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Sample records for chlorophyll micelles models

  1. Characterization of chlorophyll derivatives in micelles of polymeric surfactants aiming photodynamic applications

    NASA Astrophysics Data System (ADS)

    Gerola, Adriana Passarella; de Morais, Flavia Amanda Pedroso; Costa, Paulo Fernando A.; Kimura, Elza; Caetano, Wilker; Hioka, Noboru

    2017-02-01

    The spectrophotometric properties of chlorophylls' derivatives (Chls) formulated in the Pluronics® F-127 and P-123 were evaluated and the results have shown that the Chls were efficiently solubilized in these drug delivery systems as monomers. The relative location of the Chls in the Pluronics® was estimated from the Stokes shift and micropolarity of the micellar environment. Chls with phytyl chain were located in the micellar core, where the micropolarity is similar to ethanol, while phorbides' derivatives (without phytyl chain) were located in the outer shell of the micelle, i.e., more polar environment. In addition, the thermal stability of the micellar formulations was evaluated through electronic absorption, fluorescence emission and resonance light scattering with lowering the temperature. The Chls promote the stability of the micelles at temperatures below the Critical Micellar Temperature (CMT) of these surfactants. For F-127 formulations, the water molecules drive through inside the nano-structure at temperatures below the CMT, which increased the polarity of this microenvironment and directly affected the spectrophotometric properties of the Chls with phytyl chain. The properties of the micellar microenvironment of P-123, with more hydrophobic core due to the small PEO/PPO fraction, were less affected by lowering the temperature than for F-127. These results enable us to better understand the Chls behavior in micellar copolymers and allowed us to design new drug delivery system that maintains the photosensitizer's properties for photodynamic applications.

  2. Anion Exchange on Cationic Surfactant Micelles, and a Speciation Model for Estimating Anion Removal on Micelles during Ultrafiltration of Water.

    PubMed

    Chen, Ming; Jafvert, Chad T

    2017-07-05

    Surfactant micelles combined with ultrafiltration can partially, or sometimes nearly completely, separate various ionic and nonionic pollutants from water. To this end, the selectivity of aqueous micelles composed of either cetyltrimethylammonium (CTA(+)) bromide or cetylpyridinium (CP(+)) chloride toward many environmentally relevant anions (IO3(-), F(-), Cl(-), HCO3(-), NO2(-), Br(-), NO3(-), H2PO4(-), HPO4(2-), SO4(2-), and CrO4(2-)) was investigated. Selectivity coefficients of CTA(+) micelles (with respect to Br(-)) and CP(+) micelle (with respect to Cl(-)) for these anions were evaluated using a simple thermodynamic ion exchange model. The sequence of anion affinity for the CTA(+) micelles and for the CP(+) micelles were the same, with decreasing affinity occurring in the order of: CrO4(2-) > SO4(2-) > HPO4(2-) > NO3(-) > Br(-) > NO2(-) > Cl(-) > HCO3(-) > H2PO4(-) ≈ F(-). From the associated component mass balance and ion exchange (i.e., mass action) equations, an overall speciation model was developed to predict the distribution of all anions between the aqueous and micellar pseudophase for complex ionic mixtures. Experimental results of both artificial and real surface waters were in good agreement to model predictions. Further, the results indicated that micelles combined with ultrafiltration may be a potential technology for nutrient and other pollutant removal from natural or effluent waters.

  3. 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

  4. A simplified kinetic model for an autopoietic synthesis of micelles

    NASA Astrophysics Data System (ADS)

    Chizmadzhew, Yuri A.; Maestro, Marco; Mavelli, Fabio

    1994-08-01

    Recently, some chemical systems have been implemented which have an autopoietic behaviour according to Varela and Maturana's definition. They consist of micelles or reversed micelles which are able to produce their building material inside themselves, and, in such a way reproduce themselves. For one of these systems we have elaborated a kinetic model to rationalize the long lag phase and the abrupt rate increase displayed during the autopietic process of micellar self-replication. The theoretical predictions are in good agreement with the experimental observations available to date.

  5. 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.

  6. Modelling chlorophyll fluorescence of kiwi fruit (Actinidia deliciosa).

    PubMed

    Novo, Johanna Mendes; Iriel, Analia; Lagorio, M Gabriela

    2012-04-01

    Kiwi fruit displays chlorophyll fluorescence. A physical model was developed to reproduce the observed original fluorescence for the whole fruit, from the emission of the different parts of the kiwi fruit. The spectral distribution of fluorescence in each part of the fruit, was corrected to eliminate distortions due to light re-absorption and it was analyzed in relation to photosystem II-photosystem I ratio. Kiwi fruit also displays variable chlorophyll-fluorescence, similar to that observed from leaves. The maximum quantum efficiency of photosystem II photochemistry (F(v)/F(m)), the quantum efficiency of photosystem II (Φ(PSII)), and the photochemical and non-photochemical quenching coefficients (q(P) and q(NP) respectively) were determined and discussed in terms of the model developed. The study was extended by determining the photosynthetic parameters as a function of the storage time, at both 4 °C and room temperature for 25 days.

  7. Molecular connectivity indices for modeling the critical micelle concentration of cationic (chloride) Gemini surfactants.

    PubMed

    Mozrzymas, Anna

    2017-01-01

    The molecular connectivity indices were used to derive the simple model relating the critical micelle concentration of cationic (chloride) gemini surfactants to their structure. One index was selected as the best to describe the effect of the structure of investigated compounds on critical micelle concentration consistent with the experimental results. This index encodes the information about molecular size, the branches, and also the information about heteroatoms. The selected model can be helpful in designing novel chloride gemini surfactants.

  8. 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.

  9. [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%.

  10. Covalently linked chlorophyll a dimer: A biomimetic model of special pair chlorophyll

    PubMed Central

    Wasielewski, Michael R.; Studier, Martin H.; Katz, Joseph J.

    1976-01-01

    The synthesis of a covalent dimer of chlorophyll a which possesses properties strikingly similar to those exhibited by P700 special pair chlorophyll in vivo is described. The covalent dimer is characterized by several spectroscopic techniques. Hydrogen bonding nucleophiles, such as water, primary alcohols, and primary thiols, are effective in generating a species from solutions of 10 μM covalent dimer in hydrophobic solvents which absorbs light near 700 nm. Formation of this in vitro special pair is a rapid, spontaneous process at room temperature. The range of nucleophiles which promote this process suggests that amino acid residues may function in a similar fashion to form P700 in chlorophyll-protein complexes. The photochemical properties of this in vitro special pair mimic those of in vivo P700 species. The 697 nm absorption of the in vitro special pair undergoes photo-bleaching rapidly in the presence of iodine that results in the production of a cation radical which exhibits an electron spin resonance signal similar to that of oxidized P700 observed in Chlorella vulgaris. PMID:16592367

  11. 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.

  12. Release, Partitioning, and Conjugation Stability of Doxorubicin in Polymer Micelles Determined by Mechanistic Modeling

    PubMed Central

    Ponta, Andrei; Fugit, Kyle D.; Anderson, Bradley D.; Bae, Younsoo

    2014-01-01

    Purpose To better understand the mechanistic parameters that govern drug release from polymer micelles with acid-labile linkers. Methods A mathematical model was developed to describe drug release from block copolymer micelles composed of a poly(ethylene glycol) shell and a poly(aspartate) core, modified with drug binding linkers for pH-controlled release [hydrazide (HYD), aminobenzoate-hydrazide (ABZ), or glycine-hydrazide (GLY)]. Doxorubicin (Dox) was conjugated to the block copolymers through acid-labile hydrazone bonds. The polymer drug conjugates were used to prepare three polymer micelles (HYD-M, ABZ-M, and GLY-M). Drug release studies were performed to identify the factors governing pH-sensitive release of Dox. The effect of prolonged storage of copolymer material on release kinetics was also observed. Results Biphasic drug release kinetics were observed for all three micelle formulations. The developed model was able to quantify observed release kinetics upon the inclusion of terms for unconjugated Dox and two populations of conjugated Dox. Micelle/water partitioning of Dox was also incorporated into the model and found significant in all micelles under neutral conditions but reduced under acidic conditions. The drug binding linker played a major role in drug release as the extent of Dox release at specific time intervals was greater at pH 5.0 than at pH 7.4 (HYD-M > ABZ-M > GLY-M). Mathematical modeling was also able correlate changes in release kinetics with the instability of the hydrazone conjugation of DOX during prolonged storage. Conclusion These results illustrate the potential utility of mechanistic modeling to better assess release characteristics intrinsic to a particular drug/nanoparticle system. PMID:25407546

  13. 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.

  14. 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.

  15. [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.

  16. Anti-tumor activity of biodegradable polymer-paclitaxel conjugate micelles on Lewis lung cancer mice models.

    PubMed

    Wan, Yanhui; Zheng, Yonghui; Song, Xiangfu; Hu, Xiuli; Liu, Shi; Tong, Ti; Jing, Xiabin

    2011-01-01

    Two kinds of paclitaxel (PTX) conjugate nanomicelles were prepared for cell apoptosis and anti-tumor activity evaluation on Lewis lung cancer mice models. One (PTX micelles) was prepared by self-assembling the PTX-conjugate co-polymer, poly(ethylene glycol)-b-poly(L-lactide-co-2-methyl-2-carboxyl-propylene carbonate/PTX), and the other (FA-PTX micelles) was by co-assembling a mixture of the folic acid (FA)-carrying co-polymer poly(ethylene glycol)-b-poly(L-lactide-co-2,2-dihydroxylmethyl-propylene carbonate/FA) (PEG-b-P(LA-co-DHP/FA)), and the PTX-conjugate co-polymer. At 7 and 14 days after tail intravenous injection, the mice were killed. The inhibition rates of tumor growth for PTX and FA-PTX micelles were 50 and 90%, respectively, on the day 7, and 33 and 71%, respectively, on the day 14 after drug injection. Flow cytometry analysis showed that the cell apoptosis rates were 43, 54 and 72% for the control group, PTX micelles group and FA-PTX micelles group, respectively, on the day 7, and 16, 25 and 42 on the day 14. With the TUNEL assay, the grey values of PTX micelles and FA-PTX micelles groups were determined to be 61-62% and 43-44%, of that of the control group, on day 7 or day 14, respectively. Therefore, the PTX micelles and the FA-PTX composite micelles significantly inhibited the subcutaneously inoculated Lewis lung cancer and effectively induced the cell apoptosis, and the FA-PTX composite micelles displayed a better efficacy than the PTX-micelles, implying the contribution of the folate-mediated targeting and endocytosis effect.

  17. Modeling micelle formation and interfacial properties with iSAFT classical density functional theory

    NASA Astrophysics Data System (ADS)

    Wang, Le; Haghmoradi, Amin; Liu, Jinlu; Xi, Shun; Hirasaki, George J.; Miller, Clarence A.; Chapman, Walter G.

    2017-03-01

    Surfactants reduce the interfacial tension between phases, making them an important additive in a number of industrial and commercial applications from enhanced oil recovery to personal care products (e.g., shampoo and detergents). To help obtain a better understanding of the dependence of surfactant properties on molecular structure, a classical density functional theory, also known as interfacial statistical associating fluid theory, has been applied to study the effects of surfactant architecture on micelle formation and interfacial properties for model nonionic surfactant/water/oil systems. In this approach, hydrogen bonding is explicitly included. To minimize the free energy, the system minimizes interactions between hydrophobic components and hydrophilic components with water molecules hydrating the surfactant head group. The theory predicts micellar structure, effects of surfactant architecture on critical micelle concentration, aggregation number, and interfacial tension isotherm of surfactant/water systems in qualitative agreement with experimental data. Furthermore, this model is applied to study swollen micelles and reverse swollen micelles that are necessary to understand the formation of a middle-phase microemulsion.

  18. Inversion of chlorophyll contents by use of hyperspectral CHRIS data based on radiative transfer model

    NASA Astrophysics Data System (ADS)

    Wang, M. C.; Niu, X. F.; Chen, S. B.; Guo, P. J.; Yang, Q.; Wang, Z. J.

    2014-03-01

    Chlorophyll content, the most important pigment related to photosynthesis, is the key parameter for vegetation growth. The continuous spectrum characteristics of ground objects can be captured through hyperspectral remotely sensed data. In this study, based on the coniferous forest radiative transfer model, chlorophyll contents were inverted by use of hyperspectral CHRIS data in the coniferous forest coverage of Changbai Mountain Area. In addition, the sensitivity of LIBERTY model was analyzed. The experimental results validated that the reflectance simulation of different chlorophyll contents was coincided with that of the field measurement, and hyperspectral vegetation indices applied to the quantitative inversion of chlorophyll contents was feasible and accurate. This study presents a reasonable method of chlorophyll inversion for the coniferous forest, promotes the inversion precision, is of significance in coniferous forest monitoring.

