve shows a peak, and the position of the peak shifts toward the right (at higher concentration of C-11S) when the concentration of ChEO(20) in water is increased from 10 to 15%. On the other hand, the peak position shifts toward the left with a decrease in the ethylene oxide (EO) chain of the surfactant, i.e., in the ChEO(15) system. Viscosity increases only slightly with a longer EO chain ChEO(30) system, and it does not show any viscoelastic properties. These wormlike micelles exhibited viscoelastic behavior and could be described by the Maxwell mechanical model with a single stress relaxation mode that is sensitive to temperature. Viscosity and relaxation time were first increased and then decreased, but the plateau modulus increased continuously upon heating. These observations revealed that micelles first grew with temperature and then branched. Dynamic rheology and small-angle X-ray scattering (SAXS) further support the rheology data.

  2. A 502-Base Free-Solution Electrophoretic DNA Sequencing Method Using End-Attached Wormlike Micelles.

    PubMed

    Istivan, Stephen B; Bishop, Daniel K; Jones, Angela L; Grosser, Shane T; Schneider, James W

    2015-11-17

    We demonstrate that the use of wormlike nonionic micelles as drag-tags in end-labeled free-solution electrophoresis ("micelle-ELFSE") provides single-base resolution of Sanger sequencing products up to 502 bases in length, a nearly 2-fold improvement over reported ELFSE separations. "CiEj" running buffers containing 48 mM C12E5, 6 mM C10E5, and 3 M urea (32.5 °C) form wormlike micelles that provide a drag equivalent to an uncharged DNA fragment with a length (α) of 509 bases (effective Rh = 27 nm). Runtime in a 40 cm capillary (30 kV) was 35 min for elution of all products down to the 26-base primer. We also show that smaller Triton X-100 micelles give a read length of 103 bases in a 4 min run, so that a combined analysis of the Sanger products using the two buffers in separate capillaries could be completed in 14 min for the full range of lengths. A van Deemter analysis shows that resolution is limited by diffusion-based peak broadening and wall adsorption. Effects of drag-tag polydispersity are not observed, despite the inherent polydispersity of the wormlike micelles. We ascribe this to a stochastic size-sampling process that occurs as micelle size fluctuates rapidly during the runtime. A theoretical model of the process suggests that fluctuations occur with a time scale less than 10 ms, consistent with the monomer exchange process in nonionic micelles. The CiEj buffer has a low viscosity (2.7 cP) and appears to be semidilute in micelle concentration. The large drag-tag size of the CiEj buffers leads to steric segregation of the DNA and tag for short fragments and attendant mobility shifts.

  3. A 502-Base Free-Solution Electrophoretic DNA Sequencing Method Using End-Attached Wormlike Micelles.

    PubMed

    Istivan, Stephen B; Bishop, Daniel K; Jones, Angela L; Grosser, Shane T; Schneider, James W

    2015-11-17

    We demonstrate that the use of wormlike nonionic micelles as drag-tags in end-labeled free-solution electrophoresis ("micelle-ELFSE") provides single-base resolution of Sanger sequencing products up to 502 bases in length, a nearly 2-fold improvement over reported ELFSE separations. "CiEj" running buffers containing 48 mM C12E5, 6 mM C10E5, and 3 M urea (32.5 °C) form wormlike micelles that provide a drag equivalent to an uncharged DNA fragment with a length (α) of 509 bases (effective Rh = 27 nm). Runtime in a 40 cm capillary (30 kV) was 35 min for elution of all products down to the 26-base primer. We also show that smaller Triton X-100 micelles give a read length of 103 bases in a 4 min run, so that a combined analysis of the Sanger products using the two buffers in separate capillaries could be completed in 14 min for the full range of lengths. A van Deemter analysis shows that resolution is limited by diffusion-based peak broadening and wall adsorption. Effects of drag-tag polydispersity are not observed, despite the inherent polydispersity of the wormlike micelles. We ascribe this to a stochastic size-sampling process that occurs as micelle size fluctuates rapidly during the runtime. A theoretical model of the process suggests that fluctuations occur with a time scale less than 10 ms, consistent with the monomer exchange process in nonionic micelles. The CiEj buffer has a low viscosity (2.7 cP) and appears to be semidilute in micelle concentration. The large drag-tag size of the CiEj buffers leads to steric segregation of the DNA and tag for short fragments and attendant mobility shifts. PMID:26455271

  4. A Pyrene@Micelle Sensor for Fluorescent Oxygen Sensing

    PubMed Central

    Yuan, Yan-xia; Peng, Hong-shang; Ping, Jian-tao; Wang, Xiao-hui; You, Fang-tian

    2015-01-01

    For most fluorescent oxygen sensors developed today, their fabrication process is either time-consuming or needs specialized knowledge. In this work, a robust fluorescent oxygen sensor is facilely constructed by dissolving pyrene molecules into CTAB aqueous solution. The as-prepared pyrene@micelle sensors have submicron-sized diameter, and the concentration of utilized pyrene can be reduced as low as 0.8 mM but still can exhibit dominant excimer emission. The excimer fluorescence is sensitive to dissolved oxygen in both intensity and lifetime, and the respective Stern-Volmer plot follows a nonlinear behavior justified by a two-site model. Because of the merits of large Stokes shift (~140 nm), easy fabrication, and robustness, the pyrene@micelle sensors are very attractive for practical determination of oxygen. PMID:26539471

  5. Biodegradable micelles enhance the antiglioma activity of curcumin in vitro and in vivo.

    PubMed

    Zheng, Songping; Gao, Xiang; Liu, Xiaoxiao; Yu, Ting; Zheng, Tianying; Wang, Yi; You, Chao

    2016-01-01

    Curcumin (Cur), a natural polyphenol of Curcuma longa, has been recently reported to possess antitumor activities. However, due to its poor aqueous solubility and low biological availability, the clinical application of Cur is quite limited. The encapsulation of hydrophobic drugs into nanoparticles is an effective way to improve their pharmaceutical activities. In this research, nanomicelles loaded with Cur were formulated by a self-assembly method with biodegradable monomethoxy poly(ethylene glycol)-poly(lactide) copolymers (MPEG-PLAs). After encapsulation, the cellular uptake was increased and Cur could be released from MPEG-PLA micelles in a sustained manner. The Cur-loaded MPEG-PLA micelles (Cur/MPEG-PLA micelles) exhibited an enhanced toxicity on C6 and U251 glioma cells and induced more apoptosis on C6 glioma cells compared with free Cur. Moreover, the therapy efficiency of Cur/MPEG-PLA micelles was evaluated at length on a nude mouse model bearing glioma. The Cur/MPEG-PLA micelles were more effective on suppressing tumor growth compared with free Cur, which indicated that Cur/MPEG-PLA micelles improved the antiglioma activity of Cur in vivo. The results of immunohistochemical and immunofluorescent analysis indicated that the induction of apoptosis, antiangiogenesis, and inhibition of cell proliferation may contribute to the improvement in antiglioma effects. Our data suggested that Cur/MPEG-PLA may have potential clinic applications in glioma therapy. PMID:27354801

  6. Biodegradable micelles enhance the antiglioma activity of curcumin in vitro and in vivo

    PubMed Central

    Zheng, Songping; Gao, Xiang; Liu, Xiaoxiao; Yu, Ting; Zheng, Tianying; Wang, Yi; You, Chao

    2016-01-01

    Curcumin (Cur), a natural polyphenol of Curcuma longa, has been recently reported to possess antitumor activities. However, due to its poor aqueous solubility and low biological availability, the clinical application of Cur is quite limited. The encapsulation of hydrophobic drugs into nanoparticles is an effective way to improve their pharmaceutical activities. In this research, nanomicelles loaded with Cur were formulated by a self-assembly method with biodegradable monomethoxy poly(ethylene glycol)-poly(lactide) copolymers (MPEG-PLAs). After encapsulation, the cellular uptake was increased and Cur could be released from MPEG-PLA micelles in a sustained manner. The Cur-loaded MPEG-PLA micelles (Cur/MPEG-PLA micelles) exhibited an enhanced toxicity on C6 and U251 glioma cells and induced more apoptosis on C6 glioma cells compared with free Cur. Moreover, the therapy efficiency of Cur/MPEG-PLA micelles was evaluated at length on a nude mouse model bearing glioma. The Cur/MPEG-PLA micelles were more effective on suppressing tumor growth compared with free Cur, which indicated that Cur/MPEG-PLA micelles improved the antiglioma activity of Cur in vivo. The results of immunohistochemical and immunofluorescent analysis indicated that the induction of apoptosis, antiangiogenesis, and inhibition of cell proliferation may contribute to the improvement in antiglioma effects. Our data suggested that Cur/MPEG-PLA may have potential clinic applications in glioma therapy. PMID:27354801

  7. Dynamics of micelle-nanoparticle systems undergoing shear. A coarse-grained molecular dynamics approach

    SciTech Connect

    Rolfe, Bryan A.; Chun, Jaehun; Joo, Yong L.

    2013-09-05

    Recent experimental work has shown that polymeric micelles can template nanoparticles via interstitial sites in shear-ordered micelle solutions. In the current study, we report simulation results based on a coarse-grained molecular dynamics (CGMD) model of a solvent/polymer/nanoparticle system. Our results demonstrate the importance of polymer concentration and the micelle corona length in 2D shear-ordering of neat block copolymer solutions. Although our results do not show strong 3D ordering during shear, we find that cessation of shear allows the system to relax into a 3D configuration of greater order than without shear. It is further shown that this post-shear relaxation is strongly dependent on the length of the micelle corona. For the first time, we demonstrate the presence and importance of a flow disturbance surrounding micelles in simple shear flow at moderate Péclet numbers. This disturbance is similar to what is observed around simulated star polymers and ellipsoids. The extent of the flow disturbance increases as expected with a longer micelle corona length. It is further suggested that without proper consideration of these dynamics, a stable nanoparticle configuration would be difficult to obtain.

  8. Polysaccharide-Based Micelles for Drug Delivery

    PubMed Central

    Zhang, Nan; Wardwell, Patricia R.; Bader, Rebecca A.

    2013-01-01

    Delivery of hydrophobic molecules and proteins has been an issue due to poor bioavailability following administration. Thus, micelle carrier systems are being investigated to improve drug solubility and stability. Due to problems with toxicity and immunogenicity, natural polysaccharides are being explored as substitutes for synthetic polymers in the development of new micelle systems. By grafting hydrophobic moieties to the polysaccharide backbone, self-assembled micelles can be readily formed in aqueous solution. Many polysaccharides also possess inherent bioactivity that can facilitate mucoadhesion, enhanced targeting of specific tissues, and a reduction in the inflammatory response. Furthermore, the hydrophilic nature of some polysaccharides can be exploited to enhance circulatory stability. This review will highlight the advantages of polysaccharide use in the development of drug delivery systems and will provide an overview of the polysaccharide-based micelles that have been developed to date. PMID:24300453

  9. Micelle Catalysis of an Aromatic Substitution Reaction

    ERIC Educational Resources Information Center

    Corsaro, Gerald; Smith J. K.

    1976-01-01

    Describes an experiment in which the iodonation of aniline reaction is shown to undergo catalysis in solution of sodium lauryl sulfate which forms micelles with negatively charged pseudo surfaces. (MLH)

  10. Limitations on relating ocean surface chlorophyll to productivity

    NASA Technical Reports Server (NTRS)

    Volk, Tyler

    1987-01-01

    An important potential use of ocean color chlorophyll data is to determine other important properties of the marine biosphere, such as primary productivity, new production, and particulate fluxes at spatial scales larger and temporal scales longer than those possible with ground-based observations. Such determinations will likely progress from relatively simple empirical correlations to algorithms that are actually predictive models of ecosystem dynamics. As an example, this paper demonstrates how an empirical correlation between nitrate concentration and new production can be understood by a simple productivity model. Several models are then constructed to examine the functional relationship between total production and surface chlorophyll. The empirical correlation is substantially different than the analogous relation in the model. Understanding the relationship between surface chlorophyll and productivity on a global scale will probably require families of models for various marine ecosystems.

  11. Generation of a Chiral Giant Micelle.

    PubMed

    Ito, Thiago H; Salles, Airton G; Priebe, Jacks P; Miranda, Paulo C M L; Morgon, Nelson H; Danino, Dganit; Mancini, Giovanna; Sabadini, Edvaldo

    2016-08-23

    Over the past few years, chiral supramolecular assemblies have been successfully used for recognition, sensing and enantioselective transformations. Several approaches are available to control chirality of discrete assemblies (e.g., cages and capsules), but few are efficient in assuring chirality for micellar aggregates. Optically active amino acid-derived surfactants are commonly used to generate chiral spherical micelles. To circumvent this limitation, we benefited from the uniaxial growth of spherical micelles into long cylindrical micelles usually called wormlike or giant micelles, upon the addition of cosolutes. This paper describes the unprecedented formation of chiral giant micelles in aqueous solutions of cetyltrimethylammonium bromide (CTAB) upon increasing addition of enantiopure sodium salt of 1,1'-bi-2-naphthol (Na-binaphtholate) as a cosolute. Depending on the concentrations of CTAB and Na-binaphtholate, chiral gel-like systems are obtained. The transition from spherical to giant micellar structures was probed using rheology, cryo-transmission electron microscopy, polarimetry, and electronic circular dichroism (CD). CD can be effectively used to monitor the incorporation of Na-binaphtholate into the micelle palisade as well as to determine its transition to giant micellar structures. Our approach expands the scope for chirality induction in micellar aggregates bringing the possibility to generate "smart" chiral systems and an alternative asymmetric chiral environment to perform enantioselective transformations. PMID:27499127

  12. Colloidal Wormlike Micelles with Highly Ferromagnetic Properties.

    PubMed

    Zhao, Wenrong; Dong, Shuli; Hao, Jingcheng

    2015-10-20

    For the first time, a new fabrication method for manipulating the ferromagnetic property of molecular magnets by forming wormlike micelles in magnetic-ionic-liquid (mag-IL) complexes is reported. The ferromagnetism of the mag-IL complexes was enhanced 4-fold because of the formation of wormlike micelles, presenting new evidence for the essence of magnetism generation at a molecular level. Characteristics such as morphology and magnetic properties of the wormlike micelle gel were investigated in detail by cryogenic transmission electron microscopy (Cryo-TEM), rheological measurements, circular dichroism (CD), FT-IR spectra, and the superconducting quantum interference device method (SQUID). An explanation of ferromagnetism elevation from the view of the molecular (ionic) distribution is also given. For the changes of magnetic properties (ferromagnetism elevation) in the wormlike micelle systems, the ability of CTAFe in magnetizing AzoNa4 (or AzoH4) can be ascribed to an interplay of the magnetic [FeCl3Br](-) ions both in the Stern layer and in the cores of the wormlike micelles. Formation of colloidal aggregates, i.e., wormlike micelles, provides a new strategy to tune the magnetic properties of novel molecular magnets. PMID:26411638

  13. Cellular uptake and trafficking of polydiacetylene micelles

    NASA Astrophysics Data System (ADS)

    Gravel, Edmond; Thézé, Benoit; Jacques, Isabelle; Anilkumar, Parambath; Gombert, Karine; Ducongé, Frédéric; Doris, Eric

    2013-02-01

    Polydiacetylene (PDA) micelles coated with either carboxylate-, ammonium-, or methoxy-polyethyleneglycol (PEG) chains were assembled and loaded with a fluorescent dye (DiO). Their interaction with MCF-7 human breast tumor cells was investigated by epi-fluorescence microscopy and fluorescence-activated cell sorting (FACS) to determine their internalization pathway and intracellular fate. It was found that the ionic character of the micelles influenced their internalization kinetics through a caveolae-mediated pathway and that all micelle types behaved somewhat similarly inside cells.Polydiacetylene (PDA) micelles coated with either carboxylate-, ammonium-, or methoxy-polyethyleneglycol (PEG) chains were assembled and loaded with a fluorescent dye (DiO). Their interaction with MCF-7 human breast tumor cells was investigated by epi-fluorescence microscopy and fluorescence-activated cell sorting (FACS) to determine their internalization pathway and intracellular fate. It was found that the ionic character of the micelles influenced their internalization kinetics through a caveolae-mediated pathway and that all micelle types behaved somewhat similarly inside cells. Electronic supplementary information (ESI) available: Detailed synthetic procedures and supplementary figures. See DOI: 10.1039/c2nr34149b

  14. Polymeric micelles for acyclovir drug delivery.

    PubMed

    Sawdon, Alicia J; Peng, Ching-An

    2014-10-01

    Polymeric prodrug micelles for delivery of acyclovir (ACV) were synthesized. First, ACV was used directly to initiate ring-opening polymerization of ɛ-caprolactone to form ACV-polycaprolactone (ACV-PCL). Through conjugation of hydrophobic ACV-PCL with hydrophilic methoxy poly(ethylene glycol) (MPEG) or chitosan, polymeric micelles for drug delivery were formed. (1)H NMR, FTIR, and gel permeation chromatography were employed to show successful conjugation of MPEG or chitosan to hydrophobic ACV-PCL. Through dynamic light scattering, zeta potential analysis, transmission electron microscopy, and critical micelle concentration (CMC), the synthesized ACV-tagged polymeric micelles were characterized. It was found that the average size of the polymeric micelles was under 200nm and the CMCs of ACV-PCL-MPEG and ACV-PCL-chitosan were 2.0mgL(-1) and 6.6mgL(-1), respectively. The drug release kinetics of ACV was investigated and cytotoxicity assay demonstrates that ACV-tagged polymeric micelles were non-toxic.

  15. Particulate models of photosynthesis: Technical progress report, 1 September 1986--28 February 1989

    SciTech Connect

    Seely, G.R.

    1988-02-01

    The objective of the research is to develop photochemical energy conversion model systems based on chlorophyll adsorbed to particles of polyethylene swollen with tetradecane. A number of amphiphiles derived from histamine have been synthesized, and tested with chlorophyll on polyethylene particles. They presumably ligate chlorophyll with the imidazole group, and some are capable of accepting electrons from the singlet excited state of the pigment. During the past year, the ability of chlorophyll to interact with cationic inverted micelles of dodecylpyridium iodide in toluene has been established, primarily by NMR chemical shift measurements. A presumption that a similar association exists within polyethylene- tetradecane particles has been supported, through mainly by indirect means. There is increased interest in nitroaromatic disulfides as potentially reversible oxidants for chlorophyll in the particulate system. One of them, 2,2'-dithiobis (5-nitropyridine), reacts with chlorophyll photochemically to form derivatives with reduced fluorescence, which appear to be covalently-linked donor-acceptor complexes. Experimental procedures have been tested for correcting fluorescence spectra and estimating quantum yields in highly scattering media, with the xanthene dye, 2'7'-dichlorofluorescein, in TiO/sub 2/ suspensions. Collaborative efforts in fluorescence determination and electrochemistry have continued. 40 refs., 10 figs., 2 tabs.

  16. Interplay between micelle formation and waterlike phase transitions

    NASA Astrophysics Data System (ADS)

    Heinzelmann, G.; Figueiredo, W.; Girardi, M.

    2010-02-01

    A lattice model for amphiphilic aggregation in the presence of a structured waterlike solvent is studied through Monte Carlo simulations. We investigate the interplay between the micelle formation and the solvent phase transition in two different regions of temperature-density phase diagram of pure water. A second order phase transition between the gaseous (G) and high density liquid (HDL) phases that occurs at very high temperatures, and a first order phase transition between the low density liquid (LDL) and (HDL) phases that takes place at lower temperatures. In both cases, we find the aggregate size distribution curve and the critical micellar concentration as a function of the solvent density across the transitions. We show that micelle formation drives the LDL-HDL first order phase transition to lower solvent densities, while the transition G-HDL is driven to higher densities, which can be explained by the markedly different degrees of micellization in both cases. The diffusion coefficient of surfactants was also calculated in the LDL and HDL phases, changing abruptly its behavior due to the restructuring of waterlike solvent when we cross the first order LDL-HDL phase transition. To understand such behavior, we calculate the solvent density and the number of hydrogen bonds per water molecule close to micelles. The curves of the interfacial solvent density and the number of hydrogen bonds per water molecule in the first hydration signal a local phase change of the interfacial water, clarifying the diffusion mechanism of free surfactants in the solvent.

  17. Polymeric micelles encapsulating photosensitizer: structure/photodynamic therapy efficiency relation.

    PubMed

    Gibot, Laure; Lemelle, Arnaud; Till, Ugo; Moukarzel, Béatrice; Mingotaud, Anne-Françoise; Pimienta, Véronique; Saint-Aguet, Pascale; Rols, Marie-Pierre; Gaucher, Mireille; Violleau, Frédéric; Chassenieux, Christophe; Vicendo, Patricia

    2014-04-14

    Various polymeric micelles were formed from amphiphilic block copolymers, namely, poly(ethyleneoxide-b-ε-caprolactone), poly(ethyleneoxide-b-d,l-lactide), and poly(ethyleneoxide-b-styrene). The micelles were characterized by static and dynamic light scattering, electron microscopy, and asymmetrical flow field-flow fractionation. They all displayed a similar size close to 20 nm. The influence of the chemical structure of the block copolymers on the stability upon dilution of the polymeric micelles was investigated to assess their relevance as carriers for nanomedicine. In the same manner, the stability upon aging was assessed by FRET experiments under various experimental conditions (alone or in the presence of blood proteins). In all cases, a good stability over 48 h for all systems was encountered, with PDLLA copolymer-based systems being the first to release their load slowly. The cytotoxicity and photocytotoxicity of the carriers were examined with or without their load. Lastly, the photodynamic activity was assessed in the presence of pheophorbide a as photosensitizer on 2D and 3D tumor cell culture models, which revealed activity differences between the 2D and 3D systems. PMID:24552313

  18. Polymeric micelles encapsulating photosensitizer: structure/photodynamic therapy efficiency relation.

    PubMed

    Gibot, Laure; Lemelle, Arnaud; Till, Ugo; Moukarzel, Béatrice; Mingotaud, Anne-Françoise; Pimienta, Véronique; Saint-Aguet, Pascale; Rols, Marie-Pierre; Gaucher, Mireille; Violleau, Frédéric; Chassenieux, Christophe; Vicendo, Patricia

    2014-04-14

    Various polymeric micelles were formed from amphiphilic block copolymers, namely, poly(ethyleneoxide-b-ε-caprolactone), poly(ethyleneoxide-b-d,l-lactide), and poly(ethyleneoxide-b-styrene). The micelles were characterized by static and dynamic light scattering, electron microscopy, and asymmetrical flow field-flow fractionation. They all displayed a similar size close to 20 nm. The influence of the chemical structure of the block copolymers on the stability upon dilution of the polymeric micelles was investigated to assess their relevance as carriers for nanomedicine. In the same manner, the stability upon aging was assessed by FRET experiments under various experimental conditions (alone or in the presence of blood proteins). In all cases, a good stability over 48 h for all systems was encountered, with PDLLA copolymer-based systems being the first to release their load slowly. The cytotoxicity and photocytotoxicity of the carriers were examined with or without their load. Lastly, the photodynamic activity was assessed in the presence of pheophorbide a as photosensitizer on 2D and 3D tumor cell culture models, which revealed activity differences between the 2D and 3D systems.

  19. Predicting proton titration in cationic micelle and bilayer environments

    SciTech Connect

    Morrow, Brian H.; Shen, Jana K.; Eike, David M.; Murch, Bruce P.; Koenig, Peter H.

    2014-08-28

    Knowledge of the protonation behavior of pH-sensitive molecules in micelles and bilayers has significant implications in consumer product development and biomedical applications. However, the calculation of pK{sub a}’s in such environments proves challenging using traditional structure-based calculations. Here we apply all-atom constant pH molecular dynamics with explicit ions and titratable water to calculate the pK{sub a} of a fatty acid molecule in a micelle of dodecyl trimethylammonium chloride and liquid as well as gel-phase bilayers of diethyl ester dimethylammonium chloride. Interestingly, the pK{sub a} of the fatty acid in the gel bilayer is 5.4, 0.4 units lower than that in the analogous liquid bilayer or micelle, despite the fact that the protonated carboxylic group is significantly more desolvated in the gel bilayer. This work illustrates the capability of all-atom constant pH molecular dynamics in capturing the delicate balance in the free energies of desolvation and Coulombic interactions. It also shows the importance of the explicit treatment of ions in sampling the protonation states. The ability to model dynamics of pH-responsive substrates in a bilayer environment is useful for improving fabric care products as well as our understanding of the side effects of anti-inflammatory drugs.

  20. Predicting proton titration in cationic micelle and bilayer environments

    NASA Astrophysics Data System (ADS)

    Morrow, Brian H.; Eike, David M.; Murch, Bruce P.; Koenig, Peter H.; Shen, Jana K.

    2014-08-01

    Knowledge of the protonation behavior of pH-sensitive molecules in micelles and bilayers has significant implications in consumer product development and biomedical applications. However, the calculation of pKa's in such environments proves challenging using traditional structure-based calculations. Here we apply all-atom constant pH molecular dynamics with explicit ions and titratable water to calculate the pKa of a fatty acid molecule in a micelle of dodecyl trimethylammonium chloride and liquid as well as gel-phase bilayers of diethyl ester dimethylammonium chloride. Interestingly, the pKa of the fatty acid in the gel bilayer is 5.4, 0.4 units lower than that in the analogous liquid bilayer or micelle, despite the fact that the protonated carboxylic group is significantly more desolvated in the gel bilayer. This work illustrates the capability of all-atom constant pH molecular dynamics in capturing the delicate balance in the free energies of desolvation and Coulombic interactions. It also shows the importance of the explicit treatment of ions in sampling the protonation states. The ability to model dynamics of pH-responsive substrates in a bilayer environment is useful for improving fabric care products as well as our understanding of the side effects of anti-inflammatory drugs.

  1. Predicting proton titration in cationic micelle and bilayer environments

    PubMed Central

    Morrow, Brian H.; Eike, David M.; Murch, Bruce P.; Koenig, Peter H.; Shen, Jana K.

    2014-01-01

    Knowledge of the protonation behavior of pH-sensitive molecules in micelles and bilayers has significant implications in consumer product development and biomedical applications. However, the calculation of pKa’s in such environments proves challenging using traditional structure-based calculations. Here we apply all-atom constant pH molecular dynamics with explicit ions and titratable water to calculate the pKa of a fatty acid molecule in a micelle of dodecyl trimethylammonium chloride and liquid as well as gel-phase bilayers of diethyl ester dimethylammonium chloride. Interestingly, the pKa of the fatty acid in the gel bilayer is 5.4, 0.4 units lower than that in the analogous liquid bilayer or micelle, despite the fact that the protonated carboxylic group is significantly more desolvated in the gel bilayer. This work illustrates the capability of all-atom constant pH molecular dynamics in capturing the delicate balance in the free energies of desolvation and Coulombic interactions. It also shows the importance of the explicit treatment of ions in sampling the protonation states. The ability to model dynamics of pH-responsive substrates in a bilayer environment is useful for improving fabric care products as well as our understanding of the side effects of anti-inflammatory drugs. PMID:25173037

  2. Generic calibration of chlorophyll meter values for leaf chlorophyll content using spectral reflectances and transmittances

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Minolta SPAD-502 chlorophyll meter measures leaf transmittances at 650 and 940 nm to provide a relative value of total chlorophyll a and b contents based on Beer's Law. Many studies have calibrated chlorophyll meter values with measured chlorophyll contents, and generally found that different e...

  3. Relationship between chlorophyll density and SPAD chlorophyll meter reading for Jerusalem artichoke (Helianthus tuberosus L.)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Chlorophyll is an indicator of crop health and productivity. Measuring chlorophyll is usually done directly and requires significant time and resources. Indirect measurement of chlorophyll density using a handheld portable chlorophyll meter can reduce time. However, this information is very limit...

  4. Actively-targeted polyion complex micelles stabilized by cholesterol and disulfide cross-linking for systemic delivery of siRNA to solid tumors.

    PubMed

    Oe, Yusuke; Christie, R James; Naito, Mitsuru; Low, Stewart A; Fukushima, Shigeto; Toh, Kazuko; Miura, Yutaka; Matsumoto, Yu; Nishiyama, Nobuhiro; Miyata, Kanjiro; Kataoka, Kazunori

    2014-09-01

    For small interfering RNA (siRNA)-based cancer therapies, we report an actively-targeted and stabilized polyion complex micelle designed to improve tumor accumulation and cancer cell uptake of siRNA following systemic administration. Improvement in micelle stability was achieved using two stabilization mechanisms; covalent disulfide cross-linking and non-covalent hydrophobic interactions. The polymer component was designed to provide disulfide cross-linking and cancer cell-targeting cyclic RGD peptide ligands, while cholesterol-modified siRNA (Chol-siRNA) provided additional hydrophobic stabilization to the micelle structure. Dynamic light scattering confirmed formation of nano-sized disulfide cross-linked micelles (<50 nm in diameter) with a narrow size distribution. Improved stability of Chol-siRNA-loaded micelles (Chol-siRNA micelles) was demonstrated by resistance to both the dilution in serum-containing medium and counter polyion exchange with dextran sulfate, compared to control micelles prepared with Chol-free siRNA (Chol-free micelles). Improved stability resulted in prolonged blood circulation time of Chol-siRNA micelles compared to Chol-free micelles. Furthermore, introduction of cRGD ligands onto Chol-siRNA micelles significantly facilitated accumulation of siRNA in a subcutaneous cervical cancer model following systemic administration. Ultimately, systemically administered cRGD/Chol-siRNA micelles exhibited significant gene silencing activity in the tumor, presumably due to their active targeting ability combined with the enhanced stability through both hydrophobic interactions of cholesterol and disulfide cross-linking. PMID:24930854

  5. Deconvolution procedure of the UV-vis spectra. A powerful tool for the estimation of the binding of a model drug to specific solubilisation loci of bio-compatible aqueous surfactant-forming micelle.

    PubMed

    Calabrese, Ilaria; Merli, Marcello; Turco Liveri, Maria Liria

    2015-05-01

    UV-vis-spectra evolution of Nile Red loaded into Tween 20 micelles with pH and [Tween 20] have been analysed in a non-conventional manner by exploiting the deconvolution method. The number of buried sub-bands has been found to depend on both pH and bio-surfactant concentration, whose positions have been associated to Nile Red confined in aqueous solution and in the three micellar solubilisation sites. For the first time, by using an extended classical two-pseudo-phases-model, the robust treatment of the spectrophotometric data allows the estimation of Nile Red binding constant to the available loci. Hosting capability towards Nile Red is exalted by the pH enhancement. Comparison between binding constant values classically evaluated and those estimated by the deconvolution protocol unveiled that overall binding values perfectly match with the mean values of the local binding sites. This result suggests that deconvolution procedure provides more precise and reliable values, which are more representative of drug confinement. PMID:25703359

  6. Dependence of micelle size and shape on detergent alkyl chain length and head group.

    PubMed

    Oliver, Ryan C; Lipfert, Jan; Fox, Daniel A; Lo, Ryan H; Doniach, Sebastian; Columbus, Linda

    2013-01-01

    Micelle-forming detergents provide an amphipathic environment that can mimic lipid bilayers and are important tools for solubilizing membrane proteins for functional and structural investigations in vitro. However, the formation of a soluble protein-detergent complex (PDC) currently relies on empirical screening of detergents, and a stable and functional PDC is often not obtained. To provide a foundation for systematic comparisons between the properties of the detergent micelle and the resulting PDC, a comprehensive set of detergents commonly used for membrane protein studies are systematically investigated. Using small-angle X-ray scattering (SAXS), micelle shapes and sizes are determined for phosphocholines with 10, 12, and 14 alkyl carbons, glucosides with 8, 9, and 10 alkyl carbons, maltosides with 8, 10, and 12 alkyl carbons, and lysophosphatidyl glycerols with 14 and 16 alkyl carbons. The SAXS profiles are well described by two-component ellipsoid models, with an electron rich outer shell corresponding to the detergent head groups and a less electron dense hydrophobic core composed of the alkyl chains. The minor axis of the elliptical micelle core from these models is constrained by the length of the alkyl chain, and increases by 1.2-1.5 Å per carbon addition to the alkyl chain. The major elliptical axis also increases with chain length; however, the ellipticity remains approximately constant for each detergent series. In addition, the aggregation number of these detergents increases by ∼16 monomers per micelle for each alkyl carbon added. The data provide a comprehensive view of the determinants of micelle shape and size and provide a baseline for correlating micelle properties with protein-detergent interactions.

  7. Evaluation of the MERIS terrestrial chlorophyll index (MTCI)

    NASA Astrophysics Data System (ADS)

    Dash, J.; Curran, P. J.

    The Medium Resolution Imaging Spectrometer (MERIS), one of the payloads on Envisat, has fine spectral resolution, moderate spatial resolution and a 3-day repeat cycle. This makes MERIS a potentially valuable sensor for the measurement and monitoring of terrestrial environments at regional to global scales. The red edge, which results from an abrupt reflectance change in red and near-infrared (NIR) wavelengths has a location that is related directly to the chlorophyll content of vegetation. A new index called the MERIS terrestrial chlorophyll index (MTCI) uses data in three red/NIR wavebands centered at 681.25, 708.75 and 753.75 nm (bands 8, 9 and 10 in the MERIS standard band setting). The MTCI is easy to calculate and can be automated. Preliminary indirect evaluation using model, field and MERIS data suggested its sensitivity to chlorophyll content, notably at high values. As a result this index is now a standard level-2 product of the European Space Agency. For direct MTCI evaluation two approaches were used. First, MTCI/chlorophyll content relationships were determined using a chlorophyll content surrogate for sites in southern Vietnam and second, MTCI/chlorophyll relationships were determined using actual chlorophyll content for sites in the New Forest, UK and for plots in the greenhouse. Forests in southern Vietnam were contaminated heavily with herbicides during the Vietnam War. This led to a long term decrease in chlorophyll content within forests that have long since regained full canopy cover. The amount of herbicide dropped onto the forests between 1965 and 1971 was used as a surrogate (inverse) for contemporary chlorophyll content and was related to current MTCI at selected forest sites. The resulting relationship was both strong and negative. Further per-pixel investigation of the MTCI/herbicide concentration relationship is under way for large forest regions. In the second approach MTCI was related directly to chlorophyll content at two scales and the

  8. In situ measurement of leaf chlorophyll concentration: analysis of the optical/absolute relationship.

    PubMed

    Parry, Christopher; Blonquist, J Mark; Bugbee, Bruce

    2014-11-01

    In situ optical meters are widely used to estimate leaf chlorophyll concentration, but non-uniform chlorophyll distribution causes optical measurements to vary widely among species for the same chlorophyll concentration. Over 30 studies have sought to quantify the in situ/in vitro (optical/absolute) relationship, but neither chlorophyll extraction nor measurement techniques for in vitro analysis have been consistent among studies. Here we: (1) review standard procedures for measurement of chlorophyll; (2) estimate the error associated with non-standard procedures; and (3) implement the most accurate methods to provide equations for conversion of optical to absolute chlorophyll for 22 species grown in multiple environments. Tests of five Minolta (model SPAD-502) and 25 Opti-Sciences (model CCM-200) meters, manufactured from 1992 to 2013, indicate that differences among replicate models are less than 5%. We thus developed equations for converting between units from these meter types. There was no significant effect of environment on the optical/absolute chlorophyll relationship. We derive the theoretical relationship between optical transmission ratios and absolute chlorophyll concentration and show how non-uniform distribution among species causes a variable, non-linear response. These results link in situ optical measurements with in vitro chlorophyll concentration and provide insight to strategies for radiation capture among diverse species.

  9. Direct Measurement of the Thermodynamics of Chiral Recognition in Bile Salt Micelles.

    PubMed

    Anderson, Shauna L; Rovnyak, David; Strein, Timothy G

    2016-04-01

    Isothermal titration calorimetry (ITC) is shown to be a sensitive reporter of bile salt micellization and chiral recognition. Detailed ITC characterization of bile micelle formation as well as the chiral recognition capabilities of sodium cholate (NaC), deoxycholate (NaDC), and taurodeoxycholate (NaTDC) micelle systems are reported. The ΔH(demic) of these bile salt micelle systems is directly observable and is strongly temperature-dependent, allowing also for the determination of ΔCp(demic). Using the pseudo-phase separation model, ΔG(demic) and TΔS(demic) were also calculated. Chirally selective guest-host binding of model racemic compounds 1,1'-bi-2-napthol (BN) and 1,1'-binaphthyl-2,2'-diylhydrogenphosphate (BNDHP) to bile salt micelles was then investigated. The S-isomer was shown to bind more tightly to the bile salt micelles in all cases. A model was developed that allows for the quantitative determination of the enthalpic difference in binding affinity that corresponds to chiral selectivity, which is on the order of 1 kJ mol(-1).

  10. A tyrosine PEG-micelle magnetic resonance contrast agent for the detection of lipid rich areas in atherosclerotic plaque

    PubMed Central

    Beilvert, Anne; Cormode, David P.; Chaubet, Frédéric; Briley-Saebo, Karen C.; Mani, Venkatesh; Mulder, Willem J.M.; Vucic, Esad; Toussaint, Jean-François; Letourneur, Didier; Fayad, Zahi A.

    2010-01-01

    Vulnerable or high-risk atherosclerotic plaques often exhibit large lipid cores and thin fibrous caps that can lead to deadly vascular events via their rupture. In this study, PEG-micelles that incorporate a Gd-DTPA amphiphile were used as an MR contrast agent. In an approach inspired by lipoproteins, the micelles were functionalized with tyrosine residues, an aromatic, lipophilic amino acid, to reach the lipid rich areas of atherosclerotic plaque in a highly efficient manner. These micelles were applied to apolipoprotein E −/− mice as a model of atherosclerosis. The abdominal aortas of the animals were imaged using T1-weighted high-resolution MRI at 9.4 T before and up to 48 hours after the administration of the micelles. PEG-micelles modified with 15% tyrosine residues, yielded a significant enhancement of the abdominal aortic wall at 6 and 24 hours post-injection as compared to unmodified micelles. Fluorescence microscopy on histological sections of the abdominal aorta showed a correlation between lipid rich areas and the distribution of the functionalized contrast agent in plaque. Using a simple approach, we demonstrated that lipid-rich areas in atherosclerotic plaque of ApoE −/− mice can be detected by MRI using Gd-DTPA micelles. PMID:19780153

  11. Some Thoughts Regarding Theoretical Aspects of the Corrin-Harkins Relation and the Micellization Product of Ionic Micelles.

    PubMed

    Maeda, Hiroshi

    2001-09-01

    The dependence of the stability of ionic micelles on the ionic strength of the medium is examined analytically without recourse to any explicit expression of the surface potential of micelles. The present study is based on the idea developed by Evans, Mitchell, and Ninham (D. F. Evans, D. J. Mitchell, and B. W. Ninham, J. Phys. Chem. 88, 6344 (1984)) that the interfacial free energy at the water/hydrocarbon core interface is independent of the ionic strength of the medium. The Corrin-Harkins (C-H) relation, a linear relation between the logarithm of the critical micelle concentration (cmc) and the logarithm of the counterion concentration n(C), is obtained in the range of n(C) where the salting-out effect is negligible, under the condition that the area per monomer on the micelle surface decreases very weakly with n(C). The "micellization product" of the charged pseudophase model of ionic micelles is discussed. The linear dependence of the surface potential of ionic micelles on n(C) is derived while a part of the effects of salt on the micelle size/shape is allowed. Copyright 2001 Academic Press.

  12. Structural studies of pravastatin and simvastatin and their complexes with SDS micelles by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Rakhmatullin, I. Z.; Galiullina, L. F.; Klochkova, E. A.; Latfullin, I. A.; Aganov, A. V.; Klochkov, V. V.

    2016-02-01

    Conformational features of pravastatin and simvastatin molecules in solution and in their complexes with sodium dodecyl sulfate micelles (SDS) were studied by 2D NOESY NMR spectroscopy. On the basis of the nuclear magnetic resonance experiments it was established that pravastatin and simvastatin can form molecular complex with SDS micelles which were considered as the model of cell membrane. In addition, interatomic distances for studied compounds were calculated based on 2D NOESY NMR experiments. It was shown that pravastatin interacts only with a surface of model membrane. However, in contrast to pravastatin, simvastatin penetrates into the inner part of SDS micelles. Observed distinctions in the mechanisms of interaction of pravastatin and simvastatin with models of cell membranes could explain the differences in their pharmacological properties.

  13. Stressor-response modeling using the 2D water quality model and regression trees to predict chlorophyll-a in a reservoir system

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In order to control algal blooms, stressor-response relationships between water quality metrics, environmental variables, and algal growth should be understood and modeled. Machine-learning methods were suggested to express stressor-response relationships found by application of mechanistic water qu...