  19. Red chlorophylls in the exciton model of photosystem I.

    PubMed

    Vaitekonis, Sarunas; Trinkunas, Gediminas; Valkunas, Leonas

    2005-11-01

    Structural arrangement of pigment molecules of Photosystem I of photosynthetic cyanobacterium Synechococcus elongatus is used for theoretical modeling of the excitation energy spectrum. It is demonstrated that a straightforward application of the exciton theory with the assumption of the same molecular transition energy does not describe the red side of the absorption spectrum. Since the inhomogeneity in the molecular transition energies caused by a dispersive interaction with the molecular surrounding cannot be identified directly from the structural model, the evolutionary search procedure is used for fitting the low temperature absorption and circular dichroism spectra. As a result, one dimer, three trimers and one tetramer of chlorophyll molecules responsible for the red side of the absorption spectrum with their assignment to the spectroscopically established three bands at 708, 714 and 719 nm are determined. All of them are found to be situated not in the very close vicinity of the reaction center but are encircling it almost at the same distance. In order to explain the unusual broadening on the red side of the spectrum the exciton state mixing with the charge transfer (CT) states is considered. It is shown that two effects can be distinguished as caused by mixing of those states: (i) the oscillator strength borrowing by the CT state from the exciton transition and (ii) the borrowing of the high density of the CT state by the exciton state. The intermolecular vibrations between two counter-charged molecules determine the high density in the CT state. From the broad red absorption wing it is concluded that the CT state should be the lowest state in the complexes under consideration. Such mixing effect enables resolving the diversity in the molecular transition energies as determined by different theoretical approaches.

  20. 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

  1. Aggregation work at polydisperse micellization: Ideal solution and ``dressed micelle'' models comparing to molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Burov, S. V.; Shchekin, A. K.

    2010-12-01

    General thermodynamic relations for the work of polydisperse micelle formation in the model of ideal solution of molecular aggregates in nonionic surfactant solution and the model of "dressed micelles" in ionic solution have been considered. In particular, the dependence of the aggregation work on the total concentration of nonionic surfactant has been analyzed. The analogous dependence for the work of formation of ionic aggregates has been examined with regard to existence of two variables of a state of an ionic aggregate, the aggregation numbers of surface active ions and counterions. To verify the thermodynamic models, the molecular dynamics simulations of micellization in nonionic and ionic surfactant solutions at two total surfactant concentrations have been performed. It was shown that for nonionic surfactants, even at relatively high total surfactant concentrations, the shape and behavior of the work of polydisperse micelle formation found within the model of the ideal solution at different total surfactant concentrations agrees fairly well with the numerical experiment. For ionic surfactant solutions, the numerical results indicate a strong screening of ionic aggregates by the bound counterions. This fact as well as independence of the coefficient in the law of mass action for ionic aggregates on total surfactant concentration and predictable behavior of the "waterfall" lines of surfaces of the aggregation work upholds the model of "dressed" ionic aggregates.

  2. CHARMM-GUI micelle builder for pure/mixed micelle and protein/micelle complex systems.

    PubMed

    Cheng, Xi; Jo, Sunhwan; Lee, Hui Sun; Klauda, Jeffery B; Im, Wonpil

    2013-08-26

    Micelle Builder in CHARMM-GUI, http://www.charmm-gui.org/input/micelle , is a web-based graphical user interface to build pure/mixed micelle and protein/micelle complex systems for molecular dynamics (MD) simulation. The robustness of Micelle Builder is tested by simulating four detergent-only homogeneous micelles of DHPC (dihexanoylphosphatidylcholine), DPC (dodecylphosphocholine), TPC (tetradecylphosphocholine), and SDS (sodium dodecyl sulfate) and comparing the calculated micelle properties with experiments and previous simulations. As a representative protein/micelle model, Pf1 coat protein is modeled and simulated in DHPC micelles with three different numbers of DHPC molecules. While the number of DHPC molecules in direct contact with Pf1 protein converges during the simulation, distinct behavior and geometry of micelles lead to different protein conformations in comparison to that in bilayers. It is our hope that CHARMM-GUI Micelle Builder can be used for simulation studies of various protein/micelle systems to better understand the protein structure and dynamics in micelles as well as distribution of detergents and their dynamics around proteins.

  3. Comparison of Chlorophyll-a Measurement Using Multi Spatial Imagery and Numerical Model in Bali Strait

    NASA Astrophysics Data System (ADS)

    Hanintyo, Rizki; susilo, Eko

    2016-11-01

    One of abundance of nutrient in coastal area is chlorophyll-a, where chlorophyll-a is a driving factor to derive fishing ground location. There's several method has been used to derive chlorophyll-a concentration from insitu data, remote sensing satellite data, and ocean dynamics models, but we are not decide those data for certain area in coastal area and open ocean. In this paper, we will use Aqua-Terra MODIS, Landsat -8 and INDESO Satellite observation dataset to detect chlorophyll-a and also using dynamic modelling produced by INDESO and MyOcean/Marine Copernicus. Using a lot variation of data to understand the differences of spatial resolution and accuracy with observed insitu data. After calculating data comparison with insitu data in bali strait on 2014, we can conclude that Landsat-8 data has the highest r value r=0.41. For model data, comparison between insitu data and MyOcean data has r=0.3. in the other hand, insitu data and INDESO data model has r=0.26. In coastal areas (case 2 water), Landsat-8 data performed to give detail information of chlorophyll-a. Furthermore for open ocean areas (case 1 water), we can use numerical model from MyOcean/Marine Copernicus because it has lower resolution and able to forecast. For those data, it can help non artisanal fisheries to predict chlorophyll-a area in their fishing ground areas

  4. Molecular modeling of micelle formation and solubilization in block copolymer micelles. 2. Lattice theory for monomers with internal degrees of freedom

    SciTech Connect

    Hurter, P.N.; Hatton, T.A. . Dept. of Chemical Engineering); Scheutjens, J.M.H.M. )

    1993-09-13

    A self-consistent mean-field lattice theory of the micellization and solubilization properties of poly(ethylene oxide)-poly(propylene oxide) block copolymers is described. The polymer segments are allowed to assume both polar and nonpolar conformations (corresponding to the gauche and trans rotations of the C-C and C-O bonds), which permits the dependence of the segment-segment interactions on temperature and composition to be accounted for in a physically realistic manner. The phase diagrams of poly(ethylene oxide) and poly(propylene oxide) in water, both of which exhibit lower critical solution temperatures, can be reproduced semiquantitatively. The predictions of the theory compare favorably with published light scattering results on the aggregation behavior of block copolymers and with the authors experimental results for the solubilization of naphthalene in these micelles as a function of polymer composition and molecular weight. The dependence of the micelle-water partition coefficient on polymer composition is not simply related to the proportion of the hydrophobic constituent but depends on the detailed micelle structure. The strong effect of the molecular weight and PPO content of the polymer on the amount of naphthalene solubilized observed experimentally was interpreted in terms of the model results.

  5. 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.

  6. 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.

  7. Vegetation chlorophyll estimates in the Amazon from multi-angle MODIS observations and canopy reflectance model

    NASA Astrophysics Data System (ADS)

    Hilker, Thomas; Galvão, Lênio Soares; Aragão, Luiz E. O. C.; de Moura, Yhasmin M.; do Amaral, Cibele H.; Lyapustin, Alexei I.; Wu, Jin; Albert, Loren P.; Ferreira, Marciel José; Anderson, Liana O.; dos Santos, Victor A. H. F.; Prohaska, Neill; Tribuzy, Edgard; Barbosa Ceron, João Vitor; Saleska, Scott R.; Wang, Yujie; de Carvalho Gonçalves, José Francisco; de Oliveira Junior, Raimundo Cosme; Cardoso Rodrigues, João Victor Figueiredo; Garcia, Maquelle Neves

    2017-06-01

    As a preparatory study for future hyperspectral missions that can measure canopy chemistry, we introduce a novel approach to investigate whether multi-angle Moderate Resolution Imaging Spectroradiometer (MODIS) data can be used to generate a preliminary database with long-term estimates of chlorophyll. MODIS monthly chlorophyll estimates between 2000 and 2015, derived from a fully coupled canopy reflectance model (ProSAIL), were inspected for consistency with eddy covariance fluxes, tower-based hyperspectral images and chlorophyll measurements. MODIS chlorophyll estimates from the inverse model showed strong seasonal variations across two flux-tower sites in central and eastern Amazon. Marked increases in chlorophyll concentrations were observed during the early dry season. Remotely sensed chlorophyll concentrations were correlated to field measurements (r2 = 0.73 and r2 = 0.98) but the data deviated from the 1:1 line with root mean square errors (RMSE) ranging from 0.355 μg cm-2 (Tapajós tower) to 0.470 μg cm-2 (Manaus tower). The chlorophyll estimates were consistent with flux tower measurements of photosynthetically active radiation (PAR) and net ecosystem productivity (NEP). We also applied ProSAIL to mono-angle hyperspectral observations from a camera installed on a tower to scale modeled chlorophyll pigments to MODIS observations (r2 = 0.73). Chlorophyll pigment concentrations (ChlA+B) were correlated to changes in the amount of young and mature leaf area per month (0.59 ≤ r2 ≤ 0.64). Increases in MODIS observed ChlA+B were preceded by increased PAR during the dry season (0.61 ≤ r2 ≤ 0.62) and followed by changes in net carbon uptake. We conclude that, at these two sites, changes in LAI, coupled with changes in leaf chlorophyll, are comparable with seasonality of plant productivity. Our results allowed the preliminary development of a 15-year time series of chlorophyll estimates over the Amazon to support canopy chemistry studies using future

  8. Modelling of the Critical Micelle Concentration of Cationic Gemini Surfactants Using Molecular Connectivity Indices.

    PubMed

    Mozrzymas, Anna

    2013-01-01

    Modelling of the critical micelle concentrations (cmc) using the molecular connectivity indices was performed for a set of 21 cationic gemini surfactants with medium-length spacers. The obtained model contains only the second-order Kier and Hall molecular connectivity index. It is suggested that the index (2)χ includes some information about flexibility. The obtained model was used to predict log10 cmc of other cationic gemini surfactants. The agreement between calculated and experimental values of log10 cmc for the gemini surfactants that were not used in the correlation is very good.

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

    PubMed

    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.

  10. Estimation of leaf chlorophyll content and the fraction of light absorption by chlorophyll using MODIS images and a radiative transfer model

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Xiao, X.; Braswell, B.; Linder, E.; Moore, B.

    2005-12-01

    Photosynthetically actively radiation (PAR) absorbed by leaf chlorophyll is used for photosynthesis, therefore, there is a need to quantify the fraction of PAR absorbed by leaf chlorophyll (FAPARchl) within a vegetation canopy. We recently developed a theoretical and modeling framework to estimate leaf chlorophyll content and FAPARchl.in a vegetation canopy The modeling framework coupled a leaf radiative transfer model (PROPSECT) with a canopy radiative transfer model (SAIL-2) and incorporated a Markov Chain Monte Carlo (MCMC) method (the Metropolis algorithm) for model inversion, which provides posterior distributions of retrieved variables. Our two-step procedure is: (1) to invert biophysical and biochemical variables (including leaf chlorophyll content) with the coupled PROSPECT+SAIL-2 (PROSAIL-2) model and multiple daily images (five spectral bands) from MODerate resolution Imaging Spectroradiometer (MODIS) sensor , (2) to reproduce MODIS spectral reflectance and to calculate FAPARchl with the inverted variables from step (1). We ran the PROSAIL-2 model for a deciduous broadleaf forest, an evergreen forest and an agricultural site using MODIS data in 2001-2003. The PROSAIL-2 -reproduced reflectance agrees well with observed MODIS reflectance for the five MODIS spectral bands. The retrieved variables (leaf area index, leaf chlorophyll content) were also evaluated with available literature data. Estimated FAPARchl is substantially lower than the fraction of PAR absorbed by leaf (FAPARleaf) and by vegetation canopy (FAPARcanopy). Biogeochemical models that use either the fraction of PAR absorbed by canopy (FAPARcanopy) or the fraction of PAR absorbed by leaf (FAPARleaf) in estimating gross and net primary production are likely to overestimate the amount of PAR used in photosynthesis process, which represents one large source of error and uncertainty. The results of this study highlight the needs of field works and the potential of a radiative transfer model

  11. 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.

  12. 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

  13. Surface chlorophyll distributions in the upper Gulf of Thailand investigated using satellite imagery and ecosystem model

    NASA Astrophysics Data System (ADS)

    Buranapratheprat, Anukul

    MERIS data and Nutrient-Phytoplankton-Zooplankton-Detritus (NPZD) ecosystem model coupled with the Princeton Ocean Model (POM), were used to investigate seasonal variations in surface chlorophyll distributions and their controlling factors to clarify phytoplankton dynamics in the upper Gulf of Thailand. Chlorophyll maps were produced by application on MERIS Level 2 data an empirical algorithm derived from the regression analysis of the relationship between chlorophyll-a concentration and remote sensing reflectance ratio. The results indicated that the patterns of seasonal chlorophyll distributions corresponded to local wind and water circulations. The model simulation highlighted the importance of river water as a significant nutrient source, and its movement after discharge into the sea is controlled by seasonal circulations. High chlorophyll concentration located along the western coast following the direction of counter-clockwise circulation, forced by the northeast winds, while chlorophyll accumulation was observed in the northeastern corner of the gulf due to clockwise circulation, driven by the southwest winds. These key simulated results are consistent with those of field observations and satellite images captured in the same periods of time, and also described seasonal shifting of blooming areas previously reported. Sensitivity analysis of simulated chlorophyll distributions suggested that not only nutrients but also wind-induced vertical movement plays a significant role in controlling phytoplankton growth. Plankton blooms occur in zones of upwelling or where vertical diffusivities are low. Increasing nutrients in the water column due to river loads leads to increasing potential for severe plankton blooms when other photosynthetic factors, such as water stability and light, are optimized. The knowledge of seasonal patterns of blooming can be used to construct environmental risk maps which are very useful for planning to mitigate the eutrophic problems

  14. Modeling leaf chlorophyll content from ground, airborne and satellite reflectance data

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Leaf chlorophyll content is a paramount ecological variable and plays a central role in plant photosynthesis, can indicate vegetation stress and disturbance and provides inputs to plant productivity and carbon cycle models. However, the retrieval of leaf chlorophyll from remotely sensed data is complex because canopy reflectance in the visible and near-infrared wavelengths is also affected by leaf area index (LAI), canopy architecture, illumination and viewing geometry and understory vegetation. Whilst considerable research has been geared towards developing statistical relationships with spectral indices to predict chlorophyll content, these algorithms are often ecosystem or location specific and have limited reliability for application over large regions and different time scales. In contrast, a process modeling approach uses physical laws to account for the variation of other variables affecting canopy reflectance, which could provide a more accurate estimate of chlorophyll content over multiple vegetation species, time-frames and across broader spatial extents. This research investigates the retrieval of leaf chlorophyll content from different species, leaf structures and canopy architectures using empirical and model inversion approaches. A coupled canopy (4-Scale) and leaf (PROSPECT) model approach investigate the ability of radiative transfer models to estimate foliar chemistry and account for confounding canopy and background variables (LAI, non-photosynethic vegetation, understory) from optical remote sensing data. Canopy reflectance data was acquired from a number of remote sensing platforms (CASI, Landsat 5 TM and MERIS), representing different spectral and spatial resolutions. Over thirty sites were selected in Ontario, Canada representing different dominant vegetation species (Picea mariana, Pinus banksiana, Populus tremuloides and Acer saccharum), and a variety of canopy closures and structures. Ground data collection included LAI, measured using

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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.

  17. Modeling the Self-Assembly and Stability of DHPC Micelles Using Atomic Resolution and Coarse Grained MD Simulations.

    PubMed

    Kraft, Johan F; Vestergaard, Mikkel; Schiøtt, Birgit; Thøgersen, Lea

    2012-05-08

    Membrane mimics such as micelles and bicelles are widely used in experiments involving membrane proteins. With the aim of being able to carry out molecular dynamics simulations in environments comparable to experimental conditions, we set out to test the ability of both coarse grained and atomistic resolution force fields to model the experimentally observed behavior of the lipid 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC), which is a widely used lipid for biophysical characterization of membrane proteins. It becomes clear from our results that a satisfactory modeling of DHPC aggregates in solution poses different demands to the force field than do the modeling of bilayers. First, the representation of the short tailed lipid DHPC in the coarse grained force field MARTINI is assessed with the intend of successfully self-assemble micelles with structural characteristics comparable to experimental data. Then, the use of the recently presented polarizable water model in MARTINI is shown to be essential for producing micelles that are structurally in accordance with experiments. For the atomistic representations of DHPC micelles in solution the GROMOS96 force field with lipid parameters by A. Kukol fails to maintain stable micelles, whereas the most recent CHARMM36 lipid parameters and GROMOS96 with the so-called Berger lipid parameters both succeed in this regard.

  18. Kinetic Model for Surface-Active Enzymes Based on the Langmuir Adsorption Isotherm: Phospholipase C (Bacillus cereus) Activity toward Dimyristoyl Phosphatidylcholine/Detergent Micelles

    NASA Astrophysics Data System (ADS)

    Burns, Ramon A.; El-Sayed, Maha Y.; Roberts, Mary F.

    1982-08-01

    A simple kinetic model for the enzymatic activity of surface-active proteins against mixed micelles has been developed. This model uses the Langmuir adsorption isotherm, the classic equation for the binding of gas molecules to metal surfaces, to characterize enzyme adsorption to micelles. The number of available enzyme binding sites is equated with the number of substrate and inhibitor molecules attached to micelles; enzyme molecules are attracted to the micelle due to the affinity of the enzyme active site for the molecules in the micelle. Phospholipase C (Bacillus cereus) kinetics in a wide variety of dimyristoyl phosphatidylcholine/detergent micelles are readily explained by this model and the assumption of competitive binding of the detergent at the enzyme active site. Binding of phospholipase C to pure detergent micelles is demonstrated by gel filtration chromatography. The experimentally determined enzyme-detergent micelle binding constants are used directly in the rate equation. The Langmuir adsorption model predicts a variety of the characteristics observed for phospholipase kinetics, such as differential inhibition by various charged, uncharged, and zwitterionic detergents and surface-dilution inhibition. The essential idea of this model, that proteins can be attracted and bound to bilayers or micelles by possessing a binding site for the molecules composing the surface, may have wider application in the study of water-soluble (extrinsic) protein-membrane interactions.

  19. Retrievals of Chlorophyll Fapar for Improved Crop Gpp Modeling

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Cheng, Y. B.; Wang, Y.; Lyapustin, A.; Yao, T.

    2014-12-01

    Accurate estimation of crop gross primary productivity (GPP) is important. We have recently developed an algorithm to derive fAPAR of chlorophyll (fAPARchl), fAPAR of foliage (fAPARfoliage) and chlorophyll LAI (LAIchl) with PROSAIL2. The MODIS surface reflectance produced with MAIAC were utilized to retrieve fAPARchl, fAPARfoliage and LAIchl for three AmeriFlux sites of maize and soybean. MOD15A2 FPAR and the retrieved fAPARchl were compared with field fAPARcanopy and the fraction of PAR absorbed by green leaves of the vegetation (fAPARgreen). MOD15A2 FPAR overestimated field fAPARcanopy in spring and in fall, and underestimated field fAPARcanopy in midsummer whereas fAPARchl correctly captured the seasonal phenology. The retrieved fAPARchl agreed well with field fAPARgreen at early crop growth stage in June, and was less than field fAPARgreen in late July, August and September, which is consistent with crop physiology theory. GPP estimates with fAPARchl and with MOD15A2 FPAR were compared to tower flux GPP. GPP simulated with fAPARchl was corroborated with tower flux GPP. Improvements in crop GPP estimation were achieved by replacing MOD15A2 FPAR with fAPARchl which also reduced uncertainties of crop GPP estimates by 1.12 - 2.37 g C m-2 d-1. NDVI, EVI, WDRVIgreen, and CIgreen have also been employed to estimate GPP by other scientific teams. We investigated the scaling factors and offsets (i.e., regression slopes and offsets) between fAPARchl and the VIs. The results showed that the scaled EVI obtained the best performance. The performance of the scaled NDVI, EVI and WDRVIgreen was improved across sites, crop types and soil/background wetness conditions, compared to the original un-scaled VIs. The scaled green band indices (WDRVIgreen, CIgreen) did not exhibit superior performance to either the scaled EVI or NDVI in estimating crop daily GPP at these agricultural fields. MOD15A2 LAI and the retrieved LAIchl were implemented into CLM to simulate GPP, respectively

  20. Effect of combined treatment with the epirubicin-incorporating micelles (NC-6300) and 1,2-diaminocyclohexane platinum (II)-incorporating micelles (NC-4016) on a human gastric cancer model.

    PubMed

    Yamamoto, Yoshiyuki; Hyodo, Ichinosuke; Takigahira, Misato; Koga, Yoshikatsu; Yasunaga, Masahiro; Harada, Mitsunori; Hayashi, Tatsuyuki; Kato, Yasuki; Matsumura, Yasuhiro

    2014-07-01

    Anticancer agent-incorporating polymeric micelles accumulate effectively in tumors via the enhanced permeability and retention effect to exert potent antitumor effects. However, combined use of such micelles has not been elucidated. We compared the effect of combining the epirubicin-incorporating micelle NC-6300 and 1,2-diaminocyclohexane platinum (II) (oxaliplatin parent complex)-incorporating micelle NC-4016 (NCs) with that of epirubicin and oxaliplatin (E/O) in 44As3Luc cells using the combination index method. The in vivo antitumor activities of NCs and E/O were evaluated in mice bearing 44As3Luc xenografts. Pharmacokinetic analysis was performed by high-performance liquid chromatography and mass spectrometry. Cardiotoxicity of NC-6300 and epirubicin was assessed by echocardiography. Neurotoxicity of NC-4016 and oxaliplatin was evaluated by examining the paw withdrawal response to noxious mechanical stimuli. NCs showed a highly synergistic activity equivalent to E/O. In vivo, NCs exhibited higher antitumor activity in the subcutaneous tumor model and longer overall survival in the orthotopic tumor model than E/O (p < 0.001, p = 0.015, respectively). The intratumor concentrations of epirubicin and platinum were significantly higher following NCs than following E/O administration. Moreover, the micelles showed lower cardiotoxicity and neurotoxicity than the corresponding conventional drugs. The combined use of the micelles was associated with remarkable efficacy and favorable toxicities in the human gastric cancer model, and warrants the conduct of clinical trials. © 2013 UICC.

  1. Non-enzymatic conversion of chlorophyll-a into chlorophyll-d in vitro: a model oxidation pathway for chlorophyll-d biosynthesis.

    PubMed

    Fukusumi, Takanori; Matsuda, Kohei; Mizoguchi, Tadashi; Miyatake, Tomohiro; Ito, Satoshi; Ikeda, Tsukasa; Tamiaki, Hitoshi; Oba, Toru

    2012-07-30

    Chlorophyll-a (Chl-a) was readily converted into Chl-d under mild conditions without any enzymes. Treatment of Chl-a dissolved in dry tetrahydrofuran (THF) with thiophenol and acetic acid at room temperature successfully produced Chl-d in 31% yield. During the acidic oxidation, removal of the central magnesium, pheophytinization, was sufficiently suppressed. This mild pathway can give insights into the yet unidentified Chl-d biosynthesis.

  2. Estimation of cholesterol solubilization by a mixed micelle binding model in aqueous tauroursodeoxycholate:lecithin:cholesterol solutions.

    PubMed

    Higuchi, William I; Tzeng, Chinn-Shin; Chang, Shyh-Jye; Chiang, Huey-Jenn; Liu, Chen-Lun

    2008-01-01

    In order to interpret the clinical efficacy of conjugated ursodeoxycholate (UDC) in cholesterol (Ch) gallstone patients, the Ch solubilization in mixed micelles in 40:40:32 mM tauroursodeoxycholate (TUDC):taurochenodeoxycholate (TCDC):lecithin (L) and 80:32 mM TUDC:L systems was estimated by using a model of Ch binding to mixed micelles. The Ch solubilization limit in mixed TUDC:L micelles was found to be higher than that in mixed TUDC:TCDC:L micelles. In the 80:32 mM TUDC:L system, the dissolution of the Ch pellet decreased after vesicles (liposomes) formed on the surface of the Ch pellet whereas the dissolution of microcrystalline Ch was rapid before and after vesicle formation in the solution, indicating that the total surface area of solid Ch exposed to the solution may be another important factor in inducing the dissolution of Ch gallstones. These phenomena suggest that although vesicles, occasionally formed in the bile of patients under the therapy of conjugated UDC, make a contribution to the solubilization of Ch gallstones, the model of Ch binding to mixed TUDC:L micelles can be used to estimate Ch solubility in TUDC:L system.