  14. Molecular Exchange in Ordered Diblock Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank

    2011-03-01

    Previously, molecular exchange between spherical micelles in dilute solution (1 vol% polymer) was investigated using time-resolved small-angle neutron scattering (TR-SANS). As the concentration of spherical micelles formed by the diblock copolymers increases, the micelles begin to overlap and eventually pack onto body-centered cubic (BCC) lattice. In this study, concentrated, ordered micelles (15 vol% polymers) prepared by dispersing isotopically labeled poly(styrene- b -ethylene-alt-propylene) in an isotopic squalane mixture was investigated to understand the micellar concentration dependence of the molecular exchange. Perfectly random mixing of isotopically labeled micelles on the BCC lattice was confirmed by SANS patterns where the interparticle contribution vanishes, resulting in an intensity that directly relates to the exchange kinetics. The measured molecular exchange process for the concentrated, ordered system is qualitatively consistent with the previous observations, but the rate is more than an order of magnitude slower than that for the dilute, disordered system. Infineum(IPrime), MRSEC(NSF), NIST.

  15. How do polymeric micelles cross epithelial barriers?

    PubMed

    Pepić, Ivan; Lovrić, Jasmina; Filipović-Grčić, Jelena

    2013-09-27

    Non-parenteral delivery of drugs using nanotechnology-based delivery systems is a promising non-invasive way to achieve effective local or systemic drug delivery. The efficacy of drugs administered non-parenterally is limited by their ability to cross biological barriers, and epithelial tissues particularly present challenges. Polymeric micelles can achieve transepithelial drug delivery because of their ability to be internalized into cells and/or cross epithelial barriers, thereby delivering drugs either locally or systematically following non-parenteral administration. This review discusses the particular characteristics of various epithelial barriers and assesses their potential as non-parenteral routes of delivery. The material characteristics of polymeric micelles (e.g., size, surface charge, and surface decoration) and of unimers dissociated from polymeric micelles determine their interactions (non-specific and/or specific) with mucus and epithelial cells as well as their intracellular fate. This paper outlines the mechanisms governing the major modes of internalization of polymeric micelles into epithelial cells, with an emphasis on specific recent examples of the transport of drug-loaded polymeric micelles across epithelial barriers.

  16. Novel Redox-Responsive Amphiphilic Copolymer Micelles for Drug Delivery: Synthesis and Characterization.

    PubMed

    Bae, Jungeun; Maurya, Abhijeet; Shariat-Madar, Zia; Murthy, S Narasimha; Jo, Seongbong

    2015-11-01

    A novel redox-responsive amphiphilic polymer was synthesized with bioreductive trimethyl-locked quinone propionic acid for a potential triggered drug delivery application. The aim of this study was to synthesize and characterize the redox-responsive amphiphilic block copolymer micelles containing pendant bioreductive quinone propionic acid (QPA) switches. The redox-responsive hydrophobic block (polyQPA), synthesized from QPA-serinol and adipoyl chloride, was end-capped with methoxy poly(ethylene glycol) of molecular weight 750 (mPEG750) to achieve a redox-responsive amphiphilic block copolymer, polyQPA-mPEG750. PolyQPA-mPEG750 was able to self-assemble as micelles to show a critical micelle concentration (CMC) of 0.039% w/v (0.39 mg/ml, 0.107 mM) determined by a dye solubilization method using 1,6-diphenyl-1,3,5-hexatriene (DPH) in phosphate-buffered saline (PBS). The mean diameter of polymeric micelles was found to be 27.50 nm (PI = 0.064) by dynamic light scattering. Furthermore, redox-triggered destabilization of the polymeric micelles was confirmed by (1)H-NMR spectroscopy and particle size measurements in a simulated redox state. PolyQPA-mPEG750 underwent triggered reduction to shed pendant redox-responsive QPA groups and its polymeric micelles were swollen to be dissembled in the presence of a reducing agent, thereby enabling the release of loaded model drug, paclitaxel. The redox-responsive polyQPA-mPEG750 polymer micelles would be useful as a drug delivery system allowing triggered drug release in an altered redox state such as tumor microenvironments with an altered redox potential and/or redox enzyme upregulation.

  17. Oscillatory structural forces due to nonionic surfactant micelles: data by colloidal-probe AFM vs theory.

    PubMed

    Christov, Nikolay C; Danov, Krassimir D; Zeng, Yan; Kralchevsky, Peter A; von Klitzing, Regine

    2010-01-19

    Micellar solutions of nonionic surfactants Brij 35 and Tween 20 are confined between two surfaces in a colloidal-probe atomic-force microscope (CP-AFM). The experimentally detected oscillatory forces due to the layer-by-layer expulsion of the micelles agree very well with the theoretical predictions for hard-sphere fluids. While the experiment gives parts of the stable branches of the force curve, the theoretical model allows reconstruction of the full oscillatory curve. Therewith, the strength and range of the ordering could be determined. The resulting aggregation number from the fits of the force curves for Brij 35 is close to 70 and exhibits a slight tendency to increase with the surfactant concentration. The last layer of micelles cannot be pressed out. The measured force-vs-distance curve has nonequilibrium portions, which represent "jumps" from one to another branch of the respective equilibrium oscillatory curve. In the case of Brij 35, at concentrations <150 mM spherical micelles are present and the oscillation period is close to the micelle diameter, slightly decreasing with the rise of concentration. For elongated micelles (at concentration 200 mM), no harmonic oscillations are observed anymore; instead, the period increases with the decrease of film thickness. In the case of Tween 20, the force oscillations are almost suppressed, which implies that the micelles of this surfactant are labile and are demolished by the hydrodynamic shear stresses due to the colloidal-probe motion. The comparison of the results for the two surfactants demonstrates that in some cases the micelles can be destroyed by the CP-AFM, but in other cases they can be stable and behave as rigid particles. This behavior correlates with the characteristic times of the slow micellar relaxation process for these surfactants.

  18. Improving aqueous solubility and antitumor effects by nanosized gambogic acid-mPEG2000 micelles

    PubMed Central

    Cai, Lulu; Qiu, Neng; Xiang, Mingli; Tong, Rongsheng; Yan, Junfeng; He, Lin; Shi, Jianyou; Chen, Tao; Wen, Jiaolin; Wang, Wenwen; Chen, Lijuan

    2014-01-01

    The clinical application of gambogic acid, a natural component with promising antitumor activity, is limited due to its extremely poor aqueous solubility, short half-life in blood, and severe systemic toxicity. To solve these problems, an amphiphilic polymer-drug conjugate was prepared by attachment of low molecular weight (ie, 2 kDa) methoxy poly(ethylene glycol) methyl ether (mPEG) to gambogic acid (GA-mPEG2000) through an ester linkage and characterized by 1H nuclear magnetic resonance. The GA-mPEG2000 conjugates self-assembled to form nanosized micelles, with mean diameters of less than 50 nm, and a very narrow particle size distribution. The properties of the GA-mPEG2000 micelles, including morphology, stability, molecular modeling, and drug release profile, were evaluated. MTT (3-(4,5-dimethylthiazo l-2-yl)-2,5 diphenyl tetrazolium bromide) tests demonstrated that the GA-mPEG2000 micelle formulation had obvious cytotoxicity to tumor cells and human umbilical vein endothelial cells. Further, GA-mPEG2000 micelles were effective in inhibiting tumor growth and prolonged survival in subcutaneous B16-F10 and C26 tumor models. Our findings suggest that GA-mPEG2000 micelles may have promising applications in tumor therapy. PMID:24403830

  19. Mechanism of Molecular Exchange in Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank

    2010-03-01

    Compared to thermodynamic structure, much less has been known about the kinetics of block copolymer micelles which should underlay the attainment of thermodynamic equilibrium. In this presentation, molecular exchange between spherical micelles formed by isotopically labeled diblock copolymers was investigated using time-resolved small-angle neutron scattering. Two pairs of structurally matched poly(styrene-b-ethylene-alt-propylene) (PS-PEP) were synthesized and dispersed in isotopic mixture of squalane, highly selective to PEP block. Each pair includes polymers with fully deuterated (dPS-PEP) and a normal (hPS-PEP) PS blocks. Temperature dependence of the micelle exchange rate R(t) is consistent with melt dynamics for the core polymer. Furthermore, R(t) is significantly sensitive to the core block length N due to the thermodynamic penalty associated with ejecting a core block into the solvent. This hypersensitivity, combined with modest polydispersity in N, leads to an approximately logarithmic decay in R(t).

  20. Targeted anti-thrombotic protein micelles

    PubMed Central

    Kim, Wookhyun; Haller, Carolyn; Dai, Erbin; Wang, Xiowei; Hagemeyer, Christoph E.; Liu, David R.; Peter, Karlheinz; Chaikof, Elliot L.

    2015-01-01

    Activated platelets provide a promising target for imaging inflammatory and thrombotic events along with site-specific delivery of a variety of therapeutic agents. Herein, we report the efficient design of multifunctional protein micelles bearing targeting and therapeutic proteins by one-pot transpeptidation using an evolved sortase A. Conjugation to the corona of a single-chain antibody (scFv), which binds to the ligand induced binding site (LIBS) of activated GPIIb/IIIa receptors enabled efficient detection of thrombi. Inhibiting thrombus formation was subsequently accomplished by incorporating the catalytically active domain of thrombomodulin (TM) onto the micelle corona for local generation of activated protein C, which serves to inhibit thrombin formation. An effective strategy has been developed for preparation of protein micelles that can be targeted to sites of activated platelets with broad potential for treatment of acute thrombotic events. PMID:25504546

  1. Vibrational dynamics of ice in reverse micelles.

    PubMed

    Dokter, Adriaan M; Petersen, Christian; Woutersen, Sander; Bakker, Huib J

    2008-01-28

    The ultrafast vibrational dynamics of HDO:D(2)O ice at 180 K in anionic reverse micelles is studied by midinfrared femtosecond pump-probe spectroscopy. Solutions containing reverse micelles are cooled to low temperatures by a fast-freezing procedure. The heating dynamics of the micellar solutions is studied to characterize the micellar structure. Small reverse micelles with a water content up to approximately 150 water molecules contain an amorphous form of ice that shows remarkably different vibrational dynamics compared to bulk hexagonal ice. The micellar amorphous ice has a much longer vibrational lifetime than bulk hexagonal ice and micellar liquid water. The vibrational lifetime is observed to increase linearly from 0.7 to 4 ps with the resonance frequency ranging from 3100 to 3500 cm(-1). From the pump dependence of the vibrational relaxation the homogeneous linewidth of the amorphous ice is determined (55+/-5 cm(-1)).

  2. Stability of casein micelles in milk

    NASA Astrophysics Data System (ADS)

    Tuinier, R.; de Kruif, C. G.

    2002-07-01

    Casein micelles in milk are proteinaceous colloidal particles and are essential for the production of flocculated and gelled products such as yogurt, cheese, and ice-cream. The colloidal stability of casein micelles is described here by a calculation of the pair potential, containing the essential contributions of brush repulsion, electrostatic repulsion, and van der Waals attraction. The parameters required are taken from the literature. The results are expressed by the second osmotic virial coefficient and are quite consistent with experimental findings. It appears that the stability is mainly attributable to a steric layer of κ-casein, which can be described as a salted polyelectrolyte brush.

  3. Statistical crystallography of surface micelle spacing

    NASA Technical Reports Server (NTRS)

    Noever, David A.

    1992-01-01

    The aggregation of the recently reported surface micelles of block polyelectrolytes is analyzed using techniques of statistical crystallography. A polygonal lattice (Voronoi mosaic) connects center-to-center points, yielding statistical agreement with crystallographic predictions; Aboav-Weaire's law and Lewis's law are verified. This protocol supplements the standard analysis of surface micelles leading to aggregation number determination and, when compared to numerical simulations, allows further insight into the random partitioning of surface films. In particular, agreement with Lewis's law has been linked to the geometric packing requirements of filling two-dimensional space which compete with (or balance) physical forces such as interfacial tension, electrostatic repulsion, and van der Waals attraction.

  4. Polymeric micelles as carriers of diagnostic agents.

    PubMed

    Trubetskoy

    1999-04-01

    This review deals with diagnostic applications of polymeric micelles composed of amphiphilic block-copolymers. In aqueous solutions these polymers spontaneously form particles with diameter 20-100 nm. A variety of diagnostic moieties can be incorporated covalently or non-covalently into the particulates with high loads. Resulting particles can be used as particulate agents for diagnostic imaging using three major imaging modalities: gamma-scintigraphy, magnetic resonance imaging and computed tomography. The use of polyethyleneoxide-diacyllipid micelles loaded with chelated (111)In/Gd(3+) as well as iodine-containing amphiphilic copolymer in percutaneous lymphography and blood pool/liver imaging are discussed as specific examples.

  5. Remote sensing of ocean chlorophyll: consequence of nonuniform pigment profile.

    PubMed

    Sathyendranath, S; Platt, T

    1989-02-01

    Remote sensing of ocean color, applied to the estimation of chlorophyll biomass, is discussed for the case where the vertical distribution of phytoplankton pigments is nonuniform. Using a spectral model of reflectance, the consequences of vertical structure are evaluated by sensitivity analysis on a generalized pigment profile. It is shown that the assumption of a vertically homogeneous chlorophyll distribution can lead to significant errors (relative error exceeding 100%) in the estimation from satellite data of photic depth and total pigment content in the photic zone. The errors are shown to be functions of the parameters of the pigment profile. It is further shown that, if the shape of the pigment profile is known from independent data, the entire pigment profile may be recovered from the satellite data by making slight changes in the existing algorithms for chlorophyll retrieval.

  6. Size And Shape of Detergent Micelles Determined By Small-Angle X-Ray Scattering

    SciTech Connect

    Lipfert, Jan; Columbus, Linda; Chu, Vincent B.; Lesley, Scott A.; Doniach, Sebastian; /Stanford U., Phys. Dept. /Stanford U., Appl. Phys. Dept. /SLAC, SSRL /Pasteur Inst., Paris /Scripps Res. Inst. /Novartis Res. Found.

    2009-04-29

    We present a systematic analysis of the aggregation number and shape of micelles formed by nine detergents commonly used in the study of membrane proteins. Small-angle X-ray scattering measurements are reported for glucosides with 8 and 9 alkyl carbons (OG/NG), maltosides and phosphocholines with 10 and 12 alkyl carbons (DM/DDM and FC-10/FC-12), 1,2-dihexanoyl-sn-glycero-phosphocholine (DHPC), 1-palmitoyl-2-hydroxy-sn-glycero-3-[phospho-rac-(1-glycerol)] (LPPG), and 3-[(3-cholamidopropyl)dimethylammonio]-1-propane sulfonate (CHAPS). The SAXS intensities are well described by two-component ellipsoid models, with a dense outer shell corresponding to the detergent head groups and a less electron dense hydrophobic core. These models provide an intermediate resolution view of micelle size and shape. In addition, we show that Guinier analysis of the forward scattering intensity can be used to obtain an independent and model-free measurement of the micelle aggregation number and radius of gyration. This approach has the advantage of being easily generalizable to protein-detergent complexes, where simple geometric models are inapplicable. Furthermore, we have discovered that the position of the second maximum in the scattering intensity provides a direct measurement of the characteristic head group-head group spacing across the micelle core. Our results for the micellar aggregation numbers and dimensions agree favorably with literature values as far as they are available. We de novo determine the shape of FC-10, FC-12, DM, LPPG, and CHAPS micelles and the aggregation numbers of FC-10 and OG to be ca. 50 and 250, respectively. Combined, these data provide a comprehensive view of the determinants of micelle formation and serve as a starting point to correlate detergent properties with detergent-protein interactions.

  7. Mesoscopic simulation studies on the formation mechanism of drug loaded polymeric micelles.

    PubMed

    Wang, Yan; Zhu, Dan Dan; Zhou, Jian; Wang, Qi Lei; Zhang, Can Yang; Liu, Yue Jin; Wu, Zhi Min; Guo, Xin Dong

    2015-12-01

    In this work, the formation of polymeric micelles as drug delivery vehicles in an aqueous environment is investigated by dissipative particle dynamics (DPD) simulations. Doxorubicin (DOX) is selected as the model drug, whereas docosahexaenoic acid (DHA) conjugated His10Lys10 (DHA-His10Lys10) as the drug carrier. It is shown from DPD simulation that drug molecules and DHA-His10Lys10 molecules could aggregate and form micelles under a defined composition recipe; drug molecules are homogeneously distributed inside the carrier matrix, on whose surface the stabilizer lysine segments are absorbed. Under different compositions of drug and water, aggregate morphologies of polymeric micelles are observed as spherical, columnar, and lamellar structures. We finally proposed the formation mechanism of drug loaded polymeric micelles and apply it in practice by analyzing the simulated phenomena. All the results can effectively guide the experimental preparation of drug delivery system with desired properties or explore a novel polymeric micelle with high performance. PMID:26454543

  8. Dendrimer-TPGS mixed micelles for enhanced solubility and cellular toxicity of taxanes.

    PubMed

    Pooja, Deep; Kulhari, Hitesh; Singh, Mayank K; Mukherjee, Sudip; Rachamalla, Shyam Sunder; Sistla, Ramakrishna

    2014-09-01

    Taxanes are the most effective, efficient and broad spectrum anticancer drugs for the treatment of various cancers. However, poor aqueous solubility is the major problem in their delivery at higher concentrations in cancer cells. In this research work, poor solubility of taxanes is addressed by preparing dendrimer and d-α-tocopherol polyethylene glycol succinate (TPGS) mixed micelles by taking into consideration the advantages of TPGS such as solubility enhancement and P-glycoprotein inhibition. Dendrimer-TPGS mixed micelles were prepared by solvent casting method. Docetaxel (DTX) and paclitaxel (PTX) were chosen as model drugs representing the group of taxanes. Nanomicelles were characterized by DLS, FTIR, PXRD, in vitro drug release and hemolytic studies. Effects of pH and dendrimer to TPGS ratio on the solubility of taxanes were also studied. Solubility of DTX and PTX were increased by 20.36 and 34.95 folds, respectively, when formulated in dendrimer-TPGS mixed micelles. Drug release studies exhibited better release profile of encapsulated drug at acidic pH which is advantageous in enhanced intracellular drug release in cancer cells. Formulations were found to be biocompatible in hemolytic toxicity assay. Cytotoxicity studies revealed that anticancer activities of both drugs were enhanced after encapsulation in micelles against cancer cells while caused very low toxicity to normal cells. Thus, dendrimer-TPGS mixed micelles are promising alternate for delivery of poorly water-soluble drugs taxanes.

  9. Thermal deactivation kinetics of Pseudomonas fluorescens lipase entrapped in AOT/isooctane reverse micelles.

    PubMed

    Park, Kyung Min; Kwon, Chang Woo; Choi, Seung Jun; Son, Young-Hwan; Lim, Seokwon; Yoo, Yoonjung; Chang, Pahn-Shick

    2013-10-01

    Thermostability of the lipase (EC 3.1.1.3) was found to be increased by the enzyme-entrapment in 50 mM AOT/isooctane reverse micelles. The half-life (15.75 h) of Pseudomonas fluorescens lipase entrapped in reverse micelles at 70 °C was 9.72- and 11.41-fold longer than those solubilized in a glycerol pool or in 10 mM phosphate buffer (pH 8.0), respectively. The enzyme deactivation model considering a two-step series-type was employed, and deactivation constants for the second step (k₂) at all temperatures were drastically decreased after the lipase was entrapped in reverse micelles. In particular, k₂ (0.0354 h⁻¹) at 70 °C in reverse micelles was 12.33- and 13.14-fold lower than in a glycerol pool or in the phosphate buffer, respectively. The deactivation energies (from k₁, k₂) for the lipase entrapped in the reverse micelles, solubilized in a glycerol pool, or in the aqueous buffer were 7.51, 26.35 kcal/mol, 5.93, 21.08 kcal/mol, and 5.53, 17.57 kcal/mol, respectively.

  10. Structure and rheological behavior of casein micelle suspensions during ultrafiltration process

    NASA Astrophysics Data System (ADS)

    Pignon, F.; Belina, G.; Narayanan, T.; Paubel, X.; Magnin, A.; Gésan-Guiziou, G.

    2004-10-01

    The stability and mechanism underlying the formation of deposits of casein micelles during ultrafiltration process were investigated by small-angle and ultra small-angle x-ray scattering (SAXS and USAXS). The casein micelle dispersions consisted of phospho-caseinate model powders and the measurements probed length scales ranging from 1 to 2000 nm. Rheometric and frontal filtration measurements were combined with SAXS to establish the relationship between the rheological behavior of deposits (shear and/or compression) and the corresponding microstructure. The results revealed two characteristic length scales for the equilibrium structure with radius of gyrations Rg, about 100 and 5.6 nm pertaining to the globular micelles and their non-globular internal structure, respectively. The SAXS measurements further indicated that the increase of temperature from 20 to 70 °C or the decrease of pH from 6.6 to 6 lead to agglomeration of the globular micelles. In situ scattering measurements showed that the decrease of permeation flows is directly related to the deformation and compression of the micelles in the immediate vicinity of the membrane.

  11. Uptake of organic pollutants by silica--polycation-Immobilized micelles for groundwater remediation.

    PubMed

    Mishael, Yael G; Dubin, Paul L

    2005-11-01

    Interest has grown in designing new materials for groundwater treatment via "permeable reactive barriers". In the present case, a model siliceous surface, controlled pore glass (CPG), was treated with a polycation (quaternized polyvinyl pyridine, QPVP) which immobilizes anionic/nonionic mixed micelles, in order to solubilize a variety of hydrophobic pollutants. Polymer adsorption on CPG showed atypically slow kinetics and linear adsorption isotherms, which may be a consequence of the substrate porosity. The highest toluene solubilization efficiency was achieved for the silica-polycation-immobilized micelles (SPIM) with the highest polymer loading and lowest micelle binding, a result discussed in terms of the configuration of the bound polymer and the corresponding state of the bound micelles. The ability of SPIM to treat simultaneously a wide range of pollutants and reduce their concentration in solution by 20-90% was demonstrated. Optimization of SPIM systems for remediation calls for a better understanding of both the local environment of the bound micelles and their intrinsic affinities for different hydrophobic pollutants.

  12. Thermodynamics of mixed micelles: Determination of the aggregate composition.

    PubMed

    Letellier, Pierre; Mayaffre, Alain; Turmine, Mireille

    2008-11-01

    In most studies concerning surfactant mixtures, the determination of the composition of mixed micelles is often tricky. This composition can be obtained by different ways. One of them, undoubtedly the most used, supposes, a priori, that the surfactant in the micelle follows the regular solution model. This poses a problem on the thermodynamic point of view because in these studies, a model of behavior is first admitted for deducing a composition. In a correct thermodynamic approach, a composition should first be determined and then, a model of behavior which accounts for the observed physicochemical properties can be found. This approach is all the more questionable since the application of the Gibbs-Duhem relationship to the pseudo-phase allows aggregate composition to be determined simply, without using a solution model, because the composition of the bulk at the threshold of aggregation is known. In this article, we describe and validate a simple procedure, which supplements that proposed by Rodenas et al. [E. Rodenas, M. Valiente, M.D. Villafruela, J. Phys. Chem. B 103 (1999) 4549], and which allows determination of the activities of the components of the micellar aggregate and its composition. The results are compared to those obtained with other approaches such as molecular-thermodynamic model. PMID:18723182

  13. Multifunctional SPIO/DOX-loaded A54 Homing Peptide Functionalized Dextran-g-PLGA Micelles for Tumor Therapy and MR Imaging

    PubMed Central

    Situ, Jun-Qing; Wang, Xiao-Juan; Zhu, Xiu-Liang; Xu, Xiao-Ling; Kang, Xu-Qi; Hu, Jing-Bo; Lu, Chen-Ying; Ying, Xiao-Ying; Yu, Ri-Sheng; You, Jian; Du, Yong-Zhong

    2016-01-01

    Specific delivery of chemotherapy drugs and magnetic resonance imaging (MRI) contrast agent into tumor cells is one of the issues to highly efficient tumor targeting therapy and magnetic resonance imaging. Here, A54 peptide-functionalized poly(lactic-co-glycolic acid)-grafted dextran (A54-Dex-PLGA) was synthesized. The synthesized A54-Dex-PLGA could self-assemble to form micelles with a low critical micelle concentration of 22.51 μg. mL−1 and diameter of about 50 nm. The synthetic A54-Dex-PLGA micelles can encapsulate doxorubicin (DOX) as a model anti-tumor drug and superparamagnetic iron oxide (SPIO) as a contrast agent for MRI. The drug-encapsulation efficiency was about 80% and the in vitro DOX release was prolonged to 72 hours. The DOX/SPIO-loaded micelles could specifically target BEL-7402 cell line. In vitro MRI results also proved the specific binding ability of A54-Dex-PLGA/DOX/SPIO micelles to hepatoma cell BEL-7402. The in vivo MR imaging experiments using a BEL-7402 orthotopic implantation model further validated the targeting effect of DOX/SPIO-loaded micelles. In vitro and in vivo anti-tumor activities results showed that A54-Dex-PLGA/DOX/SPIO micelles revealed better therapeutic effects compared with Dex-PLGA/DOX/SPIO micelles and reduced toxicity compared with commercial adriamycin injection. PMID:27775017

  14. Poly(PS-b-DMA) Micelles for Reactive Oxygen Species Triggered Drug Release

    PubMed Central

    Gupta, Mukesh K.; Meyer, Travis A.; Nelson, Christopher E.; Duvall, Craig L.

    2013-01-01

    A new micelle drug carrier that consists of a diblock polymer of propylene sulfide (PS) and N,N-dimethylacrylamide (poly(PS74−b-DMA310)) has been synthesized and characterized for site-specific release of hydrophobic drugs to sites of inflammation. Propylene sulfide was first polymerized using a thioacyl group transfer (TAGT) method with the RAFT chain transfer agent (CTA) 4-cyano-4-(ethylsulfanylthiocarbonylsulfanyl) pentanoic acid (CEP), and the resultant poly(PS74−CEP) macro-CTA was used to polymerize a second polymer block of DMA using reversible addition-fragmentation chain transfer (RAFT). The formation of the poly(PS74−b-DMA310) diblock polymer was confirmed by 1H NMR spectra and gel permeation chromatography (GPC). poly(PS74−b-DMA310) formed 100 nm micelles in aqueous media as confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Micelles loaded with the model drugs Nile red and DiO were used to demonstrate the ROS-dependent drug release mechanism of these micelles following treatment with hydrogen peroxide (H2O2), 3-morpholinosydnonimine (SIN-1), and peroxynitrite. These oxidants were found to oxidize the micelle PPS core, making it more hydrophilic and triggering micelle disassembly and cargo release. Delivery of poly(PS74−b-DMA310) micelles dual-loaded with the Förster Resonance Energy Transfer (FRET) fluorophore pair DiI and DiO was used to prove that endogenous oxidants generated by lipopolysaccharide (LPS)-treated RAW 264.7 macrophages significantly increased release of nanocarrier contents relative to macrophages that were not activated. In vitro studies also demonstrated that the poly(PS74−b-DMA310) micelles were cytocompatible across a broad range of concentrations. These combined data suggest that the poly(PS74−b-DMA310) micelles synthesized using a combination of TAGT and RAFT have significant potential for site-specific drug delivery to tissues with high levels of oxidative stress. PMID:22889714

  15. Synthesis, characterization, and evaluation of mPEG–SN38 and mPEG–PLA–SN38 micelles for cancer therapy

    PubMed Central

    Xie, Jing; Zhang, Xiaomin; Teng, Meiyu; Yu, Bo; Yang, Shuang; Lee, Robert J; Teng, Lesheng

    2016-01-01

    7-Ethyl-10-hydroxy camptothecin (SN38) is a potent topoisomerase inhibitor and a metabolite of irinotecan. Its clinical development has been hampered by its poor solubility. To address this problem, methoxy poly(ethylene glycol)-2000 (mPEG2K)–SN38 and mPEG2K–poly(lactide) (PLA1.5K)–SN38 conjugates were prepared and then dispersed into an aqueous medium to form micelles. Physicochemical characteristics of SN38–polymer conjugate micelles, for example, micelle diameter, zeta potential, morphology, and drug content, were then evaluated. The results showed that the mean diameters of mPEG2K–SN38 and mPEG2K–PLA1.5K–SN38 micelles were ~130 and 20 nm, respectively. These two micelles had similar drug contents. mPEG2K–PLA1.5K–SN38 micelles were more homogeneous than mPEG2K–SN38 micelles. Moreover, in vitro drug release behavior of the micelles was studied by high performance liquid chromatography. SN38 release from mPEG2K–SN38 micelles was much faster than from mPEG2K–PLA1.5K–SN38 micelles. In vitro cytotoxicity, cellular uptake, and apoptosis assays of the SN38–polymer conjugate micelles were carried out on BEL-7402 human liver cancer cells. In vivo biodistribution and antitumor tumor efficacy studies were carried out in a nude mouse xenograft model derived from BEL-7402 cells. The results showed that mPEG2K–PLA1.5K–SN38 micelles were significantly more effective than mPEG2K–SN38 micelles in tumor inhibition, and the inhibitory effect of mPEG2K–PLA1.5K–SN38 micelles on tumor growth was significantly greater than that of mPEG2K–SN38 micelles (1,042 vs 1,837 mm) at 30 days. In conclusion, mPEG–PLA–SN38 is a promising anticancer agent that warrants further investigation. PMID:27217746

  16. Synthesis, characterization, and evaluation of mPEG-SN38 and mPEG-PLA-SN38 micelles for cancer therapy.

    PubMed

    Xie, Jing; Zhang, Xiaomin; Teng, Meiyu; Yu, Bo; Yang, Shuang; Lee, Robert J; Teng, Lesheng

    2016-01-01

    7-Ethyl-10-hydroxy camptothecin (SN38) is a potent topoisomerase inhibitor and a metabolite of irinotecan. Its clinical development has been hampered by its poor solubility. To address this problem, methoxy poly(ethylene glycol)-2000 (mPEG2K)-SN38 and mPEG2K-poly(lactide) (PLA1.5K)-SN38 conjugates were prepared and then dispersed into an aqueous medium to form micelles. Physicochemical characteristics of SN38-polymer conjugate micelles, for example, micelle diameter, zeta potential, morphology, and drug content, were then evaluated. The results showed that the mean diameters of mPEG2K-SN38 and mPEG2K-PLA1.5K-SN38 micelles were ~130 and 20 nm, respectively. These two micelles had similar drug contents. mPEG2K-PLA1.5K-SN38 micelles were more homogeneous than mPEG2K-SN38 micelles. Moreover, in vitro drug release behavior of the micelles was studied by high performance liquid chromatography. SN38 release from mPEG2K-SN38 micelles was much faster than from mPEG2K-PLA1.5K-SN38 micelles. In vitro cytotoxicity, cellular uptake, and apoptosis assays of the SN38-polymer conjugate micelles were carried out on BEL-7402 human liver cancer cells. In vivo biodistribution and antitumor tumor efficacy studies were carried out in a nude mouse xenograft model derived from BEL-7402 cells. The results showed that mPEG2K-PLA1.5K-SN38 micelles were significantly more effective than mPEG2K-SN38 micelles in tumor inhibition, and the inhibitory effect of mPEG2K-PLA1.5K-SN38 micelles on tumor growth was significantly greater than that of mPEG2K-SN38 micelles (1,042 vs 1,837 mm) at 30 days. In conclusion, mPEG-PLA-SN38 is a promising anticancer agent that warrants further investigation. PMID:27217746

  17. Micelle depletion-induced vs. micelle-mediated aggregation in nanoparticles

    SciTech Connect

    Ray, D. Aswal, V. K.

    2015-06-24

    The phase behavior anionic silica nanoparticle (Ludox LS30) with non-ionic surfactants decaethylene glycol monododecylether (C12E10) and cationic dodecyltrimethyl ammonium bromide (DTAB) in aqueous electrolyte solution has been studied by small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations of nanoparticle (1 wt%), surfactants (1 wt%) and electrolyte (0.1 M NaCl). Each of these nanoparticle–surfactant systems has been examined for different contrast conditions where individual components (nanoparticle or surfactant) are made visible. It is observed that the nanoparticle-micelle system in both the cases lead to the aggregation of nanoparticles. The aggregation is found to be micelle depletion-induced for C12E10 whereas micelle-mediated aggregation for DTAB. Interestingly, it is also found that phase behavior of mixed surfactant (C12E10 + DTAB) system is similar to that of C12E10 (unlike DTAB) micelles with nanoparticles.

  18. Thermodynamics of Micelle Formation: Prediction of Micelle Size and Size Distribution

    PubMed Central

    Tanford, Charles

    1974-01-01

    This paper presents a simple theory for the calculation of micelle size and other properties of micelleforming systems. The theory is based on the separate estimation of the components of the free energy arising from hydrophobic attraction and from head group repulsion, each as a function of micelle size. The difficult problem of an a priori calculation of the repulsive factor is circumvented by using experimental values of this parameter, derived from pressure-area curves of monolayers at an interface between an aqueous solution and liquid hydrocarbon. Though some parameters of the theory are still somewhat uncertain, self-consistent and physically realistic values can be assigned that lead to almost exact prediction of experimental micelle sizes and critical micelle concentrations for two distinctly different ionic detergents. PMID:4525294

  19. Micelle depletion-induced vs. micelle-mediated aggregation in nanoparticles

    NASA Astrophysics Data System (ADS)

    Ray, D.; Aswal, V. K.

    2015-06-01

    The phase behavior anionic silica nanoparticle (Ludox LS30) with non-ionic surfactants decaethylene glycol monododecylether (C12E10) and cationic dodecyltrimethyl ammonium bromide (DTAB) in aqueous electrolyte solution has been studied by small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations of nanoparticle (1 wt%), surfactants (1 wt%) and electrolyte (0.1 M NaCl). Each of these nanoparticle-surfactant systems has been examined for different contrast conditions where individual components (nanoparticle or surfactant) are made visible. It is observed that the nanoparticle-micelle system in both the cases lead to the aggregation of nanoparticles. The aggregation is found to be micelle depletion-induced for C12E10 whereas micelle-mediated aggregation for DTAB. Interestingly, it is also found that phase behavior of mixed surfactant (C12E10 + DTAB) system is similar to that of C12E10 (unlike DTAB) micelles with nanoparticles.

  20. Micelle dynamic simulation and physicochemical characterization of biorelevant media to reflect gastrointestinal environment in fasted and fed states.

    PubMed

    Xie, XiaoYu; Cardot, Jean-Michel; Garrait, Ghislain; Thery, Vincent; El-Hajji, Mohamed; Beyssac, Eric

    2014-10-01

    The characterization of biorelevant media simulating the upper part of the gastrointestinal tract in the fasted and fed states was investigated by classical determination of physicochemical parameters such as pH, osmolality, surface tension and results were compared to in vivo physiological data. Incorporation of fatty material, in order to better simulate the influence of high fat meal was also performed. Stability and characterization of this medium was studied and compared to classical FeSSIF. Micelle characterization and computer dynamic simulation were performed in order to understand the interaction between lecithin and taurocholate and possible interactions between mixed micelle and drugs. The addition of NaTc, lecithin, and/or fatty materials has no influence on pH and osmolality, whereas the presence of fatty material modifies the surface tension. Values of FaSSIF and FeSSIF are in accordance with in vivo parameters and the presence of micelles can simulate the gastrointestinal environment. Modelization of micelles by computer simulation led to a model of mixed micelles in which structures of NaTc interact either by their hydrophilic or hydrophobic phase to give a bilayer stable model in which the lecithin molecule can insert its long carbon chain. The micelle structure is stable and can enhance dissolution of hydrophobic molecules by hydrophobic interaction with the numerous hydrophobic spaces available in the multilayer hydrophilic/hydrophobic layer.

  1. Quantitating the association of charged molecules with ionic micelles

    NASA Astrophysics Data System (ADS)

    Stevenson, Sarah A.; Blanchard, G. J.

    2007-05-01

    We have studied micelles comprised of cationic (CTAB) and anionic (SDS) surfactants through the interactions of solution phase anionic disodium fluorescein (DSF) and cationic rhodamine 110 (R110) dyes with perylene sequestered within the micelles. Fluorescence lifetime measurements monitor energy transfer between the nonpolar optical donor within the micelle and ionic probes in the surrounding solution. The efficiency of this process is mediated by the extent to which the ionic dyes interact with the micelle palisade layer, and our fluorescence lifetime data allow us to determine the association constants for acceptor-micelle interactions.

  2. Preparation of mono-dispersed silver nanoparticles assisted by chitosan-g-poly(ɛ-caprolactone) micelles and their antimicrobial application

    NASA Astrophysics Data System (ADS)

    Gu, Chunhua; Zhang, Huan; Lang, Meidong

    2014-05-01

    Amphiphilic chitosan-graft-poly(ɛ-caprolactone) (CS-g-PCLs) copolymers were synthesized by a homogeneous coupling method and characterized by 1H NMR, FTIR and ninhydrin assay. The graft copolymers were subsequently self-assembled into micelles, which were measured by DLS and TEM. The particle size of the micelles decreased as the segment grafting fraction was increased. Thereafter, silver nanoparticles were prepared in the presence of chitosan-based micelles under UV irradiation. The molar ratio and radiation time of silver to micelles were optimized with process monitored via UV-vis spectrophotometer. DLS and TEM were used to illustrate the particle structure and size while XRD patterns were applied to characterize the crystal structures of polymer-assisted silver nanoparticles. Films impregnated with silver nanoparticles were conducted with results of strong antimicrobial activities against Escherichia coli and Staphylococcus aureus as model Gram-negative and positive bacteria.

  3. Hyperbranched polycarbonate-based multimolecular micelle with enhanced stability and loading efficiency.

    PubMed

    Su, Wei; Luo, Xiao-Hua; Wang, Hua-Fen; Li, Lei; Feng, Jun; Zhang, Xian-Zheng; Zhuo, Ren-Xi

    2011-02-16

    We herein develop a facile catalyst-free method to prepare hyperbranched hydroxyl-enriched aliphatic polycarbonate according to SCROP strategy. PEG-attached multiarm hyperbranched copolymer HEHDO-star-mPEG was further designed. It was found that HEHDO-star-mPEG can self-assemble into supramolecular multimolecular micelles in water. HEHDO-star-mPEG micelle showed excellent stability with respect to micellar size upon dilution, and displayed good cell-biocompatibility. An anticancer drug of doxorubicin with hydrogen-bonding functionality was incorporated into obtained micelles to establish a drug delivery system model. A high drug-loading content as well as sustained release pattern for HEHDO-star-mPEG based delivery system was achieved.

  4. Complex coacervate core micelles as diffusional nanoprobes.

    PubMed

    Bourouina, Nadia; Cohen Stuart, Martien A; Kleijn, J Mieke

    2014-01-14

    Because of their ease of preparation and versatile modification opportunities, complex coacervate core micelles (C3Ms) may be a good alternative for expensive diffusional probes, such as dendrimers. However, C3Ms are unstable at high salt concentrations and may fall apart in contact with other polymers or (solid) materials. Therefore, we designed and characterized small (15 nm radius), stable fluorescent C3Ms. These were formed by electrostatic interactions between poly(ethylene oxide-methacrylic acid) (PEO-PMAA) and fluorescently labelled poly(allylamine hydrochloride) (PAH) and irreversible cross-linking of the core through amide bonds. We compared the properties of the cross-linked and non-cross-linked micelles. The radii of the two types of micelles were quite similar and independent of the ionic strength. Surprisingly, both were found to be stable at salt concentrations as high as 1.5 M. However, unlike the non-cross-linked C3Ms, the stability of the cross-linked C3Ms is independent of the pH. As a first example of their application as diffusional nanoprobes, we present results on the diffusion of the fluorescent micelles measured in xanthan solutions using fluorescence recovery after photobleaching (FRAP).

  5. Impact of urea on detergent micelle properties.

    PubMed

    Broecker, Jana; Keller, Sandro

    2013-07-01

    Co-solvents, such as urea, can entail drastic changes in the micellization behavior of detergents. We present a systematic quantification of the impact of urea on the critical micellar concentration, the micellization thermodynamics, and the micelle size in three homologous series of commonly used non-ionic alkyl detergents. To this end, we performed demicellization experiments by isothermal titration calorimetry and hydrodynamic size measurements by dynamic light scattering on alkyl maltopyranosides, cyclohexyl alkyl maltopyranosides, and alkyl glucopyranosides at urea concentrations of 0-8 M. For all detergents studied, we found that the critical micellar concentration increases exponentially because the absolute Gibbs free energy of micellization decreases linearly over the entire urea concentration range, as does the micelle size. In contrast, the enthalpic and entropic contributions to micellization reveal more complex, nonlinear dependences on urea concentration. Both free energy and size changes are more pronounced for long-chain detergents, which bury more apolar surface area upon micelle formation. The Gibbs free energy increments per methylene group within each detergent series depend on urea concentration in a linear fashion, although they result from the entropic term for alkyl maltosides but are of enthalpic origin for cyclohexyl alkyl maltosides. We compare our results to transfer free energies of amino acid side chains, relate them to protein-folding data, and discuss how urea-induced changes in detergent micelle properties affect in vitro investigations on membrane proteins.

  6. Chain exchange in block copolymer micelles

    NASA Astrophysics Data System (ADS)

    Lu, Jie; Bates, Frank; Lodge, Timothy

    2014-03-01

    Block copolymer micelles are aggregates formed by self-assembly of amphiphilic copolymers dispersed in a selective solvent, driven by unfavorable interactions between the solvent and the core-forming block. Due to the relatively long chains being subject to additional thermodynamic and dynamic constraints (e.g., entanglements, crystallinity, vitrification), block copolymer micelles exhibit significantly slower equilibration kinetics than small molecule surfactants. As a result, details of the mechanism(s) of equilibration in block copolymer micelles remain unclear. This present works focuses on the chain exchange kinetics of poly(styrene-b-ethylenepropylene) block copolymers in squalane (C30H62) using time-resolved small angle neutron scattering (TR-SANS). A mixture of h-squalane and d-squalane is chosen so that it contrast matches a mixed 50/50 h/d polystyrene micelle core. When the temperature is appropriate and isotopically labeled chains undergo mixing, the mean core contrast with respect to the solvent decreases, and the scattering intensity is therefore reduced. This strategy allows direct probing of chain exchange rate from the time dependent scattering intensity I(q, t).

  7. Secondary structure formation in peptide amphiphile micelles

    NASA Astrophysics Data System (ADS)

    Tirrell, Matthew

    2012-02-01

    Peptide amphiphiles (PAs) are capable of self-assembly into micelles for use in the targeted delivery of peptide therapeutics and diagnostics. PA micelles exhibit a structural resemblance to proteins by having folded bioactive peptides displayed on the exterior of a hydrophobic core. We have studied two factors that influence PA secondary structure in micellar assemblies: the length of the peptide headgroup and amino acids closest to the micelle core. Peptide length was systematically varied using a heptad repeat PA. For all PAs the addition of a C12 tail induced micellization and secondary structure. PAs with 9 amino acids formed beta-sheet interactions upon aggregation, whereas the 23 and 30 residue peptides were displayed in an apha-helical conformation. The 16 amino acid PA experienced a structural transition from helix to sheet, indicating that kinetics play a role in secondary structure formation. A p53 peptide was conjugated to a C16 tail via various linkers to study the effect of linker chemistry on PA headgroup conformation. With no linker the p53 headgroup was predominantly alpha helix and a four alanine linker drastically changed the structure of the peptide headgroup to beta-sheet, highlighting the importance of hydrogen boding potential near the micelle core.

  8. Non-diffusing radiochromic micelle gel

    NASA Astrophysics Data System (ADS)

    Jordan, Kevin; Sekimoto, Masaya

    2010-11-01

    The addition of Laponite, a synthetic clay nanoparticle material to radiochromic leuco Malachite Green micelle hydrogel eliminates diffusion of the cationic dye by electrostatic binding. The clay nanoparticles also increased dose sensitivity ten-fold relative to the parent gel formulation. This material is a suitable 3D water equivalent dosimeter with optical CT readout.

  9. Colloidal Electrolytes and the Critical Micelle Concentration

    ERIC Educational Resources Information Center

    Knowlton, L. G.

    1970-01-01

    Describes methods for determining the Critical Micelle Concentration of Colloidal Electrolytes; methods described are: (1) methods based on Colligative Properties, (2) methods based on the Electrical Conductivity of Colloidal Electrolytic Solutions, (3) Dye Method, (4) Dye Solubilization Method, and (5) Surface Tension Method. (BR)

  10. Investigating the Control of Chlorophyll Degradation by Genomic Correlation Mining.

    PubMed

    Ghandchi, Frederick P; Caetano-Anolles, Gustavo; Clough, Steven J; Ort, Donald R

    2016-01-01

    Chlorophyll degradation is an intricate process that is critical in a variety of plant tissues at different times during the plant life cycle. Many of the photoactive chlorophyll degradation intermediates are exceptionally cytotoxic necessitating that the pathway be carefully coordinated and regulated. The primary regulatory step in the chlorophyll degradation pathway involves the enzyme pheophorbide a oxygenase (PAO), which oxidizes the chlorophyll intermediate pheophorbide a, that is eventually converted to non-fluorescent chlorophyll catabolites. There is evidence that PAO is differentially regulated across different environmental and developmental conditions with both transcriptional and post-transcriptional components, but the involved regulatory elements are uncertain or unknown. We hypothesized that transcription factors modulate PAO expression across different environmental conditions, such as cold and drought, as well as during developmental transitions to leaf senescence and maturation of green seeds. To test these hypotheses, several sets of Arabidopsis genomic and bioinformatic experiments were investigated and re-analyzed using computational approaches. PAO expression was compared across varied environmental conditions in the three separate datasets using regression modeling and correlation mining to identify gene elements co-expressed with PAO. Their functions were investigated as candidate upstream transcription factors or other regulatory elements that may regulate PAO expression. PAO transcript expression was found to be significantly up-regulated in warm conditions, during leaf senescence, and in drought conditions, and in all three conditions significantly positively correlated with expression of transcription factor Arabidopsis thaliana activating factor 1 (ATAF1), suggesting that ATAF1 is triggered in the plant response to these processes or abiotic stresses and in result up-regulates PAO expression. The proposed regulatory network includes the

  11. Investigating the Control of Chlorophyll Degradation by Genomic Correlation Mining

    PubMed Central

    Ghandchi, Frederick P.; Caetano-Anolles, Gustavo; Clough, Steven J.

    2016-01-01

    Chlorophyll degradation is an intricate process that is critical in a variety of plant tissues at different times during the plant life cycle. Many of the photoactive chlorophyll degradation intermediates are exceptionally cytotoxic necessitating that the pathway be carefully coordinated and regulated. The primary regulatory step in the chlorophyll degradation pathway involves the enzyme pheophorbide a oxygenase (PAO), which oxidizes the chlorophyll intermediate pheophorbide a, that is eventually converted to non-fluorescent chlorophyll catabolites. There is evidence that PAO is differentially regulated across different environmental and developmental conditions with both transcriptional and post-transcriptional components, but the involved regulatory elements are uncertain or unknown. We hypothesized that transcription factors modulate PAO expression across different environmental conditions, such as cold and drought, as well as during developmental transitions to leaf senescence and maturation of green seeds. To test these hypotheses, several sets of Arabidopsis genomic and bioinformatic experiments were investigated and re-analyzed using computational approaches. PAO expression was compared across varied environmental conditions in the three separate datasets using regression modeling and correlation mining to identify gene elements co-expressed with PAO. Their functions were investigated as candidate upstream transcription factors or other regulatory elements that may regulate PAO expression. PAO transcript expression was found to be significantly up-regulated in warm conditions, during leaf senescence, and in drought conditions, and in all three conditions significantly positively correlated with expression of transcription factor Arabidopsis thaliana activating factor 1 (ATAF1), suggesting that ATAF1 is triggered in the plant response to these processes or abiotic stresses and in result up-regulates PAO expression. The proposed regulatory network includes the

  12. Monitoring of maize chlorophyll content based on multispectral vegetation indices

    NASA Astrophysics Data System (ADS)

    Sun, Hong; Li, Minzan; Zheng, Lihua; Zhang, Yane; Zhang, Yajing

    2012-11-01

    In order to estimate the nutrient status of maize, the multi-spectral image was used to monitor the chlorophyll content in the field. The experiments were conducted under three different fertilizer treatments (High, Normal and Low). A multispectral CCD camera was used to collect ground-based images of maize canopy in green (G, 520~600nm), red (R, 630~690nm) and near-infrared (NIR, 760~900nm) band. Leaves of maize were randomly sampled to detect the chlorophyll content by UV-Vis spectrophotometer. The images were processed following image preprocessing, canopy segmentation and parameter calculation: Firstly, the median filtering was used to improve the visual contrast of image. Secondly, the leaves of maize canopy were segmented in NIR image. Thirdly, the average gray value (GIA, RIA and NIRIA) and the vegetation indices (DVI, RVI, NDVI, et al.) widely used in remote sensing were calculated. A new vegetation index, combination of normalized difference vegetation index (CNDVI), was developed. After the correlation analysis between image parameter and chlorophyll content, six parameters (GIA, RIA, NIRIA, GRVI, GNDVI and CNDVI) were selected to estimate chlorophyll content at shooting and trumpet stages respectively. The results of MLR predicting models showed that the R2 was 0.88 and the adjust R2 was 0.64 at shooting stage; the R2 was 0.77 and the adjust R2 was 0.31 at trumpet stage. It was indicated that vegetation indices derived from multispectral image could be used to monitor the chlorophyll content. It provided a feasible method for the chlorophyll content detection.

  13. Biomimetic oral mucin from polymer micelle networks

    NASA Astrophysics Data System (ADS)

    Authimoolam, Sundar Prasanth

    Mucin networks are formed by the complexation of bottlebrush-like mucin glycoprotein with other small molecule glycoproteins. These glycoproteins create nanoscale strands that then arrange into a nanoporous mesh. These networks play an important role in ensuring surface hydration, lubricity and barrier protection. In order to understand the functional behavior in mucin networks, it is important to decouple their chemical and physical effects responsible for generating the fundamental property-function relationship. To achieve this goal, we propose to develop a synthetic biomimetic mucin using a layer-by-layer (LBL) deposition approach. In this work, a hierarchical 3-dimensional structures resembling natural mucin networks was generated using affinity-based interactions on synthetic and biological surfaces. Unlike conventional polyelectrolyte-based LBL methods, pre-assembled biotin-functionalized filamentous (worm-like) micelles was utilized as the network building block, which from complementary additions of streptavidin generated synthetic networks of desired thickness. The biomimetic nature in those synthetic networks are studied by evaluating its structural and bio-functional properties. Structurally, synthetic networks formed a nanoporous mesh. The networks demonstrated excellent surface hydration property and were able capable of microbial capture. Those functional properties are akin to that of natural mucin networks. Further, the role of synthetic mucin as a drug delivery vehicle, capable of providing localized and tunable release was demonstrated. By incorporating antibacterial curcumin drug loading within synthetic networks, bacterial growth inhibition was also demonstrated. Thus, such bioactive interfaces can serve as a model for independently characterizing mucin network properties and through its role as a drug carrier vehicle it presents exciting future opportunities for localized drug delivery, in regenerative applications and as bio

  14. Growth Behavior, Geometrical Shape, and Second CMC of Micelles Formed by Cationic Gemini Esterquat Surfactants.

    PubMed

    Bergström, L Magnus; Tehrani-Bagha, Alireza; Nagy, Gergely

    2015-04-28

    Micelles formed by novel gemini esterquat surfactants have been investigated with small-angle neutron scattering (SANS). The growth behavior of the micelles is found to differ conspicuously depending on the length of the gemini surfactant spacer group. The gemini surfactant with a long spacer form rather small triaxial ellipsoidal tablet-shaped micelles that grow weakly with surfactant concentration in the entire range of measured concentrations. Geminis with a short spacer, on the other hand, form weakly growing oblates or tablets at low concentrations that start to grow much more strongly into polydisperse rodlike or wormlike micelles at higher concentrations. The latter behavior is consistent with the presence of a second CMC that marks the transition from the weakly to the strongly growing regime. It is found that the growth behavior in terms of aggregation number as a function of surfactant concentration always appear concave in weakly growing regimes, while switching to convex behavior in strongly growing regimes. As a result, we are able to determine the second CMC of the geminis with short spacer by means of suggesting a rather precise definition of it, located at the point of inflection of the growth curve that corresponds to the transition from concave to convex growth behavior. Our SANS results are rationalized by comparison with the recently developed general micelle model. In particular, this theory is able to explain and reproduce the characteristic appearances of the experimental growth curves, including the presence of a second CMC and the convex strongly growing regime beyond. By means of optimizing the agreement between predictions from the general micelle model and results from SANS experiments, we are able to determine the three bending elasticity constants spontaneous curvature, bending rigidity, and saddle-splay constant for each surfactant. PMID:25835031

  15. Well-defined, size-tunable, multi-functional micelles for efficient paclitaxel delivery for cancer treatment

    PubMed Central

    Luo, Juntao; Xiao, Kai; Li, Yuanpei; Lee, Joyce S.; Shi, Lifang; Tan, Yih-Horng; Xing, Li; Cheng, R. Holland; Liu, Gang-Yu; Lam, Kit S.

    2010-01-01

    We have developed a well-defined and biocompatible amphiphilic telodendrimer system (PEG-b-dendritic oligo-cholic acid) which can self-assemble into multifunctional micelles in aqueous solution for efficient delivery of hydrophobic drugs such as paclitaxel. In this telodendrimer system, cholic acid is essential for the formation of stable micelles with high drug loading capacity, owing to its facial amphiphilicity. A series of telodendrimers with variable length of PEG chain and number of cholic acid in the dendritic blocks were synthesized. The structure and molecular weight of each of these telodendrimers were characterized, and their critical micellization concentration (CMC), drug-loading properties, particle sizes and cytotoxicity were examined and evaluated for further optimization for anticancer drug delivery. The sizes of the micelles, with and without paclitaxel loading, could be tuned from 11.5 to 21 nm and from 15 to 141 nm, respectively. Optical imaging studies in xenograft models demonstrated preferential uptakes of the smaller paclitaxel-loaded micelles (17–60 nm) by the tumor, and the larger micelles (150 nm) by the liver and lung. The toxicity and anti-tumor efficacy profiles of these paclitaxel-loaded micelles in xenograft models were found to be superior to those of Taxol® and Abraxane®. PMID:20536174

  16. Paclitaxel-Loaded Polymeric Micelles Modified with MCF-7 Cell-Specific Phage Protein: Enhanced Binding to Target Cancer Cells and Increased Cytotoxicity

    PubMed Central

    Wang, Tao; Petrenko, Valery A.; Torchilin, Vladimir P.

    2010-01-01

    Polymeric micelles are used as pharmaceutical carriers to increase solubility and bioavailability of poorly water-soluble drugs. Different ligands are used to prepare targeted polymeric micelles. Earlier, we developed the method for use of specific landscape phage fusion coat proteins as targeted delivery ligands and demonstrated the efficiency of this approach with doxorubicin-loaded PEGylated liposomes. Here, we describe a MCF-7 cell-specific micellar formulation self-assembled from the mixture of the micelle-forming amphiphilic polyethylene glycol-phosphatidylethanolamine (PEG-PE) conjugate, MCF-7-specific landscape phage fusion coat protein, and the hydrophobic drug paclitaxel. These micelles demonstrated a very low CMC value and specific binding to target cells. Using an in vitro co-culture model, FACS analysis, and fluorescence microscopy we showed that MCF-7 targeted phage micelles preferential bound to target cells compared to non-target cells. As a result, targeted paclitaxel-loaded phage micelles demonstrated a significantly higher cytotoxicity towards target MCF-7 cells than free drug or non-targeted micelle formulations, but failed to show such a differential toxicity towards non-target C166 cells. Overall, cancer cell-specific phage proteins identified from phage display peptide libraries can serve as targeting ligands (“substitute antibody”) for polymeric micelle-based pharmaceutical preparations. PMID:20518562

  17. Self-Assembled Binary Nanoscale Systems: Multioutput Model with LFER-Covariance Perturbation Theory and an Experimental-Computational Study of NaGDC-DDAB Micelles.

    PubMed

    Messina, Paula V; Besada-Porto, Jose Miguel; González-Díaz, Humberto; Ruso, Juan M

    2015-11-10

    Studies of the self-aggregation of binary systems are of both theoretical and practical importance. They provide an opportunity to investigate the influence of the molecular structure of the hydrophobe on the nonideality of mixing. On the other hand, linear free energy relationship (LFER) models, such as Hansch's equations, may be used to predict the properties of chemical compounds such as drugs or surfactants. However, the task becomes more difficult once we want to predict simultaneaously the effect over multiple output properties of binary systems of perturbations under multiple input experimental boundary conditions (b(j)). As a consequence, we need computational chemistry or chemoinformatics models that may help us to predict different properties of the autoaggregation process of mixed surfactants under multiple conditions. In this work, we have developed the first model that combines perturbation theory (PT) and LFER ideas. The model uses as input covariance PT operators (CPTOs). CPTOs are calculated as the difference between covariance ΔCov((i)μ(k)) functions before and after multiple perturbations in the binary system. In turn, covariances calculated as the product of two Box-Jenkins operators (BJO) operators. BJOs are used to measure the deviation of the structure of different chemical compounds from a set of molecules measured under a given subset of experimental conditions. The best CPT-LFER model found predicted the effects of 25,000 perturbations over 9 different properties of binary systems. We also reported experimental studies of different experimental properties of the binary system formed by sodium glycodeoxycholate and didodecyldimethylammonium bromide (NaGDC-DDAB). Last, we used our CPT-LFER model to carry out a 1000 data point simulation of the properties of the NaGDC-DDAB system under different conditions not studied experimentally.

  18. Targeting Mast Cells and Basophils with Anti-FcεRIα Fab-Conjugated Celastrol-Loaded Micelles Suppresses Allergic Inflammation.

    PubMed

    Peng, Xia; Wang, Juan; Li, Xianyang; Lin, Lihui; Xie, Guogang; Cui, Zelin; Li, Jia; Wang, Yuping; Li, Li

    2015-12-01

    Mast cells and basophils are effector cells in the pathophysiology of allergic diseases. Targeted elimination of these cells may be a promising strategy for the treatment of allergic disorders. Our present study aims at targeted delivery of anti-FcεRIα Fab-conjugated celastrol-loaded micelles toward FcεRIα receptors expressed on mast cells and basophils to have enhanced anti-allergic effect. To achieve this aim, we prepared celastrol-loaded (PEO-block-PPO-block-PEO, Pluronic) polymeric nanomicelles using thin-film hydration method. The anti-FcεRIα Fab Fragment was then conjugated to carboxyl groups on drug-loaded micelles via EDC amidation reaction. The anti-FcεRIα Fab-conjugated celastrol-loaded micelles revealed uniform particle size (93.43 ± 12.93 nm) with high loading percentage (21.2 ± 1.5% w/w). The image of micelles showed oval and rod like. The anti-FcεRIα Fab-conjugated micelles demonstrated enhanced cellular uptake and cytotoxity toward target KU812 cells than non-conjugated micelles in vitro. Furthermore, diffusion of the drug into the cells allowed an efficient induction of cell apoptosis. In mouse model of allergic asthma, treatment with anti-FcεRIα Fab-conjugated micelles increased lung accumulation of micelles, and significantly reduced OVA-sIgE, histamine and Th2 cytokines (IL-4, IL-5, TNF-α) levels, eosinophils infiltration and mucus production. In addition, in mouse model of passive cutaneous anaphylaxis, anti-FcεRIα Fab-conjugated celastrol-loaded micelles treatment significantly decreased extravasated evan's in the ear. These results indicate that anti-FcεRIα Fab-conjugated celastrol-loaded micelles can target and selectively kill mast cells and basophils which express FcεRIα, and may be efficient reagents for the treatment of allergic disorders and mast cell related diseases.

  19. Complete Regression of Xenograft Tumors upon Targeted Delivery of Paclitaxel via Π-Π Stacking Stabilized Polymeric Micelles

    PubMed Central

    Shi, Yang; van der Meel, Roy; Theek, Benjamin; Blenke, Erik Oude; Pieters, Ebel H.E.; Fens, Marcel H.A.M.; Ehling, Josef; Schiffelers, Raymond M.; Storm, Gert; van Nostrum, Cornelus F.; Lammers, Twan; Hennink, Wim E.

    2015-01-01

    Treatment of cancer patients with taxane-based chemotherapeutics, such as paclitaxel (PTX), is complicated by their narrow therapeutic index. Polymeric micelles are attractive nanocarriers for tumor-targeted delivery of PTX, as they can be tailored to encapsulate large amounts of hydrophobic drugs and achieve prolonged circulation kinetics. As a result, PTX deposition in tumors is increased while drug exposure to healthy tissues is reduced. However, many PTX-loaded micelle formulations suffer from low stability and fast drug release in the circulation, limiting their suitability for systemic drug targeting. To overcome these limitations, we have developed paclitaxel (PTX)-loaded micelles which are stable without chemical crosslinking and covalent drug attachment. These micelles are characterized by excellent loading capacity and strong drug retention, attributed to π-π stacking interaction between PTX and the aromatic groups of the polymer chains in the micellar core. The micelles are based on methoxy poly(ethylene glycol)-b-(N-(2-benzoyloxypropyl) methacrylamide) (mPEG-b-p(HPMAm-Bz)) block copolymers, which improved the pharmacokinetics and the biodistribution of PTX, and substantially increased PTX tumor accumulation (by more than 2000%; as compared to Taxol® or control micellar formulations). Improved biodistribution and tumor accumulation were confirmed by hybrid μCT-FMT imaging using near-infrared labeled micelles and payload. The PTX-loaded micelles were well tolerated at different doses while they induced complete tumor regression in two different xenograft models (i.e. A431 and MDA-MB-468). Our findings consequently indicate that π-π stacking-stabilized polymeric micelles are promising carriers to improve the delivery of highly hydrophobic drugs to tumors and to increase their therapeutic index. PMID:25831471

  20. Inhibition of atherosclerosis-promoting microRNAs via targeted polyelectrolyte complex micelles

    PubMed Central

    Kuo, Cheng-Hsiang; Leon, Lorraine; Chung, Eun Ji; Huang, Ru-Ting; Sontag, Timothy J.; Reardon, Catherine A.; Getz, Godfrey S.; Tirrell, Matthew; Fang, Yun

    2015-01-01

    Polyelectrolyte complex micelles have great potential as gene delivery vehicles because of their ability to encapsulate charged nucleic acids forming a core by neutralizing their charge, while simultaneously protecting the nucleic acids from non-specific interactions and enzymatic degradation. Furthermore, to enhance specificity and transfection efficiency, polyelectrolyte complex micelles can be modified to include targeting capabilities. Here, we describe the design of targeted polyelectrolyte complex micelles containing inhibitors against dys-regulated microRNAs (miRNAs) that promote atherosclerosis, a leading cause of human mortality and morbidity. Inhibition of dys-regulated miRNAs in diseased cells associated with atherosclerosis has resulted in therapeutic efficacy in animal models and has been proposed to treat human diseases. However, the non-specific targeting of microRNA inhibitors via systemic delivery has remained an issue that may cause unwanted side effects. For this reason, we incorporated two different peptide sequences to our miRNA inhibitor containing polyelectrolyte complex micelles. One of the peptides (Arginine-Glutamic Acid-Lysine-Alanine or REKA) was used in another micellar system that demonstrated lesion-specific targeting in a mouse model of atherosclerosis. The other peptide (Valine-Histidine-Proline-Lysine-Glutamine-Histidine-Arginine or VHPKQHR) was identified via phage display and targets vascular endothelial cells through the vascular cell adhesion molecule-1 (VCAM-1). In this study we have tested the in vitro efficacy and efficiency of lesion- and cell-specific delivery of microRNA inhibitors to the cells associated with atherosclerotic lesions via peptide-targeted polyelectrolyte complex micelles. Our results show that REKA-containing micelles (fibrin-targeting) and VHPKQHR-containing micelles (VCAM-1 targeting) can be used to carry and deliver microRNA inhibitors into macrophages and human endothelial cells, respectively

  1. Multicompartment micelles with adjustable poly(ethylene glycol) shell for efficient in vivo photodynamic therapy.

    PubMed

    Synatschke, Christopher V; Nomoto, Takahiro; Cabral, Horacio; Förtsch, Melanie; Toh, Kazuko; Matsumoto, Yu; Miyazaki, Kozo; Hanisch, Andreas; Schacher, Felix H; Kishimura, Akihiro; Nishiyama, Nobuhiro; Müller, Axel H E; Kataoka, Kazunori

    2014-02-25

    We describe the preparation of well-defined multicompartment micelles from polybutadiene-block-poly(1-methyl-2-vinyl pyridinium methyl sulfate)-block-poly(methacrylic acid) (BVqMAA) triblock terpolymers and their use as advanced drug delivery systems for photodynamic therapy (PDT). A porphyrazine derivative was incorporated into the hydrophobic core during self-assembly and served as a model drug and fluorescent probe at the same time. The initial micellar corona is formed by negatively charged PMAA and could be gradually changed to poly(ethylene glycol) (PEG) in a controlled fashion through interpolyelectrolyte complex formation of PMAA with positively charged poly(ethylene glycol)-block-poly(L-lysine) (PLL-b-PEG) diblock copolymers. At high degrees of PEGylation, a compartmentalized micellar corona was observed, with a stable bottlebrush-on-sphere morphology as demonstrated by cryo-TEM measurements. By in vitro cellular experiments, we confirmed that the porphyrazine-loaded micelles were PDT-active against A549 cells. The corona composition strongly influenced their in vitro PDT activity, which decreased with increasing PEGylation, correlating with the cellular uptake of the micelles. Also, a PEGylation-dependent influence on the in vivo blood circulation and tumor accumulation was found. Fully PEGylated micelles were detected for up to 24 h in the bloodstream and accumulated in solid subcutaneous A549 tumors, while non- or only partially PEGylated micelles were rapidly cleared and did not accumulate in tumor tissue. Efficient tumor growth suppression was shown for fully PEGylated micelles up to 20 days, demonstrating PDT efficacy in vivo. PMID:24386876

  2. The interaction of Cu 2+ ions and NaDC micelles

    NASA Astrophysics Data System (ADS)

    Sun, Y.; Yang, Z.-L.; Zhang, L.; Hu, T.-D.; Soloway, R. D.; Weng, S.-F.; Wu, J.-G.

    2002-05-01

    By mixing an aqueous solution of CuCl 2 with an NaDC aqueous solution of various concentration and initial molar ratio, seven coordinated samples with distinct appearances and characters were obtained. Their structures and components were investigated by FT-IR spectroscopy, EXAFS (the extended X-ray absorption fine structure), thermal analysis, X-ray diffraction, laser light scattering, TEM (transmission electron micrograph), element analysis and ICP (inductively coupled plasma) analysis. The following conclusions were given: (1) The complexes of Cu 2+-NaDC with distinct appearances and properties were synthesized. (2) After Cu(DC) 2 dissolved in NaDC aqueous solution, larger micelles (30-90 nm diameter) formed in the supernate, it is a mixed micelle with Cu(DC) 2 and NaDC. So these micelles are a new kind of micelle containing two kinds of metal ions. This is a new result using metal ions as bridges to form micelle. (3) According to the different concentration of Cu 2+ to NaDC, the complexes formed as gel or poly-crystals. Both the composition of gel complexes and the coordination structure of carboxyl groups with metal ions varied with the initial molar ratio of Cu 2+ to Na +. The gel complexes exhibits the non-stoichiometric character. (4) These results are in agreement with physiological condition. All the different states such as gel, precipitate, micelles of various structures are present in bile of gallbladder. We can suggest an ideal model of the interaction between Cu 2+ and bile salts in vivo.

  3. Ocean Primary Production Estimates from Terra MODIS and Their Dependency on Satellite Chlorophyll Alpha Algorithms

    NASA Technical Reports Server (NTRS)

    Essias, Wayne E.; Abbott, Mark; Carder, Kendall; Campbell, Janet; Clark, Dennis; Evans, Robert; Brown, Otis; Kearns, Ed; Kilpatrick, Kay; Balch, W.

    2003-01-01

    Simplistic models relating global satellite ocean color, temperature, and light to ocean net primary production (ONPP) are sensitive to the accuracy and limitations of the satellite estimate of chlorophyll and other input fields, as well as the primary productivity model. The standard MODIS ONPP product uses the new semi-analytic chlorophyll algorithm as its input for two ONPP indexes. The three primary MODIS chlorophyll Q estimates from MODIS, as well as the SeaWiFS 4 chlorophyll product, were used to assess global and regional performance in estimating ONPP for the full mission, but concentrating on 2001. The two standard ONPP algorithms were examined with 8-day and 39 kilometer resolution to quantify chlorophyll algorithm dependency of ONPP. Ancillary data (MLD from FNMOC, MODIS SSTD1, and PAR from the GSFC DAO) were identical. The standard MODIS ONPP estimates for annual production in 2001 was 59 and 58 GT C for the two ONPP algorithms. Differences in ONPP using alternate chlorophylls were on the order of 10% for global annual ONPP, but ranged to 100% regionally. On all scales the differences in ONPP were smaller between MODIS and SeaWiFS than between ONPP models, or among chlorophyll algorithms within MODIS. Largest regional ONPP differences were found in the Southern Ocean (SO). In the SO, application of the semi-analytic chlorophyll resulted in not only a magnitude difference in ONPP (2x), but also a temporal shift in the time of maximum production compared to empirical algorithms when summed over standard oceanic areas. The resulting increase in global ONPP (6-7 GT) is supported by better performance of the semi-analytic chlorophyll in the SO and other high chlorophyll regions. The differences are significant in terms of understanding regional differences and dynamics of ocean carbon transformations.

  4. Structure of polyglycerol oleic acid ester nonionic surfactant reverse micelles in decane: growth control by headgroup size.

    PubMed

    Shrestha, Lok Kumar; Dulle, Martin; Glatter, Otto; Aramaki, Kenji

    2010-05-18

    The structure of polyglycerol oleic acid ester nonionic surfactant micelles in n-decane has been investigated at room temperature by small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), and densiometry techniques. The scattering data were evaluated by indirect Fourier transformation (IFT) or generalized indirect Fourier transformation (GIFT) methods depending on the volume fractions of the surfactants and also by model fit. A simple route to the growth control of reverse micelles by headgroup size of the surfactant was investigated. Additionally, the dependence of reverse micellar structure (shape and size) on temperature, composition, and added water was also investigated. The indirect Fourier transformation gives the real space pair-distance distribution function, p(r): a facile way for the quantitative estimation of structure parameters of the aggregates. It was found that the size of the reverse micelles increases with increasing the headgroup size of the surfactant. Globular type of micelles with maximum diameter ca. 6 nm observed in the monoglycerol oleic acid ester/decane system at 25 degrees C transferred into elongated prolate type micelles with maximum diameter ca. 19.5 nm in the hexaglycerol oleic acid ester/decane system. In a particular surfactant and oil system, increasing temperature decreased the micellar size. The size of the micelle was decreased by approximately 25% upon increasing temperature from 25 to 75 degrees C in the 5 wt % diglycerol oleic acid ester/decane system. Concentration could not modulate the structure of micelles despite a wide variation in the surfactant concentration (5-25 wt %). Nevertheless, increasing surfactant concentration reduces the intermicellar distance, and a strong repulsive interaction peak was observed in the scattering curves at higher surfactant concentrations. Besides, the results obtained from the dynamic light scattering have shown the signature of diffusion hindrance relative to hard sphere

  5. Folding Behaviors of Protein (Lysozyme) Confined in Polyelectrolyte Complex Micelle.

    PubMed

    Wu, Fu-Gen; Jiang, Yao-Wen; Chen, Zhan; Yu, Zhi-Wu

    2016-04-19

    -polyelectrolyte systems. Hence, the present protein-PEGylated poly(amino acid) mixture provides an ideal water-soluble model system to study the important role of electrostatic interaction in the complexation between proteins and polymers, leading to important new knowledge on the protein-polymer interactions. Moreover, the polyelectrolyte complex micelle formed between protein and PEGylated polymer may provide a good drug delivery vehicle for therapeutic proteins. PMID:27022665

  6. Mechano-responsive hydrogels crosslinked by reactive block copolymer micelles

    NASA Astrophysics Data System (ADS)

    Xiao, Longxi

    Hydrogels are crosslinked polymeric networks that can swell in water without dissolution. Owing to their structural similarity to the native extracelluar matrices, hydrogels have been widely used in biomedical applications. Synthetic hydrogels have been designed to respond to various stimuli, but mechanical signals have not incorporated into hydrogel matrices. Because most tissues in the body are subjected to various types of mechanical forces, and cells within these tissues have sophisticated mechano-transduction machinery, this thesis is focused on developing hydrogel materials with built-in mechano-sensing mechanisms for use as tissue engineering scaffolds or drug release devices. Self-assembled block copolymer micelles (BCMs) with reactive handles were employed as the nanoscopic crosslinkers for the construction of covalently crosslinked networks. BCMs were assembled from amphiphilic diblock copolymers of poly(n-butyl acrylate) and poly(acrylic acid) partially modified with acrylate. Radical polymerization of acrylamide in the presence of micellar crosslinkers gave rise to elastomeric hydrogels whose mechanical properties can be tuned by varying the BCM composition and concentration. TEM imaging revealed that the covalently integrated BCMs underwent strain-dependent reversible deformation. A model hydrophobic drug, pyrene, loaded into the core of BCMs prior to the hydrogel formation, was dynamically released in response to externally applied mechanical forces, through force-induced reversible micelle deformation and the penetration of water molecules into the micelle core. The mechano-responsive hydrogel has been studied for tissue repair and regeneration purposes. Glycidyl methacrylate (GMA)-modified hyaluronic acid (HA) was photochemically crosslinked in the presence of dexamethasone (DEX)-loaded crosslinkable BCMs. The resultant HA gels (HAxBCM) contain covalently integrated micellar compartments with DEX being sequestered in the hydrophobic core. Compared

  7. Effect of xanthophyll composition on the chlorophyll excited state lifetime in plant leaves and isolated LHCII

    NASA Astrophysics Data System (ADS)

    Johnson, Matthew P.; Zia, Ahmad; Horton, Peter; Ruban, Alexander V.

    2010-07-01

    Xanthophyll excited states have been implicated by transient absorption and two-photon excitation studies in playing a key role in the regulation of photosynthetic light harvesting via photoprotective energy dissipation. For any proposed quenching mechanism to be effective it must reduce the chlorophyll excited state lifetime from 2 ns to ˜0.5-0.4 ns. In the presented study the effect of xanthophyll composition on the chlorophyll excited state lifetime in Arabidopsis leaves in the light harvesting ( F m) and photoprotective (NPQ) states was determined. The data was compared to the chlorophyll excited state lifetime of native isolated LHCII and CP26 in detergent micelles with varying xanthophyll composition. It was found that although the differences in xanthophyll composition between LHC complexes from various Arabidopsis mutants were sufficient to explain the varying F m lifetime (and varying PSII efficiency), they were not of a sufficient scale to fully explain the observed differences in the NPQ lifetimes. Only when the LHC complexes were exposed to a low detergent/low pH media, a condition known to mimic the conformational state of LHCII associated with NPQ in vivo, were variations in excited state lifetime large enough to explain the differences observed in leaves. Furthermore, the data reveal that the replacement of lutein by either zeaxanthin or violaxanthin in the internal xanthophyll binding sites of LHCII and CP26 reduces the efficiency of energy dissipation in the photoprotective state in leaves and isolated complexes.

  8. Orientation of emitting dipoles of chlorophyll A in thylakoids: considerations on the orientation factor in vivo.

    PubMed Central

    Garab, G I; Kiss, J G; Mustárdy, L A; Michel-Villaz, M

    1981-01-01

    Orientation angles of five emitting dipoles of chlorophyll a in thylakoids were estimated from low temperature fluorescence polarization ratio spectra of magnetically oriented chloroplasts. A simple expression is given also for the evaluation of data from linear dichroism measurements. It is shown that the Qy dipoles of chlorophylls lie more in the plane of the membranes and span a larger angular interval than was previously thought. Values for the orientation factor are calculated using various models corresponding to different degrees of local order of the Qy dipoles of chlorophylls in the thylakoid. We show that the characteristic orientation pattern of the Qy dipoles of chlorophylls in the membrane, i.e., increasing dichroism toward longer wavelengths, may favour energy transfer between the antenna chlorophylls as well as funnel the excitation energy into the reaction centers. Images FIGURE 1 FIGURE 4 PMID:7248470

  9. Retrieving Canopy Chlorophyll Content Of Potato Crops Using Sentinel-2 Bands

    NASA Astrophysics Data System (ADS)

    Clevers, J. G. P. W.; Kooistra, L.

    2013-12-01

    In this paper the potential of Sentinel-2 for estimating canopy chlorophyll content is evaluated. First, the PROSAIL radiative transfer model was used to study the relationship between reflectance and canopy chlorophyll content. Subsequently, relationships were tested for potato crops by studying in-situ crop variables and radiometer measurements obtained for three different growing seasons (2010 - 2012). Finally, results were evaluated using spaceborne RapidEye and WorldView-2 images obtained in the 2010 growing season for the potato field studied. Results show that the optimal wavelength position for the denominator in the red-edge chlorophyll index (CIred-edge) is between 695 nm and 725 nm. The red-edge band of Sentinel-2 at 705 nm is optimally located. In addition to the CIred-edge, the green chlorophyll index (CIgreen) had a similar performance in estimating canopy chlorophyll content. Finally, these results were confirmed using a WorldView-2 image acquired June 2010.

  10. Structural changes in block copolymer micelles induced by cosolvent mixtures

    SciTech Connect

    Kelley, Elizabeth G.; Smart, Thomas P.; Jackson, Andrew J.; Sullivan, Millicent O.; Epps, III, Thomas H.

    2012-11-26

    We investigated the influence of tetrahydrofuran (THF) addition on the structure of poly(1,2-butadiene-b-ethylene oxide) [PB-PEO] micelles in aqueous solution. Our studies showed that while the micelles remained starlike, the micelle core-corona interfacial tension and micelle size decreased upon THF addition. The detailed effects of the reduction in interfacial tension were probed using contrast variations in small angle neutron scattering (SANS) experiments. At low THF contents (high interfacial tensions), the SANS data were fit to a micelle form factor that incorporated a radial density distribution of corona chains to account for the starlike micelle profile. However, at higher THF contents (low interfacial tensions), the presence of free chains in solution affected the scattering at high q and required the implementation of a linear combination of micelle and Gaussian coil form factors. These SANS data fits indicated that the reduction in interfacial tension led to broadening of the core-corona interface, which increased the PB chain solvent accessibility at intermediate THF solvent fractions. We also noted that the micelle cores swelled with increasing THF addition, suggesting that previous assumptions of the micelle core solvent content in cosolvent mixtures may not be accurate. Control over the size, corona thickness, and extent of solvent accessible PB in these micelles can be a powerful tool in the development of targeting delivery vehicles.

  11. Decadal Changes in Global Ocean Chlorophyll

    NASA Technical Reports Server (NTRS)

    Gregg, Watson W.; Conkright, Margarita E.; Koblinsky, Chester J. (Technical Monitor)

    2001-01-01

    The global ocean chlorophyll archive produced by the Coastal Zone Color Scanner (CZCS) was revised using compatible algorithms with the Sea-viewing Wide Field-of-view Sensor (SeaWIFS), and both were blended with in situ data. This methodology permitted a quantitative comparison of decadal changes in global ocean chlorophyll from the CZCS (1979-1986) and SeaWiFS (Sep. 1997-Dec. 2000) records. Global seasonal means of ocean chlorophyll decreased over the two observational segments, by 8% in winter to 16% in autumn. Chlorophyll in the high latitudes was responsible for most of the decadal change. Conversely, chlorophyll concentrations in the low latitudes increased. The differences and similarities of the two data records provide evidence of how the Earth's climate may be changing and how ocean biota respond. Furthermore, the results have implications for the ocean carbon cycle.

  12. Completing the Feedback Loop: The Impact of Chlorophyll Data Assimilation on the Ocean State

    NASA Technical Reports Server (NTRS)

    Borovikov, Anna; Keppenne, Christian; Kovach, Robin

    2015-01-01

    In anticipation of the integration of a full biochemical model into the next generation GMAO coupled system, an intermediate solution has been implemented to estimate the penetration depth (1Kd_PAR) of ocean radiation based on the chlorophyll concentration. The chlorophyll is modeled as a tracer with sources-sinks coming from the assimilation of MODIS chlorophyll data. Two experiments were conducted with the coupled ocean-atmosphere model. In the first, climatological values of Kpar were used. In the second, retrieved daily chlorophyll concentrations were assimilated and Kd_PAR was derived according to Morel et al (2007). No other data was assimilated to isolate the effects of the time-evolving chlorophyll field. The daily MODIS Kd_PAR product was used to validate the skill of the penetration depth estimation and the MERRA-OCEAN re-analysis was used as a benchmark to study the sensitivity of the upper ocean heat content and vertical temperature distribution to the chlorophyll input. In the experiment with daily chlorophyll data assimilation, the penetration depth was estimated more accurately, especially in the tropics. As a result, the temperature bias of the model was reduced. A notably robust albeit small (2-5 percent) improvement was found across the equatorial Pacific ocean, which is a critical region for seasonal to inter-annual prediction.