  3. Scaling effect on the estimation of chlorophyll content using narrow band NDVIs based on radiative transfer model

    NASA Astrophysics Data System (ADS)

    Wang, Hong; Shi, Runhe; Liu, Pudong; Cong, Zhou

    2015-09-01

    The aim of this work is to use narrow band normalized difference vegetation indices to compare the estimations of chlorophyll contents at foliar level and canopy level, through a large number of simulated canopy reflectance spectra under different chlorophyll contents based on PROSPECT model and SAIL model. 10 narrow band NDVIs were selected at the identified ranges that can effectively assess foliar chlorophyll content. We analyzed the correlations between canopy chlorophyll contents and the ten narrow band NDVIs firstly, and then analyze these indices' sensitivities to all canopy parameters, the adaptation of the 10 narrow band NDVIs used in assessing the canopy chlorophyll content were evaluated finally. We found that only two narrow band NDVIs (i.e., NDVI(875, 725) and NDVI(900,720)) can be applied for the estimation of chlorophyll contents at canopy level.

  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. 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.

  6. 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

  7. Model simulation for sensitivity of hyperspectral indices to LAI, leaf chlorophyll, and internal structure parameter

    NASA Astrophysics Data System (ADS)

    Yuan, Jinguo; Niu, Zheng; Fu, Wenxue

    2007-06-01

    The sensitivity of hyperspectral indices to LAI, chlorophyll contents and leaf internal structure at canopy level are investigated using simulated canopy reflectance dataset, this method can avoid expensive and impractical surface reflectance measurement, providing a theoretical basis for satellite-borne remote sensing. The model employed is PROSAIL that couples leaf reflectance model PROSPECT and canopy radiative transfer model SAIL. Hyperspectral indices used are NDVI, EVI, GI, RI, TVI, SIPI, PRI, TCARI, OSAVI, TCARI/ OSAVI, mNDVI705 and NDWI. Using PROSAIL model, leaf and canopy reflectance under different chlorophyll contents, leaf internal structures, LAI and water contents are first simulated and compared. Then using PROSAIL simulated canopy reflectance data, different hyperspectral indices are calculated, the sensitivity of vegetation indices to LAI and chlorophyll contents is analyzed in detail. And the sensitivity of vegetation indices to leaf internal structure is also analyzed. Results show that relationships between hyperspectral indices and LAI are approximately logarithmic while the relationship between hyperspectral indices and leaf internal structure is linear. EVI and TVI are good indicators to estimate LAI. GI, RI, TCARI, MNDVI 705 can be used to estimate chlorophyll content. N has great influence on hyperspectral indices.

  8. The seasonal cycle of surface chlorophyll in the Peruvian upwelling system: A modelling study

    NASA Astrophysics Data System (ADS)

    Echevin, V.; Aumont, O.; Ledesma, J.; Flores, G.

    2008-10-01

    The seasonal variability of surface chlorophyll in the northern Humboldt Current System is studied using satellite data, in situ observations and model simulations. The data show that surface chlorophyll concentration is highest in austral summer and decreases during austral winter, in phase opposition with coastal upwelling intensity. A regional model coupling ocean dynamics and biogeochemical cycles is used to investigate the processes which control this apparently paradoxical seasonal cycle. Model results suggest that the seasonal variability of the mixed layer depth is the main controlling factor of the seasonality. In winter, the mixed layer deepening reduces the surface chlorophyll accumulation because of a dilution effect and light limitation. In summer, biomass concentrates near the surface in the shallow mixed layer and nitrate limitation occurs, resulting in a biomass decrease in the middle of summer. Intense blooms occur during the spring restratification period, when winter light limitation relaxes, and during the fall destratification period, when the surface layer is supplied with new nutrients. Model sensitivity experiments show that the seasonal variations in insolation and surface temperature have little impact on the surface chlorophyll variability.

  9. Satellite retrievals of leaf chlorophyll and photosynthetic capacity for improved modeling of GPP

    USDA-ARS?s Scientific Manuscript database

    This study investigates the utility of in-situ and satellite-based leaf chlorophyll (Chl) estimates for quantifying leaf photosynthetic capacity and for constraining model simulations of Gross Primary Productivity (GPP) over a corn field in Maryland, U.S.A. The maximum rate of carboxylation (Vmax) r...

  10. Fluorescence visualization and modeling of a micelle-free zone formed at the interface between an oil and an aqueous micellar phase during interfacial surfactant transport.

    PubMed

    Bhole, Nikhil S; Huang, Fenfen; Maldarelli, Charles

    2010-10-19

    This study examines the transport of surfactant that occurs when an aqueous micellar phase is placed in contact with a clean oil phase in which the surfactant is soluble. Upon contact with oil, surfactant monomer on the aqueous side of the interface adsorbs onto the oil/water interface and subsequently desorbs into the oil and diffuses away from the surface. The depletion of aqueous monomer underneath the interface disturbs the monomer-micelle equilibrium, and aggregates break down to replenish the monomer concentration and accelerate the interfacial transport. The depletion of monomer and micelles drives the diffusive flux of these species toward the surface, and the combined effects of diffusion and aggregate kinetic disassembly, alongside kinetic adsorption and desorption at the interface and diffusion away from the interface into the oil, determine the interfacial transport rate. This interfacial transport is examined here in the quasi-static limit in which the diffusion of monomer and micelles in the aqueous phase is much slower than the time scale for micelle disassembly. In this limit, when the initial bulk concentration of micelles in the aqueous solution is small, the micelle diffusive flux to the surface cannot keep up with the micelle breakdown under the interface, and a micelle-free zone forms. This zone extends from the surface into the aqueous phase up to a boundary that demarcates the beginning of a zone, containing micelles, that extends further into the aqueous phase. Micelles diffuse from the micelle zone to the boundary, where they break down, causing the boundary to retreat. Released monomer diffuses through the micelle-free zone and partitions into the oil phase. The focus of this study is to verify this transport picture by visualizing the micelle-free zone and comparing the movement of the zone to predictions obtained from a transport model based on this two-zone picture. A small hydrophobic dye molecule (Nile red) is incorporated into the

  11. 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.

  12. [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.

  13. [Study on influencing factors and universality of chlorophyll-a retrieval model in inland water body].

    PubMed

    Huang, Chang-Chun; Li, Yun-Mei; Xu, Liang-Jiang; Yang, Hao; Lü, Heng; Chen, Xia; Wang, Yan-Hua

    2013-02-01

    The semi-analytical three-and four-band model and bio-optical analytical model of chlorophyll-a were checked by the 'mh, constituents and optical properties with high spatio-temporal variation. The influencing factors and universality of the retrieval model were studied by the modeling checking results. The study results indicate that the unjversality of bio-optical analytical model is much higher than the three-and four-band model, and the accuracy of the retrieval model is acceptable, but the accuracy of the retrieval model was highly affected by the specific absorption coefficient of chlorophyll-a. The accuracy of the three-and four-band model higher than the bio-optical analytical model. However, the universality of the three-and four-band model is not very high, because of the optimal wavelength position of the retrieval factors and the greater variability of the retrieval model parameters. The spectral shape of particle backscattering coefficient and chlorophyll-a specific absorption coefficient are the dominant influencing factors of the three and four-band retrieval model.

  14. Consecutive binding of chlorophylls a and b during the assembly in vitro of light-harvesting chlorophyll-a/b protein (LHCIIb).

    PubMed

    Horn, Ruth; Grundmann, Götz; Paulsen, Harald

    2007-02-23

    The apoprotein of the major light-harvesting chlorophyll a/b complex (LHCIIb) is post-translationally imported into the chloroplast, where membrane insertion, protein folding, and pigment binding take place. The sequence and molecular mechanism of the latter steps is largely unknown. The complex spontaneously self-organises in vitro to form structurally authentic LHCIIb upon reconstituting the unfolded recombinant protein with the pigments chlorophyll a, b, and carotenoids in detergent micelles. Former measurements of LHCIIb assembly had revealed two apparent kinetic phases, a faster one (tau1) in the range of 10 s to 1 min, and a slower one (tau2) in the range of several min. To unravel the sequence of events we analysed the binding of chlorophylls into the complex by using time-resolved fluorescence measurements of resonance energy transfer from chlorophylls to an acceptor dye attached to the apoprotein. Chlorophyll a, offered in the absence of chlorophyll b, bound with the faster kinetics (tau1) exclusively whereas chlorophyll b, in the absence of chlorophyll a, bound predominantly with the slower kinetics (tau2). In double-jump experiments, LHCIIb assembly could be dissected into a faster chlorophyll a and a subsequent, predominantly slower chlorophyll b-binding step. The assignment of the faster and the slower kinetic phase to predominantly chlorophyll a and exclusively chlorophyll b binding, respectively, was verified by analysing the assembly kinetics with a circular dichroism signal in the visible domain presumably reflecting the establishment of pigment-pigment interactions. We propose that slow chlorophyll binding is confined to the exclusively chlorophyll b binding sites whereas faster binding occurs to the chlorophyll a binding sites. The latter sites can bind both chlorophylls a and b but in a reversible fashion as long as the complex is not stabilised by proper occupation of the chlorophyll b sites. The resulting two-step model of LHCIIb assembly is

  15. Using satellite-derived backscattering coefficients in addition to chlorophyll data to constrain a simple marine biogeochemical model

    NASA Astrophysics Data System (ADS)

    Kettle, H.

    2009-08-01

    Biogeochemical models of the ocean carbon cycle are frequently validated by, or tuned to, satellite chlorophyll data. However, ocean carbon cycle models are required to accurately model the movement of carbon, not chlorophyll, and due to the high variability of the carbon to chlorophyll ratio in phytoplankton, chlorophyll is not a robust proxy for carbon. Using inherent optical property (IOP) inversion algorithms it is now possible to also derive the amount of light backscattered by the upper ocean (bb) which is related to the amount of particulate organic carbon (POC) present. Using empirical relationships between POC and bb, a 1-D marine biogeochemical model is used to simulate bb at 490 nm thereby allowing the model to be compared with both remotely-sensed chlorophyll or bb data. Here I investigate the possibility of using bb in conjunction with chlorophyll data to help constrain the parameters in a simple 1-D NPZD model. The parameters of the biogeochemical model are tuned with a genetic algorithm, so that the model is fitted to either chlorophyll data or to both chlorophyll and bb data at three sites in the Atlantic with very different characteristics. Several inherent optical property (IOP) algorithms are available for estimating bb, three of which are used here. The effect of the different bb datasets on the behaviour of the tuned model is examined to ascertain whether the uncertainty in bb is significant. The results show that the addition of bb data does not consistently alter the same model parameters at each site and in fact can lead to some parameters becoming less well constrained, implying there is still much work to be done on the mechanisms relating chlorophyll to POC and bb within the model. However, this study does indicate that including bb data has the potential to significantly effect the modelled mixed layer detritus and that uncertainties in bb due to the different IOP algorithms are not particularly significant.

  16. Doxorubicin-Loaded PEG-PCL-PEG Micelle Using Xenograft Model of Nude Mice: Effect of Multiple Administration of Micelle on the Suppression of Human Breast Cancer.

    PubMed

    Cuong, Nguyen-Van; Jiang, Jian-Lin; Li, Yu-Lun; Chen, Jim-Ray; Jwo, Shyh-Chuan; Hsieh, Ming-Fa

    2010-12-28

    The triblock copolymer is composed of two identical hydrophilic segments: Monomethoxy poly(ethylene glycol) (mPEG) and one hydrophobic segment poly(ε‑caprolactone) (PCL); which is synthesized by coupling of mPEG-PCL-OH and mPEG‑COOH in a mild condition using dicyclohexylcarbodiimide and 4-dimethylamino pyridine. The amphiphilic block copolymer can self-assemble into nanoscopic micelles to accommodate doxorubixin (DOX) in the hydrophobic core. The physicochemical properties and in vitro tests, including cytotoxicity of the micelles, have been characterized in our previous study. In this study, DOX was encapsulated into micelles with a drug loading content of 8.5%. Confocal microscopy indicated that DOX was internalized into the cytoplasm via endocystosis. A dose-finding scheme of the polymeric micelle (placebo) showed a safe dose of PEG-PCL-PEG micelles was 71.4 mg/kg in mice. Importantly, the circulation time of DOX-loaded micelles in the plasma significantly increased compared to that of free DOX in rats. A biodistribution study displayed that plasma extravasation of DOX in liver and spleen occurred in the first four hours. Lastly, the tumor growth of human breast cancer cells in nude mice was suppressed by multiple injections (5 mg/kg, three times daily on day 0, 7 and 14) of DOX-loaded micelles as compared to multiple administrations of free DOX.