  13. Triggered-release polymeric conjugate micelles for on-demand intracellular drug delivery

    NASA Astrophysics Data System (ADS)

    Cao, Yanwu; Gao, Min; Chen, Chao; Fan, Aiping; Zhang, Ju; Kong, Deling; Wang, Zheng; Peer, Dan; Zhao, Yanjun

    2015-03-01

    Nanoscale drug delivery platforms have been developed over the past four decades that have shown promising clinical results in several types of cancer and inflammatory disorders. These nanocarriers carrying therapeutic payloads are maximizing the therapeutic outcomes while minimizing adverse effects. Yet one of the major challenges facing drug developers is the dilemma of premature versus on-demand drug release, which influences the therapeutic regiment, efficacy and potential toxicity. Herein, we report on redox-sensitive polymer-drug conjugate micelles for on-demand intracellular delivery of a model active agent, curcumin. Biodegradable methoxy poly(ethylene glycol)-poly(lactic acid) copolymer (mPEG-PLA) was conjugated with curcumin via a disulfide bond or ester bond (control), respectively. The self-assembled redox-sensitive micelles exhibited a hydrodynamic size of 115.6 ± 5.9 (nm) with a zeta potential of -10.6 ± 0.7 (mV). The critical micelle concentration was determined at 6.7 ± 0.4 (μg mL-1). Under sink conditions with a mimicked redox environment (10 mM dithiothreitol), the extent of curcumin release at 48 h from disulfide bond-linked micelles was nearly three times higher compared to the control micelles. Such rapid release led to a lower half maximal inhibitory concentration (IC50) in HeLa cells at 18.5 ± 1.4 (μg mL-1), whereas the IC50 of control micelles was 41.0 ± 2.4 (μg mL-1). The cellular uptake study also revealed higher fluorescence intensity for redox-sensitive micelles. In conclusion, the redox-sensitive polymeric conjugate micelles could enhance curcumin delivery while avoiding premature release, and achieving on-demand release under the high glutathione concentration in the cell cytoplasm. This strategy opens new avenues for on-demand drug release of nanoscale intracellular delivery platforms that ultimately might be translated into pre-clinical and future clinical practice.

  14. Measurement of Sun Induced Chlorophyll Fluorescence Using Hyperspectral Satellite Imagery

    NASA Astrophysics Data System (ADS)

    Irteza, S. M.; Nichol, J. E.

    2016-06-01

    Solar Induced Chlorophyll Fluorescence (SIF), can be used as an indicator of stress in vegetation. Several scientific approaches have been made and there is considerable evidence that steady state Chlorophyll fluorescence is an accurate indicator of plant stress hence a reliable tool to monitor vegetation health status. Retrieval of Chlorophyll fluorescence provides an insight into photochemical and carbon sequestration processes within vegetation. Detection of Chlorophyll fluorescence has been well understood in the laboratory and field measurement. Fluorescence retrieval methods were applied in and around the atmospheric absorption bands 02B (Red wavelength) approximately 690 nm and 02A (Far red wavelengths) 740 nm. Hyperion satellite images were acquired for the years 2012 to 2015 in different seasons. Atmospheric corrections were applied using the 6S Model. The Fraunhofer Line Discrimanator (FLD) method was applied for retrieval of SIF from the Hyperion images by measuring the signal around the absorption bands in both vegetated and non vegetated land cover types. Absorption values were extracted in all the selected bands and the fluorescence signal was detected. The relationships between NDVI and Fluorescence derived from the satellite images are investigated to understand vegetation response within the absorption bands.

  15. Enzyme-assisted extraction of stabilized chlorophyll from spinach.

    PubMed

    Özkan, Gülay; Ersus Bilek, Seda

    2015-06-01

    Zinc complex formation with chlorophyll derivatives in spinach pulp was studied by adding 300ppm Zn(2+) for production of stable food colorant, followed by the heating at 110°C for 15min. Zinc complex formation increased at pH values of 7.0 or greater. Pectinex Ultra SP-L was selected for enzyme-assisted release of zinc-chlorophyll derivatives from spinach pulp. Effect of enzyme concentration (1-9%), treatment temperature (30-60°C), and time (30-210min) on total chlorophyll content (TCC) were optimized using response surface methodology. A quadratic regression model (R(2)=0.9486) was obtained from the experimental design. Optimum treatment conditions were 8% enzyme concentration, 45°C, and 30min, which yielded a 50.747mgTCC/100g spinach pulp. Enzymatic treatment was followed by solvent extraction with ethanol at a solvent-to-sample ratio of 2.5:1 at 60°C for 45min for the highest TCC recovery. Pretreatment with enzyme and extraction in ethanol resulted in 39% increase in Zn-chlorophyll derivative yield.

  16. Chlorophyll accumulation is enhanced by osmotic stress in graminaceous chlorophyllic cells.

    PubMed

    García-Valenzuela, Xóchitl; Garcá-Moya, Edmundo; Rascón-Cruz, Quintín; Herrera-Estrella, Luis; Aguado-Santacruz, Gerardo Armando

    2005-06-01

    We have developed a new chlorophyllic cell line ('TADH-XO') from the highly water stress tolerant grass Bouteloua gracilis (blue grama). When grown under normal (non-stress) conditions, this new cell line accumulates higher levels of chlorophyll (up to 368.1 microg total chlorophyll g(-1) FW) than a previously obtained cell line ('TIANSJ98'). Both cell lines are capable of developing substantially higher amounts of chlorophyll when subjected to osmotic stress. In order to explain these changes in the chlorophyll kinetics of the chlorophyllic cells, we analyzed the following population variables in cells subjected to polyethylene glycol 8000-induced osmotic stress: growth, viability, chlorophyll (total, 'a' and 'b'), cell size, percentage of green cells and chloroplast (number and size). Although previous studies in some chlorophyllic cells of dicots have already reported that chlorophyll increases under saline stress, in this report we show that, at least in this graminaceous cell line, the increase in chlorophyll is an immediate and proportional response to the osmotic stress applied and not the result of a progressive adaptation process. Consistent with previous studies, the increase in chlorophyll accumulation could be the result of chloroplast development (increased thylakoid number per chloroplast). On the basis of our results, the increases in chlorophyll accumulation previously observed in salt-adapted dicot cells may be the result of the osmotic shock (water deficit), rather than the ionic effect of salt on the physiology of chlorophyllic cells of dicots. Under the cell population experimental approach we followed, our study provides important insights related to the physiological behavior of chlorophyllic cells subjected to osmotic stress.

  17. Production Scaleup of Reverse Micelle Synthesis

    SciTech Connect

    Morrison,S.; Cahill, C.; Carpenter, E.; Harris, V.

    2006-01-01

    A wide range of techniques for the successful synthesis of nanosized materials have been developed recently. These procedures are sufficient for normal scientific investigation; however, for these materials to be incorporated into any practical application, the process for making them must be scalable to a larger volume. In this work, we focus on a published recipe for manganese zinc ferrite (MZFO) nanoparticles, which uses the reverse micelle synthesis technique. The normal bench-top synthesis has been scaled by a factor of 40 and successfully adapted to a 30-L pilot plant. The product of this synthesis is similar to the bench-top sample, which is also comparable to a ceramic MZFO standard. Through this work, we have demonstrated that the reverse micelle process is scalable to larger volumes.

  18. Structure of β-casein micelles

    NASA Astrophysics Data System (ADS)

    Leclerc, E.; Calmettes, P.

    β-casein is a flexible milk protein which forms micelles. Up to now their structure was controversial. Small-angle neutron scattering was used to determine the protein conformation in the aggregates. Whatever the mean aggregation number, the scattering profiles show that β-casein micelles are spherical and keep an almost constant radius of 135 Å. They consist of a relatively large and dense core surrounded by a shell of much lower density. In the latter, hydrophilic protein strands and loops protrude in the solvent as polymers grafted on a surface. The core contains most of the hydrophobic residues and some hydrophilic ones. Though its density increases with the aggregation number it is never compact.

  19. Molecular exchange in block copolymer micelles: when corona chains overlap

    NASA Astrophysics Data System (ADS)

    Lu, Jie; Lodge, Timothy; Bates, Frank; Choi, Soohyung

    2013-03-01

    The chain exchange kinetics of poly(styrene-b-ethylenepropylene) (PS-PEP) diblock copolymer micelles in squalane (C30H62) was investigated using time-resolved small angle neutron scattering (TR-SANS). The solvent is a mixture of h-squalane and d-squalane that contrast-matches a mixed 50/50 h/d PS micelle core. As isotope labeled chains exchange, the core contrast decreases, leading to a reduction in scattering intensity. This strategy therefore allows direct probing of the chain exchange rate. Separate copolymer micellar solutions containing either deuterium labeled (dPS) or normal (hPS) poly(styrene) core blocks were prepared and mixed at room temperature, below the core glass transition temperature. The samples were heated to several temperatures (around 100 °C) and monitored by TR-SANS every 5 min. As polymer concentration was increased from 1% to 15% by volume, we observed a significant slowing down of chain exchange rate. Similar retarded kinetics was found when part of the solvent in the 1% solution was replaced by homopolymer PEP (comparable size as corona block). Furthermore, if all the solvent is replaced with PEP, no exchange was detected for up to 3hr at 200 °C. These results will be discussed in terms of a molecular model for chain exchange Infineum, Iprime, NIST, ORNL

  20. Toward a Standard Protocol for Micelle Simulation.

    PubMed

    Johnston, Michael A; Swope, William C; Jordan, Kirk E; Warren, Patrick B; Noro, Massimo G; Bray, David J; Anderson, Richard L

    2016-07-01

    In this paper, we present protocols for simulating micelles using dissipative particle dynamics (and in principle molecular dynamics) that we expect to be appropriate for computing micelle properties for a wide range of surfactant molecules. The protocols address challenges in equilibrating and sampling, specifically when kinetics can be very different with changes in surfactant concentration, and with minor changes in molecular size and structure, even using the same force field parameters. We demonstrate that detection of equilibrium can be automated and is robust, for the molecules in this study and others we have considered. In order to quantify the degree of sampling obtained during simulations, metrics to assess the degree of molecular exchange among micellar material are presented, and the use of correlation times are prescribed to assess sampling and for statistical uncertainty estimates on the relevant simulation observables. We show that the computational challenges facing the measurement of the critical micelle concentration (CMC) are somewhat different for high and low CMC materials. While a specific choice is not recommended here, we demonstrate that various methods give values that are consistent in terms of trends, even if not numerically equivalent. PMID:27096611

  1. Toward a Standard Protocol for Micelle Simulation.

    PubMed

    Johnston, Michael A; Swope, William C; Jordan, Kirk E; Warren, Patrick B; Noro, Massimo G; Bray, David J; Anderson, Richard L

    2016-07-01

    In this paper, we present protocols for simulating micelles using dissipative particle dynamics (and in principle molecular dynamics) that we expect to be appropriate for computing micelle properties for a wide range of surfactant molecules. The protocols address challenges in equilibrating and sampling, specifically when kinetics can be very different with changes in surfactant concentration, and with minor changes in molecular size and structure, even using the same force field parameters. We demonstrate that detection of equilibrium can be automated and is robust, for the molecules in this study and others we have considered. In order to quantify the degree of sampling obtained during simulations, metrics to assess the degree of molecular exchange among micellar material are presented, and the use of correlation times are prescribed to assess sampling and for statistical uncertainty estimates on the relevant simulation observables. We show that the computational challenges facing the measurement of the critical micelle concentration (CMC) are somewhat different for high and low CMC materials. While a specific choice is not recommended here, we demonstrate that various methods give values that are consistent in terms of trends, even if not numerically equivalent.

  2. Self-assembly of amphiphilic plasmonic micelle-like nanoparticles in selective solvents.

    PubMed

    He, Jie; Huang, Xinglu; Li, Yan-Chun; Liu, Yijing; Babu, Taarika; Aronova, Maria A; Wang, Shouju; Lu, Zhongyuan; Chen, Xiaoyuan; Nie, Zhihong

    2013-05-29

    Amphiphilic plasmonic micelle-like nanoparticles (APMNs) composed of gold nanoparticles (AuNPs) and amphiphilic block copolymers (BCPs) structurally resemble polymer micelles with well-defined architectures and chemistry. The APMNs can be potentially considered as a prototype for modeling a higher-level self-assembly of micelles. The understanding of such secondary self-assembly is of particular importance for the bottom-up design of new hierarchical nanostructures. This article describes the self-assembly, modeling, and applications of APMN assemblies in selective solvents. In a mixture of water/tetrahydrofuran, APMNs assembled into various superstructures, including unimolecular micelles, clusters with controlled number of APMNs, and vesicles, depending on the lengths of polymer tethers and the sizes of AuNP cores. The delicate interplay of entropy and enthalpy contributions to the overall free energy associated with the assembly process, which is strongly dependent on the spherical architecture of APMNs, yields an assembly diagram that is different from the assembly of linear BCPs. Our experimental and computational studies suggested that the morphologies of assemblies were largely determined by the deformability of the effective nanoparticles (that is, nanoparticles together with tethered chains as a whole). The assemblies of APMNs resulted in strong absorption in near-infrared range due to the remarkable plasmonic coupling of Au cores, thus facilitating their biomedical applications in bioimaging and photothermal therapy of cancer.

  3. Self-assembly of amphiphilic plasmonic micelle-like nanoparticles in selective solvents.

    PubMed

    He, Jie; Huang, Xinglu; Li, Yan-Chun; Liu, Yijing; Babu, Taarika; Aronova, Maria A; Wang, Shouju; Lu, Zhongyuan; Chen, Xiaoyuan; Nie, Zhihong

    2013-05-29

    Amphiphilic plasmonic micelle-like nanoparticles (APMNs) composed of gold nanoparticles (AuNPs) and amphiphilic block copolymers (BCPs) structurally resemble polymer micelles with well-defined architectures and chemistry. The APMNs can be potentially considered as a prototype for modeling a higher-level self-assembly of micelles. The understanding of such secondary self-assembly is of particular importance for the bottom-up design of new hierarchical nanostructures. This article describes the self-assembly, modeling, and applications of APMN assemblies in selective solvents. In a mixture of water/tetrahydrofuran, APMNs assembled into various superstructures, including unimolecular micelles, clusters with controlled number of APMNs, and vesicles, depending on the lengths of polymer tethers and the sizes of AuNP cores. The delicate interplay of entropy and enthalpy contributions to the overall free energy associated with the assembly process, which is strongly dependent on the spherical architecture of APMNs, yields an assembly diagram that is different from the assembly of linear BCPs. Our experimental and computational studies suggested that the morphologies of assemblies were largely determined by the deformability of the effective nanoparticles (that is, nanoparticles together with tethered chains as a whole). The assemblies of APMNs resulted in strong absorption in near-infrared range due to the remarkable plasmonic coupling of Au cores, thus facilitating their biomedical applications in bioimaging and photothermal therapy of cancer. PMID:23642094

  4. Assembly of water-soluble chlorophyll-binding proteins with native hydrophobic chlorophylls in water-in-oil emulsions.

    PubMed

    Bednarczyk, Dominika; Takahashi, Shigekazu; Satoh, Hiroyuki; Noy, Dror

    2015-03-01

    The challenges involved in studying cofactor binding and assembly, as well as energy- and electron transfer mechanisms in the large and elaborate transmembrane protein complexes of photosynthesis and respiration have prompted considerable interest in constructing simplified model systems based on their water-soluble protein analogs. Such analogs are also promising templates and building blocks for artificial bioinspired energy conversion systems. Yet, development is limited by the challenge of introducing the essential cofactors of natural proteins that are highly water-insoluble into the water-soluble protein analogs. Here we introduce a new efficient method based on water-in-oil emulsions for overcoming this challenge. We demonstrate the effectiveness of the method in the assembly of native chlorophylls with four recombinant variants of the water-soluble chlorophyll-binding protein of Brassicaceae plants. We use the method to gain new insights into the protein-chlorophyll assembly process, and demonstrate its potential as a fast screening system for developing novel chlorophyll-protein complexes.

  5. Regional variability among nonlinear chlorophyll-phosphorus relationships in lakes

    USGS Publications Warehouse

    Filstrup, Christopher T.; Wagner, Tyler; Soranno, Patricia A.; Stanley, Emily H.; Stow, Craig A.; Webster, Katherine E.; Downing, John A.

    2014-01-01

    The relationship between chlorophyll a (Chl a) and total phosphorus (TP) is a fundamental relationship in lakes that reflects multiple aspects of ecosystem function and is also used in the regulation and management of inland waters. The exact form of this relationship has substantial implications on its meaning and its use. We assembled a spatially extensive data set to examine whether nonlinear models are a better fit for Chl a—TP relationships than traditional log-linear models, whether there were regional differences in the form of the relationships, and, if so, which regional factors were related to these differences. We analyzed a data set from 2105 temperate lakes across 35 ecoregions by fitting and comparing two different nonlinear models and one log-linear model. The two nonlinear models fit the data better than the log-linear model. In addition, the parameters for the best-fitting model varied among regions: the maximum and lower Chl aasymptotes were positively and negatively related to percent regional pasture land use, respectively, and the rate at which chlorophyll increased with TP was negatively related to percent regional wetland cover. Lakes in regions with more pasture fields had higher maximum chlorophyll concentrations at high TP concentrations but lower minimum chlorophyll concentrations at low TP concentrations. Lakes in regions with less wetland cover showed a steeper Chl a—TP relationship than wetland-rich regions. Interpretation of Chl a—TP relationships depends on regional differences, and theory and management based on a monolithic relationship may be inaccurate.

  6. Mediterranean Ocean Colour Chlorophyll trend

    NASA Astrophysics Data System (ADS)

    rinaldi, eleonora; colella, simone; santoleri, rosalia

    2014-05-01

    Monitoring chlorophyll (Chl) concentration, seen as a proxy for phytoplankton biomass, is an efficient tool in order to understand the response of marine ecosystem to human pressures. This is particularly important along the coastal regions, in which the strong anthropization and the irrational exploitation of resources represent a persistent threat to the biodiversity. The aim of this work is to assess the effectiveness and feasibility of using Ocean Color (OC) data to monitor the environmental changes in Mediterranean Sea and to develop a method for detecting trend from OC data that can constitute a new indicator of the water quality within the EU Marine Strategy Framework Directive implementation. In this study the Mediterranean merged Case1-Case2 chlorophyll product, produced by CNR-ISAC and distributed in the framework of MyOcean, is analyzed. This product is obtained by using two different bio-optical algorithms for open ocean (Case1) and coastal turbid (Case2) waters; this improves the quality of the Chl satellite estimates, especially near the coast. In order to verify the real capability of the this product for estimating Chl trend and for selecting the most appropriated statistical test to detect trend in the Mediterranean Sea, a comparison between OC and in situ data are carried out. In-situ Chl data are part of the European Environment Information and Observation Network (Eionet) of the European Environmental Agency (EEA). Four different statistical approaches to estimate trend have been selected and used to compare trend values obtained with in-situ and OC data. Results show that the best agreement between in-situ and OC trend is achieved using the Mann- Kendall test. The Mediterranean trend map obtained applying this test to the de-seasonalized OC time series shows that, in accordance with the results of many authors, the case 1 waters of Mediterranean sea are characterized by a negative trend. However, the most intense trend signals, both negative

  7. Dendrimeric micelles for controlled drug release and targeted delivery

    PubMed Central

    Ambade, Ashootosh V.; Savariar, Elamprakash N.; Thayumanavan, S.

    2008-01-01

    This review highlights the developments in dendrimer-based micelles for drug delivery. Dendrimers, the perfectly branched monodisperse macromolecules, have certain structural advantages that make them attractive candidates as drug carriers for controlled release or targeted delivery. As polymeric micelle-based approaches precede the work in dendrimers, these are also discussed briefly. The review concludes with a perspective on possible applications of biaryl-based dendrimeric micelles that exhibit environment-dependent conformations, in drug delivery. PMID:16053329

  8. Photosynthetic bark: Use of chlorophyll absorption continuum index to estimate Boswellia papyrifera bark chlorophyll content

    NASA Astrophysics Data System (ADS)

    Girma, Atkilt; Skidmore, Andrew K.; de Bie, C. A. J. M.; Bongers, Frans; Schlerf, Martin

    2013-08-01

    Quantification of chlorophyll content provides useful insight into the physiological performance of plants. Several leaf chlorophyll estimation techniques, using hyperspectral instruments, are available. However, to our knowledge, a non-destructive bark chlorophyll estimation technique is not available. We set out to assess Boswellia papyrifera tree bark chlorophyll content and to provide an appropriate bark chlorophyll estimation technique using hyperspectral remote sensing techniques. In contrast to the leaves, the bark of B. papyrifera has several outer layers masking the inner photosynthetic bark layer. Thus, our interest includes understanding how much light energy is transmitted to the photosynthetic inner bark and to what extent the inner photosynthetic bark chlorophyll activity could be remotely sensed during both the wet and the dry season. In this study, chlorophyll estimation using the chlorophyll absorption continuum index (CACI) yielded a higher R2 (0.87) than others indices and methods, such as the use of single band, simple ratios, normalized differences, and conventional red edge position (REP) based estimation techniques. The chlorophyll absorption continuum index approach considers the increase or widening in area of the chlorophyll absorption region, attributed to high concentrations of chlorophyll causing spectral shifts in both the yellow and the red edge. During the wet season B. papyrifera trees contain more bark layers than during the dry season. Having less bark layers during the dry season (leaf off condition) is an advantage for the plants as then their inner photosynthetic bark is more exposed to light, enabling them to trap light energy. It is concluded that B. papyrifera bark chlorophyll content can be reliably estimated using the chlorophyll absorption continuum index analysis. Further research on the use of bark signatures is recommended, in order to discriminate the deciduous B. papyrifera from other species during the dry season.

  9. The critical micelle concentration of tetraethylammonium perfluorooctylsulfonate in water.

    PubMed

    López-Fontán, José L; González-Pérez, Alfredo; Costa, Julian; Ruso, Juan M; Prieto, Gerardo; Schulz, Pablo C; Sarmiento, Félix

    2006-02-15

    The aggregation characteristics of tetraethylammonium perfluorooctylsulfonate in water were studied by several techniques: conductivity, pH, ion-selective electrodes, and surface tension. It was concluded that the aggregation process is gradual and starts with the formation of oligomers such as ion pairs that grow to give spherical micelles, which become wormlike with increasing concentration. Because of the size and hydrophobicity of the counterion, micelles quickly increase in ionization degree up to about 0.5. Differences among different critical micelle concentration values in the literature are explained on the basis of the gradual formation of micelles.

  10. Diclofenac/biodegradable polymer micelles for ocular applications

    NASA Astrophysics Data System (ADS)

    Li, Xingyi; Zhang, Zhaoliang; Li, Jie; Sun, Shumao; Weng, Yuhua; Chen, Hao

    2012-07-01

    In this paper, methoxypoly(ethylene glycol)-poly(ε-caprolactone) (MPEG-PCL) micelle formulations as promising nano-carriers for poorly water soluble drugs were investigated for the delivery of diclofenac to the eye. Diclofenac loaded MPEG-PCL micelles were prepared by a simple solvent-diffusion method and characterized by dynamic light scattering (DLS), atomic force microscopy (AFM), Fourier transform infra-red (FTIR), X-ray diffraction (XRD), differential scanning calorimetery (DSC), etc. With the analysis of XRD and DSC, the diclofenac was present as an amorphous state in the formulation. The in vitro release profile indicated a sustained release manner of diclofenac from the micelles. Meanwhile, in vivo studies on eye irritation were performed with blank MPEG-PCL micelles (200 mg ml-1). The results showed that the developed MPEG-PCL micelles were non-irritants to the eyes of rabbits. In vitro penetration studies across the rabbit cornea demonstrated that the micelle formulations exhibited a 17-fold increase in penetration compared with that of diclofenac phosphate buffered saline (PBS) solution. The in vivo pharmacokinetics profile of the micelle parent drug in the aqueous humor of the rabbit was evaluated and the data showed that the diclofenac loaded MPEG-PCL micelles exhibited a 2-fold increase in AUC0-24 h than that of the diclofenac PBS solution eye drops. These results suggest a great potential of our micelle formulations as a novel ocular drug delivery system to improve the bioavailability of the drugs.

  11. Mesoscale crystallization of calcium phosphate nanostructures in protein (casein) micelles

    NASA Astrophysics Data System (ADS)

    Thachepan, Surachai; Li, Mei; Mann, Stephen

    2010-11-01

    Aqueous micelles of the multi-protein calcium phosphate complex, casein, were treated at 60 °C and pH 7 over several months. Although partial dissociation of the micelles into 12 nm sized amorphous calcium phosphate (ACP)/protein nanoparticles occurred within a period of 14 days, crystallization of the ACP nanoclusters into bundles of hydroxyapatite (HAP) nanofilaments was not observed until after 12 weeks. The HAP nanofilaments were formed specifically within the partially disrupted protein micelles suggesting a micelle-mediated pathway of mesoscale crystallization. Similar experiments using ACP-containing synthetic micelles prepared from β-casein protein alone indicated that co-aligned bundles of HAP nanofilaments were produced within the protein micelle interior after 24 hours at temperatures as low as 35 °C. The presence of Mg2+ ions in the casein micelles, as well as a possible synergistic effect associated with the multi-protein nature of the native aggregates, could account for the marked inhibition in mesoscale crystallization observed in the casein micelles compared with the single-component β-casein constructs.Aqueous micelles of the multi-protein calcium phosphate complex, casein, were treated at 60 °C and pH 7 over several months. Although partial dissociation of the micelles into 12 nm sized amorphous calcium phosphate (ACP)/protein nanoparticles occurred within a period of 14 days, crystallization of the ACP nanoclusters into bundles of hydroxyapatite (HAP) nanofilaments was not observed until after 12 weeks. The HAP nanofilaments were formed specifically within the partially disrupted protein micelles suggesting a micelle-mediated pathway of mesoscale crystallization. Similar experiments using ACP-containing synthetic micelles prepared from β-casein protein alone indicated that co-aligned bundles of HAP nanofilaments were produced within the protein micelle interior after 24 hours at temperatures as low as 35 °C. The presence of Mg2+ ions in

  12. Preparation and Characterization of Lipophilic Doxorubicin Pro-drug Micelles.

    PubMed

    Li, Feng; Snow-Davis, Candace; Du, Chengan; Bondarev, Mikhail L; Saulsbury, Marilyn D; Heyliger, Simone O

    2016-01-01

    Micelles have been successfully used for the delivery of anticancer drugs. Amphiphilic polymers form core-shell structured micelles in an aqueous environment through self-assembly. The hydrophobic core of micelles functions as a drug reservoir and encapsulates hydrophobic drugs. The hydrophilic shell prevents the aggregation of micelles and also prolongs their systemic circulation in vivo. In this protocol, we describe a method to synthesize a doxorubicin lipophilic pro-drug, doxorubicin-palmitic acid (DOX-PA), which will enhance drug loading into micelles. A pH-sensitive hydrazone linker was used to conjugate doxorubicin with the lipid, which facilitates the release of free doxorubicin inside cancer cells. Synthesized DOX-PA was purified with a silica gel column using dichloromethane/methanol as the eluent. Purified DOX-PA was analyzed with thin layer chromatography (TLC) and (1)H-Nuclear Magnetic Resonance Spectroscopy ((1)H-NMR). A film dispersion method was used to prepare DOX-PA loaded DSPE-PEG micelles. In addition, several methods for characterizing micelle formulations are described, including determination of DOX-PA concentration and encapsulation efficiency, measurement of particle size and distribution, and assessment of in vitro anticancer activities. This protocol provides useful information regarding the preparation and characterization of drug-loaded micelles and thus will facilitate the research and development of novel micelle-based cancer nanomedicines. PMID:27584689

  13. Brij-micelle and polyacrylic acid interaction investigated by Cu 2+-induced pyrene fluorescence: Effect of brij-micelle structure

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, Prasun; Ghosh, Amit K.; Bandyopadhyay, Sayan

    2009-07-01

    Fluorescence response of pyrene has been studied in the presence of polyacrylic acid (PAA) and brij surfactant micelles with Cu 2+ as an ionic quencher. The quenched pyrene emission is completely recovered with the addition of PAA (conc. 2.4 × 10 -4 M) for brij 35 (poly-oxyethylene-23 lauryl ether) micelle indicating PAA-Cu 2+ complex formation at the micelle-water interface. This could be due to the relatively easier accessibility of PAA polymer chains near poly-oxyethylene chain of brij 35 micelle compared to brij 30 (poly-oxyethylene-4 lauryl ether) micelle. The interaction between brij-micelle and polymer is confirmed by turbidimetry and NMR spectroscopy.

  14. Interaction of triplet sensitizers with chlorophyll: Formation of singlet chlorophyll

    SciTech Connect

    Bohne, C.; Scaiano, J.C. )

    1989-03-29

    The interaction of several triplet sensitizers with chlorophyll a (Chla) has been examined using laser techniques. For the carbonyl sensitizers (with triplet energies > 53 kcal/mol) it was possible to measure the quenching rate constants; these were systematically {>=} 10{sup 10} M{sup {minus}1} s{sup {minus}1}. In the cases of acetone, benzophenone, and p-methoxyacetophenone the quenching process leads to the formation of the fluorescent singlet state of Chla. For benzophenone (k{sub q} = 2.4 {times} 10{sup 10} M{sup {minus}1} s{sup {minus}1}) approximately 3% of the quenching events lead to the formation of excited Chla. Several sensitizers (decafluorobenzophenone, benzil, and fluorenone) do not induce Chla fluorescence (or do it very inefficiently) in spite of having triplet energies above the S{sub 1} level of Chla. In light of their results the most probable mechanism involves energy transfer from the triplet sensitizer to an upper triple state of Chla ({sup 3}Chla**) which can undergo reverse intersystem crossing to the singlet manifold of Chla and thus induce fluorescence. The inefficient sensitizers are those where electron transfer between the excited singlet of Chla or {sup 3}Chla** and ground-state sensitizers is energetically favorable, leading to rapid in-cage quenching of the initially formed excited states of Chla. Formation of radical-ion pair between the triplet sensitizer and Chla followed by the generation of singlet Chla in the recombination of the radical ions could not be completely discarded.

  15. Physical drivers of interannual chlorophyll variability in the eastern subtropical North Atlantic

    NASA Astrophysics Data System (ADS)

    Pastor, M. V.; Palter, J. B.; Pelegrí, J. L.; Dunne, J. P.

    2013-08-01

    Interannual chlorophyll variability and its driving mechanisms are evaluated in the eastern subtropical North Atlantic, where elevated surface chlorophyll concentrations regularly extend more than 1500 km into the central subtropical North Atlantic and modulate the areal extent of the North Atlantic's lowest chlorophyll waters. We first characterize the considerable interannual variability in the size of the high chlorophyll region using SeaWiFS satellite data. We then evaluate the relationship between satellite chlorophyll and sea surface height (SSH), which are anticorrelated in the study region, most likely as a result of the inverse relationship between SSH and nutricline depth. To put these results in a longer temporal context, we study a hindcast simulation of a global ocean model with biogeochemistry (GFDL's MOM4.1 with TOPAZ biogeochemistry), after evaluating the model's skill at simulating chlorophyll and SSH relative to observations. In the simulation, the variability seen during the satellite era appears to be imbedded in a much larger multidecadal modulation. The drivers of such variability are assessed by evaluating all the terms in the nutrient budget of the euphotic zone. Because diffusive processes are not a dominant control on nutrient supply, stratification is not a good indicator of nutrient supply. Rather, vertical advection of nutrients, strongly tied to Ekman pumping, is the leading driver of variability in the size of the high chlorophyll region and the productivity within the study area.

  16. Stability, interaction, size, and microenvironmental properties of mixed micelles of decanoyl-N-methylglucamide and sodium dodecyl sulfate.

    PubMed

    Hierrezuelo, J M; Aguiar, J; Ruiz, C Carnero

    2004-11-23

    The mixed micellization between the nonionic surfactant decanoyl-N-methylglucamide (MEGA-10) and the common sodium dodecyl sulfate (SDS) in aqueous solutions of 0.1 M NaCl was investigated by the fluorescence probe method. The critical micelle concentrations were determined by the pyrene 1:3 ratio method. The experimental data are discussed in light of two mixing thermodynamic models within the framework of the pseudophase separation model, including the conventional regular solution theory and a recent treatment proposed by Maeda (J. Phys. Chem. B 2004, 108, 6043). This last approach provides a more appropriate description of the mixed system, particularly in two aspects: the nature of the interactions responsible for the stability of the mixed micelle and the behavior of the excess free energy per monomer of the system. By using the static quenching method, the mean micellar aggregation numbers of mixed micelles in the whole range of compositions were obtained. It was found that the micellar aggregation number initially increases with the content of the ionic component, then remains roughly constant, and, finally, decreases slightly for high content of this component. This behavior was analyzed taking into account the effects produced by the presence of the charged headgroups of sodium dodecyl sulfate, as this component increases its participation in the mixed micelle. The micropolarity of the mixed micelles was studied by the pyrene 1:3 ratio index. It was observed that the increasing participation of the ionic component induces the formation of micelles with a more dehydrated structure. Data of micellar microviscosity were obtained by using different methods, including fluorescence intensity measurements of Auramine O and steady-state fluorescence anisotropy of rhodamine B and diphenylbutadiene. The results obtained from these experiments are in good agreement and suggest the formation of mixed micelles with a less ordered structure as the content of SDS

  17. Determination of the Optimal Training Principle and Input Variables in Artificial Neural Network Model for the Biweekly Chlorophyll-a Prediction: A Case Study of the Yuqiao Reservoir, China

    PubMed Central

    Liu, Yu; Xi, Du-Gang; Li, Zhao-Liang

    2015-01-01

    Predicting the levels of chlorophyll-a (Chl-a) is a vital component of water quality management, which ensures that urban drinking water is safe from harmful algal blooms. This study developed a model to predict Chl-a levels in the Yuqiao Reservoir (Tianjin, China) biweekly using water quality and meteorological data from 1999-2012. First, six artificial neural networks (ANNs) and two non-ANN methods (principal component analysis and the support vector regression model) were compared to determine the appropriate training principle. Subsequently, three predictors with different input variables were developed to examine the feasibility of incorporating meteorological factors into Chl-a prediction, which usually only uses water quality data. Finally, a sensitivity analysis was performed to examine how the Chl-a predictor reacts to changes in input variables. The results were as follows: first, ANN is a powerful predictive alternative to the traditional modeling techniques used for Chl-a prediction. The back program (BP) model yields slightly better results than all other ANNs, with the normalized mean square error (NMSE), the correlation coefficient (Corr), and the Nash-Sutcliffe coefficient of efficiency (NSE) at 0.003 mg/l, 0.880 and 0.754, respectively, in the testing period. Second, the incorporation of meteorological data greatly improved Chl-a prediction compared to models solely using water quality factors or meteorological data; the correlation coefficient increased from 0.574-0.686 to 0.880 when meteorological data were included. Finally, the Chl-a predictor is more sensitive to air pressure and pH compared to other water quality and meteorological variables. PMID:25768650

  18. E-photosynthesis: a comprehensive modeling approach to understand chlorophyll fluorescence transients and other complex dynamic features of photosynthesis in fluctuating light.

    PubMed

    Nedbal, Ladislav; Cervený, Jan; Rascher, Uwe; Schmidt, Henning

    2007-01-01

    Plants are exposed to a temporally and spatially heterogeneous environment, and photosynthesis is well adapted to these fluctuations. Understanding of the complex, non-linear dynamics of photosynthesis in fluctuating light requires novel-modeling approaches that involve not only the primary light and dark biochemical reactions, but also networks of regulatory interactions. This requirement exceeds the capacity of the existing molecular models that are typically reduced to describe a partial process, dynamics of a specific complex or its particular dynamic feature. We propose a concept of comprehensive model that would represent an internally consistent, integral framework combining information on the reduced models that led to its construction. This review explores approaches and tools that exist in engineering, mathematics, and in other domains of biology that can be used to develop a comprehensive model of photosynthesis. Equally important, we investigated techniques by which one can rigorously reduce such a comprehensive model to models of low dimensionality, which preserve dynamic features of interest and, thus, contribute to a better understanding of photosynthesis under natural and thus fluctuating conditions. The web-based platform www.e-photosynthesis.org is introduced as an arena where these concepts and tools are being introduced and tested.

  19. E-photosynthesis: a comprehensive modeling approach to understand chlorophyll fluorescence transients and other complex dynamic features of photosynthesis in fluctuating light.

    PubMed

    Nedbal, Ladislav; Cervený, Jan; Rascher, Uwe; Schmidt, Henning

    2007-01-01

    Plants are exposed to a temporally and spatially heterogeneous environment, and photosynthesis is well adapted to these fluctuations. Understanding of the complex, non-linear dynamics of photosynthesis in fluctuating light requires novel-modeling approaches that involve not only the primary light and dark biochemical reactions, but also networks of regulatory interactions. This requirement exceeds the capacity of the existing molecular models that are typically reduced to describe a partial process, dynamics of a specific complex or its particular dynamic feature. We propose a concept of comprehensive model that would represent an internally consistent, integral framework combining information on the reduced models that led to its construction. This review explores approaches and tools that exist in engineering, mathematics, and in other domains of biology that can be used to develop a comprehensive model of photosynthesis. Equally important, we investigated techniques by which one can rigorously reduce such a comprehensive model to models of low dimensionality, which preserve dynamic features of interest and, thus, contribute to a better understanding of photosynthesis under natural and thus fluctuating conditions. The web-based platform www.e-photosynthesis.org is introduced as an arena where these concepts and tools are being introduced and tested. PMID:17492490

  20. Identification of genes associated with chlorophyll accumulation in flower petals.

    PubMed

    Ohmiya, Akemi; Hirashima, Masumi; Yagi, Masafumi; Tanase, Koji; Yamamizo, Chihiro

    2014-01-01

    Plants have an ability to prevent chlorophyll accumulation, which would mask the bright flower color, in their petals. In contrast, leaves contain substantial amounts of chlorophyll, as it is essential for photosynthesis. The mechanisms of organ-specific chlorophyll accumulation are unknown. To identify factors that determine the chlorophyll content in petals, we compared the expression of genes related to chlorophyll metabolism in different stages of non-green (red and white) petals (very low chlorophyll content), pale-green petals (low chlorophyll content), and leaves (high chlorophyll content) of carnation (Dianthus caryophyllus L.). The expression of many genes encoding chlorophyll biosynthesis enzymes, in particular Mg-chelatase, was lower in non-green petals than in leaves. Non-green petals also showed higher expression of genes involved in chlorophyll degradation, including STAY-GREEN gene and pheophytinase. These data suggest that the absence of chlorophylls in carnation petals may be caused by the low rate of chlorophyll biosynthesis and high rate of degradation. Similar results were obtained by the analysis of Arabidopsis microarray data. In carnation, most genes related to chlorophyll biosynthesis were expressed at similar levels in pale-green petals and leaves, whereas the expression of chlorophyll catabolic genes was higher in pale-green petals than in leaves. Therefore, we hypothesize that the difference in chlorophyll content between non-green and pale-green petals is due to different levels of chlorophyll biosynthesis. Our study provides a basis for future molecular and genetic studies on organ-specific chlorophyll accumulation.

  1. Biopolymer-based supramolecular micelles from β-cyclodextrin and methylcellulose.

    PubMed

    Du, Jiaojiao; Guo, Xin; Tu, Jiaxing; Xiao, Longqiang; Jia, Xiangxiang; Liao, Liqiong; Liu, Lijian

    2012-09-01

    Supramolecular polymer micelles (SMPMs) were constructed from natural and natural-derived polymers: β-cyclodextrin (β-CD)/maleic anhydride modified β-cyclodextrin (MAh-β-CD) and methylcellulose (MC) in aqueous solution by one-pot self-assembly procedure, in which, β-CD and MAh-β-CD inclusion complexes were used as the hydrophilic shell and the free MC as the core. The shapes of the SMPMs were regular spheres with diameters of 25±5 nm. The critical micelle concentrations, calculated from steady-state fluorescence emission spectra, were around 15.13 and 20.89 mg/L for MC/β-CD and MC/MAh-β-CD SMPMs, respectively. The in vitro drug release behaviors of the micelles were studied using prednisone acetate as a model drug, and the results showed that the MC/MAh-β-CD micelle had a drug-enrichment core and excellent drug released behaviors with a sustaining release time of 700 h.

  2. Solubilization of Polycyclic Aromatic Compounds into n-Decyltrimethylammonium Perfluorocarboxylate Micelles.

    PubMed

    Yoshida; Moroi

    2000-12-01

    Solubilization of polycyclic aromatic compounds in aqueous dilute solutions of three cationic amphiphiles was studied. The maximum additive concentrations (MACs) of the aromatic compounds were constant below their critical micelle concentrations (cmcs) and monotonically increased above the cmcs. The first stepwise association constants (K(1)) between a solubilizate monomer and a vacant micelle were evaluated from the MACs for the solubilizates using the mass action model for solubilization into micelles in the dilute solution. The standard Gibbs energy changes of solubilization (DeltaG degrees ) were calculated from K(1), and the enthalpy and entropy changes of solubilization were estimated from the temperature dependence. MACs of each surfactant at the same surfactant concentration above the cmc were different depending on the cmc, but there was little difference in the DeltaG degrees values. Some differences appeared in the enthalpy and entropy values in accordance with their micellar size or degrees of counterion binding to micelles. DeltaG degrees for solubilization decreased linearly with carbon number of aromatic solubilizate for each micellar solution. Copyright 2000 Academic Press.

  3. Adsorptive partitioning of an organic compound onto polyelectrolyte-immobilized micelles on porous glass and sand.

    PubMed

    Wang, Y; Banziger, J; Dubin, P L; Filippelli, G; Nuraje, N

    2001-06-15

    Halting the spread of organic contaminants in subsurface aquifers is a critical environmental problem. We describe a novel "permeable reactive barrier" that results when organophile-solubilizing properties are conferred on siliceous materials by treating them with a cationic polymer and oppositely charged mixed surfactant micelles. Controlled pore glass, quartz sand, and sea sand were treated with poly(diallyldimethylammonium chloride) and with mixed micelles of Triton X-100 and sodium dodecyl sulfate, either sequentially or simultaneously, following different treatment procedures. A model organophilic compound, Orange OT, was adsorbed and retained under aqueous agitation on the siliceous treated surfaces but not on untreated surfaces or those treated with micelle only. The aspect of the treatment procedure producing the most significant effect on Orange OT solubilization was the ionic strength. The retention of Orange OT in a layer of polyelectrolyte-micelle-treated sand under flow, within a column of untreated sand, demonstrates the possibility of using similar processes as a permeable reactive barrier to trap organic pollutants.

  4. Polymeric micelles encapsulating fisetin improve the therapeutic effect in colon cancer.

    PubMed

    Chen, Yishan; Wu, Qinjie; Song, Linjiang; He, Tao; Li, Yuchen; Li, Ling; Su, Weijun; Liu, Lei; Qian, Zhiyong; Gong, Changyang

    2015-01-14

    The natural flavonoid fisetin (3,3',4',7-tetrahydroxyflavone) was discovered to possess antitumor activity, revealing its potential value in future chemotherapy. However, its poor water solubility makes it difficult for intravenous administration. In this study, the monomethyl poly(ethylene glycol)-poly(ε-caprolactone) (MPEG-PCL) copolymer was applied to prepare nanoassemblies of fisetin by a self-assembly procedure. The prepared fisetin micelles gained a mean particle size of 22 ± 3 nm, polydisperse index of 0.163 ± 0.032, drug loading of 9.88 ± 0.14%, and encapsulation efficiency of 98.53 ± 0.02%. Compared with free fisetin, fisetin micelles demonstrated a sustained and prolonged in vitro release behavior, as well as enhanced cytotoxicity, cellular uptake, and fisetin-induced apoptosis in CT26 cells. As for in vivo studies, fisetin micelles were more competent for suppressing tumor growth and prolonging survival time than free fisetin in the subcutaneous CT26 tumor model. Furthermore, histological analysis, terminal deoxynucleotidyl transferase-mediated nick-end labeling assay, immunohistochemical detection of Ki-67, and microvessel density detection were conducted, demonstrating that fisetin micelles gained increased tumor apoptosis induction, proliferation suppression, and antiangiogenesis activities. In conclusion, we have successfully produced a MPEG-PCL-based nanocarrier encapsulating fisetin with enhanced antitumor activity.

  5. The Eastern Equatorial Pacific Chlorophyll Dynamics: Update of the `Equatorial Box' Project

    NASA Astrophysics Data System (ADS)

    Westberry, T.; Wang, X.; Murtugudde, R.; Behrenfeld, M.; Roesler, C.

    2006-12-01

    The `Equatorial Box' Project utilizes the mooring observations along the 125 and 140 TAO lines to provide carbon component data, including chlorophyll, primary production, POC and DOC. These parameters together with other oceanographic properties can be used to validate ocean circulation-ecosystem models. In turn, a validated model can offer considerable promise for not only filling the gaps in the spatial and temporal coverage from the available observations, but also enhancing our understanding of the mechanisms underlying the variability. Here, we present both measured and simulated vertical-meridional chlorophyll distributions and primary production along 125W and 140W. While there is a permanent layer of deep chlorophyll maximum at 30-60 m, there is no deep maximum in phytoplankton carbon biomass or primary production. Our analyses focus on impact of nutrient stress and light conditions on chlorophyll dynamics in the eastern equatorial Pacific. We also compare modeled primary productivity with ocean color derived rates.

  6. Light Absorption in Arctic Sea Ice - Black Carbon vs Chlorophyll

    NASA Astrophysics Data System (ADS)

    Ogunro, O. O.; Wingenter, O. W.; Elliott, S.; Hunke, E. C.; Flanner, M.; Wang, H.; Dubey, M. K.; Jeffery, N.

    2015-12-01

    The fingerprint of climate change is more obvious in the Arctic than any other place on Earth. This is not only because the surface temperature there has increased at twice the rate of global mean temperature but also because Arctic sea ice extent has reached a record low of 49% reduction relative to the 1979-2000 climatology. Radiation absorption through black carbon (BC) deposited on Arctic snow and sea ice surface is one of the major hypothesized contributors to the decline. However, we note that chlorophyll-a absorption owing to increasing biology activity in this region could be a major competitor during boreal spring. Modeling of sea-ice physical and biological processes together with experiments and field observations promise rapid progress in the quality of Arctic ice predictions. Here we develop a dynamic ice system module to investigate discrete absorption of both BC and chlorophyll in the Arctic, using BC deposition fields from version 5 of Community Atmosphere Model (CAM5) and vertically distributed layers of chlorophyll concentrations from Sea Ice Model (CICE). To this point, our black carbon mixing ratios compare well with available in situ data. Both results are in the same order of magnitude. Estimates from our calculations show that sea ice and snow around the Canadian Arctic Archipelago and Baffin Bay has the least black carbon absorption while values at the ice-ocean perimeter in the region of the Barents Sea peak significantly. With regard to pigment concentrations, high amounts of chlorophyll are produced in Arctic sea ice by the bottom microbial community, and also within the columnar pack wherever substantial biological activity takes place in the presence of moderate light. We show that the percentage of photons absorbed by chlorophyll in the spring is comparable to the amount attributed to BC, especially in areas where the total deposition rates are decreasing with time on interannual timescale. We expect a continuous increase in

  7. Optimal Reflectance, Transmittance, and Absorptance Wavebands and Band Ratios for the Estimation of Leaf Chlorophyll Concentration

    NASA Technical Reports Server (NTRS)

    Carter, Gregory A.; Spiering, Bruce A.

    2000-01-01

    The present study utilized regression analysis to identify: wavebands and band ratios within the 400-850 nm range that could be used to estimate total chlorophyll concentration with minimal error; and simple regression models that were most effective in estimating chlorophyll concentrations were measured for two broadleaved species, a broadleaved vine, a needle-leaved conifer, and a representative of the grass family.Overall, reflectance, transmittance, and absorptance corresponded most precisely with chlorophyll concentration at wavelengths near 700 nm, although regressions were strong as well in the 550-625 nm range.

  8. Using a biochemical C4 photosynthesis model and combined gas exchange and chlorophyll fluorescence measurements to estimate bundle-sheath conductance of maize leaves differing in age and nitrogen content.

    PubMed

    Yin, Xinyou; Sun, Zhouping; Struik, Paul C; Van der Putten, Peter E L; Van Ieperen, Wim; Harbinson, Jeremy

    2011-12-01

    Bundle-sheath conductance (g(bs) ) affects CO(2) leakiness, and, therefore, the efficiency of the CO(2) -concentrating mechanism (CCM) in C(4) photosynthesis. Whether and how g(bs) varies with leaf age and nitrogen status is virtually unknown. We used a C(4) -photosynthesis model to estimate g(bs) , based on combined measurements of gas exchange and chlorophyll fluorescence on fully expanded leaves of three different ages of maize (Zea mays L.) plants grown under two contrasting nitrogen levels. Nitrogen was replenished weekly to maintain leaf nitrogen content (LNC) at a similar level across the three leaf ages. The estimated g(bs) values on leaf-area basis ranged from 1.4 to 10.3 mmol m(-2) s(-1) and were affected more by LNC than by leaf age, although g(bs) tended to decrease as leaves became older. When converted to resistance (r(bs) = 1/g(bs)), r(bs) decreased monotonically with LNC. The correlation was presumably associated with nitrogen effects on leaf anatomy such as on wall thickness of bundle-sheath cells. Despite higher g(bs), meaning less efficient CCM, the calculated loss due to photorespiration was still low for high-nitrogen leaves. Under the condition of ambient CO(2) and saturating irradiance, photorespiratory loss accounted for 3-5% of fixed carbon for the high-nitrogen, versus 1-2% for the low-nitrogen, leaves. PMID:21883288

  9. Tryptophan octyl ester in detergent micelles of dodecylmaltoside: fluorescence properties and quenching by brominated detergent analogs.

    PubMed Central

    de Foresta, B; Gallay, J; Sopkova, J; Champeil, P; Vincent, M

    1999-01-01

    The fluorescence properties of tryptophan octyl ester (TOE), a hydrophobic model of Trp in proteins, were investigated in various mixed micelles of dodecylmaltoside (DM) and 7,8-dibromododecyl beta-maltoside (BrDM) or 10,11-dibromoundecanoyl beta-maltoside (BrUM). This study focuses on the mechanism via which these brominated detergents quench the fluorescence of TOE in a micellar system. The experiments were performed at a pH at which TOE is uncharged and almost completely bound to detergent micelles. TOE binding was monitored by its enhanced fluorescence in pure DM micelles or its quenched fluorescence in pure BrUM or BrDM micelles. In DM/BrUM and DM/BrDM mixed micelles, the fluorescence intensity of TOE decreased, as a nonlinear function of the molar fraction of brominated detergent, to almost zero in pure brominated detergent. The indole moiety of TOE is therefore highly accessible to the bromine atoms located on the detergent alkyl chain because quenching by bromines occurs by direct contact with the fluorophore. TOE is simultaneously poorly accessible to iodide (I(-)), a water-soluble collisional quencher. TOE time-resolved fluorescence intensity decay is heterogeneous in pure DM micelles, with four lifetimes (from 0.2 to 4.4 ns) at the maximum emission wavelength. Such heterogeneity may arise from dipolar relaxation processes in a motionally restricted medium, as suggested by the time-dependent (nanoseconds) red shift (11 nm) of the TOE emission spectrum, and from the existence of various TOE conformations. Time-resolved quenching experiments for TOE in mixed micelles showed that the excited-state lifetime values decreased only slightly with increases in the proportion of BrDM or BrUM. In contrast, the relative amplitude of the component with the longest lifetime decreased significantly relative to that of the short-lived species. This is consistent with a mainly static mechanism for the quenching of TOE by brominated detergents. Molecular modeling of TOE

  10. Monolayers and multilayers of chlorophyll [correction of chlorophyl] a on a mercury electrode.

    PubMed

    Moncelli, M R; Becucci, L; Dolfi, A; Tadini Buoninsegni, F; Agostiano, A

    2002-05-15

    A novel experimental technique used to investigate chlorophyll films on a hanging mercury drop electrode is described. Two different procedures are employed to prepare self-assembled chlorophyll monolayers and multilayers on the mercury electrode. Upon illuminating the chlorophyll a (Chl)-coated mercury electrode with an appropriate light source, the photocurrents generated by the Chl aggregates are measured under short-circuit conditions in the absence of photoartefacts. The preliminary results obtained by this novel technique are presented. PMID:12009465

  11. Dual-Purpose Magnetic Micelles for MRI and Gene Delivery

    PubMed Central

    Wang, Chunyan; Ravi, Sowndharya; Martinez, Gary.V.; Chinnasamy, Vignesh; Raulji, Payal; Howell, Mark; Davis, Yvonne; Seehra, Mohindar S.; Mohapatra, Subhra

    2013-01-01

    Gene therapy is a promising therapeutic approach for treating disease, but the efficient delivery of genes to desired locations with minimal side effects remains a challenge. In addition to gene therapy, it is also highly desirable to provide sensitive imaging information in patients for disease diagnosis, screening and post-therapy monitoring. Here, we report on the development of dual-purpose chitosan and polyethyleneimine (PEI) coated magnetic micelles (CP-mag-micelles) that can deliver nucleic acid-based therapeutic agents and also provide magnetic resonance imaging (MRI). These ‘theranostic’ CP-mag-micelles are composed of monodisperse hydrophobic superparamagnetic iron oxide nanoparticles (SPIONs) loaded into the cores of micelles that are self-assembled from a block copolymer of poly (D, L-lactide) (PLA) and monomethoxy polyethylene glycol (mPEG). For efficient loading and protection of the nucleic acids the micelles were coated with cationic polymers, such as chitosan and PEI. The morphology and size distribution of the CP-mag-micelles were characterized and their potential for use as an MRI-probe was tested using an MRI scanner. The T2 relaxivity of micelles was similar to CP-mag-micelles confirming that coating with cationic polymers did not alter magnetism. Nanoparticles coated with chitosan:PEI at a weight ratio of 5:5 showed higher transfection efficiency in HEK293, 3T3 and PC3 cells than with weight ratios of 3:7 or 7:3. CP-mag-micelles are biocompatible, can be delivered to various organs and are safe. A single injection of CP-mag-micelles carrying reporter plasmids in vivo expressed genes for at least one week. Collectively, our results demonstrate that a structural reinforcement of SPIONs loaded in the core of an mPEG-PLA micelle coated with cationic polymers provides efficient DNA delivery and enhanced MRI potential, and affords a promising candidate for theranostics in the future. PMID:22561339

  12. Crystal nucleation of zincophosphate open frameworks in reverse micelle nanoreactors

    NASA Astrophysics Data System (ADS)

    Castagnola, Mario J.

    The synthesis of microporous zincophosphates was studied through a novel synthetic route based on reactants encapsulated in reverse micelles. The zincophosphate analog of sodalite had been previously synthesized in a reverse micelle system using Aerosol OT (AOT) as surfactant. The synthesis of open framework zincophosphates using this detergent proved unsuccessful. By studying the conventional synthesis of zincophosphates and the AOT reverse micelle aqueous environment through Raman microscopy, FTIR, NMR and XRD, it was found that the relatively high concentrations of sodium ions and the disordered structure of water present in the AOT reverse micelles prevented the synthesis of open framework structures. Based on these results, a system containing reverse micelles of the cationic surfactant dioctyldimethylammonium chloride (DODMAC) was developed. Zn 2+- and PO43--containing DODMAC reverse micelles were characterized by dynamic light scattering and conductivity measurements, indicating a rod-like shape for the former and a spherical shape for the latter reverse micelles. Combination of the two reverse micelle solutions led to the first successful reverse micelle based synthesis of the zincophosphate analog of Zeolite-X, ZnPO-X. The size of the crystals was controlled by modifying the volume ratio between the individual reagent micellar solutions. Nanocrystals of the order of 20 nm were obtained by interrupting the reaction at early stages. Studies of both the conventional aqueous and the reverse micelle based syntheses of ZnPO-X revealed that the morphology of the ZnPO-X crystals was controlled by the concentration of tetramethylammonium ions (TMA+). The ZnPO-X crystals synthesized via the reverse micelles were obtained as a single phase. Using Raman spectroscopy, it was determined that, during conventional synthesis, H+ ions promote the hydrolysis of the ZnPO-X crystals that leads to hopeite formation. Ion-exchange by monovalent cations indicated that the crystal

  13. Organization of chlorophyll biosynthesis and insertion of chlorophyll into the chlorophyll-binding proteins in chloroplasts.

    PubMed

    Wang, Peng; Grimm, Bernhard

    2015-12-01

    Oxygenic photosynthesis requires chlorophyll (Chl) for the absorption of light energy, and charge separation in the reaction center of photosystem I and II, to feed electrons into the photosynthetic electron transfer chain. Chl is bound to different Chl-binding proteins assembled in the core complexes of the two photosystems and their peripheral light-harvesting antenna complexes. The structure of the photosynthetic protein complexes has been elucidated, but mechanisms of their biogenesis are in most instances unknown. These processes involve not only the assembly of interacting proteins, but also the functional integration of pigments and other cofactors. As a precondition for the association of Chl with the Chl-binding proteins in both photosystems, the synthesis of the apoproteins is synchronized with Chl biosynthesis. This review aims to summarize the present knowledge on the posttranslational organization of Chl biosynthesis and current attempts to envision the proceedings of the successive synthesis and integration of Chl into Chl-binding proteins in the thylakoid membrane. Potential auxiliary factors, contributing to the control and organization of Chl biosynthesis and the association of Chl with the Chl-binding proteins during their integration into photosynthetic complexes, are discussed in this review.

  14. Mediterranean Ocean Colour Chlorophyll Trends.

    PubMed

    Colella, Simone; Falcini, Federico; Rinaldi, Eleonora; Sammartino, Michela; Santoleri, Rosalia

    2016-01-01

    In being at the base of the marine food web, phytoplankton is particularly important for marine ecosystem functioning (e.g., biodiversity). Strong anthropization, over-exploitation of natural resources, and climate change affect the natural amount of phytoplankton and, therefore, represent a continuous threat to the biodiversity in marine waters. In particular, a concerning risks for coastal waters is the increase in nutrient inputs of terrestrial/anthropogenic origin that can lead to undesirable modifications of phytoplankton concentration (i.e., eutrophication). Monitoring chlorophyll (Chl) concentration, which is a proxy of phytoplankton biomass, is an efficient tool for recording and understanding the response of the marine ecosystem to human pressures and thus for detecting eutrophication. Here, we compute Chl trends over the Mediterranean Sea by using satellite data, also highlighting the fact that remote sensing may represent an efficient and reliable solution to synoptically control the "good environmental status" (i.e., the Marine Directive to achieve Good Environmental Status of EU marine waters by 2020) and to assess the application of international regulations and environmental directives. Our methodology includes the use of an ad hoc regional (i.e., Mediterranean) algorithm for Chl concentration retrieval, also accounting for the difference between offshore (i.e., Case I) and coastal (i.e., Case II) waters. We apply the Mann-Kendall test and the Sens's method for trend estimation to the Chl concentration de-seasonalized monthly time series, as obtained from the X-11 technique. We also provide a preliminary analysis of some particular trends by evaluating their associated inter-annual variability. The high spatial resolution of our approach allows a clear identification of intense trends in those coastal waters that are affected by river outflows. We do not attempt to attribute the observed trends to specific anthropogenic events. However, the trends

  15. Mediterranean Ocean Colour Chlorophyll Trends

    PubMed Central

    Colella, Simone; Falcini, Federico; Rinaldi, Eleonora; Sammartino, Michela; Santoleri, Rosalia

    2016-01-01

    In being at the base of the marine food web, phytoplankton is particularly important for marine ecosystem functioning (e.g., biodiversity). Strong anthropization, over-exploitation of natural resources, and climate change affect the natural amount of phytoplankton and, therefore, represent a continuous threat to the biodiversity in marine waters. In particular, a concerning risks for coastal waters is the increase in nutrient inputs of terrestrial/anthropogenic origin that can lead to undesirable modifications of phytoplankton concentration (i.e., eutrophication). Monitoring chlorophyll (Chl) concentration, which is a proxy of phytoplankton biomass, is an efficient tool for recording and understanding the response of the marine ecosystem to human pressures and thus for detecting eutrophication. Here, we compute Chl trends over the Mediterranean Sea by using satellite data, also highlighting the fact that remote sensing may represent an efficient and reliable solution to synoptically control the “good environmental status” (i.e., the Marine Directive to achieve Good Environmental Status of EU marine waters by 2020) and to assess the application of international regulations and environmental directives. Our methodology includes the use of an ad hoc regional (i.e., Mediterranean) algorithm for Chl concentration retrieval, also accounting for the difference between offshore (i.e., Case I) and coastal (i.e., Case II) waters. We apply the Mann-Kendall test and the Sens’s method for trend estimation to the Chl concentration de-seasonalized monthly time series, as obtained from the X-11 technique. We also provide a preliminary analysis of some particular trends by evaluating their associated inter-annual variability. The high spatial resolution of our approach allows a clear identification of intense trends in those coastal waters that are affected by river outflows. We do not attempt to attribute the observed trends to specific anthropogenic events. However, the

  16. [Detection of chlorophyll content in water body based on two-dimensional correlation spectroscopy].

    PubMed

    Zhang, Yao; Zheng, Li-Hua; Sun, Hong; Li, Min-Zan

    2014-02-01

    Twenty five samples were collected from 10 different ponds in Jiangsu Province of China. According to the different water status and surface area of each pond, different numbers of water samples were collected. The present paper aims to detect chlorophyll content in water body based on hyperspectrum. The visible and near infrared spectral transmittance of the water samples was measured by using a Shimadzu UV-2450 spectrograph. At the same time, the chlorophyll content of each sample was measured using hot-ethanol extraction method in the laboratory. Then the spectral characteristics were analyzed for the water samples and the results showed that with chlorophyll concentration increasing, spectral transmittance decreased gradually. There is an apparent transmission valley at 676 nm. And then two dimensional correlation spectrum technology was used to analyze the sensitive absorption band of chlorophyll in water body. Comprehensive observation of the spectral characteristics of water samples can be carried out much accurately by analyzing two-dimensional correlation spectra of synchronous and asynchronous spectrograms. And the effective spectral response bands of the chlorophyll content were found at 488 and 676 nm. Then the NDWCI (normalized difference water chlorophyll index) was established with the transmittance of red band and blue band. Two regression models were built to predict the chlorophyll concentration in water. One is a multiple linear regression model based on the original transmittances at 488 and 676 nm. The other is the linear regression model based on NDWCI. By comparison, the model based on NDWCI was better. The R2 of its training model reached to 0.7712, and the root mean square error of calibration was 45.5099 mg x L(-1). The R2 of prediction model reached to 0.7658, and the root mean square error of prediction was 39.5038 mg x L(-1). It reached to a practical level to predict the chlorophyll content in water body rapidly.

  17. In Vivo Participation of Red Chlorophyll Catabolite Reductase in Chlorophyll Breakdown[W

    PubMed Central

    Pružinská, Adriana; Anders, Iwona; Aubry, Sylvain; Schenk, Nicole; Tapernoux-Lüthi, Esther; Müller, Thomas; Kräutler, Bernhard; Hörtensteiner, Stefan

    2007-01-01

    A central reaction of chlorophyll breakdown, porphyrin ring opening of pheophorbide a to the primary fluorescent chlorophyll catabolite (pFCC), requires pheophorbide a oxygenase (PAO) and red chlorophyll catabolite reductase (RCCR), with red chlorophyll catabolite (RCC) as a presumably PAO-bound intermediate. In subsequent steps, pFCC is converted to different fluorescent chlorophyll catabolites (FCCs) and nonfluorescent chlorophyll catabolites (NCCs). Here, we show that RCCR-deficient Arabidopsis thaliana accumulates RCC and three RCC-like pigments during senescence, as well as FCCs and NCCs. We also show that the stereospecificity of Arabidopsis RCCR is defined by a small protein domain and can be reversed by a single Phe-to-Val exchange. Exploiting this feature, we prove the in vivo participation of RCCR in chlorophyll breakdown. After complementation of RCCR mutants with RCCRs exhibiting alternative specificities, patterns of chlorophyll catabolites followed the specificity of complementing RCCRs. Light-dependent leaf cell death observed in different RCCR-deficient lines strictly correlated with the accumulation of RCCs and the release of singlet oxygen, and PAO induction preceded lesion formation. These findings suggest that RCCR absence causes leaf cell death as a result of the accumulation of photodynamic RCC. We conclude that RCCR (together with PAO) is required for the detoxification of chlorophyll catabolites and discuss the biochemical role(s) for this enzyme. PMID:17237353

  18. In vivo participation of red chlorophyll catabolite reductase in chlorophyll breakdown.

    PubMed

    Pruzinská, Adriana; Anders, Iwona; Aubry, Sylvain; Schenk, Nicole; Tapernoux-Lüthi, Esther; Müller, Thomas; Kräutler, Bernhard; Hörtensteiner, Stefan

    2007-01-01

    A central reaction of chlorophyll breakdown, porphyrin ring opening of pheophorbide a to the primary fluorescent chlorophyll catabolite (pFCC), requires pheophorbide a oxygenase (PAO) and red chlorophyll catabolite reductase (RCCR), with red chlorophyll catabolite (RCC) as a presumably PAO-bound intermediate. In subsequent steps, pFCC is converted to different fluorescent chlorophyll catabolites (FCCs) and nonfluorescent chlorophyll catabolites (NCCs). Here, we show that RCCR-deficient Arabidopsis thaliana accumulates RCC and three RCC-like pigments during senescence, as well as FCCs and NCCs. We also show that the stereospecificity of Arabidopsis RCCR is defined by a small protein domain and can be reversed by a single Phe-to-Val exchange. Exploiting this feature, we prove the in vivo participation of RCCR in chlorophyll breakdown. After complementation of RCCR mutants with RCCRs exhibiting alternative specificities, patterns of chlorophyll catabolites followed the specificity of complementing RCCRs. Light-dependent leaf cell death observed in different RCCR-deficient lines strictly correlated with the accumulation of RCCs and the release of singlet oxygen, and PAO induction preceded lesion formation. These findings suggest that RCCR absence causes leaf cell death as a result of the accumulation of photodynamic RCC. We conclude that RCCR (together with PAO) is required for the detoxification of chlorophyll catabolites and discuss the biochemical role(s) for this enzyme.

  19. Remote sensing of chlorophyll fluorescence with GOSAT

    NASA Astrophysics Data System (ADS)

    Somkuti, Peter; Boesch, Hartmut; Parker, Robert

    2015-04-01

    Sun-induced chlorophyll fluorescence (Fs) emitted by plants as a by-product during photosynthesis carries information about their photosynthetic activity. It is possible to exploit space-based remote sensing measurements to retrieve the fluorescence signal and thus indirectly study carbon fluxes on a global scale. We implement a fluorescence retrieval based on the method pioneered by Frankenberg et al. (2011) into the framework of the University of Leicester Full-Physics GOSAT CO2 retrieval (UoL-FP). This physically-based approach is applied to high-resolution spectra at the edges of the O2 A-Band in the red to NIR range, that feature strong solar as well as a few weak O2 absorption lines. The fluorescence signal, which acts as an additional source, results in an in-filling of the measured solar absorption lines that are used to distinguish Fs from reflectance effects. By analysing GOSAT soundings from 2009 onwards, we examine global and regional long-term trends of Fs and compare them with parameters related to plant physiology, such as spectral vegetation indices and MODIS-derived model GPP values. Following Guanter et al. (2012) and Frankenberg et al. (2011), different regions and biomes are considered and we find that seasonal trends of both model GPP data as well as greenness indicators are well reproduced by our GOSAT-retrieved Fs.

  20. Biodegradable mixed MPEG-SS-2SA/TPGS micelles for triggered intracellular release of paclitaxel and reversing multidrug resistance

    PubMed Central

    Dong, Kai; Yan, Yan; Wang, Pengchong; Shi, Xianpeng; Zhang, Lu; Wang, Ke; Xing, Jianfeng; Dong, Yalin

    2016-01-01

    In this study, a type of multifunctional mixed micelles were prepared by a novel biodegradable amphiphilic polymer (MPEG-SS-2SA) and a multidrug resistance (MDR) reversal agent (d-α-tocopheryl polyethylene glycol succinate, TPGS). The mixed micelles could achieve rapid intracellular drug release and reversal of MDR. First, the amphiphilic polymer, MPEG-SS-2SA, was synthesized through disulfide bonds between poly (ethylene glycol) monomethyl ether (MPEG) and stearic acid (SA). The structure of the obtained polymer was similar to poly (ethylene glycol)-phosphatidylethanolamine (PEG-PE). Then the mixed micelles, MPEG-SS-2SA/TPGS, were prepared by MPEG-SS-2SA and TPGS through the thin film hydration method and loaded paclitaxel (PTX) as the model drug. The in vitro release study revealed that the mixed micelles could rapidly release PTX within 24 h under a reductive environment because of the breaking of disulfide bonds. In cell experiments, the mixed micelles significantly inhibited the activity of mitochondrial respiratory complex II, also reduced the mitochondrial membrane potential, and the content of adenosine triphosphate, thus effectively inhibiting the efflux of PTX from cells. Moreover, in the confocal laser scanning microscopy, cellular uptake and 3-(4,5-dimethyl-thiazol-2-yl)-2,5-diphenyl-tetrazolium bromide assays, the MPEG-SS-2SA/TPGS micelles achieved faster release and more uptake of PTX in Michigan Cancer Foundation-7/PTX cells and showed better antitumor effects as compared with the insensitive control. In conclusion, the biodegradable mixed micelles, MPEG-SS-2SA/TPGS, could be potential vehicles for delivering hydrophobic chemotherapeutic drugs in MDR cancer therapy. PMID:27785018

  1. cRGD-installed polymeric micelles loading platinum anticancer drugs enable cooperative treatment against lymph node metastasis.

    PubMed

    Makino, Jun; Cabral, Horacio; Miura, Yutaka; Matsumoto, Yu; Wang, Ming; Kinoh, Hiroaki; Mochida, Yuki; Nishiyama, Nobuhiro; Kataoka, Kazunori

    2015-12-28

    Lymph node metastasis (LNM) is correlated with decreased survival, indicating high tumor malignancy and being a potential source for subsequent fatal metastases. Targeted therapies inhibiting the formation of LNM, while eliminating established metastatic foci, could provide synergistic effects by reducing the incidence and growth of metastasis. Based on the inhibitory activity of cRGD peptide against the development of metastasis, and the LNM targeting ability of systemically injected drug-loaded polymeric micelles, herein, we studied the capability of cRGD-installed polymeric micelles incorporating the platinum anticancer drug (1,2-diaminocylohexane)platinum(II) (DACHPt) for cooperatively inhibiting the formation and progression of LNM. As cRGD-installed DACHPt-loaded micelles (cRGD-DACHPt/m) presented similar size, drug loading and surface charge to non-conjugated micelles (MeO-DACHPt/m), the differences in the biological performance of the micelles were endorsed to the effect of the ligand. In a syngeneic melanoma model, both MeO-DACHPt/m and cRGD-DACHPt/m showed comparable antitumor activity against the primary tumors and the established metastatic foci in lymph nodes. However, cRGD-DACHPt/m significantly enhanced the efficacy against LNM draining from primary tumors through the effective inhibition of the spreading of cancer cells. This improved inhibition was associated with the ability of cRGD-DACHPt/m to reduce the migration of melanoma cells, which was higher than that of MeO-DACHPt/m, free cRGD and their combination. These results support our strategy of using cRGD-installed micelles for attaining cooperative therapies against LNM exploiting the inhibitory function of the peptide and the cytotoxic effect of the micelles. PMID:26474676

  2. Optimization of Landscape Phage Fusion Protein-Modified Polymeric PEG-PE Micelles for Improved Breast Cancer Cell Targeting

    PubMed Central

    Wang, Tao; Petrenko, Valery A.; Torchilin, Vladimir P.

    2015-01-01

    Amphiphilic landscape phage fusion proteins with high affinity and selectivity towards breast cancer MCF-7 (Michigan Cancer Foundation-7) cells self-assemble with polymeric PEG-PE conjugates to form mixed micelles (phage-micelles) capable of cancer cell-targeted delivery of poorly-soluble drugs. While the PEG corona provides the stability and longevity to the micelles, its presence is a potential steric difficulties for the interaction of phage fusion protein with cell surface targets. We attempted to address this problem by controlling the length of the PEG block and the phage fusion protein quantity, selecting the optimal ones to produce a reasonable retention of the targeting affinity and selectivity of the MCF-7-specific phage fusion protein. Three PEG-PE conjugates with different PEG lengths were used to construct phage- and plain-micelles, followed by FACS analysis of the effect of the PEG length on their binding affinity and selectivity towards target MCF-7 cells using either a MCF-7 cell monoculture or a cell co-culture model composed of target cancer MCF-7 cells and non-target, non-cancer C166 cells expressing GFP (Green Fluorescent Protein). Both, the length of PEG and quantity of phage fusion protein had a profound impact on the targetability of the phage-micelles. Phage-micelles prepared with PEG2k-PE achieved a desirable binding affinity and selectivity. Incorporation of a minimal concentration of phage protein, up to 0.5%, produced maximal targeting efficiency towards MCF-7 cells. Overall, phage-micelles with PEG2k-PE and 0.5% of phage protein represent the optimal formulation for targeting towards breast cancer cells. PMID:26451274

  3. Water requirements in monomer folding and dimerization of triosephosphate isomerase in reverse micelles. Intrinsic fluorescence of conformers related to reactivation.

    PubMed

    Fernández-Velasco, D A; Sepúlveda-Becerra, M; Galina, A; Darszon, A; Tuena de Gómez-Puyou, M; Gómez-Puyou, A

    1995-01-10

    The possibility of using reverse micelles to stabilize monomers prior to formation of dimeric triosephosphate isomerase (TPI) from rabbit muscle was studied. TPI denatured with guanidine hydrochloride undergoes reactivation in reverse micelles formed with n-octane, hexanol, cetyltrimethylammonium bromide, and water. Reactivation of around 80% is observed at TPI concentrations of about 2 micrograms/mL of reverse micelles and water concentrations above 4.0%. With 3.0% water, reactivation is about 10%. If denatured TPI is incubated for a few seconds in reverse micelles with 5.0% water (or higher) followed by incubation in 3.0% water, reactivation is between 35% and 50%. That is, a brief exposure of denatured TPI to reverse micelles with a relatively high water concentration yielded a significant amount of structures competent for formation of catalytically active dimers. As evidenced by kinetic data, these structures correspond to monomers of TPI [Garza-Ramos, G. Tuena de Gómez-Puyou, M., Gómez-Puyou, A., & Gracy R. W. (1992) Eur. J. Biochem. 208, 389-395]. After a 5-2.0% water transition, competent monomers were stabilized for at least 30 min; a subsequent rise in water concentration led to dimerization and appearance of activity. By changes in the amount of water, it was possible to determine in reverse micelles the amount of water required for monomer folding and dimerization; i.e., less water was required in the dimerization step. Experiments with a model system, trypsin and the soybean inhibitor, showed that, in reverse micelles with 2.0% water, protein-protein interactions readily take place.(ABSTRACT TRUNCATED AT 250 WORDS)

  4. Molecular Simulations of Dodecyl-β-maltoside Micelles in Water: Influence of the Headgroup Conformation and Force field Parameters

    PubMed Central

    Abel, Stéphane; Dupradeau, François-Yves; Raman, E. Prabhu; MacKerell, Alexander D.; Marchi, Massimo

    2011-01-01

    This paper deals with the development and validation of new potential parameter sets, based on the CHARMM36 and GLYCAM06 force fields, to simulate micelles of the two anomeric forms (α and β) of N-Dodecyl-ß-maltoside (C12G2), a surfactant widely used in the extraction and purification of membrane proteins. In this context, properties such as size, shape, internal structure and hydration of the C12G2 anomer micelles were thoroughly investigated by molecular dynamics simulations and the results compared with experiments. Additional simulations were also performed with the older CHARMM22 force field for carbohydrates (Kuttel, M. et al. J. Comp. Chem. 2002, 23, 1236-1243). We find that our CHARMM and GLYCAM parameter sets yields similar results in case of properties related to the micelle structure, but differ for other properties such as the headgroup conformation or the micelle hydration. In agreement with experiments, our results show that for all model potentials the β-C12G2 micelles have a more pronounced ellipsoidal shape than those containing α anomers. The computed radius of gyration is 20.2 Å and 25.4 Å for the α- and β-anomer micelles, respectively. Finally, we show that depending on the potential the water translational diffusion of the interfacial water is 7 - 11.5 times slower than that of bulk water due to the entrapment of the water in the micelle crevices. This retardation is independent of the headgroup in α- or β- anomers. PMID:21192681

  5. Efficiency of chlorophyll in gross primary productivity: A proof of concept and application in crops.

    PubMed

    Gitelson, Anatoly A; Peng, Yi; Viña, Andrés; Arkebauer, Timothy; Schepers, James S

    2016-08-20

    One of the main factors affecting vegetation productivity is absorbed light, which is largely governed by chlorophyll. In this paper, we introduce the concept of chlorophyll efficiency, representing the amount of gross primary production per unit of canopy chlorophyll content (Chl) and incident PAR. We analyzed chlorophyll efficiency in two contrasting crops (soybean and maize). Given that they have different photosynthetic pathways (C3 vs. C4), leaf structures (dicot vs. monocot) and canopy architectures (a heliotrophic leaf angle distribution vs. a spherical leaf angle distribution), they cover a large spectrum of biophysical conditions. Our results show that chlorophyll efficiency in primary productivity is highly variable and responds to various physiological and phenological conditions, and water availability. Since Chl is accessible through non-destructive, remotely sensed techniques, the use of chlorophyll efficiency for modeling and monitoring plant optimization patterns is practical at different scales (e.g., leaf, canopy) and under widely-varying environmental conditions. Through this analysis, we directly related a functional characteristic, gross primary production with a structural characteristic, canopy chlorophyll content. Understanding the efficiency of the structural characteristic is of great interest as it allows explaining functional components of the plant system. PMID:27374843

  6. Efficiency of chlorophyll in gross primary productivity: A proof of concept and application in crops.

    PubMed

    Gitelson, Anatoly A; Peng, Yi; Viña, Andrés; Arkebauer, Timothy; Schepers, James S

    2016-08-20

    One of the main factors affecting vegetation productivity is absorbed light, which is largely governed by chlorophyll. In this paper, we introduce the concept of chlorophyll efficiency, representing the amount of gross primary production per unit of canopy chlorophyll content (Chl) and incident PAR. We analyzed chlorophyll efficiency in two contrasting crops (soybean and maize). Given that they have different photosynthetic pathways (C3 vs. C4), leaf structures (dicot vs. monocot) and canopy architectures (a heliotrophic leaf angle distribution vs. a spherical leaf angle distribution), they cover a large spectrum of biophysical conditions. Our results show that chlorophyll efficiency in primary productivity is highly variable and responds to various physiological and phenological conditions, and water availability. Since Chl is accessible through non-destructive, remotely sensed techniques, the use of chlorophyll efficiency for modeling and monitoring plant optimization patterns is practical at different scales (e.g., leaf, canopy) and under widely-varying environmental conditions. Through this analysis, we directly related a functional characteristic, gross primary production with a structural characteristic, canopy chlorophyll content. Understanding the efficiency of the structural characteristic is of great interest as it allows explaining functional components of the plant system.