  17. Incorporating Uncertainties in Satellite-Derived Chlorophyll into Model Forecasts

    DTIC Science & Technology

    2012-10-01

    2007JC004472. F. Chai, R.C. Dugdale, T.-H. Peng, F.P. Wilkerson, and R.T. Barber. 2002. "One-dimensional ecosystem model of the equatorial Pacific ...THIS PAGE Unclassified 17. LIMITATION OF ABSTRACT uu 18. NUMBER OF PAGES 12 19a. NAME OF RESPONSIBLE PERSON Richard Gould 19b. TELEPHONE

  18. A Multilayered Cell Culture Model for Transport Study in Solid Tumors: Evaluation of Tissue Penetration of Polyethyleneimine Based Cationic Micelles

    PubMed Central

    Miura, Seiji; Suzuki, Hidenori; Bae, You Han

    2014-01-01

    Limited drug distribution is partially responsible for the efficacy gap between preclinical and clinical studies of nano-sized drug carriers for cancer therapy. In this study, we examined the transport behavior of cationic micelles formed from a triblock copolymer of poly(D,L-lactide-co-glycolide)-block-branched polyethyleneimine-block-poly(D,L-lactide-co-glycolide) using a unique in vitro tumor model composed of a multilayered cell culture (MCC) and an Ussing chamber system. The Cy3-labeled cationic micelles showed remarkable Cy3 distribution in the MCC whereas charge-shielded micelles with a poly(ethylene glycol) surface accumulated on the surface of the MCC. Penetration occurred against convectional flow caused by a hydraulic pressure gradient. The study using fluorescence resonance energy transfer (FRET) showed that the cationic micelles dissociate at the interface between the culture media and the MCC or possibly inside of the first-layer cells and penetrates into the MCC as unimers. The penetration and distribution were energy-dependent and suppressed by various endocytic inhibitors. These suggest that cationic unimers mainly utilized clathrin-mediated endocytosis and macropinocytosis for cellular entry and a significant fraction were exocytosed by an unknown mechanism. PMID:25866552

  19. [Muti-model collaborative retrieval of chlorophyll a in Taihu lake based on data assimilation ].

    PubMed

    Li, Yuan; Li, Yun-mei; Lü, Heng; Zhu, Li; Wu, Chuan-qing; Du, Cheng-gong; Wang, Shuai

    2014-09-01

    Under the efforts of many scholars, large amount of remote retrieval models of water quality parameters have been developed. However, each model could only reflect the "true value" from one level because of the natural limitation of remote sensing. To get the relatively true value by combining various retrieval models, in this work, we developed a multi-model collaborative retrieval algorithm for retrieving the concentration of Chlorophyll a based on data assimilation. We measured water quality parameters and water reflectance spectra in Taihu Lake during 2006 to 2009. There were seven retrieve models established and six models were selected to participate in the multi-model collaborative retrieval algorithm. Then these selected models were combined to establish a multi-model for retrieving the concentration of Chlorophyll a. The results indicated: (1) the accuracy of multi-model retrieval algorithm was better than that of single-model retrieval method, with an optimal MAPE of only 22. 4% ; (2) with more models participating in the multi-model collaborative retrieval algorithm, the accuracy became better, the average MAPE was decreased from 25. 6% to 23. 4% , the average RMSE was decreased from 15. 082 μg.L-1 to 14. 575 μg.L-1, and the average correlation coefficient was improved from 0.91 to 0. 92; (3) the accuracy and errors of retrieval products could be effective evaluated through calculating the confidence interval, which makes possible the acquirement of spatial and temporal error distribution of Chlorophyll a concentration retrieval in Taihu Lake.

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

    PubMed

    Malek, Sorayya; Syed Ahmad, Sharifah Mumtazah; Singh, Sarinder Kaur Kashmir; Milow, Pozi; Salleh, Aishah

    2011-01-01

    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. 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 the performance

  1. Reactivity and models for anion distribution: specific iodide binding to sulfobetaine micelles.

    PubMed

    Farrukh, M Akhyar; Beber, Rosane C; Priebe, Jacks P; Lal Satnami, Manmohan; Micke, Gustavo A; Costa, Ana C O; Fiedler, Haidi D; Bunton, Clifford A; Nome, Faruk

    2008-11-18

    The reaction of I (-) with methyl naphthalene-2-sulfonate (MeONs) is accelerated by the micellized sulfobetaine surfactants N-decyl, N-dodecyl, N-tetradecyl, and N-hexadecyl- N, N-dimethylammonio-1-propanesulfonate. Concentrations of micellar-bound I (-) were determined by using ion-selective electrodes (ISE), and capillary electrophoresis. At low concentrations, I (-) incorporation fits Langmuir isotherms and is related to changes in micellar surface potentials. Rate effects of dilute KI are fitted quantitatively by a pseudophase model that describes I (-) binding in terms of a sorption isotherm, but at higher [KI], where the simple model predicts saturation, rates increase due to electrolyte invasion. This model considers transfer equilibria of both reactants between water and micelles and second-order rate constants in each pseudophase. Estimated second-order rate constants for reaction of MeONs with I (-) in the micellar pseudophase are 3.2- to 3.5-fold higher than the second-order rate constant, k 2w, in water, depending on surfactant structure and assumptions in the treatment.

  2. 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

  3. Multimeric grain-marked micelles for highly efficient photodynamic therapy and magnetic resonance imaging of tumors.

    PubMed

    Lee, Ung Yeol; Oh, Young Taik; Kim, Dongin; Lee, Eun Seong

    2014-08-25

    Multimeric grain-marked micelles consisting of an inner core micelle (for Fe3O4 encapsulation) and outer multi-grain micelles (for chlorin e6 (Ce6, a model drug) encapsulation) were fabricated using a micelle-to-micelle conjugation method. Grain micelles (mono-thiol functionalized micelles) were chemically linked to the surface of the core micelle (multi-maleimide functionalized micelle). These micelles enable discrete compartments for Ce6 and iron oxide (Fe3O4) that enable a significantly increased in vivo photodynamic tumor inhibition while preserving high contrast magnetic resonance (MR) imaging of the tumor in vivo.

  4. Complexation of AB+, AB+C, ACB+, and A(B+-stat-C) block copolymer micelles with poly(styrene sulfonate) as models for tunable gene delivery vectors

    NASA Astrophysics Data System (ADS)

    Laaser, Jennifer; Jiang, Yaming; Lohmann, Elise; Reineke, Theresa; Lodge, Timothy

    We investigate the complexation of poly(styrene sulfonate) with micelles with mixed cationic/hydrophilic coronas as models for tunable gene delivery vectors. The micelles are self-assembled from AB+, AB+C, ACB+, and A(B+-stat-C) block polymer architectures, where the hydrophobic A blocks (poly(styrene)) form the micelle cores, and the cationic B blocks (poly(dimethylamino ethyl methacrylate)) and hydrophilic, nonionic C blocks (poly(poly(ethylene glycol) methyl ether methacrylate)) form the coronas. We find that hydrophilic units do not change the colloidal stability of the complexes, and complexes based on all four micelle architectures form broad, multimodal size distributions. While complexes based on the AB+, AB+C, and ACB+polymer architectures are kinetically trapped at low ionic strength, however, those based on the A(B+-stat-C) architecture rapidly rearrange into single-micelle complexes when the linear polyanion is in excess. This suggests that the randomly-placed hydrophilic units break up the ion pairing between the cationic and anionic chains and promote formation of over-charged complexes. Design of the micelle architecture may thus provide a powerful way control the structure and stability of micelle-polyelectrolyte complexes for gene delivery applications.

  5. 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.

  6. Modelling satellite-level solar-induced chlorophyll fluorescence and its comparison with OCO-2 observations

    NASA Astrophysics Data System (ADS)

    Pradhan, Rohit; Gohel, Ankit

    2016-04-01

    Solar Induced chlorophyll Fluorescence (SIF) is a direct measure of photosynthesis rate as it is emitted by the photosynthetic system. This paper reports a method to model SIF over India by assimilating spatial inputs (LAI, Chlorophyll content etc.) into FluorMOD leaf and canopy model. Modelled SIF was then compared to Orbiting Carbon Observatory (OCO-2) SIF observations from September 2014 to August 2015. Modelled SIF at 757 nm averaged over the country varied between 0.18 to 0.33 W m-2 sr-1 μm-1 whereas SIF at 771 nm varied between 0.10 to 0.19 W m-2 sr-1 μm-1. OCO-2 observed SIF at 757 nm averaged over the country ranged from 0.18 to 0.42 Wm-2sr-1μm-1. Fairly good agreement (r=0.77, p<0.01 at 757nm; r=0.71, p<0.05 at 771 nm) was observed between modelled and observed SIF except for summer months of April and May. This paper presents a new approach to upscale a leaf and canopy level model to estimate SIF over entire country.

  7. Assessing trends and uncertainties in satellite-era ocean chlorophyll using space-time modeling

    NASA Astrophysics Data System (ADS)

    Hammond, Matthew L.; Beaulieu, Claudie; Sahu, Sujit K.; Henson, Stephanie A.

    2017-07-01

    The presence, magnitude, and even direction of long-term trends in phytoplankton abundance over the past few decades are still debated in the literature, primarily due to differences in the data sets and methodologies used. Recent work has suggested that the satellite chlorophyll record is not yet long enough to distinguish climate change trends from natural variability, despite the high density of coverage in both space and time. Previous work has typically focused on using linear models to determine the presence of trends, where each grid cell is considered independently from its neighbors. However, trends can be more thoroughly evaluated using a spatially resolved approach. Here a Bayesian hierarchical spatiotemporal model is fitted to quantify trends in ocean chlorophyll from September 1997 to December 2013. The approach used in this study explicitly accounts for the dependence between neighboring grid cells, which allows us to estimate trend by "borrowing strength" from the spatial correlation. By way of comparison, a model without spatial correlation is also fitted. This results in a notable loss of accuracy in model fit. Additionally, we find an order of magnitude smaller global trend, and larger uncertainty, when using the spatiotemporal model: -0.023 ± 0.12% yr-1 as opposed to -0.38 ± 0.045% yr-1 when the spatial correlation is not taken into account. The improvement in accuracy of trend estimates and the more complete account of their uncertainty emphasize the solution that space-time modeling offers for studying global long-term change.

  8. Modeling the relationship between extractable chlorophyll and SPAD-502 readings for endangered plant species research

    Treesearch

    Tracy S. Hawkins; Emile S. Gardiner; Greg S. Comer

    2009-01-01

    Handheld chlorophyll meters have proven to be useful tools for rapid, nondestructive assessment of chlorophyll and nutrient status in various agricultural and arborescent plant species. We proposed that a SPAD-502 chlorophyll meter would provide valuable information when monitoring life cycle changes and intraspecific variation in...

  9. A model considering light reabsorption processes to correct in vivo chlorophyll fluorescence spectra in apples.

    PubMed

    Ramos, María E; Lagorio, María G

    2006-05-01

    Chlorophyll-a contained in the peel of Granny Smith apples emits fluorescence upon excitation with blue light. The observed emission, collected by an external detector and corrected by its spectral response, is still distorted by light reabsorption processes taking place in the fruit skin and differs appreciably from the true spectral distribution of fluorescence emerging from chlorophyll molecules in the biological tissue. Reabsorption processes particularly affect the ratio of fluorescence intensities at 680 nm and at 730 nm. A model to obtain the correct spectral distribution of the emission, from the experimental fluorescence recorded at a fluorometer detector and corrected for the detector spectral sensitivity, is developed in the present work. Measurements of the whole fruit reflectance, the peel transmittance and the flesh reflectance allow the calculation of the reabsorption-corrected spectra. The model is validated by comparing the corrected emission spectra with that obtained for a thin layer of apple-peel-chloroplasts, where no reabsorption takes place. It is recommended to correct distortions in emission spectra of intact fruits due to light reabsorption effects whenever a correlation between the physiological state of the fruit and its fluorescence spectra is investigated.

  10. Application of Genetic Algorithm in the Modeling of Leaf Chlorophyll Level Based on Vis/Nir Reflection Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yang, Haiqing; Yang, Haiqing; He, Yong

    In order to detect leaf chlorophyll level nondestructively and instantly, VIS/NIR reflection spectroscopy technique was examined. In the test, 70 leaf samples were collected for model calibration and another 50 for model verification. Each leaf sample was optically measured by USB4000, a modular spectrometer. By the observation of spectral curves, the spectral range between 650nm and 750nm was found significant for mathematic modeling of leaf chlorophyll level. SPAD-502 meter was used for chemometrical measurement of leaf chlorophyll value. In the test, it was found necessary to put leaf thickness into consideration. The procedure of shaping the prediction model is as follows: First, leaf chlorophyll level prediction equation was created with uncertain parameters. Second, a genetic algorithm was programmed by Visual Basic 6.0 for parameter optimization. As the result of the calculation, the optimal spectral range was narrowed within 683.24nm and 733.91nm. Compared with the R2=0.2309 for calibration set and R2=0.5675 for on the spectral modeling is significant: the R2 of calibration set and verification set has been improved as high as 0.8658 and 0.9161 respectively. The test showed that it is practical to use VIS/NIR reflection spectrometer for the quantitative determination of leaf chlorophyll level.

  11. 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.

  12. Modeling SST and chlorophyll patterns in a coupled estuary-coastal system of Portugal: The Tagus case study

    NASA Astrophysics Data System (ADS)

    Vaz, N.; Mateus, M.; Plecha, S.; Sousa, M. C.; Leitão, P. C.; Neves, R.; Dias, J. M.