  7. Exploring the effect of hydrophilic and hydrophobic structure of grafted polymeric micelles on drug loading.

    PubMed

    Shi, Chenjun; Sun, Yujiao; Wu, Haiyang; Zhu, Chengyun; Wei, Guoguang; Li, Jinfeng; Chan, Tenglan; Ouyang, Defang; Mao, Shirui

    2016-10-15

    The objective of this paper is to explore the effect of hydrophilic and hydrophobic structure of grafted polymeric micelles on drug loading, and elucidate whether drug-polymer compatibility, as predicted by Hansen solubility parameters (HSPs), can be used as a tool for drug-polymer pairs screening and guide the design of grafted polymeric micelles. HSPs of 27 drugs and three grafted copolymers were calculated according to group contribution method. The drug-polymer compatibilities were evaluated using the approaches of Flory-Huggins interaction parameters (χFH) and polarity difference (△Xp). Two models, model A and B, were put forward for drug-polymer compatibility prediction. In model A, hydrophilic/hydrophobic part as a whole was regarded as one segment. And, in model B, hydrophilic and hydrophobic segments were evaluated individually. First of all, using chitosan (CS)-grafted-glyceryl monooeate (GMO) based micelle as an example, the suitability of model A and model B for predicating drug-polymer compatibility was evaluated theoretically. Thereafter, corresponding experiments were carried out to check the validity of the theoretical prediction. It was demonstrated that Model B, which evaluates drug compatibility with both hydrophilic and hydrophobic segments of the copolymer, is more reliable for drug-polymer compatibility prediction. Moreover, the approach of model B allows for the selection of a defined grafted polymer with for a specific drug and vice versa. Thus, drug compatibility evaluation via HSPs with both hydrophilic and hydrophobic segments is a suitable tool for the rational design of grafted polymeric micelles. The molecular dynamics (MD) simulation study provided further support to the established model and experimental results. PMID:27576669

  8. Exploring the effect of hydrophilic and hydrophobic structure of grafted polymeric micelles on drug loading.

    PubMed

    Shi, Chenjun; Sun, Yujiao; Wu, Haiyang; Zhu, Chengyun; Wei, Guoguang; Li, Jinfeng; Chan, Tenglan; Ouyang, Defang; Mao, Shirui

    2016-10-15

    The objective of this paper is to explore the effect of hydrophilic and hydrophobic structure of grafted polymeric micelles on drug loading, and elucidate whether drug-polymer compatibility, as predicted by Hansen solubility parameters (HSPs), can be used as a tool for drug-polymer pairs screening and guide the design of grafted polymeric micelles. HSPs of 27 drugs and three grafted copolymers were calculated according to group contribution method. The drug-polymer compatibilities were evaluated using the approaches of Flory-Huggins interaction parameters (χFH) and polarity difference (△Xp). Two models, model A and B, were put forward for drug-polymer compatibility prediction. In model A, hydrophilic/hydrophobic part as a whole was regarded as one segment. And, in model B, hydrophilic and hydrophobic segments were evaluated individually. First of all, using chitosan (CS)-grafted-glyceryl monooeate (GMO) based micelle as an example, the suitability of model A and model B for predicating drug-polymer compatibility was evaluated theoretically. Thereafter, corresponding experiments were carried out to check the validity of the theoretical prediction. It was demonstrated that Model B, which evaluates drug compatibility with both hydrophilic and hydrophobic segments of the copolymer, is more reliable for drug-polymer compatibility prediction. Moreover, the approach of model B allows for the selection of a defined grafted polymer with for a specific drug and vice versa. Thus, drug compatibility evaluation via HSPs with both hydrophilic and hydrophobic segments is a suitable tool for the rational design of grafted polymeric micelles. The molecular dynamics (MD) simulation study provided further support to the established model and experimental results.

  9. Systems approach to excitation-energy and electron transfer reaction networks in photosystem II complex: model studies for chlorophyll a fluorescence induction kinetics.

    PubMed

    Matsuoka, Takeshi; Tanaka, Shigenori; Ebina, Kuniyoshi

    2015-09-01

    Photosystem II (PS II) is a protein complex which evolves oxygen and drives charge separation for photosynthesis employing electron and excitation-energy transfer processes over a wide timescale range from picoseconds to milliseconds. While the fluorescence emitted by the antenna pigments of this complex is known as an important indicator of the activity of photosynthesis, its interpretation was difficult because of the complexity of PS II. In this study, an extensive kinetic model which describes the complex and multi-timescale characteristics of PS II is analyzed through the use of the hierarchical coarse-graining method proposed in the authors׳ earlier work. In this coarse-grained analysis, the reaction center (RC) is described by two states, open and closed RCs, both of which consist of oxidized and neutral special pairs being in quasi-equilibrium states. Besides, the PS II model at millisecond scale with three-state RC, which was studied previously, could be derived by suitably adjusting the kinetic parameters of electron transfer between tyrosine and RC. Our novel coarse-grained model of PS II can appropriately explain the light-intensity dependent change of the characteristic patterns of fluorescence induction kinetics from O-J-I-P, which shows two inflection points, J and I, between initial point O and peak point P, to O-J-D-I-P, which shows a dip D between J and I inflection points.

  10. Vesicle-to-Micelle Oscillations and Spatial Patterns

    SciTech Connect

    Lagzi, Istvan; Wang, Dawei; Kowalczyk, Bartlomiej; Grzybowski, Bartosz A.

    2010-09-07

    A pH oscillator is coupled to and controls rhythmic interconversion of nanoscopic vesicles and micelles made of fatty acids. When changes in pH are combined with diffusion, self-assembly produces spatially extended patterns of vesicle/micelle “stripes” or concentric “shells”.

  11. PLA2-responsive and SPIO-loaded phospholipid micelles

    PubMed Central

    Gao, Qiang; Yan, Lesan; Chiorazzo, Michael; Delikatny, E. James; Tsourkas, Andrew; Cheng, Zhiliang

    2015-01-01

    A PLA2-responsive and superparamagnetic iron oxide (SPIO) nanoparticle-loaded phospholipid micelle was developed. The release of phospholipid-conjugated dye from these micelles was triggered due to phospholipid degradation by phospholipase A2. High relaxivity of the encapsulated SPIO could enable non-invasive magnetic resonance imaging. PMID:26139589

  12. Designing Dendrimers to Offer Micelle-Type Nanocontainers

    ERIC Educational Resources Information Center

    King, Angela G.

    2005-01-01

    The properties of a dendrimer with hydrophobic and hydrophilic substituents on an orthogonal plane is synthesized and studied. The resulting polymer contains one of the substituents in its concave interior and the other at the convex surface and the design promotes micelle-like behavior in polar solvent and inverted micelle arrangement in…

  13. Application of a partial least-squares regression model to retrieve chlorophyll- a concentrations in coastal waters using hyper-spectral data

    NASA Astrophysics Data System (ADS)

    Ryan, Kimberly; Ali, Khalid

    2016-03-01

    Coastal and inland waters represent a diverse set of resources that support natural habitats and provide valuable ecosystem services to the human population. Monitoring the quality of these waters is essential to maintaining the resources they provide, and long-term monitoring may offer a better understanding of the relationship between human development and the health of these resource producers. The implementation of conventional monitoring is typically time-intensive and limited in geographic scale. Alternatively, the use of airborne and spaceborne remote sensors provides a synoptic view of water quality with better spatial coverage to more accurately identify dynamic and unique parameters. Concentrations of optically active constituents (OACs) such as suspended sediments and the phytoplankton pigment chlorophylla (CHL a), act as proxies for water quality and can be detected by optical sensors. Traditional remote sensing techniques were developed using multispectral sensors, and employ band ratio algorithms that seek to predict the concentrations of OACs in relation to water quality. In complex coastal waters, overlapping spectral signatures of OACs often confound these algorithms and reduce their predictive capacity. The objective of this study was to develop a dataset to test the predictive capabilities of partial least-squares regression, a multivariate statistical method, for hyperspectral remote sensing and in situ CHL a concentrations. This paper presents the model performance for a dataset developed in Long Bay, a ~160 km arcuate bay that spans the border between North and South Carolina. The model uses multivariate-based statistical modeling to capitalize on the spectral advantage gained by hyperspectral sensors when observing such waters. Following this approach, a multivariate-based monitoring tool for the prediction of CHL a concentrations is presented with a partial least-squares regression (PLSR) method using hyperspectral and laboratory

  14. Indian Ocean Dipole and El Niño/Southern Oscillation impacts on regional chlorophyll anomalies in the Indian Ocean

    NASA Astrophysics Data System (ADS)

    Currie, J. C.; Lengaigne, M.; Vialard, J.; Kaplan, D. M.; Aumont, O.; Naqvi, S. W. A.; Maury, O.

    2013-10-01

    The Indian Ocean Dipole (IOD) and the El Niño/Southern Oscillation (ENSO) are independent climate modes, which frequently co-occur, driving significant interannual changes within the Indian Ocean. We use a four-decade hindcast from a coupled biophysical ocean general circulation model, to disentangle patterns of chlorophyll anomalies driven by these two climate modes. Comparisons with remotely sensed records show that the simulation competently reproduces the chlorophyll seasonal cycle, as well as open-ocean anomalies during the 1997/1998 ENSO and IOD event. Results suggest that anomalous surface and euphotic-layer chlorophyll blooms in the eastern equatorial Indian Ocean in fall, and southern Bay of Bengal in winter, are primarily related to IOD forcing. A negative influence of IOD on chlorophyll concentrations is shown in a region around the southern tip of India in fall. IOD also depresses depth-integrated chlorophyll in the 5-10° S thermocline ridge region, yet the signal is negligible in surface chlorophyll. The only investigated region where ENSO has a greater influence on chlorophyll than does IOD, is in the Somalia upwelling region, where it causes a decrease in fall and winter chlorophyll by reducing local upwelling winds. Yet unlike most other regions examined, the combined explanatory power of IOD and ENSO in predicting depth-integrated chlorophyll anomalies is relatively low in this region, suggestive that other drivers are important there. We show that the chlorophyll impact of climate indices is frequently asymmetric, with a general tendency for larger positive than negative chlorophyll anomalies. Our results suggest that ENSO and IOD cause significant and predictable regional re-organisation of chlorophyll via their influence on near-surface oceanography. Resolving the details of these effects should improve our understanding, and eventually gain predictability, of interannual changes in Indian Ocean productivity, fisheries, ecosystems and carbon

  15. Protein unfolding in detergents: effect of micelle structure, ionic strength, pH, and temperature.

    PubMed Central

    Otzen, Daniel E

    2002-01-01

    The 101-residue monomeric protein S6 unfolds in the anionic detergent sodium dodecyl sulfate (SDS) above the critical micelle concentration, with unfolding rates varying according to two different modes. Our group has proposed that spherical micelles lead to saturation kinetics in unfolding (mode 1), while cylindrical micelles prevalent at higher SDS concentrations induce a power-law dependent increase in the unfolding rate (mode 2). Here I investigate in more detail how micellar properties affect protein unfolding. High NaCl concentrations, which induce cylindrical micelles, favor mode 2. This is consistent with our model, though other effects such as electrostatic screening cannot be discounted. Furthermore, unfolding does not occur in mode 2 in the cationic detergent LTAB, which is unable to form cylindrical micelles. A strong retardation of unfolding occurs at higher LTAB concentrations, possibly due to the formation of dead-end protein-detergent complexes. A similar, albeit much weaker, effect is seen in SDS in the absence of salt. Chymotrypsin inhibitor 2 exhibits the same modes of unfolding in SDS as S6, indicating that this type of protein unfolding is not specific for S6. The unfolding process in mode 1 has an activation barrier similar in magnitude to that in water, while the activation barrier in mode 2 is strongly concentration-dependent. The strong pH-dependence of unfolding in SDS and LTAB suggests that the rate of unfolding in anionic detergent is modulated by repulsion between detergent headgroups and anionic side chains, while cationic side chains modulate unfolding rates in cationic detergents. PMID:12324439

  16. Periodic Arrays of Interfacial Cylindrical reverse Micelles

    SciTech Connect

    Nelson,M.; Cain, N.; Ocko, B.; Gin, D.; Hammond, S.; Schwartz, D.

    2005-01-01

    We report an approach for the fabrication of periodic molecular nanostructures on surfaces. The approach involves biomimetic self-organization of synthetic wedge-shaped amphiphilic molecules into multilayer arrays of cylindrical reverse micelles. The films were characterized by atomic force microscopy and X-ray reflectivity. These nanostructured films self-assemble in solution but remain stable upon removal and exposure to ambient conditions, making them potentially suitable for a variety of dry pattern transfer methods. We illustrate the generality of this approach by using two distinct molecular systems that vary in size by a factor of 2.

  17. Cooperative catalysis with block copolymer micelles: a combinatorial approach.

    PubMed

    Bukhryakov, Konstantin V; Desyatkin, Victor G; O'Shea, John-Paul; Almahdali, Sarah R; Solovyeva, Vera; Rodionov, Valentin O

    2015-02-01

    A rapid approach to identifying complementary catalytic groups using combinations of functional polymers is presented. Amphiphilic polymers with "clickable" hydrophobic blocks were used to create a library of functional polymers, each bearing a single functionality. The polymers were combined in water, yielding mixed micelles. As the functional groups were colocalized in the hydrophobic microphase, they could act cooperatively, giving rise to new modes of catalysis. The multipolymer "clumps" were screened for catalytic activity, both in the presence and absence of metal ions. A number of catalyst candidates were identified across a wide range of model reaction types. One of the catalytic systems discovered was used to perform a number of preparative-scale syntheses. Our approach provides easy access to a range of enzyme-inspired cooperative catalysts.

  18. Magainin II modified polydiacetylene micelles for cancer therapy

    NASA Astrophysics Data System (ADS)

    Yang, Danling; Zou, Rongfeng; Zhu, Yu; Liu, Ben; Yao, Defan; Jiang, Juanjuan; Wu, Junchen; Tian, He

    2014-11-01

    Polydiacetylene (PDA) micelles have been widely used to deliver anticancer drugs in the treatment of a variety of tumours and for imaging living cells. In this study, we developed an effective strategy to directly conjugate magainin II (MGN-II) to the surface of PDA micelles using a fluorescent dye. These stable and well-defined PDA micelles had high cytotoxicity in cancer cell lines, and were able to reduce the tumour size in mice. The modified PDA micelles improved the anticancer effects of MGN-II in the A549 cell line only at a concentration of 16.0 μg mL-1 (IC50). In addition, following irradiation with UV light at 254 nm, the PDA micelles gave rise to an energy transfer from the fluorescent dye to the backbone of PDA micelles to enhance the imaging of living cells. Our results demonstrate that modified PDA micelles can not only be used in the treatment of tumors in vitro and in vivo in a simple and directed way, but also offer a new platform for designing functional liposomes to act as anticancer agents.Polydiacetylene (PDA) micelles have been widely used to deliver anticancer drugs in the treatment of a variety of tumours and for imaging living cells. In this study, we developed an effective strategy to directly conjugate magainin II (MGN-II) to the surface of PDA micelles using a fluorescent dye. These stable and well-defined PDA micelles had high cytotoxicity in cancer cell lines, and were able to reduce the tumour size in mice. The modified PDA micelles improved the anticancer effects of MGN-II in the A549 cell line only at a concentration of 16.0 μg mL-1 (IC50). In addition, following irradiation with UV light at 254 nm, the PDA micelles gave rise to an energy transfer from the fluorescent dye to the backbone of PDA micelles to enhance the imaging of living cells. Our results demonstrate that modified PDA micelles can not only be used in the treatment of tumors in vitro and in vivo in a simple and directed way, but also offer a new platform for

  19. A novel temperature-responsive micelle for enhancing combination therapy

    PubMed Central

    Peng, Cheng-Liang; Chen, Yuan-I; Liu, Hung-Jen; Lee, Pei-Chi; Luo, Tsai-Yueh; Shieh, Ming-Jium

    2016-01-01

    A novel thermosensitive polymer p(N-isopropylacrylamide-co-poly[ethylene glycol] methyl ether acrylate)-block-poly(epsilon-caprolactone), p(NIPAAM-co-PEGMEA)-b-PCL, was synthesized and developed as nanomicelles. The hydrophobic heat shock protein 90 inhibitor 17-allylamino-17-demethoxygeldanamycin and the photosensitizer cyanine dye infrared-780 were loaded into the core of the micelles to achieve both chemotherapy and photothermal therapy simultaneously at the tumor site. The release of the drug could be controlled by varying the temperature due to the thermosensitive nature of the micelles. The micelles were less than 200 nm in size, and the drug encapsulation efficiency was >50%. The critical micelle concentrations were small enough to allow micelle stability upon dilution. Data from cell viability and animal experiments indicate that this combination treatment using photothermal therapy with chemotherapy had synergistic effects while decreasing side effects. PMID:27524894

  20. A novel temperature-responsive micelle for enhancing combination therapy.

    PubMed

    Peng, Cheng-Liang; Chen, Yuan-I; Liu, Hung-Jen; Lee, Pei-Chi; Luo, Tsai-Yueh; Shieh, Ming-Jium

    2016-01-01

    A novel thermosensitive polymer p(N-isopropylacrylamide-co-poly[ethylene glycol] methyl ether acrylate)-block-poly(epsilon-caprolactone), p(NIPAAM-co-PEGMEA)-b-PCL, was synthesized and developed as nanomicelles. The hydrophobic heat shock protein 90 inhibitor 17-allylamino-17-demethoxygeldanamycin and the photosensitizer cyanine dye infrared-780 were loaded into the core of the micelles to achieve both chemotherapy and photothermal therapy simultaneously at the tumor site. The release of the drug could be controlled by varying the temperature due to the thermosensitive nature of the micelles. The micelles were less than 200 nm in size, and the drug encapsulation efficiency was >50%. The critical micelle concentrations were small enough to allow micelle stability upon dilution. Data from cell viability and animal experiments indicate that this combination treatment using photothermal therapy with chemotherapy had synergistic effects while decreasing side effects. PMID:27524894

  1. Defining Chlorophyll-a Reference Conditions in European Lakes

    PubMed Central

    Alves, Maria Helena; Argillier, Christine; van den Berg, Marcel; Buzzi, Fabio; Hoehn, Eberhard; de Hoyos, Caridad; Karottki, Ivan; Laplace-Treyture, Christophe; Solheim, Anne Lyche; Ortiz-Casas, José; Ott, Ingmar; Phillips, Geoff; Pilke, Ansa; Pádua, João; Remec-Rekar, Spela; Riedmüller, Ursula; Schaumburg, Jochen; Serrano, Maria Luisa; Soszka, Hanna; Tierney, Deirdre; Urbanič, Gorazd; Wolfram, Georg

    2010-01-01

    The concept of “reference conditions” describes the benchmark against which current conditions are compared when assessing the status of water bodies. In this paper we focus on the establishment of reference conditions for European lakes according to a phytoplankton biomass indicator—the concentration of chlorophyll-a. A mostly spatial approach (selection of existing lakes with no or minor human impact) was used to set the reference conditions for chlorophyll-a values, supplemented by historical data, paleolimnological investigations and modelling. The work resulted in definition of reference conditions and the boundary between “high” and “good” status for 15 main lake types and five ecoregions of Europe: Alpine, Atlantic, Central/Baltic, Mediterranean, and Northern. Additionally, empirical models were developed for estimating site-specific reference chlorophyll-a concentrations from a set of potential predictor variables. The results were recently formulated into the EU legislation, marking the first attempt in international water policy to move from chemical quality standards to ecological quality targets. PMID:20401659

  2. Cosolubilization of Coumarin30 and Warfarin in Cationic, Anionic, and Nonionic Micelles: A Micelle-Water Interfacial Charge Dependent FRET.

    PubMed

    Dar, Aijaz Ahmad; Chat, Oyais Ahmad

    2015-09-01

    Solubilization of structurally varied coumarins, viz., Warfarin (WF; a 4-hydroxy coumarin) and Coumarin30 (C30, a 7-amino coumarin) individually and in mixed states (cosolubilization) within the aqueous surfactant self-assemblies of varying architectures has been explored, exploiting steady-state, time-resolved fluorimetric, and spectrophotometric techniques. Cosolubilization studies within micelles, which have rarely been done in the literature, were specifically undertaken with the aim of understanding the effect of micelles on their photophysical phenomena when simultaneously present within these nanocarriers and assess their prospective use as an efficient FRET pair. WF solubilizes within CTAB micelles, whereas little or no solubilization is observed in Brij30 and SDS micelles. On the other hand, C30 solubilizes deep into the palisade layer of CTAB micelles, between negatively charged head groups in SDS micelles and between OE groups in Brij30 micelles. C30 and WF maintain their solubilization sites during cosolubilization. In SDS and Brij30 micelles, an increase in WF causes fluorescence quenching of C30 molecules, while in CTAB, an increase in WF causes an increase in fluorescence of C30 by excited WF molecules indicating FRET between the two molecules. PMID:26244283

  3. Functionalized nanoscale micelles with brain targeting ability and intercellular microenvironment biosensitivity for anti-intracranial infection applications.

    PubMed

    Shao, Kun; Zhang, Yu; Ding, Ning; Huang, Shixian; Wu, Jiqin; Li, Jianfeng; Yang, Chunfu; Leng, Qibin; Ye, Liya; Lou, Jinning; Zhu, Liping; Jiang, Chen

    2015-01-28

    Due to complication factors such as blood-brain barrier (BBB), integrating high efficiency of brain target ability with specific cargo releasing into one nanocarrier seems more important. A brain targeting nanoscale system is developed using dehydroascorbic acid (DHA) as targeting moiety. DHA has high affinity with GLUT1 on BBB. More importantly, the GLUT1 transportation of DHA represents a "one-way" accumulative priority from blood into brain. The artificial micelles are fabricated by a disulfide linkage, forming a bio-responsive inner barrier, which can maintain micelles highly stable in circulation and shield the leakage of entrapped drug before reaching the targeting cells. The designed micelles can cross BBB and be further internalized by brain cells. Once within the cells, the drug release can be triggered by high intracellular level of glutathione (GSH). Itraconazole (ITZ) is selected as the model drug because of its poor brain permeability and low stability in blood. It demonstrates that the functionalized nanoscale micelles can achieve highly effective direct drug delivery to targeting site. Based on the markedly increased stability in blood circulation and improved brain delivery efficiency of ITZ, DHA-modified micelles show highly effective in anti-intracranial infection. Therefore, this smart nanodevice shows a promising application for the treatment of brain diseases. PMID:25124929

  4. Nature of CTAB/Water/Chloroform Reverse Micelles at Above- and Subzero Temperatures Studied by NMR and Molecular Dynamics Simulations.

    PubMed

    Klíčová, Lubica; Muchová, Eva; Šebej, Peter; Slavíček, Petr; Klán, Petr

    2015-08-01

    The nature and stability of cetyltrimethylammonium bromide (CTAB) reverse micelles in chloroform formed above the critical micellar concentration at above- and subzero temperatures were examined by NMR and molecular dynamics simulations. The experiments showed that the supercooled micellar water pool becomes unstable upon cooling to relatively high temperatures (253 K), and smaller micelles are formed. Upon freezing at lower temperatures (233 K), micelles become completely frozen and remain intact in the solution. With an average hydrodynamic radius of approximately 1.3 nm, we estimate that the water pool contains approximately 50 water molecules, which is well below the onset of ice crystal formation. To support the experimental results, molecular dynamics simulations were used to model the structure of CTAB/water/chloroform reverse micelles of different sizes. The MD simulations show that the reverse micelles contain a water pool with bromide anions residing on its surface and their shape is nonspherical, especially in the case of larger water pools. Upon fast freezing, the mobility of the water molecules is suppressed, and the pool becomes more spherical.

  5. Flt1 peptide-hyaluronate conjugate micelle-like nanoparticles encapsulating genistein for the treatment of ocular neovascularization.

    PubMed

    Kim, Hyemin; Choi, Jun-Sub; Kim, Ki Su; Yang, Jeong-A; Joo, Choun-Ki; Hahn, Sei Kwang

    2012-11-01

    Flt1 peptide of GNQWFI is an antagonistic peptide for vascular endothelial growth factor receptor 1 (VEGFR1 or Flt1). In this work, Flt1 peptide-hyaluronate (HA) conjugates were successfully synthesized and the resulting micelle-like nanoparticles were exploited to encapsulate genistein, an inhibitor of tyrosine-specific protein kinases, for the treatment of ocular neovascularization. The mean diameter of genistein-loaded Flt1 peptide-HA conjugate micelles was measured to be 172.0±18.7 nm, with a drug-loading efficiency of 40-50%. In vitro release tests of genistein from the genistein-loaded Flt1 peptide-HA conjugate micelles exhibited the controlled release for longer than 24h. In vitro biological activity of genistein/Flt1 peptide-HA micelles was corroborated from the synergistic anti-proliferation of human umbilical vein endothelial cells (HUVECs). Furthermore, we could confirm the anti-angiogenic effect of genistein/Flt1 peptide-HA micelles from the statistically significant suppression of corneal neovascularization in silver nitrate cauterized corneas of SD rats. The retinal vascular hyperpermeability was also drastically reduced by the treatment in diabetic retinopathy model rats. PMID:22824530

  6. Therapeutic surfactant-stripped frozen micelles

    PubMed Central

    Zhang, Yumiao; Song, Wentao; Geng, Jumin; Chitgupi, Upendra; Unsal, Hande; Federizon, Jasmin; Rzayev, Javid; Sukumaran, Dinesh K.; Alexandridis, Paschalis; Lovell, Jonathan F.

    2016-01-01

    Injectable hydrophobic drugs are typically dissolved in surfactants and non-aqueous solvents which can induce negative side-effects. Alternatives like ‘top-down' fine milling of excipient-free injectable drug suspensions are not yet clinically viable and ‘bottom-up' self-assembled delivery systems usually substitute one solubilizing excipient for another, bringing new issues to consider. Here, we show that Pluronic (Poloxamer) block copolymers are amenable to low-temperature processing to strip away all free and loosely bound surfactant, leaving behind concentrated, kinetically frozen drug micelles containing minimal solubilizing excipient. This approach was validated for phylloquinone, cyclosporine, testosterone undecanoate, cabazitaxel and seven other bioactive molecules, achieving sizes between 45 and 160 nm and drug to solubilizer molar ratios 2–3 orders of magnitude higher than current formulations. Hypertonic saline or co-loaded cargo was found to prevent aggregation in some cases. Use of surfactant-stripped micelles avoided potential risks associated with other injectable formulations. Mechanistic insights are elucidated and therapeutic dose responses are demonstrated. PMID:27193558

  7. Therapeutic surfactant-stripped frozen micelles

    NASA Astrophysics Data System (ADS)

    Zhang, Yumiao; Song, Wentao; Geng, Jumin; Chitgupi, Upendra; Unsal, Hande; Federizon, Jasmin; Rzayev, Javid; Sukumaran, Dinesh K.; Alexandridis, Paschalis; Lovell, Jonathan F.

    2016-05-01

    Injectable hydrophobic drugs are typically dissolved in surfactants and non-aqueous solvents which can induce negative side-effects. Alternatives like `top-down' fine milling of excipient-free injectable drug suspensions are not yet clinically viable and `bottom-up' self-assembled delivery systems usually substitute one solubilizing excipient for another, bringing new issues to consider. Here, we show that Pluronic (Poloxamer) block copolymers are amenable to low-temperature processing to strip away all free and loosely bound surfactant, leaving behind concentrated, kinetically frozen drug micelles containing minimal solubilizing excipient. This approach was validated for phylloquinone, cyclosporine, testosterone undecanoate, cabazitaxel and seven other bioactive molecules, achieving sizes between 45 and 160 nm and drug to solubilizer molar ratios 2-3 orders of magnitude higher than current formulations. Hypertonic saline or co-loaded cargo was found to prevent aggregation in some cases. Use of surfactant-stripped micelles avoided potential risks associated with other injectable formulations. Mechanistic insights are elucidated and therapeutic dose responses are demonstrated.

  8. Formation of wormlike micelle in a mixed amino-acid based anionic surfactant and cationic surfactant systems.

    PubMed

    Shrestha, Rekha Goswami; Shrestha, Lok Kumar; Aramaki, Kenji

    2007-07-01

    Formation of wormlike micelles in mixed anionic/cationic system without the addition of any salt has been studied. Amino-acid based anionic surfactant N-dodecylglutamic acid (LAD), which is practically immiscible with water at 25 degrees C upon neutralization by 2,2',2''-nitrilotriethanol (TEA) forms small micellar aggregates and the solution behaves like a Newtonian fluid. The rheological behavior of LAD/water/hexadecyltrimethylammonium bromide (CTAB) and LAD/water/dodecyltrimethylammonium bromide (DTAB) systems were investigated at different degrees of neutralization of the LAD depending on the concentration of the cationic surfactants and on temperature. Addition of CTAB to the dilute aqueous solution of the LAD-TEA-x (the neutralized product, where x represents the mole ratio of TEA) causes one dimensional micellar growth. After certain concentration the elongated micelles entangle forming a rigid network of viscoelastic wormlike micelles. Thus formed viscoelastic solutions follow Maxwellian behavior over a wide range of frequency and thus are considered to consist of transient network of wormlike micelles. By varying the degree of neutralization from 1:1 via 1:1.5 to 1:2 (molar ratio) phase and rheological behavior were modified in that the highly viscous region of viscoelastic wormlike micelles shifted to higher CTAB concentrations and no maxima in the zero-shear viscosity could be observed for the higher degree of neutralization of the LAD (1:1.5 and 1:2). However, the obtained rheological parameters showed scaling relationships that were consistent with the living polymer model. The zero-shear viscosity decays exponentially with temperature following Arrhenius behavior. The flow activation energy calculated from the Arrhenius plot is very close to the value reported for the typical wormlike micellar solution. In contrast to CTAB no formation of viscoelastic wormlike micelles could be observed with DTAB, although, the solution viscosity increases. The

  9. Chlorophyll enhances oxidative stress tolerance in Caenorhabditis elegans and extends its lifespan

    PubMed Central

    Wang, Erjia

    2016-01-01

    Green vegetables are thought to be responsible for several beneficial properties such as antioxidant, anti-mutagenic, and detoxification activities. It is not known whether these effects are due to chlorophyll which exists in large amounts in many foods or result from other secondary metabolites. In this study, we used the model system Caenorhabditis elegans to investigate the anti-oxidative and anti-aging effects of chlorophyll in vivo. We found that chlorophyll significantly improves resistance to oxidative stress. It also enhances the lifespan of C. elegans by up to 25% via activation of the DAF-16/FOXO-dependent pathway. The results indicate that chlorophyll is absorbed by the worms and is thus bioavailable, constituting an important prerequisite for antioxidant and longevity-promoting activities inside the body. Our study thereby supports the view that green vegetables may also be beneficial for humans. PMID:27077003

  10. Reverse micelle synthesis of nanoscale metal containing catalysts

    SciTech Connect

    Darab, J.G.; Fulton, J.L.; Linehan, J.C.

    1993-03-01

    The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction and precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni{sub 3}Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.

  11. Solution NMR analysis of the interaction between the actinoporin sticholysin I and DHPC micelles--correlation with backbone dynamics.

    PubMed

    López-Castilla, Aracelys; Pazos, Fabiola; Schreier, Shirley; Pires, José Ricardo

    2014-06-01

    Sticholysin I (StI), an actinoporin expressed as a water-soluble protein by the sea anemone Stichodactyla helianthus, binds to natural and model membranes, forming oligomeric pores. It is proposed that the first event of a multistep pore formation mechanism consists of the monomeric protein attachment to the lipid bilayer. To date there is no high-resolution structure of the actinoporin pore or other membrane-bound form available. Here we evaluated StI:micelle complexes of variable lipid composition to look for a suitable model for NMR studies. Micelles of pure or mixed lysophospholipids and of dihexanoyl phosphatidylcholine (DHPC) were examined. The StI:DHPC micelle was found to be the best system, yielding a stable sample and good quality spectra. A comprehensive chemical shift perturbation analysis was performed to map the StI membrane recognition site in the presence of DHPC micelles. The region mapped (residues F(51), R(52), S(53) in loop 3; F(107), D(108), Y(109), W(111), Y(112), W(115) in loop 7; Q(129), Y(132), D(134), M(135), Y(136), Y(137), G(138) in helix-α2) is in agreement with previously reported data, but additional residues were found to interact, especially residues V(81), A(82), T(83), G(84) in loop 5, and A(85), A(87) in strand-β5. Backbone dynamics measurements of StI free in solution and bound to micelles highlighted the relevance of protein flexibility for membrane binding and suggested that a conformer selection process may take place during protein-membrane interaction. We conclude that the StI:DHPC micelles system is a suitable model for further characterization of an actinoporin membrane-bound form by solution NMR. PMID:24218049

  12. Cloud effects on chlorophyll retrieval algorithm of MODIS

    NASA Astrophysics Data System (ADS)

    Du, KePing; Gao, Yonggang; Lee, ZhongPing; Xi, Ying; Wang, Jindi

    2006-12-01

    Ocean environment attracts more and more attention, whereas monitoring ocean environment using ocean color imagery (e.g., MODIS) has become one of the important fields in modern oceanography. After analyzing a few individual modules of the radiative transfer process, an end-to-end numerical model for ocean remote sensing is developed. This model combines MODTRAN and HYDROLIGHT, both are state-of-the-art radiative transfer models for atmosphere and water, respectively. Also, a simple but realistic cloud model is added to it. This combined model calculates the downward radiance on water surface using MODTRAN and the independent cloud model, which replaces the empirical and semi-empirical models used in RADTRAN (Gregg and Carder 1991). Especially, with information of cloud's location and brightness from by the cloud model, the combined model provides more accurate radiance on water surface. Further, the effects of cloud position (from 30 degree to 180 degree for the cloud central azimuth angle) and coverage (from about 10% to 80%) on retrieved chlorophyll concentration by standard MODIS algorithm is analyzed. It is found that the nearer the cloud to the Sun the smaller the effect on the derived chlorophyll.

  13. Space charge limited release of charged inverse micelles in non-polar liquids.

    PubMed

    Prasad, Manoj; Strubbe, Filip; Beunis, Filip; Neyts, Kristiaan

    2016-07-28

    Charged inverse micelles (CIMs) generated during a continuous polarizing voltage between electrodes in the model system of polyisobutylene succinimide in dodecane do not populate a diffuse double layer like CIMs present in equilibrium (regular CIMs), but instead end up in interface layers. When the applied voltage is reversed abruptly after a continuous polarizing voltage step, two peaks are observed in the transient current. The first peak is due to the release of regular CIMs from the diffuse double layers formed during the polarizing voltage step, which is understood on the basis of the Poisson-Nernst-Planck equations. The second peak is due to the release of a small fraction of generated negative CIMs from the interface layer. A model based on space charge limited release of the generated negative CIMs from the interface layer is presented and the results of the model are compared with several types of measurements. For the situation in which the bulk is deprived of regular CIMs and neutral inverse micelles, the results of the model are in agreement with the experimental results. However, for the situation in which regular CIMs and neutral inverse micelles are present, the model shows discrepancies with the experiment for high voltages and high charge contents. These discrepancies are attributed to electrohydrodynamic flow caused by local variations in the electric field at the vicinity of the electrodes, which occur during the reversal voltage. Also the long term decrease of the amount of released generated CIMs is studied and it is found that the presence of regular CIMs and neutral inverse micelles speeds up the decrease. This study provides a deeper insight in the electrodynamics of CIMs and is relevant for various applications in non-polar liquids. PMID:27374418

  14. Chlorophyll modifications and their spectral extension in oxygenic photosynthesis.

    PubMed

    Chen, Min

    2014-01-01

    Chlorophylls are magnesium-tetrapyrrole molecules that play essential roles in photosynthesis. All chlorophylls have similar five-membered ring structures, with variations in the side chains and/or reduction states. Formyl group substitutions on the side chains of chlorophyll a result in the different absorption properties of chlorophyll b, chlorophyll d, and chlorophyll f. These formyl substitution derivatives exhibit different spectral shifts according to the formyl substitution position. Not only does the presence of various types of chlorophylls allow the photosynthetic organism to harvest sunlight at different wavelengths to enhance light energy input, but the pigment composition of oxygenic photosynthetic organisms also reflects the spectral properties on the surface of the Earth. Two major environmental influencing factors are light and oxygen levels, which may play central roles in the regulatory pathways leading to the different chlorophylls. I review the biochemical processes of chlorophyll biosynthesis and their regulatory mechanisms.

  15. Surfactant micelles containing solubilized oil decrease foam film thickness stability.

    PubMed

    Lee, Jongju; Nikolov, Alex; Wasan, Darsh

    2014-02-01

    Many practical applications involving three-phase foams (aqueous foams containing oil) commonly employ surfactants at several times their critical micelle concentration (CMC); in these applications, the oil can exist in two forms: (1) oil drops or macroemulsions and (2) oil solubilized within the micelles. We have recently observed that in the case of aqueous foams stabilized with sodium dodecyl sulfate (SDS) and n-dodecane as an oil, the oil drops did not alter the foam stability but the solubilized oil (swollen micelles) greatly influenced the foam's stability. In order to explain the effect of oil solubilized in the surfactant micelles on foam stability, we studied the stability of a single foam film containing swollen micelles of SDS using reflected light microinterferometry. The film thinning occurs in stepwise manner (stratification). In addition, we obtained data for the film-meniscus contact angle versus film thickness (corresponding to the different number of micellar layers) and used it to calculate the film structural energy isotherm. The results of this study showed that the structural energy stabilization barrier decreased in the presence of swollen micelles in the film, thereby decreasing the foam stability. These results provide a better understanding of the role of oil solubilized by the micelles in affecting foam stability. PMID:24267325

  16. Evaluation of Doxorubicin-loaded 3-Helix Micelles as Nanocarriers

    PubMed Central

    Dube, Nikhil; Shu, Jessica Y.; Dong, He; Seo, Jai W.; Ingham, Elizabeth; Kheirolomoom, Azadeh; Chen, Pin-Yuan; Forsayeth, John; Bankiewicz, Krystof; Ferrara, Katherine W.; Xu, Ting

    2013-01-01

    Designing stable drug nanocarriers, 10-30 nm in size, would have significant impact on their transport in circulation, tumor penetration and therapeutic efficacy. In the present study, biological properties of 3-helix micelles loaded with 8 wt% doxorubicin (DOX), ~15 nm in size, were characterized to validate their potential as a nanocarrier platform. DOX-loaded micelles exhibited high stability in terms of size and drug retention in concentrated protein environments similar to conditions after intravenous injections. DOX-loaded micelles were cytotoxic to PPC-1 and 4T1 cancer cells at levels comparable to free DOX. 3-helix micelles can be disassembled by proteolytic degradation of peptide shell to enable drug release and clearance to minimize long-term accumulation. Local administration to normal rat striatum by convection enhanced delivery (CED) showed greater extent of drug distribution and reduced toxicity relative to free drug. Intravenous administration of DOX-loaded 3-helix micelles demonstrated improved tumor half-life and reduced toxicity to healthy tissues in comparison to free DOX. In vivo delivery of DOX-loaded 3-helix micelles through two different routes clearly indicates the potential of 3-helix micelles as safe and effective nanocarriers for cancer therapeutics. PMID:24050265

  17. Novel pluronic-chitosan micelle as an ocular delivery system.

    PubMed

    Lin, Hong-Ru; Chang, Pei-Csang

    2013-07-01

    Pluronic micelles were prepared for ophthalmic delivery by incorporation of ethyl acetate as a dispersion agent and their surfaces were modified by chitosan to improve their bioavailability. The micelles disperse well in the solution and have a core-shell like structure with a particle size ranging from 93 to 181 nm for drug unloaded, 123-232 nm for drug-loaded, and a zeta potential between 6.1 and 9.2 mV, indicating very suitable use as ophthalmic carrier. The in vitro serum stability tests indicate the particle size of the micelles was very stable during the serum absorption. The turbidity test reveals that the prepared micelles were very stable under phosphate buffered saline environment, which can prevent the blurred vision. The loading efficiency of metipranolol in micelles can be as high as 83%. Finally, the in vitro and in vivo studies indicate the pluronic micelles modified by chitosan have sustained release behavior and good pharmacological response. As the results, the pluroic-chitosan micelles system provides a potential opportunity in decreasing frequency of administration and improving patient compliance for ocular drug delivery.

  18. Temporal disparity in leaf chlorophyll content and leaf area index across a growing season in a temperate deciduous forest

    NASA Astrophysics Data System (ADS)

    Croft, H.; Chen, J. M.; Zhang, Y.

    2014-12-01

    Spatial and temporal variations in canopy structure and leaf biochemistry have considerable influence on fluxes of CO2, water and energy and nutrient cycling in vegetation. Two vegetation indices (VI), NDVI and Macc01, were used to model the spatio-temporal variability of broadleaf chlorophyll content and leaf area index (LAI) across a growing season. Ground data including LAI, hyperspectral leaf reflectance factors (400-2500 nm) and leaf chlorophyll content were measured across the growing season and satellite-derived canopy reflectance data was acquired for 33 dates at 1200 m spatial resolution. Key phenological information was extracted using the TIMESAT software. Results showed that LAI and chlorophyll start of season (SOS) dates were at day of year (DOY) 130 and 157 respectively, and total season duration varied by 57 days. The spatial variability of chlorophyll and LAI phenology was also analyzed at the landscape scale to investigate phenological patterns over a larger spatial extent. Whilst a degree of spatial variability existed, results showed that chlorophyll SOS lagged approximately 20-35 days behind LAI SOS, and the end of season (EOS) LAI dates were predominantly between 20 and 30 days later than chlorophyll EOS. The large temporal differences between VI-derived chlorophyll content and LAI has important implications for biogeochemical models using NDVI or LAI to represent the fraction of photosynthetically active radiation absorbed by a canopy, in neglecting to account for delays in chlorophyll production and thus photosynthetic capacity.

  19. Stereocomplex micelle from nonlinear enantiomeric copolymers efficiently transports antineoplastic drug

    NASA Astrophysics Data System (ADS)

    Wang, Jixue; Shen, Kexin; Xu, Weiguo; Ding, Jianxun; Wang, Xiaoqing; Liu, Tongjun; Wang, Chunxi; Chen, Xuesi

    2015-05-01

    Nanoscale polymeric micelles have attracted more and more attention as a promising nanocarrier for controlled delivery of antineoplastic drugs. Herein, the doxorubicin (DOX)-loaded poly(D-lactide)-based micelle (PDM/DOX), poly(L-lactide)-based micelle (PLM/DOX), and stereocomplex micelle (SCM/DOX) from the equimolar mixture of the enantiomeric four-armed poly(ethylene glycol)-polylactide (PEG-PLA) copolymers were successfully fabricated. In phosphate-buffered saline (PBS) at pH 7.4, SCM/DOX exhibited the smallest hydrodynamic diameter ( D h) of 90 ± 4.2 nm and the slowest DOX release compared with PDM/DOX and PLM/DOX. Moreover, PDM/DOX, PLM/DOX, and SCM/DOX exhibited almost stable D hs of around 115, 105, and 90 nm at above normal physiological condition, respectively, which endowed them with great potential in controlled drug delivery. The intracellular DOX fluorescence intensity after the incubation with the laden micelles was different degrees weaker than that incubated with free DOX · HCl within 12 h, probably due to the slow DOX release from micelles. As the incubation time reached to 24 h, all the cells incubated with the laden micelles, especially SCM/DOX, demonstrated a stronger intracellular DOX fluorescence intensity than free DOX · HCl-cultured ones. More importantly, all the DOX-loaded micelles, especially SCM/DOX, exhibited potent antineoplastic efficacy in vitro, excellent serum albumin-tolerance stability, and satisfactory hemocompatibility. These encouraging data indicated that the loading micelles from nonlinear enantiomeric copolymers, especially SCM/DOX, might be promising in clinical systemic chemotherapy through intravenous injection.

  20. Enhanced solubility and targeted delivery of curcumin by lipopeptide micelles.

    PubMed

    Liang, Ju; Wu, Wenlan; Lai, Danyu; Li, Junbo; Fang, Cailin

    2015-01-01

    A lipopeptide (LP)-containing KKGRGDS as the hydrophilic heads and lauric acid (C12) as the hydrophobic tails has been designed and prepared by standard solid-phase peptide synthesis technique. LP can self-assemble into spherical micelles with the size of ~30 nm in PBS (phosphate buffer saline) (pH 7.4). Curcumin-loaded LP micelles were prepared in order to increase the water solubility, sustain the releasing rate, and improve the tumor targeted delivery of curcumin. Water solubility, cytotoxicity, in vitro release behavior, and intracellular uptake of curcumin-loaded LP micelles were investigated. The results showed that LP micelles can increase the water solubility of curcumin 1.1 × 10(3) times and sustain the release of curcumin in a low rate. Curcumin-loaded LP micelles showed much higher cell inhibition than free curcumin on human cervix carcinoma (HeLa) and HepG2 cells. When incubating these curcumin-loaded micelles with HeLa and COS7 cells, due to the over-expression of integrins on cancer cells, the micelles can efficiently use the tumor-targeting function of RGD (functionalized peptide sequences: Arg-Gly-Asp) sequence to deliver the drug into HeLa cells, and better efficiency of the self-assembled LP micelles for curcumin delivery than crude curcumin was also confirmed by LCSM (laser confocal scanning microscope) assays. Combined with the enhanced solubility and higher cell inhibition, LP micelles reported in this study may be promising in clinical application for targeted curcumin delivery.

  1. Thallous ion interaction with gramicidin incorporated in micelles studies by thallium-205 nuclear magnetic resonance

    SciTech Connect

    Hinton, J.F.; Young, G.; Millett, F.S.

    1982-02-16

    A study has been made of the interaction between the thallous and gramicidin dimers incorporated into micelles by using /sup 205/Tl NMR spectroscopy. The chemical shift data obtained are interpreted in terms of a model in which the dimer has only one tight binding site. The binding constant for this site was determined to be 900 M/sup -1/ at 30omicronC. The thallous ion also appears to be partially solvated in the channel.

  2. Selective intracellular drug delivery from pH-responsive polyion complex micelle for enhanced malignancy suppression in vivo.

    PubMed

    Wang, Jixue; Xu, Weiguo; Guo, Hui; Ding, Jianxun; Chen, Jinjin; Guan, Jingjing; Wang, Chunxi

    2015-11-01

    The pH-triggered intracellular drug delivery platforms have attracted great interest in malignancy therapy. Herein, a pH-responsive polyion complex (PIC) micelle from anionic acid-sensitive methoxy poly(ethylene glycol)-block-poly(N(ϵ)-((1-carboxy-cis-cyclohexene)-2-carbonyl)-L-lysine) (mPEG-b-PCLL) and cationic doxorubicin (DOX), a model anthracycline antitumor drug, was constructed by electrostatic interaction for directional intracellular drug delivery in malignancy chemotherapy. The PIC micelle kept constant diameter at physiological condition (i.e., pH 7.4), while gradually swelled and finally disassembled at mimicking intratumoral pH (i.e., 6.8) and especially intracellular endo/lysosomal pH (i.e., 5.5). The DOX release from the PIC micelle at pH 7.4 was slow, whereas obviously accelerated at the intracellular acidic condition of pH 5.5. These results should be related to the rapid cleavage of the side amide bond of mPEG-b-PCLL in an acidic environment. The PIC micelle exhibited satisfactory tumor suppression toward the H22 hepatoma-bearing BALB/c mouse model compared with free DOX, which was demonstrated by the upregulated tumor inhibition rate, and the increased necrotic and apoptosis areas in tumor tissue. Furthermore, the enhanced security was also observed in the PIC micelle group in relation to that of free DOX. The above results strongly supported that the acid-sensitive PIC micelle was promising for selective intracellular drug delivery along with upregulated malignancy inhibition.

  3. Anomalous phase separation kinetics observed in a micelle system

    SciTech Connect

    Wilcoxon, J.P.; Martin, J.E.

    1995-01-01

    The authors report a real-time, two-dimensional light scattering study of the evolution of structure of a two component nonionic micelle system undergoing phase separation. The micelles act like molecular slug-a-beds whose domain growth is lethargic (i.e. slower than the cube root of time prediction for simple binary fluids). In fact, the growth kinetics can be empirically described as a stretched exponential approach to a pinned domain size. Although the kinetics are not yet understood, the anomalous behavior may be due to the ability of the spherical micelles to reorganize into more complex structures.

  4. Biocleavable Polycationic Micelles as Highly Efficient Gene Delivery Vectors

    NASA Astrophysics Data System (ADS)

    Zhang, Min; Xue, Ya-Nan; Liu, Min; Zhuo, Ren-Xi; Huang, Shi-Wen

    2010-11-01

    An amphiphilic disulfide-containing polyamidoamine was synthesized by Michael-type polyaddition reaction of piperazine to equimolar N, N'-bis(acryloyl)cystamine with 90% yield. The polycationic micelles (198 nm, 32.5 mV), prepared from the amphiphilic polyamidoamine by dialysis method, can condense foreign plasmid DNA to form nanosized polycationic micelles/DNA polyelectrolyte complexes with positive charges, which transfected 293T cells with high efficiency. Under optimized conditions, the transfection efficiencies of polycationic micelles/DNA complexes are comparable to, or even higher than that of commercially available branched PEI (Mw 25 kDa).

  5. Redox-Responsive, Core Cross-Linked Polyester Micelles

    PubMed Central

    Zhang, Zhonghai; Yin, Lichen; Tu, Chunlai; Song, Ziyuan; Zhang, Yanfeng; Xu, Yunxiang; Tong, Rong; Zhou, Qin; Ren, Jie; Cheng, Jianjun

    2013-01-01

    Monomethoxy poly(ethylene glycol)-b-poly(Tyr(alkynyl)-OCA), a biodegradable amphiphilic block copolymer, was synthesized by means of ring-opening polymerization of 5-(4-(prop-2-yn-1-yloxy)benzyl)-1,3-dioxolane-2,4-dione (Tyr(alkynyl)-OCA) and used to prepare core cross-linked polyester micelles via click chemistry. Core cross-linking not only improved the structural stability of the micelles but also allowed controlled release of cargo molecules in response to the reducing reagent. This new class of core cross-linked micelles can potentially be used in controlled release and drug delivery applications. PMID:23536920

  6. Biomimetic oxidation studies. 11: Alkane functionalization in aqueous solution utilizing in situ formed [Fe{sub 2}O({eta}{sup 1}-H{sub 2}O)({eta}{sup 1}-OAc)(TPA){sub 2}]{sup 3+}, as an MMO model precatalyst, embedded in surface-derivatized silica and contained in micelles

    SciTech Connect

    Neimann, K.; Neumann, R.; Rabion, A. |; Buchanan, R.M.; Fish, R.H.

    1999-07-26

    The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe{sub 2}O({eta}{sup 1}-H{sub 2}O)({eta}{sup 1}-OAc)(TPA){sub 2}]{sup 3+} (TPA = tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe{sub 2}O({mu}-OAc)(TPA){sub 2}]{sup 3+}, 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O{sub 2} in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of {approximately}3:1:2. The balance between poly(ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O{sub 2} in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of {approximately}2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO{sup {sm_bullet}} and t-BuOO{sup {sm_bullet}} radicals. The t-BuO{sup {sm_bullet}} radical initiates the C-H functionalization reaction to form the carbon radical, followed by O{sub 2} trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t

  7. Chlorophyll b degradation by chlorophyll b reductase under high-light conditions.

    PubMed

    Sato, Rei; Ito, Hisashi; Tanaka, Ayumi

    2015-12-01

    The light-harvesting chlorophyll a/b binding protein complex of photosystem II (LHCII) is the main antenna complex of photosystem II (PSII). Plants change their LHCII content depending on the light environment. Under high-light conditions, the content of LHCII should decrease because over-excitation damages the photosystem. Chlorophyll b is indispensable for accumulating LHCII, and chlorophyll b degradation induces LHCII degradation. Chlorophyll b degradation is initiated by chlorophyll b reductase (CBR). In land plants, NON-YELLOW COLORING 1 (NYC1) and NYC1-Like (NOL) are isozymes of CBR. We analyzed these mutants to determine their functions under high-light conditions. During high-light treatment, the chlorophyll a/b ratio was stable in the wild-type (WT) and nol plants, and the LHCII content decreased in WT plants. The chlorophyll a/b ratio decreased in the nyc1 and nyc1/nol plants, and a substantial degree of LHCII was retained in nyc1/nol plants after the high-light treatment. These results demonstrate that NYC1 degrades the chlorophyll b on LHCII under high-light conditions, thus decreasing the LHCII content. After the high-light treatment, the maximum quantum efficiency of the PSII photochemistry was lower in nyc1 and nyc1/nol plants than in WT and nol plants. A larger light-harvesting system would damage PSII in nyc1 and nyc1/nol plants. The fluorescence spectroscopy of the leaves indicated that photosystem I was also damaged by the excess LHCII in nyc1/nol plants. These observations suggest that chlorophyll b degradation by NYC1 is the initial reaction for the optimization of the light-harvesting capacity under high-light conditions.

  8. Structural investigation of nonionic fluorinated micelles by SANS in relation to mesoporous silica materials.

    PubMed

    Michaux, Florentin; Blin, Jean-Luc; Teixeira, José; Stébé, Marie José

    2012-01-12

    In an attempt to answer the question if there is dependence between the pore ordering of the mesoporous silica, obtained through the cooperative template mechanism, and the shape of the micellar aggregates of the surfactant solutions, the micellar structures of two nonionic fluorinated surfactant based-systems are studied by SANS. By fitting the experimental spectra with theoretical models, the structural evolution of the molecular aggregates can be described, and some important parameters can be obtained, such as the water and eventually oil penetration into the surfactant film, the aggregation number, the area per polar head of the surfactant, and the surfactant chain conformations. We have shown that for the C(8)F(17)C(2)H(4)(OC(2)H(4))(9)OH system, the micelles are prolate spheroids. The increase of the surfactant concentration in water does not change the characteristics of the interfacial film, but the aggregation number raises and the particles become more elongated. By contrast, the experimental curves of C(7)F(15)C(2)H(4)(OC(2)H(4))(8)OH cannot be fitted considering a small particle model. However, progressive incorporation of fluorocarbon induces a change of size and shape of the globules, which become smaller and more and more spherical. Regarding the material mesopore ordering, it appears that the micelles that lead to hexagonal mesoporous silica materials are described with a model of quasi-spherical globules. On the contrary, when large micelles are found, only wormhole-like structures are obtained.

  9. Trends in ocean colour and chlorophyll concentration from 1889 to 2000, worldwide.

    PubMed

    Wernand, Marcel R; van der Woerd, Hendrik J; Gieskes, Winfried W C

    2013-01-01

    Marine primary productivity is an important agent in the global cycling of carbon dioxide, a major 'greenhouse gas', and variations in the concentration of the ocean's phytoplankton biomass can therefore explain trends in the global carbon budget. Since the launch of satellite-mounted sensors globe-wide monitoring of chlorophyll, a phytoplankton biomass proxy, became feasible. Just as satellites, the Forel-Ule (FU) scale record (a hardly explored database of ocean colour) has covered all seas and oceans--but already since 1889. We provide evidence that changes of ocean surface chlorophyll can be reconstructed with confidence from this record. The EcoLight radiative transfer numerical model indicates that the FU index is closely related to chlorophyll concentrations in open ocean regions. The most complete FU record is that of the North Atlantic in terms of coverage over space and in time; this dataset has been used to test the validity of colour changes that can be translated to chlorophyll. The FU and FU-derived chlorophyll data were analysed for monotonously increasing or decreasing trends with the non-parametric Mann-Kendall test, a method to establish the presence of a consistent trend. Our analysis has not revealed a globe-wide trend of increase or decrease in chlorophyll concentration during the past century; ocean regions have apparently responded differentially to changes in meteorological, hydrological and biological conditions at the surface, including potential long-term trends related to global warming. Since 1889, chlorophyll concentrations have decreased in the Indian Ocean and in the Pacific; increased in the Atlantic Ocean, the Mediterranean, the Chinese Sea, and in the seas west and north-west of Japan. This suggests that explanations of chlorophyll changes over long periods should focus on hydrographical and biological characteristics typical of single ocean regions, not on those of 'the' ocean.

  10. Trends in Ocean Colour and Chlorophyll Concentration from 1889 to 2000, Worldwide

    PubMed Central

    Wernand, Marcel R.; van der Woerd, Hendrik J.; Gieskes, Winfried W. C.

    2013-01-01

    Marine primary productivity is an important agent in the global cycling of carbon dioxide, a major ‘greenhouse gas’, and variations in the concentration of the ocean's phytoplankton biomass can therefore explain trends in the global carbon budget. Since the launch of satellite-mounted sensors globe-wide monitoring of chlorophyll, a phytoplankton biomass proxy, became feasible. Just as satellites, the Forel-Ule (FU) scale record (a hardly explored database of ocean colour) has covered all seas and oceans – but already since 1889. We provide evidence that changes of ocean surface chlorophyll can be reconstructed with confidence from this record. The EcoLight radiative transfer numerical model indicates that the FU index is closely related to chlorophyll concentrations in open ocean regions. The most complete FU record is that of the North Atlantic in terms of coverage over space and in time; this dataset has been used to test the validity of colour changes that can be translated to chlorophyll. The FU and FU-derived chlorophyll data were analysed for monotonously increasing or decreasing trends with the non-parametric Mann-Kendall test, a method to establish the presence of a consistent trend. Our analysis has not revealed a globe-wide trend of increase or decrease in chlorophyll concentration during the past century; ocean regions have apparently responded differentially to changes in meteorological, hydrological and biological conditions at the surface, including potential long-term trends related to global warming. Since 1889, chlorophyll concentrations have decreased in the Indian Ocean and in the Pacific; increased in the Atlantic Ocean, the Mediterranean, the Chinese Sea, and in the seas west and north-west of Japan. This suggests that explanations of chlorophyll changes over long periods should focus on hydrographical and biological characteristics typical of single ocean regions, not on those of ‘the’ ocean. PMID:23776435

  11. Trends in ocean colour and chlorophyll concentration from 1889 to 2000, worldwide.

    PubMed

    Wernand, Marcel R; van der Woerd, Hendrik J; Gieskes, Winfried W C

    2013-01-01

    Marine primary productivity is an important agent in the global cycling of carbon dioxide, a major 'greenhouse gas', and variations in the concentration of the ocean's phytoplankton biomass can therefore explain trends in the global carbon budget. Since the launch of satellite-mounted sensors globe-wide monitoring of chlorophyll, a phytoplankton biomass proxy, became feasible. Just as satellites, the Forel-Ule (FU) scale record (a hardly explored database of ocean colour) has covered all seas and oceans--but already since 1889. We provide evidence that changes of ocean surface chlorophyll can be reconstructed with confidence from this record. The EcoLight radiative transfer numerical model indicates that the FU index is closely related to chlorophyll concentrations in open ocean regions. The most complete FU record is that of the North Atlantic in terms of coverage over space and in time; this dataset has been used to test the validity of colour changes that can be translated to chlorophyll. The FU and FU-derived chlorophyll data were analysed for monotonously increasing or decreasing trends with the non-parametric Mann-Kendall test, a method to establish the presence of a consistent trend. Our analysis has not revealed a globe-wide trend of increase or decrease in chlorophyll concentration during the past century; ocean regions have apparently responded differentially to changes in meteorological, hydrological and biological conditions at the surface, including potential long-term trends related to global warming. Since 1889, chlorophyll concentrations have decreased in the Indian Ocean and in the Pacific; increased in the Atlantic Ocean, the Mediterranean, the Chinese Sea, and in the seas west and north-west of Japan. This suggests that explanations of chlorophyll changes over long periods should focus on hydrographical and biological characteristics typical of single ocean regions, not on those of 'the' ocean. PMID:23776435

  12. Multicompartmental Microcapsules from Star Copolymer Micelles

    SciTech Connect

    Choi, Ikjun; Malak, Sidney T.; Xu, Weinan; Heller, William T.; Tsitsilianis, Constantinos; Tsukruk, Vladimir V.

    2013-02-26

    We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2-pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into the LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic

  13. Interregional difference in spring neap variations in stratification and chlorophyll fluorescence during summer in a tidal sea (Yatsushiro Sea, Japan)

    NASA Astrophysics Data System (ADS)

    Aoki, Kazuhiro; Onitsuka, Goh; Shimizu, Manabu; Matsuo, Hitoshi; Kitadai, Yuuki; Ochiai, Hironori; Yamamoto, Takeshi; Furukawa, Shinpei

    2016-10-01

    Spring neap variations in stratification and chlorophyll fluorescence were studied during the summers of 2011-2014 in a tidal sea (Yatsushiro Sea, Japan) using monitoring data and hydrodynamic models. Vertical profiles of salinity, temperature and chlorophyll fluorescence were collected nearly weekly from nine stations in this sea during the same period. Composite analysis using vertical profiles of density clearly indicated enhancement of the stratification during the neap tide and a vertically mixed water column during the spring tide in the tidal area. Interregional differences were revealed in the variation of chlorophyll fluorescence with the spring neap tidal cycle. More notable increases in chlorophyll fluorescence were observed during the neap tide in the tidal area around the narrow strait than in the inner area. Temporal stratification led to an increase in the chlorophyll fluorescence in the tidal strait during the neap tide.

  14. Identification of Genes Associated with Chlorophyll Accumulation in Flower Petals

    PubMed Central

    Ohmiya, Akemi; Hirashima, Masumi; Yagi, Masafumi; Tanase, Koji; Yamamizo, Chihiro

    2014-01-01

    Plants have an ability to prevent chlorophyll accumulation, which would mask the bright flower color, in their petals. In contrast, leaves contain substantial amounts of chlorophyll, as it is essential for photosynthesis. The mechanisms of organ-specific chlorophyll accumulation are unknown. To identify factors that determine the chlorophyll content in petals, we compared the expression of genes related to chlorophyll metabolism in different stages of non-green (red and white) petals (very low chlorophyll content), pale-green petals (low chlorophyll content), and leaves (high chlorophyll content) of carnation (Dianthus caryophyllus L.). The expression of many genes encoding chlorophyll biosynthesis enzymes, in particular Mg-chelatase, was lower in non-green petals than in leaves. Non-green petals also showed higher expression of genes involved in chlorophyll degradation, including STAY-GREEN gene and pheophytinase. These data suggest that the absence of chlorophylls in carnation petals may be caused by the low rate of chlorophyll biosynthesis and high rate of degradation. Similar results were obtained by the analysis of Arabidopsis microarray data. In carnation, most genes related to chlorophyll biosynthesis were expressed at similar levels in pale-green petals and leaves, whereas the expression of chlorophyll catabolic genes was higher in pale-green petals than in leaves. Therefore, we hypothesize that the difference in chlorophyll content between non-green and pale-green petals is due to different levels of chlorophyll biosynthesis. Our study provides a basis for future molecular and genetic studies on organ-specific chlorophyll accumulation. PMID:25470367

  15. pH-Sensitive micelles self-assembled from amphiphilic copolymer brush for delivery of poorly water-soluble drugs.

    PubMed

    Yang, You Qiang; Zheng, Ling Shan; Guo, Xin Dong; Qian, Yu; Zhang, Li Juan

    2011-01-10

    A novel pH-sensitive amphiphilic copolymer brush poly(methyl methacrylate-co-methacrylic acid)-b-poly(poly(ethylene glycol) methyl ether monomethacrylate) [P(MMA-co-MAA)-b-PPEGMA] was defined and synthesized by atom transfer radical polymerization (ATRP) technique. The molecular structures and characteristics of this copolymer and its precursors were confirmed by (1)H NMR, FT-IR, and GPC. The CMC of P(MMA-co-MAA)-b-PPEGMA in aqueous medium was determined to be 1-4 mg/L. This copolymer could self-assemble into micelles in aqueous solution with an average size of 120-250 nm determined by DLS. The morphologies of the micelles were found to be spherical by SEM and TEM. Ibuprofen (IBU), a poorly water-soluble drug, was selected as the model drug and wrapped into the core of micelles via dialysis method. Drug entrapment efficiency reached to 90%. The in vitro release behavior of IBU from these micelles was pH-dependent. The cumulative release percent of IBU was less than 20% of the initial drug content in simulated gastric fluid (SGF, pH 1.2) over 12 h, but 90% was released in simulated intestinal fluid (SIF, pH 7.4) within 6 h. The release profiles showed that the P(MMA-co-MAA)-b-PPEGMA micelles could inhibit the premature burst drug release under the intestinal conditions. All the results indicate that the P(MMA-co-MAA)-b-PPEGMA micelle may be a potential oral drug delivery carrier for poorly water-soluble drugs. PMID:21121600

  16. Micelle-induced folding of spinach thylakoid soluble phosphoprotein of 9 kDa and its functional implications.

    PubMed

    Song, Jikui; Lee, Min S; Carlberg, Inger; Vener, Alexander V; Markley, John L

    2006-12-26

    Thylakoid soluble phosphoprotein of 9 kDa (TSP9) has been identified as a plant-specific protein in the photosynthetic thylakoid membrane (Carlberg et al. (2003) Proc. Natl. Acad. Sci. 100, 757-762). Nonphosphorylated TSP9 is associated with the membrane, whereas, after light-induced phosphorylation, a fraction of the phosphorylated TSP9 is released into the aqueous stroma. By NMR spectroscopy, we have determined the structural features of nonphosphorylated TSP9 both in aqueous solution and in membrane mimetic micelles. The results show that both wild type nonphosphorylated TSP9 and a triple-mutant (T46E + T53E + T60E) mimic of the triphosphorylated form of TSP9 are disordered under aqueous conditions, but adopt an ordered conformation in the presence of detergent micelles. The micelle-induced structural features, which are similar in micelles either of SDS or dodecylphosphocholine (DPC), consist of an N-terminal alpha-helix, which may represent the primary site of interaction between TSP9 and binding partners, and a less structured helical turn near the C-terminus. These structured elements contain mainly hydrophobic residues. NMR relaxation data for nonphosphorylated TSP9 in SDS micelles indicated that the molecule is highly flexible with the highest order in the N-terminal alpha-helix. Intermolecular NOE signals, as well as spin probe-induced broadening of NMR signals, demonstrated that the SDS micelles contact both the structured and a portion of the unstructured regions of TSP9, in particular, those containing the three phosphorylation sites (T46, T53, and T60). This interaction may explain the selective dissociation of phosphorylated TSP9 from the membrane. Our study presents a structural model for the role played by the structured and unstructured regions of TSP9 in its membrane association and biological function. PMID:17176085

  17. Micelle-induced Folding of Spinach Thylakoid Soluble Phosphoprotein of 9 kDa and its Functional Implications †, ‡

    PubMed Central

    Song, Jikui; Lee, Min S.; Carlberg, Inger; Vener, Alexander V.; Markley, John L

    2008-01-01

    Thylakoid soluble phosphoprotein of 9 kDa (TSP9) has been identified as a plant-specific protein in the photosynthetic thylakoid membrane (Carlberg et al., Proc. Natl. Acad. Sci. 2003, 100, 757–762). Non-phosphorylated TSP9 is associated with the membrane, whereas after light-induced phosphorylation, a fraction of the phosphorylated TSP9 is released into the aqueous stroma. By NMR spectroscopy, we have determined the structural features of non-phosphorylated TSP9 in both aqueous solution and in membrane mimetic micelles. The results show that both wild type non-phosphorylated TSP9 and a triple-mutant (T46E+T53E+T60E) mimic of the tri-phosphorylated form of TSP9 are disordered under aqueous conditions, but adopt an ordered conformation in the presence of detergent micelles. The micelle induced structural features, which are similar in micelles either of SDS or dodecylphosphocholine (DPC), consist of an N-terminal α-helix, which may represent the primary site of interaction between TSP9 and binding partners, and a less structured helical turn near the C-terminus. These structured elements contain mainly hydrophobic residues. NMR relaxation data for non-phosphorylated TSP9 in DPC micelles indicated that the molecule is highly flexible with the highest order in the N-terminal α-helix. Intermolecular NOE signals, as well as spin probe-induced broadening of NMR signals, demonstrated that the SDS micelles contact both the structured and a portion of the unstructured regions of TSP9, in particular, those containing the three phosphorylation sites (T46, T53, and T60). This interaction may explain dissociation of phosphorylated TSP9 from the membrane. Our study presents a structural model for the role played by the structured and unstructured regions of TSP9 in its membrane association and biological function. PMID:17176085

  18. Green-fleshed watermelon contains chlorophyll

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Many popular and technical reports on watermelon ignore an uncommon color, green, even though mention of this color has been in the literature since 1901. However, what causes the green hue has not been reported. Since some cucurbits have chloroplasts, and chlorophyll in the flesh tissue, we surmi...

  19. Thin Layer Chromatography (TLC) of Chlorophyll Pigments.

    ERIC Educational Resources Information Center

    Foote, Jerry

    1984-01-01

    Background information, list of materials needed, procedures used, and discussion of typical results are provided for an experiment on the thin layer chromatography of chlorophyll pigments. The experiment works well in high school, since the chemicals used are the same as those used in paper chromatography of plant pigments. (JN)

  20. Synthesis and characterization of Fe colloid catalysts in inverse micelle solutions

    SciTech Connect

    Martino, A.; Stoker, M.; Hicks, M.

    1995-12-31

    Surfactant molecules, possessing a hydrophilic head group and a hydrophobic tail group, aggregate in various solvents to form structured solutions. In two component mixtures of surfactant and organic solvents (e.g., toluene and alkanes), surfactants aggregate to form inverse micelles. Here, the hydrophilic head groups shield themselves by forming a polar core, and the hydrophobic tails groups are free to move about in the surrounding oleic phase. The formation of Fe clusters in inverse miscelles was studied.Iron salts are solubilized within the polar interior of inverse micelles, and the addition of the reducing agent LiBH{sub 4} initiates a chemical reduction to produce monodisperse, nanometer sized Fe based particles. The reaction sequence is sustained by material exchange between inverse micelles. The surfactant interface provides a spatial constraint on the reaction volume, and reactions carried out in these micro-heterogeneous solutions produce colloidal sized particles (10-100{Angstrom}) stabilized in solution against flocculation of surfactant. The clusters were stabilized with respect to size with transmission electron microscopy (TEM) and with respect to chemical composition with Mossbauer spectroscopy, electron diffraction, and x-ray photoelectron spectroscopy (XPS). In addition, these iron based clusters were tested for catalytic activity in a model hydrogenolysis reaction. The hydrogenolysis of naphthyl bibenzyl methane was used as a model for coal pyrolysis.

  1. Noncovalent interaction-assisted polymeric micelles for controlled drug delivery.

    PubMed

    Ding, Jianxun; Chen, Linghui; Xiao, Chunsheng; Chen, Li; Zhuang, Xiuli; Chen, Xuesi

    2014-10-01

    Polymeric micelles are one of the most promising nanovehicles for drug delivery. In addition to amphiphilicity, various individual or synergistic noncovalent interplays including strong hydrophobic, electrostatic, host-guest, hydrogen bonding, stereocomplex and coordination interactions have been recently employed to improve the physical stability of micelles, and even provide them with certain intelligences or bioactivities. Through the ingenious designs and precise preparations, many noncovalent-mediated micelles display great prospects in the realm of controlled drug delivery, and certain species have been promoted to clinical trials. The current review presents the diverse noncovalent interactions that are applied to enhance polymeric micelles as drug nanocarriers, and preliminarily discusses the future directions and perspectives of this field.

  2. Progress of drug-loaded polymeric micelles into clinical studies.

    PubMed

    Cabral, Horacio; Kataoka, Kazunori

    2014-09-28

    Targeting tumors with long-circulating nano-scaled carriers is a promising strategy for systemic cancer treatment. Compared with free small therapeutic agents, nanocarriers can selectively accumulate in solid tumors through the enhanced permeability and retention (EPR) effect, which is characterized by leaky blood vessels and impaired lymphatic drainage in tumor tissues, and achieve superior therapeutic efficacy, while reducing side effects. In this way, drug-loaded polymeric micelles, i.e. self-assemblies of amphiphilic block copolymers consisting of a hydrophobic core as a drug reservoir and a poly(ethylene glycol) (PEG) hydrophilic shell, have demonstrated outstanding features as tumor-targeted nanocarriers with high translational potential, and several micelle formulations are currently under clinical evaluation. This review summarizes recent efforts in the development of these polymeric micelles and their performance in human studies, as well as our recent progress in polymeric micelles for the delivery of nucleic acids and imaging. PMID:24993430

  3. Reverse micelle synthesis of oxide nanopowders: mechanisms of precipitate formation and agglomeration effects.

    PubMed

    Graeve, Olivia A; Fathi, Hoorshad; Kelly, James P; Saterlie, Michael S; Sinha, Kaustav; Rojas-George, Gabriel; Kanakala, Raghunath; Brown, David R; Lopez, Enrique A

    2013-10-01

    We present an analysis of reverse micelle stability in four model systems. The first two systems, composed of unstable microemulsions of isooctane, water, and Na-AOT with additions of either iron sulfate or yttrium nitrate, were used for the synthesis of iron oxide or yttrium oxide powders. These oxide powders were of nanocrystalline character, but with some level of agglomeration that was dependent on calcination temperature and cleaning procedures. Results show that even though the reverse micellar solutions were unstable, nanocrystalline powders with very low levels of agglomeration could be obtained. This effect can be attributed to the protective action of the surfactant on the surfaces of the powders that prevents neck formation until after all the surfactant has volatilized. A striking feature of the IR spectra collected on the iron oxide powders is the absence of peaks in the ~1715 cm(-1) to 1750 cm(-1) region, where absorption due to the symmetric C=O (carbonyl) stretching occurs. The lack of such peaks strongly suggests the carbonyl group is no longer free, but is actively participating in the surfactant-precipitate interaction. The final two microemulsion systems, containing CTAB as the surfactant, showed that loss of control of the reverse micelle synthesis process can easily occur when the amount of salt in the water domains exceeds a critical concentration. Both model systems eventually resulted in agglomerated powders of broad size distributions or particles that were large compared to the sizes of the reverse micelles, consistent with the notion that the microemulsions were not stable and the powders were precipitated in an uncontrolled fashion. This has implications for the synthesis of nanopowders by reverse micelle synthesis and provides a benchmark for process control if powders of the highest quality are desired. PMID:23906861

  4. Evaluation of Bio-optical Algorithms for Chlorophyll Mapping in the Southwestern Atlantic

    NASA Astrophysics Data System (ADS)

    Garcia, V. M.; Garcia, C. A.; Signorini, S.; McClain, C. R.

    2005-05-01

    Efforts have been made over the past decade to study bio-optical properties of seawater in the Southwestern Atlantic for mapping chlorophyll concentration from space. Coastal regions deserve a greater attention due to the optical complexity from continental influence. Here we present an attempt to derive reliable bio-optical chlorophyll algorithms in the shelf region 25-40o S and 60-45o W. This area is subject to large optical interference by continental runoffs from La Plata River and Patos Lagoon. Spectral upwelling radiance and surface chlorophyll concentration data have been collected in the past years and have been used to generate a regional version of the NASA's OC2v4 model. The regional 2-band algorithm (termed OC2-LP), reduces chlorophyll positive bias to 11% as compared to the global SeaWiFS OC4v4 algorithm (bias = 27%). However, OC2-LP remains with an overall inaccuracy of over 40% in chlorophyll concentration, as calculated by the absolute percentage difference between in-situ and model-derived values. In-situ chlorophyll data from two cruises to the study region (La Plata I - winter of 2003 and La Plata II - summer of 2004) have been used to test the accuracy of the derived algorithm as well as the global version. A marked seasonal difference was found, where both OC4v4 and OC2-LP overestimate chlorophyll in summer at a higher magnitude than in the winter. These results indicate the need for other approaches rather than use of empirical band-ratio models in coastal waters of this region.

  5. Predicting crappie recruitment in Ohio reservoirs with spawning stock size, larval density, and chlorophyll concentrations

    USGS Publications Warehouse

    Bunnell, David B.; Hale, R. Scott; Vanni, Michael J.; Stein, Roy A.

    2006-01-01

    Stock-recruit models typically use only spawning stock size as a predictor of recruitment to a fishery. In this paper, however, we used spawning stock size as well as larval density and key environmental variables to predict recruitment of white crappies Pomoxis annularis and black crappies P. nigromaculatus, a genus notorious for variable recruitment. We sampled adults and recruits from 11 Ohio reservoirs and larvae from 9 reservoirs during 1998-2001. We sampled chlorophyll as an index of reservoir productivity and obtained daily estimates of water elevation to determine the impact of hydrology on recruitment. Akaike's information criterion (AIC) revealed that Ricker and Beverton-Holt stock-recruit models that included chlorophyll best explained the variation in larval density and age-2 recruits. Specifically, spawning stock catch per effort (CPE) and chlorophyll explained 63-64% of the variation in larval density. In turn, larval density and chlorophyll explained 43-49% of the variation in age-2 recruit CPE. Finally, spawning stock CPE and chlorophyll were the best predictors of recruit CPE (i.e., 74-86%). Although larval density and recruitment increased with chlorophyll, neither was related to seasonal water elevation. Also, the AIC generally did not distinguish between Ricker and Beverton-Holt models. From these relationships, we concluded that crappie recruitment can be limited by spawning stock CPE and larval production when spawning stock sizes are low (i.e., CPE , 5 crappies/net-night). At higher levels of spawning stock sizes, spawning stock CPE and recruitment were less clearly related. To predict recruitment in Ohio reservoirs, managers should assess spawning stock CPE with trap nets and estimate chlorophyll concentrations. To increase crappie recruitment in reservoirs where recruitment is consistently poor, managers should use regulations to increase spawning stock size, which, in turn, should increase larval production and recruits to the fishery.

  6. Preparation and characterization of magnetic thermosensitive fluorouracil micelles.

    PubMed

    Zhang, Min; Jin, Xueqin; Gou, Guojing

    2016-01-01

    In this study, we synthesized P(NIPAM-co-DMAM)-b-PLA polymers with free radical polymerization and ring-opening addition polymerization, and immediately assembled 'dextran magnetic layered double hydroxide fluorouracil' (DMF) magnetic particles into the core of the amphiphilic polymer micelles with synchronous hydration and dialysis, to generate a magnetic thermosensitive fluorouracil drug delivery system. The basic properties of the micelle particles, such as the core-shell-type structure, size, and zeta potential, were studied with (1)H-NMR, FTIR, TEM, TGA, laser nanoparticle size analysis, and other characterization techniques. The thermosensitivity of the micelles was investigated by measuring parameters such as the lower critical solution temperature (LCST) and the relationship between the particle size variation and temperature. The drug release curves for the micelles at different temperatures were constructed with a dialysis method. The LCST of the triblock polymers was 42 °C. The particle sizes of the blank micelles and DMF-loaded micelles were 493.6 ± 1.8 nm and 464.9 ± 4.1 nm, respectively, at 25 °C. When the temperature was higher than LSCT, a contraction phase change in the micelle structure occurred, a significant characteristic of the core-shell-type structure, and reversible phase transition phenomena. The release behavior of the drug-loaded micelles showed obvious variations with temperature. Therefore, the magnetic thermosensitive fluorouracil drug delivery system has a good magnetic response and excellent temperature controlled release characteristics, so it can be used as a drug delivery system in magnetically and thermally targeted chemotherapy for tumors. PMID:26948946

  7. New self-assembled nanocrystal micelles for biolabels and biosensors.

    SciTech Connect

    Tallant, David Robert; Wilson, Michael C. (University of New Mexico, Albuquerque, NM); Leve, Erik W. (University of New Mexico, Albuquerque, NM); Fan, Hongyou; Brinker, C. Jeffrey; Gabaldon, John (University of New Mexico, Albuquerque, NM); Scullin, Chessa (University of New Mexico, Albuquerque, NM)

    2005-12-01

    The ability of semiconductor nanocrystals (NCs) to display multiple (size-specific) colors simultaneously during a single, long term excitation holds great promise for their use in fluorescent bio-imaging. The main challenges of using nanocrystals as biolabels are achieving biocompatibility, low non-specific adsorption, and no aggregation. In addition, functional groups that can be used to further couple and conjugate with biospecies (proteins, DNAs, antibodies, etc.) are required. In this project, we invented a new route to the synthesis of water-soluble and biocompatible NCs. Our approach is to encapsulate as-synthesized, monosized, hydrophobic NCs within the hydrophobic cores of micelles composed of a mixture of surfactants and phospholipids containing head groups functionalized with polyethylene glycol (-PEG), -COOH, and NH{sub 2} groups. PEG provided biocompatibility and the other groups were used for further biofunctionalization. The resulting water-soluble metal and semiconductor NC-micelles preserve the optical properties of the original hydrophobic NCs. Semiconductor NCs emit the same color; they exhibit equal photoluminescence (PL) intensity under long-time laser irradiation (one week) ; and they exhibit the same PL lifetime (30-ns). The results from transmission electron microscopy and confocal fluorescent imaging indicate that water-soluble semiconductor NC-micelles are biocompatible and exhibit no aggregation in cells. We have extended the surfactant/lipid encapsulation techniques to synthesize water-soluble magnetic NC-micelles. Transmission electron microscopy results suggest that water-soluble magnetic NC-micelles exhibit no aggregation. The resulting NC-micelles preserve the magnetic properties of the original hydrophobic magnetic NCs. Viability studies conducted using yeast cells suggest that the magnetic nanocrystal-micelles are biocompatible. We have demonstrated, for the first time, that using external oscillating magnetic fields to manipulate

  8. Rheology and phase behavior of dense casein micelle dispersions

    NASA Astrophysics Data System (ADS)

    Bouchoux, A.; Debbou, B.; Gésan-Guiziou, G.; Famelart, M.-H.; Doublier, J.-L.; Cabane, B.

    2009-10-01

    Casein micelle dispersions have been concentrated through osmotic stress and examined through rheological experiments. In conditions where the casein micelles are separated from each other, i.e., below random-close packing, the dispersions have exactly the flow and dynamic properties of the polydisperse hard-sphere fluid, demonstrating that the micelles interact only through excluded volume effects in this regime. These interactions cause the viscosity and the elastic modulus to increase by three orders of magnitude approaching the concentration of random-close packing estimated at Cmax≈178 g/l. Above Cmax, the dispersions progressively turn into "gels" (i.e., soft solids) as C increases, with elastic moduli G' that are nearly frequency independent. In this second regime, the micelles deform and/or deswell as C increases, and the resistance to deformation results from the formation of bonds between micelles combined with the intrinsic mechanical resistance of the micelles. The variation in G' with C is then very similar to that observed with concentrated emulsions where the resistance to deformation originates from a set of membranes that separate the droplets. As in the case of emulsions, the G' values at high frequency are also nearly identical to the osmotic pressures required to compress the casein dispersions. The rheology of sodium caseinate dispersions in which the caseins are not structured into micelles is also reported. Such dispersions have the behavior of associative polymer solutions at all the concentrations investigated, further confirming the importance of structure in determining the rheological properties of casein micelle systems.