    2015-07-01

    This work studies the influence of the Tagus estuary, Portugal, on the near coastal system using a model application to describe the main physical and biogeochemical processes in the Region of Freshwater Influence (ROFI). It was used as nested modeling approach, downscaling the solution for the general circulation from a larger domain model (the Portuguese coast), to the local Tagus estuary domain. The model is evaluated during a very dynamic and biologic productive period of the year, corresponding to the winter and early summer (January-May 2007). Also during this period, there is a strong freshwater inflow into the Tagus estuary, which in turn modulates the estuarine outflow to the Tagus ROFI. The results focus on water temperature and chlorophyll and a skill assessment was made, given the lack of data required to perform a thorough validation. Simulation results reveal an adequate reproduction of the vertical thermal structure and chlorophyll concentrations. While a fairly reasonable agreement is seen for water temperature, showing no significant thermal stratification at the study area (average surface-to-bottom difference ranging from 1.3 °C to 1.6 °C), chlorophyll vertical profiles show some differences between the model results and the measurements. Maximum model bias for surface temperature is 1.4 °C and ranges from 1 to 2 mg m- 3 for chlorophyll, revealing an underestimation of the predicted chlorophyll and surface temperature for the area in the vicinity of the Tagus mouth. The general trends of surface chlorophyll and surface water temperature are satisfactorily reproduced by the model.

  13. Seasonal controls of canopy chlorophyll content on forest carbon uptake: Implications for GPP modeling

    NASA Astrophysics Data System (ADS)

    Croft, H.; Chen, J. M.; Froelich, N. J.; Chen, B.; Staebler, R. M.

    2015-08-01

    Forested ecosystems represent an important part of the global carbon cycle, with accurate estimates of gross primary productivity (GPP) crucial for understanding ecosystem response to environmental controls and improving global carbon models. This research investigated the relationships between leaf area index (LAI) and leaf chlorophyll content (ChlLeaf) with forest carbon uptake. Ground measurements of LAI and ChlLeaf were taken approximately every 9 days across the 2013 growing season from day of year (DOY) 130 to 290 at Borden Forest, Ontario. These biophysical measurements were supported by on-site eddy covariance flux measurements. Differences in the temporal development of LAI and ChlLeaf were considerable, with LAI reaching maximum values within approximately 10 days of bud burst at DOY 141. In contrast, ChlLeaf accumulation only reached maximum values at DOY 182. This divergence has important implications for GPP models which use LAI to represent the fraction of light absorbed by a canopy (fraction of absorbed photosynthetic active radiation (fAPAR)). Daily GPP values showed the strongest relationship with canopy chlorophyll content (ChlCanopy; R2 = 0.69, p < 0.001), with the LAI and GPP relationship displaying nonlinearity at the start and end of the growing season (R2 = 0.55, p < 0.001). Modeled GPP derived from LAI × PAR and ChlCanopy × PAR was tested against measured GPP, giving R2 = 0.63, p < 0.001 and R2 = 0.82, p < 0.001, respectively. This work demonstrates the importance of considering canopy pigment status in deciduous forests, with models that use fAPARLAI rather than fAPARChl neglecting to account for the importance of leaf photosynthetic potential.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. Joint leaf chlorophyll and leaf area index retrieval using a regularized canopy reflectance model inversion system

    NASA Astrophysics Data System (ADS)

    Houborg, R.; McCabe, M. F.; Gitelson, A. A.

    2013-12-01

    Leaf area index (LAI) and leaf chlorophyll (Chl) represent key biophysical and biochemical controls on water, energy and carbon exchange processes in the terrestrial biosphere. In combination LAI and Chl provide critical information on vegetation density and phenology, the vitality of vegetation and photosynthetic functioning, and joint satellite-based retrievals can be used to inform land surface models and reduce uncertainties of model predicted ecosystem fluxes in space and time. Simultaneous retrieval of LAI and Chl from space observations is however extremely challenging as the interference of atmospheric effects, canopy characteristics and background reflectance may confound the detection of relatively subtle differences in canopy reflectance resulting from changes in Chl. Regularization strategies are therefore required to increase robustness and accuracy of retrieved properties and more reliably separate soil, leaf and canopy variables. Here we describe recent refinements to the REGularized canopy reFLECtance model (REGFLEC) retrieval system, which includes enhanced regularization techniques for exploiting ancillary LAI and temporal information derived from multiple satellite scenes over a given growing season. REGFLEC is applied to Landsat time-series data and retrieval results evaluated against in-situ LAI and Chl collected over maize and soybean sites in central Nebraska over a 5-year period (2001-2005). While REGFLEC may provide useful information on the density and vitality of vegetation, the results reflect the challenges associated with accurately extracting the relatively small leaf-level chlorophyll signal from the total satellite signal when using a few standard broad bands available operationally (i.e. blue, green, red and near-infrared) as input to a homogeneous canopy reflectance model. A noteworthy and novel aspect of the REGFLEC approach is the fact that no site-specific data were used to calibrate the model that may be run in a completely

  20. DART: Recent Advances in Remote Sensing Data Modeling With Atmosphere, Polarization, and Chlorophyll Fluorescence

    NASA Technical Reports Server (NTRS)

    Gastellu-Etchegorry, Jean-Phil; Lauret, Nicolas; Yin, Tiangang; Landier, Lucas; Kallel, Abdelaziz; Malenovsky, Zbynek; Bitar, Ahmad Al; Aval, Josselin; Benhmida, Sahar; Qi, Jianbo; hide

    2017-01-01

    To better understand the life-essential cycles and processes of our planet and to further develop remote sensing (RS) technology, there is an increasing need for models that simulate the radiative budget (RB) and RS acquisitions of urban and natural landscapes using physical approaches and considering the three-dimensional (3-D) architecture of Earth surfaces. Discrete anisotropic radiative transfer (DART) is one of the most comprehensive physically based 3-D models of Earth-atmosphere radiative transfer, covering the spectral domain from ultraviolet to thermal infrared wavelengths. It simulates the optical 3-DRB and optical signals of proximal, aerial, and satellite imaging spectrometers and laser scanners, for any urban and/or natural landscapes and for any experimental and instrumental configurations. It is freely available for research and teaching activities. In this paper, we briefly introduce DART theory and present recent advances in simulated sensors (LiDAR and cameras with finite field of view) and modeling mechanisms (atmosphere, specular reflectance with polarization and chlorophyll fluorescence). A case study demonstrating a novel application of DART to investigate urban landscapes is also presented.

  1. 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

  2. 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.

  3. New Caledonia surface lagoon chlorophyll modeling as coastal reef area health indicator

    NASA Astrophysics Data System (ADS)

    Fuchs, R.; Pinazo, C.; Douillet, P.; Dupouy, C.; Faure, V.; Mangin, A.

    2010-10-01

    The major part of the New Caledonia (NC) lagoon was classified as UNESCO Natural Site of Humanity Patrimony. Indeed, 22 175 km2 of tropical coral lagoon area exhibit high biodiversity. The NC lagoon is semi enclosed and connected to the Coral Sea through a barrier reef segmented by narrow passes. The environment is oligotrophic, due to important flush during trade winds events, and bathymetry is highly variable. In order to predict eutrophication events, we used an extension of a 3D coupled physical-biogeochemical model recently developed on NC south western lagoon. The model is based on the Nitrogen and Carbon cycles, relating the variable stoechiometry of the elements in each biological compartment. The ecological model was developed to include an explicit description of the microbial loop. The resulting coupled model, forced by tide, wind, light, temperature and freshwater inputs, was used to calculate phytoplankton biomass, bacterial production, dissolved organic matter concentrations and nutrient recycling. Here we present results issued from the 3D coupled model ECO3M_LAGOON (biogeochemical, LOPB-IRD) and MARS3D (regional physical model, IFREMER-IRD) describing spatial and temporal interactions between water motion and biology, on larger domain including reef barrier and water exchanges through ocean-lagoon interface. To validate physical processes in the lagoon we used in situ data collected during field cruise (ValHyBio 2008, La Niña episode). Surface chlorophyll concentrations are compared with water color data from ValHyBio cruise and satellite data (MODIS/MERIS) corrected from bathymetry effects.

  4. 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

  5. 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.

  6. Convection enhanced delivery of panobinostat (LBH589)-loaded pluronic nano-micelles prolongs survival in the F98 rat glioma model

    PubMed Central

    Singleton, WG; Collins, AM; Bienemann, AS; Killick-Cole, CL; Haynes, HR; Asby, DJ; Butts, CP; Wyatt, MJ; Barua, NU; Gill, SS

    2017-01-01

    Background The pan-histone deacetylase inhibitor panobinostat is a potential therapy for malignant glioma, but it is water insoluble and does not cross the blood–brain barrier when administered systemically. In this article, we describe the in vitro and in vivo efficacy of a novel water-soluble nano-micellar formulation of panobinostat designed for administration by convection enhanced delivery (CED). Materials and methods The in vitro efficacy of panobinostat-loaded nano-micelles against rat F98, human U87-MG and M059K glioma cells and against patient-derived glioma stem cells was measured using a cell viability assay. Nano-micelle distribution in rat brain was analyzed following acute CED using rhodamine-labeled nano-micelles, and toxicity was assayed using immunofluorescent microscopy and synaptophysin enzyme-linked immunosorbent assay. We compared the survival of the bioluminescent syngenic F98/Fischer344 rat glioblastoma model treated by acute CED of panobinostat-loaded nano-micelles with that of untreated and vehicle-only-treated controls. Results Nano-micellar panobinostat is cytotoxic to rat and human glioma cells in vitro in a dose-dependent manner following short-time exposure to drug. Fluorescent rhodamine-labelled nano-micelles distribute with a volume of infusion/volume of distribution (Vi/Vd) ratio of four and five respectively after administration by CED. Administration was not associated with any toxicity when compared to controls. CED of panobinostat-loaded nano-micelles was associated with significantly improved survival when compared to controls (n=8 per group; log-rank test, P<0.001). One hundred percent of treated animals survived the 60-day experimental period and had tumour response on post-mortem histological examination. Conclusion CED of nano-micellar panobinostat represents a potential novel therapeutic option for malignant glioma and warrants translation into the clinic. PMID:28260886

  7. Convection enhanced delivery of panobinostat (LBH589)-loaded pluronic nano-micelles prolongs survival in the F98 rat glioma model.

    PubMed

    Singleton, W G; Collins, A M; Bienemann, A S; Killick-Cole, C L; Haynes, H R; Asby, D J; Butts, C P; Wyatt, M J; Barua, N U; Gill, S S

    2017-01-01

    The pan-histone deacetylase inhibitor panobinostat is a potential therapy for malignant glioma, but it is water insoluble and does not cross the blood-brain barrier when administered systemically. In this article, we describe the in vitro and in vivo efficacy of a novel water-soluble nano-micellar formulation of panobinostat designed for administration by convection enhanced delivery (CED). The in vitro efficacy of panobinostat-loaded nano-micelles against rat F98, human U87-MG and M059K glioma cells and against patient-derived glioma stem cells was measured using a cell viability assay. Nano-micelle distribution in rat brain was analyzed following acute CED using rhodamine-labeled nano-micelles, and toxicity was assayed using immunofluorescent microscopy and synaptophysin enzyme-linked immunosorbent assay. We compared the survival of the bioluminescent syngenic F98/Fischer344 rat glioblastoma model treated by acute CED of panobinostat-loaded nano-micelles with that of untreated and vehicle-only-treated controls. Nano-micellar panobinostat is cytotoxic to rat and human glioma cells in vitro in a dose-dependent manner following short-time exposure to drug. Fluorescent rhodamine-labelled nano-micelles distribute with a volume of infusion/volume of distribution (Vi/Vd) ratio of four and five respectively after administration by CED. Administration was not associated with any toxicity when compared to controls. CED of panobinostat-loaded nano-micelles was associated with significantly improved survival when compared to controls (n=8 per group; log-rank test, P<0.001). One hundred percent of treated animals survived the 60-day experimental period and had tumour response on post-mortem histological examination. CED of nano-micellar panobinostat represents a potential novel therapeutic option for malignant glioma and warrants translation into the clinic.