  9. Self-assembly of polymeric micelles into complex but regular superstructures based on highly controllable core-core fusion between the micelles.

    PubMed

    Wang, Liangyan; Wang, Yafen; Miao, Han; Chen, Daoyong

    2016-06-14

    Herein, we report a facile but highly controllable method to induce core-core fusion for not only spherical but also worm-like polymeric micelles, leading to various complex but regular superstructures including "random worm-like co-micelles", "block worm-like co-micelles" and octopus-like superparticles. PMID:27192018

  10. pH-sensitive poly(histidine)-PEG/DSPE-PEG co-polymer micelles for cytosolic drug delivery

    PubMed Central

    Wu, Hong; Zhu, Lin; Torchilin, Vladimir P.

    2013-01-01

    To introduce pH sensitivity into the DSPE-PEG-based micellar system and achieve the quick intracellular drug release in response to the acidity in endosomes, a mixed polymeric micelle was developed based on three grafted copolymers, including 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-polyethylene glycol-2000(DSPE-PEG2000), antinucleosome antibody (mAb 2C5)-modified DSPE-PEG3400 (DSPE-PEG3400-2C5), and poly(ethylene glycol)-coupled poly(l-histidine) (PHIS-PEG2000). The structure of PHIS-PEG2000 was confirmed by 1H NMR spectroscopy. The mixed micelles with the diameter ranging from 110 to 135nm were prepared using a dialysis method against pH 7.6 PBS. Paclitaxel (PCT) was used as a model drug, the encapsulation efficiency and loading content of PCT were 88% and 5%, respectively. The mixed micelles composed with 50wt% of PHIS-PEG2000 showed the desired pH-dependent drug release property with much faster drug release than micelles without PHIS-PEG2000. At pH around 5.5, about 75–95% of the loaded drug was released within 2 h. The MTT assay showed PCT-loaded mixed micelles had higher cytotoxicity at pH 5.8 than that at pH 7.4. Further modification of the mixed micelles with anti-cancer nucleosome- specific monoclonal antibody 2C5 significantly increased their cellular uptake efficiency and cytotoxicity. Thus, the low pH in endosomes could trigger the PCT release from the pH-sensitive mixed micelles after 2C5-mediated endocytosis. The results of this study suggest that the mixed micelles (DSPE-PEG2000/DSPE-PEG3400-2C5/PHIS-PEG2000) could enhance the tumor cell-specific internalization and trigger the quick drug release, resulting in the improved anti-cancer efficacy. PMID:23102622

  11. pH-sensitive poly(histidine)-PEG/DSPE-PEG co-polymer micelles for cytosolic drug delivery.

    PubMed

    Wu, Hong; Zhu, Lin; Torchilin, Vladimir P

    2013-01-01

    To introduce pH sensitivity into the DSPE-PEG-based micellar system and achieve the quick intracellular drug release in response to the acidity in endosomes, a mixed polymeric micelle was developed based on three grafted copolymers, including 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-polyethylene glycol-2000(DSPE-PEG(2000)), antinucleosome antibody (mAb 2C5)-modified DSPE-PEG(3400) (DSPE-PEG(3400)-2C5), and poly(ethylene glycol)-coupled poly(L-histidine) (PHIS-PEG(2000)). The structure of PHIS-PEG(2000) was confirmed by (1)H NMR spectroscopy. The mixed micelles with the diameter ranging from 110 to 135 nm were prepared using a dialysis method against pH 7.6 PBS. Paclitaxel (PCT) was used as a model drug, the encapsulation efficiency and loading content of PCT were 88% and 5%, respectively. The mixed micelles composed with 50 wt% of PHIS-PEG(2000) showed the desired pH-dependent drug release property with much faster drug release than micelles without PHIS-PEG(2000). At pH around 5.5, about 75-95% of the loaded drug was released within 2 h. The MTT assay showed PCT-loaded mixed micelles had higher cytotoxicity at pH 5.8 than that at pH 7.4. Further modification of the mixed micelles with anti-cancer nucleosome-specific monoclonal antibody 2C5 significantly increased their cellular uptake efficiency and cytotoxicity. Thus, the low pH in endosomes could trigger the PCT release from the pH-sensitive mixed micelles after 2C5-mediated endocytosis. The results of this study suggest that the mixed micelles (DSPE-PEG(2000)/DSPE-PEG(3400)-2C5/PHIS-PEG(2000)) could enhance the tumor cell-specific internalization and trigger the quick drug release, resulting in the improved anti-cancer efficacy. PMID:23102622

  12. Tumor targeting by pH-sensitive, biodegradable, cross-linked N-(2-hydroxypropyl) methacrylamide copolymer micelles.

    PubMed

    Zhou, Zhou; Li, Lian; Yang, Yang; Xu, Xiuli; Huang, Yuan

    2014-08-01

    Increasing the molecular weight of N-(2-hydroxypropyl) methacrylamide (HPMA) copolymers by using micellar structures could result in more pronounced enhanced permeability and retention effect, thus increase the tumor accumulation of drug. However, most micellar formulations are relatively unstable and release their drug non-specifically. To improve on these disadvantages, we developed a micellar drug delivery system based on self-assembly of HPMA copolymers. Amphiphilic conjugates were synthesized by conjugating the hydrophobic drug doxorubicin and hydrophobic β-sitosterol to the hydrophilic HPMA polymer backbone via pH-sensitive hydrazone linkages. This linkage is quite stable at physiological pH but hydrolyzes easily at acidic pH. After conjugates self-assembly into micelles, HPMA copolymer side chains were cross-linked through the hydrazone linkages to ensure micelle stability in the blood. Using this approach, cross-linked micelles were obtained with molecular weight of 1030 KD and diameter of 10-20 nm. These micelles remained stable with undetectable doxorubicin release at pH 7.4 or mouse plasma, whereas collapsed quickly with 80% of the drug released at pH 5 which corresponds to the pH of lyso/endosome compartments of tumor cells. Both cross-linked and non-cross-linked micelles displayed similar in vitro anti-tumor activity as linear copolymer conjugates in Hep G2 and A549 cancer cell lines with internalization mechanism by caveolin, clathrin, and giant macropinocytosis. In vivo studies in an H22 mouse xenograft model of hepatocarcinoma showed the tumor accumulation (1633 μCi/L*h) and anti-tumor rate (71.8%) of cross-linked micelles were significantly higher than non-cross-linked ones (698 μCi/L*h, 64.3%). Neither type of micelle showed significant toxicity in heart, lung, liver, spleen or kidney. These results suggest that cross-linked HPMA copolymer micelles with pH-sensitivity and biodegradability show excellent potential as carriers of anti

  13. Structure and stability of complex coacervate core micelles with lysozyme.

    PubMed

    Lindhoud, Saskia; Vries, Renko de; Norde, Willem; Stuart, Martien A Cohen

    2007-07-01

    Encapsulation of enzymes by polymers is a promising method to influence their activity and stability. Here, we explore the use of complex coacervate core micelles for encapsulation of enzymes. The core of the micelles consists of negatively charged blocks of the diblock copolymer PAA42PAAm417 and the positively charged homopolymer PDMAEMA150. For encapsulation, part of the positively charged homopolymer was replaced by the positively charged globular protein lysozyme. We have studied the formation, structure, and stability of the resulting micelles for three different mixing ratios of homopolymer and lysozyme: a system predominantly consisting of homopolymer, a system predominantly consisting of lysozyme, and a system where the molar ratio between the two positively charged molecules was almost one. We also studied complexes made of only lysozyme and PAA42PAAm417. Complex formation and the salt-induced disintegration of the complexes were studied using dynamic light-scattering titrations. Small-angle neutron scattering was used to investigate the structures of the cores. We found that micelles predominantly consisting of homopolymer are spherical but that complex coacervate core micelles predominantly consisting of lysozyme are nonspherical. The stability of the micelles containing a larger fraction of lysozyme is lower.

  14. Tuning micelle dimensions and properties with binary surfactant mixtures.

    PubMed

    Oliver, Ryan C; Lipfert, Jan; Fox, Daniel A; Lo, Ryan H; Kim, Justin J; Doniach, Sebastian; Columbus, Linda

    2014-11-11

    Detergent micelles are used in many areas of research and technology, in particular, as mimics of the cellular membranes in the purification and biochemical and structural characterization of membrane proteins. Applications of detergent micelles are often hindered by the limited set of properties of commercially available detergents. Mixtures of micelle-forming detergents provide a means to systematically obtain additional micellar properties and expand the repertoire of micelle features available; however, our understanding of the properties of detergent mixtures is still limited. In this study, the shape and size of binary mixtures of seven different detergents commonly used in molecular host-guest systems and membrane protein research were investigated. The data suggests that the detergents form ideally mixed micelles with sizes and shapes different from those of pure individual micelles. For most measurements of size, the mixtures varied linearly with detergent mole fraction and therefore can be calculated from the values of the pure detergents. We propose that properties such as the geometry, size, and surface charge can be systematically and predictably tuned for specific applications.

  15. Applications of polymer micelles for imaging and drug delivery.

    PubMed

    Movassaghian, Sara; Merkel, Olivia M; Torchilin, Vladimir P

    2015-01-01

    Polymeric micelles, self-assembling nano-constructs of amphiphilic copolymers, are widely considered as convenient nano-carriers for a variety of applications, such as diagnostic imaging, and drug and gene delivery. They have demonstrated a variety of favorable properties including biocompatibility, longevity, high stability in vitro and in vivo, capacity to effectively solubilize a variety of poorly soluble drugs, changing the release profile of the incorporated pharmaceutical agents, and the ability to accumulate in the target zone based on the enhanced permeability and retention effect. Moreover, additional functions can be imparted to the micelle-based delivery systems by engineering their surface for specific applications. Various targeting ligands can be attached for cell or intracellular accumulation at a site of interest. Also, the chelation or incorporation of imaging moieties into the micelle structure enables in vivo biodistribution studies. Moreover, pH-, thermo-, ultrasound-, enzyme- and light-sensitive block-copolymers allow for controlled micelle dissociation and triggered drug release in response to the pathological environment-specific stimuli and/or externally applied signals. The combination of these approaches can further improve specificity and efficacy of micelle-based drug delivery to promote the development of smart multifunctional micelles. PMID:25683687

  16. A thermodynamic analysis of charged mixed micelles in water.

    PubMed

    Maeda, Hiroshi

    2005-08-25

    A thermodynamic analysis is presented for electrically charged mixed micelles in water on the basis of the Gibbs-Duhem relation proposed by Hall in combination with the information on the degree of counterion binding. The proposed analyses are shown to work well for both ionic/nonionic mixed micelles and those consisting of ionic surfactants of like charges. Conclusions for ionic/nonionic mixed micelles are as follows. (1) The contribution from counterions is significant. (2) In media of low ionic strengths, the counterion concentration varies with the micellar mole fraction of the ionic species x. The dependency of the activity coefficients and the excess free energy on x is significantly influenced by this effect, but it can be corrected to a large extent in terms of the Corrin-Harkins relation. (3) The regular solution theory (RST) is not always valid even when the excess free energy is described well with the RST expression unless the observed range of the micelle composition is wide enough. (4) The RST overestimates x and underestimates the activity coefficient of the ionic species when applied to the mixed micelles to which it is inapplicable. For the ionic mixed micelles consisting of surfactants of like charges, the Lange-Shinoda approach is shown to be consistent with the present analysis in terms of the Gibbs-Duhem relation, but Motomura's approach is found to be not exact but approximate.

  17. The effect of co-delivery of paclitaxel and curcumin by transferrin-targeted PEG-PE-based mixed micelles on resistant ovarian cancer in 3-D spheroids and in vivo tumors.

    PubMed

    Sarisozen, Can; Abouzeid, Abraham H; Torchilin, Vladimir P

    2014-10-01

    Multicellular 3D cancer cell culture (spheroids) resemble to in vivo tumors in terms of shape, cell morphology, growth kinetics, gene expression and drug response. However, these characteristics cause very limited drug penetration into deeper parts of the spheroids. In this study, we used multi drug resistant (MDR) ovarian cancer cell spheroid and in vivo tumor models to evaluate the co-delivery of paclitaxel (PCL) and a potent NF-κB inhibitor curcumin (CUR). PCL and CUR were co-loaded into the polyethylene glycol-phosphatidyl ethanolamine (PEG-PE) based polymeric micelles modified with transferrin (TF) as the targeting ligand. Cytotoxicity, cellular association and accumulation into the deeper layers were investigated in the spheroids and compared with the monolayer cell culture. Comparing to non-targeted micelles, flow cytometry and confocal imaging proved significantly deeper and higher micelle penetration into the spheroids with TF-targeting. Both in monolayers and in spheroids, PCL cytotoxicity was significantly increased when co-delivered with CUR in non-targeted micelles or as single agent in TF-targeted micelles, whereas TF-modification of co-loaded micelles did not further enhance the cytotoxicity. In vivo tumor inhibition studies showed good correlation with the 3D cell culture experiments, which suggests the current spheroid model can be used as an intermediate model for the evaluation of co-delivery of anticancer compounds in targeted micelles. PMID:25016976

  18. The effect of co-delivery of paclitaxel and curcumin by transferrin-targeted PEG-PE-based mixed micelles on resistant ovarian cancer in 3-D spheroids and in vivo tumors

    PubMed Central

    Sarisozen, Can; Abouzeid, Abraham H.; Torchilin, Vladimir P.

    2014-01-01

    Multicellular 3D cancer cell culture (spheroids) resemble to in vivo tumors in terms of shape, cell morphology, growth kinetics, gene expression and drug response. However, these characteristics cause very limited drug penetration into deeper parts of the spheroids. In this study, we used multi drug resistant (MDR) ovarian cancer cell spheroid and in vivo tumor models to evaluate the co-delivery of paclitaxel (PCL) and a potent NF-κB inhibitor curcumin (CUR). PCL and CUR were co-loaded into the polyethylene glycol-phosphatidyl ethanolamine (PEG-PE) based polymeric micelles modified with Transferrin (TF) as the targeting ligand. Cytotoxicity, cellular association and accumulation into the deeper layers were investigated in the spheroids and compared with the monolayer cell culture. Comparing to non-targeted micelles, flow cytometry and confocal imaging proved significantly deeper and higher micelle penetration into the spheroids with TF-targeting. Both in monolayers and spheroids, PCL cytotoxicity was significantly increased when co-delivered with CUR in non-targeted micelles or as single agent in TF-targeted micelles, whereas TF-modification of co-loaded micelles did not further enhance the cytotoxicity. In vivo tumor inhibition studies showed good correlation with the 3D cell culture experiments, which suggests the current spheroid model can be used as an intermediate model for evaluation of co-delivery of anticancer compounds in targeted micelles. PMID:25016976

  19. Cationic drug-based self-assembled polyelectrolyte complex micelles: Physicochemical, pharmacokinetic, and anticancer activity analysis.

    PubMed

    Ramasamy, Thiruganesh; Poudel, Bijay Kumar; Ruttala, Himabindu; Choi, Ju Yeon; Hieu, Truong Duy; Umadevi, Kandasamy; Youn, Yu Seok; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

    2016-10-01

    Nanofabrication of polymeric micelles through self-assembly of an ionic block copolymer and oppositely charged small molecules has recently emerged as a promising method of formulating delivery systems. The present study therefore aimed to investigate the interaction of cationic drugs doxorubicin (DOX) and mitoxantrone (MTX) with the anionic block polymer poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) and to study the influence of these interactions on the pharmacokinetic stability and antitumor potential of the formulated micelles in clinically relevant animal models. To this end, individual DOX and MTX-loaded polyelectrolyte complex micelles (PCM) were prepared, and their physicochemical properties and pH-responsive release profiles were studied. MTX-PCM and DOX-PCM exhibited a different release profile under all pH conditions tested. MTX-PCM exhibited a monophasic release profile with no initial burst, while DOX-PCM exhibited a biphasic release. DOX-PCM showed a higher cellular uptake than that shown by MTX-PCM in A-549 cancer cells. Furthermore, DOX-PCM induced higher apoptosis of cancer cells than that induced by MTX-PCM. Importantly, both MTX-PCM and DOX-PCM showed prolonged blood circulation. MTX-PCM improved the AUCall of MTX 4-fold compared to a 3-fold increase by DOX-PCM for DOX. While a definite difference in blood circulation was observed between MTX-PCM and DOX-PCM in the pharmacokinetic study, both MTX-PCM and DOX-PCM suppressed tumor growth to the same level as the respective free drugs, indicating the potential of PEGylated polymeric micelles as effective delivery systems. Taken together, our results show that the nature of interactions of cationic drugs with the polyionic copolymer can have a tremendous influence on the biological performance of a delivery system. PMID:27318960

  20. Cationic drug-based self-assembled polyelectrolyte complex micelles: Physicochemical, pharmacokinetic, and anticancer activity analysis.

    PubMed

    Ramasamy, Thiruganesh; Poudel, Bijay Kumar; Ruttala, Himabindu; Choi, Ju Yeon; Hieu, Truong Duy; Umadevi, Kandasamy; Youn, Yu Seok; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

    2016-10-01

    Nanofabrication of polymeric micelles through self-assembly of an ionic block copolymer and oppositely charged small molecules has recently emerged as a promising method of formulating delivery systems. The present study therefore aimed to investigate the interaction of cationic drugs doxorubicin (DOX) and mitoxantrone (MTX) with the anionic block polymer poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) and to study the influence of these interactions on the pharmacokinetic stability and antitumor potential of the formulated micelles in clinically relevant animal models. To this end, individual DOX and MTX-loaded polyelectrolyte complex micelles (PCM) were prepared, and their physicochemical properties and pH-responsive release profiles were studied. MTX-PCM and DOX-PCM exhibited a different release profile under all pH conditions tested. MTX-PCM exhibited a monophasic release profile with no initial burst, while DOX-PCM exhibited a biphasic release. DOX-PCM showed a higher cellular uptake than that shown by MTX-PCM in A-549 cancer cells. Furthermore, DOX-PCM induced higher apoptosis of cancer cells than that induced by MTX-PCM. Importantly, both MTX-PCM and DOX-PCM showed prolonged blood circulation. MTX-PCM improved the AUCall of MTX 4-fold compared to a 3-fold increase by DOX-PCM for DOX. While a definite difference in blood circulation was observed between MTX-PCM and DOX-PCM in the pharmacokinetic study, both MTX-PCM and DOX-PCM suppressed tumor growth to the same level as the respective free drugs, indicating the potential of PEGylated polymeric micelles as effective delivery systems. Taken together, our results show that the nature of interactions of cationic drugs with the polyionic copolymer can have a tremendous influence on the biological performance of a delivery system.

  1. Indian Ocean Dipole and El Niño/Southern Oscillation impacts on regional chlorophyll anomalies in the Indian Ocean

    NASA Astrophysics Data System (ADS)

    Currie, J. C.; Lengaigne, M.; Vialard, J.; Kaplan, D. M.; Aumont, O.; Naqvi, S. W. A.; Maury, O.

    2013-03-01

    The Indian Ocean Dipole (IOD) and the El Niño-Southern Oscillation (ENSO) frequently co-occur, driving significant interannual changes within the Indian Ocean. We use a four-decade hindcast from a coupled bio-physical ocean general circulation model, to disentangle patterns of chlorophyll anomalies driven by these two climate modes. Comparisons with remotely-sensed records show that the simulation competently reproduces the chlorophyll seasonal cycle, as well as open-ocean anomalies during the 1997-1998 ENSO and IOD event. Results show that anomalous surface and euphotic-layer chlorophyll blooms in the eastern equatorial Indian Ocean in fall, and southern Bay of Bengal in winter, are primarily related to IOD forcing. IOD depresses integrated chlorophyll in the 5° S-10° S thermocline ridge region, even though the signal is negligible in surface chlorophyll. A previously-unreported negative influence of IOD on chlorophyll concentrations is also shown in a region around the southern tip of India. The only investigated region where ENSO has a greater influence on chlorophyll than does IOD, is in the Somalia upwelling region, where it causes a decrease in fall and winter chlorophyll by reducing local upwelling winds. Lastly, we show that the chlorophyll impact of climate indices is frequently asymmetric, with a general tendency for larger positive than negative chlorophyll anomalies. ENSO and IOD cause significant and predictable regional re-organisation of phytoplankton productivity via their influence on near-surface oceanography. Resolving the details of these effects should improve our understanding, and eventually gain predictability, of interannual changes in Indian Ocean productivity, fisheries, ecosystems and carbon budgets.

  2. Core-Crosslinked Polymeric Micelles: Principles, Preparation, Biomedical Applications and Clinical Translation

    PubMed Central

    Rijcken, Cristianne J.; Kiessling, Fabian; Hennink, Wim E.; Lammers, Twan

    2015-01-01

    Polymeric micelles (PM) are extensively used to improve the delivery of hydrophobic drugs. Many different PM have been designed and evaluated over the years, and some of them have steadily progressed through clinical trials. Increasing evidence suggests, however, that for prolonged circulation times and for efficient EPR-mediated drug targeting to tumors and to sites of inflammation, PM need to be stabilized, to prevent premature disintegration. Core-crosslinking is among the most popular methods to improve the in vivo stability of PM, and a number of core-crosslinked polymeric micelles (CCPM) have demonstrated promising efficacy in animal models. The latter is particularly true for CCPM in which (pro−) drugs are covalently entrapped. This ensures proper drug retention in the micelles during systemic circulation, efficient drug delivery to pathological sites via EPR, and tailorable drug release kinetics at the target site. We here summarize recent advances in the CCPM field, addressing the chemistry involved in preparing them, their in vitro and in vivo performance, potential biomedical applications, and guidelines for efficient clinical translation. PMID:25893004

  3. c(RGDyK)-decorated Pluronic micelles for enhanced doxorubicin and paclitaxel delivery to brain glioma

    PubMed Central

    Huang, YuKun; Liu, Wenchao; Gao, Feng; Fang, Xiaoling; Chen, Yanzuo

    2016-01-01

    Brain glioma therapy is an important challenge in oncology. Here, doxorubicin (DOX) and paclitaxel (PTX)-loaded cyclic arginine-glycine-aspartic acid peptide (c(RGDyK))-decorated Pluronic micelles (cyclic arginine-glycine-aspartic acid peptide-decorated Pluronic micelles loaded with doxorubicin and paclitaxel [RGD-PF-DP]) were designed as a potential targeted delivery system to enhance blood–brain barrier penetration and improve drug accumulation via integrin-mediated transcytosis/endocytosis and based on integrin overexpression in blood–brain barrier and glioma cells. The physicochemical characterization of RGD-PF-DP revealed a satisfactory size of 28.5±0.12 nm with uniform distribution and core-shell structure. The transport rates across the in vitro blood–brain barrier model, cellular uptake, cytotoxicity, and apoptosis of U87 malignant glioblastoma cells of RGD-PF-DP were significantly greater than those of non-c(RGDyK)-decorated Pluronic micelles. In vivo fluorescence imaging demonstrated the specificity and efficacy of intracranial tumor accumulation of RGD-PF-DP. RGD-PF-DP displayed an extended median survival time of 39 days, with no serious body weight loss during the regimen. No acute toxicity to major organs was observed in mice receiving treatment doses via intravenous administration. In conclusion, RGD-PF-DP could be a promising vehicle for enhanced doxorubicin and paclitaxel delivery in patients with brain glioma. PMID:27143884

  4. Micelle-induced depletion interaction and resultant structure in charged colloidal nanoparticle system

    SciTech Connect

    Ray, D.; Aswal, V. K.; Kohlbrecher, J.

    2015-04-28

    The evolution of the interaction and the resultant structure in the mixed system of anionic silica nanoparticles (Ludox LS30) and non-ionic surfactant decaethylene glycol monododecylether (C12E10), undergoing phase separation, have been studied using small-angle neutron scattering and dynamic light scattering. The measurements have been carried out for a fixed concentration of nanoparticle (1 wt. %) with varying concentration of surfactant (0 to 1 wt. %), in the absence and presence of an electrolyte. It is found that the micelles of non-ionic surfactant adsorb on the nanoparticle in the absence of electrolyte (form stable system), whereas these micelles become non-adsorbing in the presence of electrolyte (show phase separation). The phase separation arises because of C12E10 micelles, causing depletion interaction between nanoparticles and leading to their aggregation. The interaction is modeled by double Yukawa potential accounting for attractive depletion as well as repulsive electrostatic forces. Both the interactions (attraction and repulsion) are found to be of long-range. The nanoparticle aggregation (phase separation) is governed by the increase in the magnitude and the range of the depletion attraction with the increase in the surfactant concentration. The nanoparticle aggregates formed are quite large in size (order of micron) and are characterized by the surface fractal having simple cubic packing of nanoparticles within the aggregates.

  5. Controlled drug delivery attributes of co-polymer micelles and xanthan-O-carboxymethyl hydrogel particles.

    PubMed

    Maiti, Sabyasachi; Mukherjee, Susweta

    2014-09-01

    Herein, C16 alkyl chain-grafted-xanthan copolymer was synthesized and characterized. The copolymer self-assembled into nanometer-size spherical micellar structures in water and incorporated ∼100% glibenclamide into its deeper lipophilic confines. The micellar dispersion exhibited negative zeta potential value (-27.6 mV). The copolymer micelles controlled the drug release rate in phosphate buffer solution (pH 6.8) for an extended period. Further incorporation of drug-loaded copolymer micelles into O-carboxymethyl xanthan hydrogel particles slowed the drug release rate in HCl solution (pH 1.2) as well as in phosphate-buffered solution (pH 6.8) (releasing only ∼8% drug in 2 h). The drug release data correlated well with the degree of swelling of the hydrogel particles in different drug release media. Scanning electron microscopy revealed spherical shape of the hydrogel particles (600 μm). X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy analyses suggested amorphous encapsulation of the drug and its chemical compatibility with the polymers, respectively. Pharmacodynamic evaluation suggested that the formulations had an immense potential in controlling blood glucose level in animal model over a longer duration. In summary, it was pointed out that the copolymer micelles of glibenclamide, a poor water-soluble anti-diabetic, and their subsequent entrapment into hydrogel particles could be a promising approach in the controlled and effective management of diabetes. PMID:24954271

  6. Dielectric depolarisation and concerted collective dynamics in AOT reverse micelles with and without ubiquitin.

    PubMed

    Schmollngruber, Michael; Braun, Daniel; Oser, Daniel; Steinhauser, Othmar

    2016-02-01

    In this computational study we present molecular dynamics (MD) simulations of reverse micelles, i.e. nano-scale water pools encapsulated by sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and dissolved in isooctane. Although consisting of highly polar components, such micro-emulsions exhibit surprisingly low dielectric permittivity, both static and frequency-dependent. This finding is well supported by experimental dielectric measurements. Furthermore, the computational dielectric spectra of reverse micelles with and without the polar protein ubiquitin are almost identical. A detailed component analysis of our simulated systems reveals the underlying mechanism of the observed dielectric depolarisation. While each component by itself would make a remarkable contribution to the static dielectric permittivity, mutual compensation leads to the observed marginal net result. This compensatory behavior is maintained for all but the highest frequencies. Dielectric model theory adapted to the peculiarities of reverse micelles provides an explanation: embedding a system in a cavity engulfed by a low dielectric medium automatically leads to depolarization. In this sense experiment, simulation and theory are in accordance.

  7. Polymeric micelles loaded with platinum anticancer drugs target preangiogenic micrometastatic niches associated with inflammation.

    PubMed

    Wu, Hailiang; Cabral, Horacio; Toh, Kazuko; Mi, Peng; Chen, Yi-Chun; Matsumoto, Yu; Yamada, Naoki; Liu, Xueying; Kinoh, Hiroaki; Miura, Yutaka; Kano, Mitsunobu R; Nishihara, Hiroshi; Nishiyama, Nobuhiro; Kataoka, Kazunori

    2014-09-10

    Nanocarriers have been used for specific delivery of therapeutic agents to solid tumors based on the enhanced permeability and retention in cancerous tissues. Despite metastasis is the main reason of cancer-related death and a priority for nanocarrier-based therapies, the targeting ability of nanocarriers to the metastatic disease is poorly understood, especially for preangiogenic micrometastases as nanocarriers usually use the malignant neovasculature for enhancing their accumulation. Thus, herein, we studied the ability of micellar nanocarriers incorporating (1,2-diaminocyclohexane)platinum(II) (DACHPt) for treating liver metastases of bioluminescent murine colon adenocarcinoma C-26, during overt and preangiogenic metastatic stages. After intravenous injection, DACHPt-loaded micelles (DACHPt/m) effectively inhibited the tumor growth in both metastatic tumor models. While the anticancer activity of the micelles against overt metastases was associated with their selective accumulation in cancerous tissues having neovasculature, the ability of DACHPt/m to target preangiogenic metastases was correlated with the inflammatory microenvironment of the niche. This targeting capability of polymeric micelles to preangiogenic metastasis may provide a novel approach for early diagnosis and treatment of metastases. PMID:24956488

  8. Paramagnetic Phospholipid-Based Micelles Targeting VCAM-1 Receptors for MRI Visualization of Inflammation.

    PubMed

    Pagoto, Amerigo; Stefania, Rachele; Garello, Francesca; Arena, Francesca; Digilio, Giuseppe; Aime, Silvio; Terreno, Enzo

    2016-08-17

    Inflammation is signaled by the overexpression of epitopes on the vascular endothelium that primarily aim at recruiting immune cells into the inflamed area. The intravascular localization of these biomarkers makes them suitable targets for the MRI visualization of inflammation. Phospholipid-based nanosystems appear excellent candidates in virtue of their good biocompatibility, ability to deliver a high number of imaging units at the target site, and for the easy functionalization with targeting vectors. In this work, phospholipid-based micelles (hydrodynamic diameter of 20 nm) loaded with the amphiphilic Gd(III)-complex Gd-DOTAMA(C18)2 were vectorized with a small peptide able to specifically bind VCAM-1 receptors. The micelles displayed a high longitudinal relaxivity (36.4 s(-1)mmolGd(-1) at 25 °C and 0.7 T). A (1)H- and (17)O-water relaxometry study indicated that the paramagnetic complex embedded in the nanoparticles adopted two isomeric conformations, likely reflecting the well-known square antiprismatic (SAP) and twisted square antiprismatic (TSAP) configurations typically observed in DOTA-like lanthanide complexes. Interestingly, the TSAP structure, showing a much faster exchange rate for the water molecule coordinated to the metal ion, was the most abundant, thus explaining the high relaxivity of the micellar agent. The systemic administration of the micelles into a lipopolysaccharide-induced murine model of acute inflammation successfully demonstrated the ability of the targeting agents to detect the diseased area by T1 contrast enhanced MRI. PMID:27315634

  9. Magnetic micelles for DNA delivery to rat brains after mild traumatic brain injury.

    PubMed

    Das, Mahasweta; Wang, Chunyan; Bedi, Raminder; Mohapatra, Shyam S; Mohapatra, Subhra

    2014-10-01

    Traumatic brain injury (TBI) causes significant mortality, long term disability and psychological symptoms. Gene therapy is a promising approach for treatment of different pathological conditions. Here we tested chitosan and polyethyleneimine (PEI)-coated magnetic micelles (CP-mag micelles or CPMMs), a potential MRI contrast agent, to deliver a reporter DNA to the brain after mild TBI (mTBI). CPMM-tomato plasmid (ptd) conjugate expressing a red-fluorescent protein (RFP) was administered intranasally immediately after mTBI or sham surgery in male SD rats. Evans blue extravasation following mTBI suggested CPMM-ptd entry into the brain via the compromised blood-brain barrier. Magnetofection increased the concentration of CPMMs in the brain. RFP expression was observed in the brain (cortex and hippocampus), lung and liver 48 h after mTBI. CPMM did not evoke any inflammatory response by themselves and were excreted from the body. These results indicate the possibility of using intranasally administered CPMM as a theranostic vehicle for mTBI. From the clinical editor: In this study, chitosan and PEI-coated magnetic micelles (CPMM) were demonstrated as potentially useful vehicles in traumatic brain injury in a rodent model. Magnetofection increased the concentration of CPMMs in the brain and, after intranasal delivery, CPMM did not evoke any inflammatory response and were excreted from the body. PMID:24486465

  10. Revisiting the interpretation of casein micelle SAXS data.

    PubMed

    Ingham, B; Smialowska, A; Erlangga, G D; Matia-Merino, L; Kirby, N M; Wang, C; Haverkamp, R G; Carr, A J

    2016-08-17

    An in-depth, critical review of model-dependent fitting of small-angle X-ray scattering (SAXS) data of bovine skim milk has led us to develop a new mathematical model for interpreting these data. Calcium-edge resonant soft X-ray scattering data provides unequivocal evidence as to the shape and location of the scattering due to colloidal calcium phosphate, which is manifested as a correlation peak centred at q = 0.035 Å(-1). In SAXS data this feature is seldom seen, although most literature studies attribute another feature centred at q = 0.08-0.1 Å(-1) to CCP. This work shows that the major SAXS features are due to protein arrangements: the casein micelle itself; internal regions approximately 20 nm in size, separated by water channels; and protein structures which are inhomogeneous on a 1-3 nm length scale. The assignment of these features is consistent with their behaviour under various conditions, including hydration time after reconstitution, addition of EDTA (a Ca-chelating agent), addition of urea, and reduction of pH. PMID:27491477

  11. Ultrafast energy transfer in water-AOT reverse micelles.

    PubMed

    Cringus, Dan; Bakulin, Artem; Lindner, Jörg; Vöhringer, Peter; Pshenichnikov, Maxim S; Wiersma, Douwe A

    2007-12-27

    A spectroscopic investigation of the vibrational dynamics of water in a geometrically confined environment is presented. Reverse micelles of the ternary microemulsion H2O/AOT/n-octane (AOT = bis-2-ethylhexyl sulfosuccinate or aerosol-OT) with diameters ranging from 1 to 10 nm are used as a model system for nanoscopic water droplets surrounded by a soft-matter boundary. Femtosecond nonlinear infrared spectroscopy in the OH-stretching region of H2O fully confirms the core/shell model, in which the entrapped water molecules partition onto two molecular subensembles: a bulk-like water core and a hydration layer near the ionic surfactant headgroups. These two distinct water species display different relaxation kinetics, as they do not exchange vibrational energy. The observed spectrotemporal ultrafast response exhibits a local character, indicating that the spatial confinement influences approximately one molecular layer located near the water-amphiphile boundary. The core of the encapsulated water droplet is similar in its spectroscopic properties to the bulk phase of liquid water, i.e., it does not display any true confinement effects such as droplet-size-dependent vibrational lifetimes or rotational correlation times. Unlike in bulk water, no intermolecular transfer of OH-stretching quanta occurs among the interfacial water molecules or from the hydration shell to the bulk-like core, indicating that the hydrogen bond network near the H2O/AOT interface is strongly disrupted. PMID:18047308

  12. Leaf Chlorophyll Content Estimation of Winter Wheat Based on Visible and Near-Infrared Sensors.

    PubMed

    Zhang, Jianfeng; Han, Wenting; Huang, Lvwen; Zhang, Zhiyong; Ma, Yimian; Hu, Yamin

    2016-03-25

    The leaf chlorophyll content is one of the most important factors for the growth of winter wheat. Visual and near-infrared sensors are a quick and non-destructive testing technology for the estimation of crop leaf chlorophyll content. In this paper, a new approach is developed for leaf chlorophyll content estimation of winter wheat based on visible and near-infrared sensors. First, the sliding window smoothing (SWS) was integrated with the multiplicative scatter correction (MSC) or the standard normal variable transformation (SNV) to preprocess the reflectance spectra images of wheat leaves. Then, a model for the relationship between the leaf relative chlorophyll content and the reflectance spectra was developed using the partial least squares (PLS) and the back propagation neural network. A total of 300 samples from areas surrounding Yangling, China, were used for the experimental studies. The samples of visible and near-infrared spectroscopy at the wavelength of 450,900 nm were preprocessed using SWS, MSC and SNV. The experimental results indicate that the preprocessing using SWS and SNV and then modeling using PLS can achieve the most accurate estimation, with the correlation coefficient at 0.8492 and the root mean square error at 1.7216. Thus, the proposed approach can be widely used for winter wheat chlorophyll content analysis.

  13. Estimation of chlorophyll-a concentration in turbid productive waters using airborne hyperspectral data.

    PubMed

    Moses, Wesley J; Gitelson, Anatoly A; Perk, Richard L; Gurlin, Daniela; Rundquist, Donald C; Leavitt, Bryan C; Barrow, Tadd M; Brakhage, Paul

    2012-03-15

    Algorithms based on red and near infra-red (NIR) reflectances measured using field spectrometers have been previously shown to yield accurate estimates of chlorophyll-a concentration in turbid productive waters, irrespective of variations in the bio-optical characteristics of water. The objective of this study was to investigate the performance of NIR-red models when applied to multi-temporal airborne reflectance data acquired by the hyperspectral sensor, Airborne Imaging Spectrometer for Applications (AISA), with non-uniform atmospheric effects across the dates of data acquisition. The results demonstrated the capability of the NIR-red models to capture the spatial distribution of chlorophyll-a in surface waters without the need for atmospheric correction. However, the variable atmospheric effects did affect the accuracy of chlorophyll-a retrieval. Two atmospheric correction procedures, namely, Fast Line-of-sight Atmospheric Adjustment of Spectral Hypercubes (FLAASH) and QUick Atmospheric Correction (QUAC), were applied to AISA data and their results were compared. QUAC produced a robust atmospheric correction, which led to NIR-red algorithms that were able to accurately estimate chlorophyll-a concentration, with a root mean square error of 5.54 mg m(-3) for chlorophyll-a concentrations in the range 2.27-81.17 mg m(-3). PMID:22209281

  14. Leaf Chlorophyll Content Estimation of Winter Wheat Based on Visible and Near-Infrared Sensors

    PubMed Central

    Zhang, Jianfeng; Han, Wenting; Huang, Lvwen; Zhang, Zhiyong; Ma, Yimian; Hu, Yamin

    2016-01-01

    The leaf chlorophyll content is one of the most important factors for the growth of winter wheat. Visual and near-infrared sensors are a quick and non-destructive testing technology for the estimation of crop leaf chlorophyll content. In this paper, a new approach is developed for leaf chlorophyll content estimation of winter wheat based on visible and near-infrared sensors. First, the sliding window smoothing (SWS) was integrated with the multiplicative scatter correction (MSC) or the standard normal variable transformation (SNV) to preprocess the reflectance spectra images of wheat leaves. Then, a model for the relationship between the leaf relative chlorophyll content and the reflectance spectra was developed using the partial least squares (PLS) and the back propagation neural network. A total of 300 samples from areas surrounding Yangling, China, were used for the experimental studies. The samples of visible and near-infrared spectroscopy at the wavelength of 450,900 nm were preprocessed using SWS, MSC and SNV. The experimental results indicate that the preprocessing using SWS and SNV and then modeling using PLS can achieve the most accurate estimation, with the correlation coefficient at 0.8492 and the root mean square error at 1.7216. Thus, the proposed approach can be widely used for winter wheat chlorophyll content analysis. PMID:27023550

  15. Dielectric Analysis for the Spherical and Rodlike Micelle Aggregates Formed from a Gemini Surfactant: Driving Forces of Micellization and Stability of Micelles.

    PubMed

    Wang, Shanshan; Zhao, Kongshuang

    2016-08-01

    The self-aggregation behavior of Gemini surfactant 12-2-12 (ethanediyl-1,2-bis(dimethyldodecylammonium bromide)) in water was investigated by dielectric relaxation spectroscopy (DRS) over a frequency range from 40 Hz to 110 MHz. Dielectric determination shows that well-defined spherical micelles formed when the concentration of the surfactant was above a critical micelle concentration CMC1 of 3 mM and rodlike micelles formed above CMC2, 16 mM. The formation mechanism of the spherical micelles and their transition mechanism to clubbed micelles were proposed by calculating the degree of counterion binding of the micelles. The interactions between the head groups and the hydrophobic chains of the surfactant led to the formation of the micelles, whereas the transition is mainly attributed to the interaction among the hydrophobic chains. By analyzing the dielectric relaxation observed at about 10(7) Hz based on the interface polarization theory, the permittivity and conductivity of micelle aggregates (spherical and clubbed) and volume fraction of micelles were calculated theoretically as well as the electrical properties of the solution medium. Furthermore, we also calculated the electrokinetic parameters of the micelle particle surface, surface conductivity, surface charge density, and zeta potential, using the relaxation param