  8. Estimation of chlorophyll content of Phragmites australis based on PROSPECT and DART models in the saltmarsh of Yangtze Estuary

    NASA Astrophysics Data System (ADS)

    Zeng, Yuyan; Shi, Runhe; Liu, Pudong; Zhang, Chao; Wang, Jiapeng; Liu, Chaoshun; Chen, Maosi

    2016-09-01

    Phragmites australis is a native dominant specie in the Yangtze Estuary, which plays a key role in the structure and function of wetland ecosystem. One key question is how to estimate the Chlorophyll content quickly and effectively at large scales, which could be used to reflect the growth condition and calculate the vegetation productivity. The aim of this work was to estimate Chlorophyll content of P. australis based on the PROSPECT and DART (Discrete Anisotropic Radiative Transfer) model. A total of 6 widely used Vegetation indices (VIs) were chosen (i.e., Normalized Difference Vegetation Index (NDVI), Structure Insensitive Pigment Index (SIPI), Colouration Index (COI), Simple Ratio Index (SR), Cater Index (CAI), and Red-edge Position Linear Interpolation (REP_Li)) and calculated, and then the relationship between VIs and Cab were analyzed. Results showed that COI and SIPI were sensitive to the leaf chlorophyll content as the chlorophyll content changes at the leaf scale. Meanwhile, no obvious saturation phenomenon was observed for these two indices compared to other indices.

  9. [Algorithm for estimating chlorophyll-a concentration in case II water body based on bio-optical model].

    PubMed

    Yang, Wei; Chen, Jin; Mausushita, Bunki

    2009-01-01

    In the present study, a novel retrieval method for estimating chlorophyll-a concentration in case II waters based on bio-optical model was proposed and was tested with the data measured in the laboratory. A series of reflectance spectra, with which the concentration of each sample constituent (for example chlorophyll-a, NPSS etc.) was obtained from accurate experiments, were used to calculate the absorption and backscattering coefficients of the constituents of the case II waters. Then non-negative least square method was applied to calculate the concentration of chlorophyll-a and non-phytoplankton suspended sediments (NPSS). Green algae was firstly collected from the Kasumigaura lake in Japan and then cultured in the laboratory. The reflectance spectra of waters with different amounts of phytoplankton and NPSS were measured in the dark room using FieldSpec Pro VNIR (Analytical Spectral Devises Inc. , Boulder, CO, USA). In order to validate whether this method can be applied in multispectral data (for example Landsat TM), the spectra measured in the laboratory were resampled with Landsat TM bands 1, 2, 3 and 4. Different combinations of TM bands were compared to derive the most appropriate wavelength for detecting chlorophyll-a in case II water for green algae. The results indicated that the combination of TM bands 2, 3 and 4 achieved much better accuracy than other combinations, and the estimated concentration of chlorophyll-a was significantly more accurate than empirical methods. It is expected that this method can be directly applied to the real remotely sensed image because it is based on bio-optical model.

  10. Modeling chlorophyll-a and dissolved oxygen concentration in tropical floodplain lakes (Paraná River, Brazil).

    PubMed

    Rocha, R R A; Thomaz, S M; Carvalho, P; Gomes, L C

    2009-06-01

    The need for prediction is widely recognized in limnology. In this study, data from 25 lakes of the Upper Paraná River floodplain were used to build models to predict chlorophyll-a and dissolved oxygen concentrations. Akaike's information criterion (AIC) was used as a criterion for model selection. Models were validated with independent data obtained in the same lakes in 2001. Predictor variables that significantly explained chlorophyll-a concentration were pH, electrical conductivity, total seston (positive correlation) and nitrate (negative correlation). This model explained 52% of chlorophyll variability. Variables that significantly explained dissolved oxygen concentration were pH, lake area and nitrate (all positive correlations); water temperature and electrical conductivity were negatively correlated with oxygen. This model explained 54% of oxygen variability. Validation with independent data showed that both models had the potential to predict algal biomass and dissolved oxygen concentration in these lakes. These findings suggest that multiple regression models are valuable and practical tools for understanding the dynamics of ecosystems and that predictive limnology may still be considered a powerful approach in aquatic ecology.

  11. 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.

  12. Modeling micelle-templated mesoporous material SBA-15: atomistic model and gas adsorption studies.

    PubMed

    Bhattacharya, Supriyo; Coasne, Benoit; Hung, Francisco R; Gubbins, Keith E

    2009-05-19

    We report the development of a realistic molecular model for mesoporous silica SBA-15, which includes both the large cylindrical mesopores and the smaller micropores in the pore walls. The methodology for modeling the SBA-15 structure involves molecular and mesoscale simulations combined with geometrical interpolation techniques. First, a mesoscale model is prepared by mimicking the synthesis process using lattice Monte Carlo simulations. The main physical features of this mesoscale pore model are then carved out of an atomistic silica block; both the mesopores and the micropores are incorporated from the mimetic simulations. The calculated pore size distribution, surface area, and simulated TEM images of the model structure are in good agreement with those obtained from experimental samples of SBA-15. We then investigate the adsorption of argon in this structure using Grand Canonical Monte Carlo (GCMC) simulations. The adsorption results for our SBA-15 model are compared with those for a similar model that does not include the micropores; we also compare with results obtained in a regular cylindrical pore. The simulated adsorption isotherm for the SBA-15 model shows semiquantitative agreement with the experimental isotherm for a SBA-15 sample having a similar pore size. We observe that the presence of the micropores leads to increased adsorption at low pressure compared to the case of a model without micropores in the pore walls. At higher pressures, for all models, the filling proceeds via the monolayer-multilayer adsorption on the mesopore surface followed by capillary condensation, which is mainly controlled by the mesopore diameter and is not influenced by the presence of the micropores.

  13. "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

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

    NASA Astrophysics Data System (ADS)

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

    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

  15. 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

  16. Stereochemical determination of chlorophyll-d molecule from Acaryochloris marina and its modification to a self-aggregative chlorophyll as a model of green photosynthetic bacterial antennae.

    PubMed

    Mizoguchi, Tadashi; Shoji, Ayumi; Kunieda, Michio; Miyashita, Hideaki; Tsuchiya, Tohru; Mimuro, Mamoru; Tamiaki, Hitoshi

    2006-03-01

    Acaryochloris marina is a unique photosynthetic prokaryote containing chlorophyll(Chl)-d as a major photoactive pigment (over 95%). The molecular structure of Chl-d is proposed as the 3-formyl analog of Chl-a. However, the stereochemistry of Chl-d at the 13(2)-, 17- and 18-positions has not yet been established unambiguously. In the first part of this paper, we describe the determination of their stereochemistries to be 13(2)-(R)-, 17-(S)- and 18-(S)-configurations by using 1H-1H NOE correlations in 1H-NMR and circular dichroism spectra as well as chemical modification of Chl-a to produce stereochemically defined Chl derivatives. In the second part of the paper, we report a facile synthesis of a self-aggregative Chl by modifying isolated Chl-d. Since Chl-d was characterized by its reactive 3-formyl group, the formyl group was reduced with t-BuNH2BH3 to afford the desirable Chl, 3-deformyl-3-hydroxymethyl-pyrochlorophyll-d (3(1)-OH-pyroChl-d). The synthetic 3(1)-OH-pyroChl-d molecules spontaneously self-organized to form well-ordered aggregates in a non-polar organic solvent. The self-aggregates are a good model of major light-harvesting antenna systems of green photosynthetic bacteria, chlorosomes, in terms of the following three findings. (1) Both the red-shifted electronic absorption band above 750 nm and its induced reverse S-shape CD signal around 750 nm were observed in 0.5% (v/v) THF-cyclohexane. (2) The stretching mode of the 13-carbonyl group was downshifted by about 35 cm(-1) from the wavenumber of its free carbonyl. (3) The self-aggregates were quite stable on titration of pyridine to the suspension, in comparison with those of natural chlorosomal bacteriochlorophyll-d possessing the 3-(1-hydroxyethyl) group.

  17. Oceanic primary production: 1. Adaptation of a spectral light-photosynthesis model in view of application to satellite chlorophyll observations

    NASA Astrophysics Data System (ADS)

    Antoine, David; Morel, André

    1996-03-01

    A global equation, designed to estimate the column-integrated oceanic primary production realized by a given phytoplankton biomass under various environmental conditions, is used to develop a practical method to assess the primary production (P) from the chlorophyll concentration as provided by satellite imagery. This basic equation combines three terms, namely the photosynthetically available radiation impinging at the sea surface, PAR(0+), the column-integrated chlorophyll content, tot, and the cross section for photosynthesis per unit of chlorophyll, Ψ*. Global monitoring of incident irradiance and near-surface algal biomass is now achievable from space, and thus the next step toward a monitoring of oceanic primary production would be to dispose in parallel of a "climatological field" of the Ψ* quantity. Actually, Ψ* depends on the two other terms of the equation (PAR(0+) and tot,), and, in addition, on temperature (also detectable from satellite). Therefore such a "climatological field" is variable and complex and it can be conveniently replaced by lookup tables allowing easy interpolation. The entries are date, latitude, cloudiness, temperature, and remotely sensed chlorophyll concentration. This upper layer concentration is extended downward owing to previous results of a statistical analysis of the chlorophyll vertical distribution; accordingly, two parallel tables, corresponding to well-mixed or stratified upper layers with uniform or non uniform chlorophyll vertical profiles, respectively, are constructed. These tables are produced by systematically using a previously published spectral light-photosynthesis model. For such extensive computations, the model necessarily relies on, and is operated with, a standard set of ecological and physiological parameters. Therefore sensitivity analyses have been carried out in view of assessing the impact on Ψ*, and on the resulting production of deviations in these parameters or parameterizations, vis

  18. Polymer micelle assisted transport and delivery of model hydrophilic components inside a biological lipid vesicle: a coarse-grain simulation study.

    PubMed

    Srinivas, Goundla; Mohan, Ram V; Kelkar, Ajit D

    2013-10-10

    Understanding drug transportation and delivery mechanism from a molecular viewpoint is essential to find better treatment pathways. Despite the fact that many significant drugs such as anticancer doxorubicin and mitoxantrone are predominantly hydrophilic, an efficient methodology to deliver hydrophilic drug components is not well established. Here we explore this problem by studying "patchy" polymeric micelle assisted hydrophilic component transportation across a lipid membrane and delivery inside a biological lipid vesicle. Using the MARTINI force field as the basis, we study the interaction of polymeric micelle with DPPC lipid vesicles in detail. In order to facilitate hydrophilic drug transportation study, a primitive CG model for hydrophilic drug component is used. Extensive simulations carried out over hundreds of nanoseconds demonstrate successful encapsulation, transportation of hydrophilic components by patchy polymeric micelles. Results show the polymeric micelle releases a significant portion of hydrophilic contents inside the lipid vesicle. The present simulation study also reveals a possible mechanism for efficient hydrophilic component transportation and delivery. Insights from this study could potentially help the experimental community to design better delivery vehicles, especially for hydrophilic drug molecules.

  19. Nanomedicine based curcumin and doxorubicin combination treatment of glioblastoma with scFv-targeted micelles: In vitro evaluation on 2D and 3D tumor models.

    PubMed

    Sarisozen, Can; Dhokai, Shekhar; Tsikudo, Edcar G; Luther, Ed; Rachman, Ilya M; Torchilin, Vladimir P

    2016-11-01

    NF-κB is strongly associated with poor prognosis of different cancer types and an important factor responsible for the malignant phenotype of glioblastoma. Overcoming chemotherapy-induced resistance caused by activation of PI3K/Akt and NF-κB pathways is crucial for successful glioblastoma therapy. We developed an all-in-one nanomedicine formulation for co-delivery of a chemotherapeutic agent (topoisomerase II inhibitor, doxorubicin) and a multidrug resistance modulator (NF-κB inhibitor, curcumin) for treatment of glioblastoma due to their synergism. Both agents were incorporated into PEG-PE-based polymeric micelles. The glucose transporter-1 (GLUT1) is overexpressed in many tumors including glioblastoma. The micellar system was decorated with GLUT1 antibody single chain fragment variable (scFv) as the ligand to promote blood brain barrier transport and glioblastoma targeting. The combination treatment was synergistic (combination index, CI of 0.73) against U87MG glioblastoma cells. This synergism was improved by micellar encapsulation (CI: 0.63) and further so with GLUT1 targeting (CI: 0.46). Compared to non-targeted micelles, GLUT1 scFv surface modification increased the association of micelles (>20%, P<0.01) and the nuclear localization of doxorubicin (∼3-fold) in U87MGcells, which also translated into enhanced cytotoxicity. The increased caspase 3/7 activation by targeted micelles indicates successful apoptosis enhancement by combinatory treatment. Moreover, GLUT1 targeted micelles resulted in deeper penetration into the 3D spheroid model. The increased efficacy of combination nanoformulations on the spheroids compared to a single agent loaded, or to non-targeted formulations, reinforces the rationale for selection of this combination and successful utilization of GLUT1 scFv as a targeting agent for glioblastoma treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Polar Solvents Trigger Formation of Reverse Micelles.

    PubMed

    Khoshnood, Atefeh; Firoozabadi, Abbas

    2015-06-09

    We use molecular dynamics simulations and molecular thermodynamics to investigate the formation of reverse micelles in a system of surfactants and nonpolar solvents. Since the early observation of reverse micelles, the question has been whether the existence of polar solvent molecules such as water is the driving force for the formation of reverse micelles in nonpolar solvents. In this work, we use a simple coarse-grained model of surfactants and solvents to show that a small number of polar solvent molecules triggers the formation of large permanent aggregates. In the absence of polar molecules, both the thermodynamic model and molecular simulations show that small aggregates are more populated in the solution and larger ones are less frequent as the system evolves over time. The size and shape of reverse micelles depend on the size of the polar core: the shape is spherical for a large core and ellipsoidal for a smaller one. Using the coarse-grained model, we also investigate the effect of temperature and surfactant tail length. Our results reveal that the number of surfactant molecules in the micelle decreases as the temperature increases, but the average diameter does not change because the size of the polar core remains invariant. A reverse micelle with small polar core attracts fewer surfactants when the tail is long. The uptake of solvent particles by a micelle of longer surfactant tail is less than shorter ones when the polar solvent particles are initially distributed randomly.

  1. Determination and importance of temperature dependence of retention coefficient (RPHPLC) in QSAR model of nitrazepams' partition coefficient in bile acid micelles.

    PubMed

    Posa, Mihalj; Pilipović, Ana; Lalić, Mladena; Popović, Jovan

    2011-02-15

    Linear dependence between temperature (t) and retention coefficient (k, reversed phase HPLC) of bile acids is obtained. Parameters (a, intercept and b, slope) of the linear function k=f(t) highly correlate with bile acids' structures. Investigated bile acids form linear congeneric groups on a principal component (calculated from k=f(t)) score plot that are in accordance with conformations of the hydroxyl and oxo groups in a bile acid steroid skeleton. Partition coefficient (K(p)) of nitrazepam in bile acids' micelles is investigated. Nitrazepam molecules incorporated in micelles show modified bioavailability (depo effect, higher permeability, etc.). Using multiple linear regression method QSAR models of nitrazepams' partition coefficient, K(p) are derived on the temperatures of 25°C and 37°C. For deriving linear regression models on both temperatures experimentally obtained lipophilicity parameters are included (PC1 from data k=f(t)) and in silico descriptors of the shape of a molecule while on the higher temperature molecular polarisation is introduced. This indicates the fact that the incorporation mechanism of nitrazepam in BA micelles changes on the higher temperatures. QSAR models are derived using partial least squares method as well. Experimental parameters k=f(t) are shown to be significant predictive variables. Both QSAR models are validated using cross validation and internal validation method. PLS models have slightly higher predictive capability than MLR models.

  2. 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.

  3. Curcumin Micelles Remodel Tumor Microenvironment and Enhance Vaccine Activity in an Advanced Melanoma Model

    PubMed Central

    Lu, Yao; Miao, Lei; Wang, Yuhua; Xu, Zhenghong; Zhao, Yi; Shen, Youqing; Xiang, Guangya; Huang, Leaf

    2016-01-01

    Previously, we have reported a lipid-based Trp2 peptide vaccine for immunotherapy against melanoma. The suppressive immune microenvironment in the tumor is a major hurdle for an effective vaccine therapy. We hypothesized that curcumin (CUR) would remodel the tumor microenvironment to improve the vaccine activity. Curcumin–polyethylene glycol conjugate (CUR–PEG), an amphiphilic CUR-based micelle, was delivered intravenously (i.v.) to the tumor. Indeed, in the B16F10 tumor–bearing mice, the combination of CUR–PEG and vaccine treatment resulted in a synergistic antitumor effect (P < 0.001) compared to individual treatments. In the immune organs, the combination therapy significantly boosted in vivo cytotoxic T-lymphocyte response (41.0 ± 5.0% specific killing) and interferon-γ (IFN-γ) production (sevenfold increase). In the tumor microenvironment, the combination therapy led to significantly downregulated levels of immunosuppressive factors, such as decreased numbers of myeloid-derived suppressor cells and regulatory T cells (Treg) cells and declined levels of interleukin-6 and chemokine ligand 2—in correlation with increased levels of proinflammatory cytokines, including tumor necrosis factor-α and IFN-γ as well as an elevation in the CD8+ T-cell population. The results indicated a distinct M2 to M1 phenotype switch in the treated tumors. Combining CUR–PEG and vaccine also dramatically downregulated the signal transducer and activator of transcription 3 pathway (76% reduction). Thus, we conclude that CUR–PEG is an effective agent to improve immunotherapy for advanced melanoma. PMID:26334519

  4. 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.

  5. 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.

  6. Modeling the seasonal and interannual variability (2001-2010) of chlorophyll-a in the Iberian margin

    NASA Astrophysics Data System (ADS)

    Reboreda, Rosa; Cordeiro, Nuno G. F.; Nolasco, Rita; Castro, Carmen G.; Álvarez-Salgado, Xosé A.; Queiroga, Henrique; Dubert, Jesus

    2014-10-01

    A modeling study of the seasonal and interannual variability of chlorophyll-a has been carried out for the period 2001-2010 along the Iberian shelf and adjacent ocean. A high resolution regional configuration of the three-dimensional Regional Ocean Modeling System (ROMS) has been used, coupled to a N2PZD2-type biogeochemical model. Chlorophyll-a concentration ([Chl]) model outputs were compared to regional objective analysis of remotely sensed [Chl] data for the same period. The spatio-temporal variability of modeled and satellite derived [Chl] was analyzed applying an individual Empirical Orthogonal Function (EOF) analysis to monthly time series. Three main modes of sea surface [Chl] variability explained more than 90% of modeled variability and more than 85% of remotely sensed variability. The first EOF accounted for the spring phytoplankton bloom (March-April). The second EOF was related to the spring-summer coastal upwelling season (April-September). The third EOF showed a recurrent [Chl] minimum in winter coinciding with the maximum vertical mixing (February) for the northern part of the region. The influence of the hydrographic conditions on [Chl] variability was explored through a cross-correlation analysis of the three EOFs and an assortment of physical descriptors given by the model: namely the mixing/stratification cycles and the occurrence of coastal upwelling.

  7. 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.

  8. Influence of succinylation on the conformation of yak casein micelles.

    PubMed

    Yang, Min; Cui, Na; Fang, Yan; Shi, Ying; Yang, Jitao; Wang, Jiangyu

    2015-07-15

    Succinylation modifies the physicochemical characteristics and improves the functional properties of proteins. This study assessed the effects of succinylation on the conformation of yak casein micelles with seven degree of modification. The results revealed that succinylation contributed to the dissociation of casein micelles. With the increase of succinylated degree, soluble nitrogen and minerals content increased, while casein micelle size and polydispersity index of micelles decreased. Succinylation affected the spatial conformation of yak casein micelles: turn decreased, ß-sheet and α-helix increased, and irregular structure were non-significantly affected. The intrinsic and ANS fluorescence intensity decreased and the maximum emission wavelength shifted red with increasing succinylation. Based on the results, the structure of yak casein micelles was characteristic of the sub-micelle model.

  9. Casein Micelle Dispersions under Osmotic Stress

    PubMed Central

    Bouchoux, Antoine; Cayemitte, Pierre-Emerson; Jardin, Julien; Gésan-Guiziou, Geneviève; Cabane, Bernard

    2009-01-01

    Abstract Casein micelles dispersions have been concentrated and equilibrated at different osmotic pressures using equilibrium dialysis. This technique measured an equation of state of the dispersions over a wide range of pressures and concentrations and at different ionic strengths. Three regimes were found. i), A dilute regime in which the osmotic pressure is proportional to the casein concentration. In this regime, the casein micelles are well separated and rarely interact, whereas the osmotic pressure is dominated by the contribution from small residual peptides that are dissolved in the aqueous phase. ii), A transition range that starts when the casein micelles begin to interact through their κ-casein brushes and ends when the micelles are forced to get into contact with each other. At the end of this regime, the dispersions behave as coherent solids that do not fully redisperse when osmotic stress is released. iii), A concentrated regime in which compression removes water from within the micelles, and increases the fraction of micelles that are irreversibly linked to each other. In this regime the osmotic pressure profile is a power law of the residual free volume. It is well described by a simple model that considers the micelle to be made of dense regions separated by a continuous phase. The amount of water in the dense regions matches the usual hydration of proteins. PMID:19167314

  10. Anti-tumor activity of folate targeted biodegradable polymer-paclitaxel conjugate micelles on EMT-6 breast cancer model.

    PubMed

    Wu, Di; Zheng, Yonghui; Hu, Xiuli; Fan, Zhimin; Jing, Xiabin

    2015-08-01

    Paclitaxel (PTX) is a first line chemotherapy drug for breast cancer. There have been few studies reported concerning the therapeutic efficacy of paclitaxel-conjugated polymeric micelles in breast cancer in vivo. Two kinds of PTX conjugate micelles, one of which (M(PTX)) contained 25 wt.% of PTX and the other (M(FA/PTX)) contained 22.5 wt.% of PTX and 1.4 wt.% of folate (FA), were prepared for cell apoptosis and anti-tumor activity evaluation on EMT-6 mice breast cancer models in comparison with 0.9 wt.% saline (control) and equivalent PTX. Cell apoptosis was analyzed by flow cytometry. Breast tumors were examined histologically with H&E staining and immunohistochemically by examining Bax and Bcl-2 expression. The survival status of tumor-bearing mice with different treatments was also examined. On day 5 of the drug administration, the average tumor masses were 0.49, 0.33, 0.22, and 0.18 g for the control, PTX, M(PTX) and M(FA/PTX) groups, respectively. The inhibition rates of tumor growth calculated for the three drug groups were 32.6%, 51.6% and 62.3%, respectively. The percentage of cell apoptosis based on flow cytometry was 1.0%, 36.6%, 55.9% and 66.1%, respectively, which showed statistically significant differences (p<0.05) between three drug groups and the control group. Bcl-2 expression of PTX and M(FA/PTX) groups was lower than control group (p<0.05). Bax expression of drug groups was higher than control group (p<0.05). At an equivalent paclitaxel dose of 26.7 mg/kg, the average survival time was 33 days, 31 days, 34 days and 42 days, respectively (p<0.05). The M(FA/PTX) have better anti-tumor activity and are promising in treatment of human breast cancers. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Using leaf chlorophyll to parameterize light-use-efficiency within a thermal-based carbon, water and energy exchange model

    USDA-ARS?s Scientific Manuscript database

    Chlorophylls absorb photosynthetically active radiation and thus function as vital pigments for photosynthesis, which makes leaf chlorophyll content (Cab) useful for monitoring vegetation productivity and an important indicator of the overall plant physiological condition. This study investigates th...

  12. Improved Retrieval of Chlorophyll and Carotenoids Contents at the Canopy Scale Using Hyperspectral CAO Data and PROSAIL Model

    NASA Astrophysics Data System (ADS)

    Feret, J.; Asner, G. P.; Jacquemoud, S.; François, C.

    2008-12-01

    The sustainability of biodiversity requires frequent and spatially detailed assessment of species number and distribution, among other information. Remote sensing is one of the most promising way to achieve this environmental management due to reasonable cost and accuracy. However, the use of airborne and spaceborne data remains challenging: sensors must combine the appropriate spatial and spectral resolutions to retrieve pertinent environmental parameters that will permit identification of specific properties of organisms present in an ecosystem. Leaf area index (LAI), canopy structure and pigment composition of vegetation are valuable information to study ecosystem dynamics and distinguish between many species. Chlorophyll and carotenoid pigments are of particular interest because they are involved in photosynthesis, but until now, remote sensing was unable to assess these pigments separately and accurately. Some advances have been made recently with the separation of these pigments in PROSPECT-5, a radiative transfer model that simulates leaf spectral reflectance and transmittance at 1 nm resolution. PROSAIL, the joint vegetation canopy reflectance model associating PROSPECT-5 with 4SAIL, the latest version of the SAIL model, was first run in direct mode to design vegetation indices sensitive to leaf pigments. Subsequently, we retrieved chlorophyll and carotenoid contents using PROSAIL with CAO (Carnegie Airborne Observatory) data acquired in Hawaii. The CAO, an imaging spectrometer coupled with a 3-D laser scanner, has already demonstrated its ability to manage biodiversity in various ecosystems like tropical rainforests or savannah. Its performance make it particularly adapted to assess vegetation structure, biochemistry, and then fluxes. The first results obtained when processing CAO images with PROSAIL are promising in terms of chlorophyll and carotenoid retrieval at the canopy scale. They show that our approach can provide original information on vegetation

  13. 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 ).

  14. Indicators: Chlorophyll a

    EPA Pesticide Factsheets

    Chlorophyll allows plants (including algae) to photosynthesize, i.e., use sunlight to convert simple molecules into organic compounds. Chlorophyll a is the predominant type of chlorophyll found in green plants and algae.

  15. 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.

  16. 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

  17. Modeling regional cropland GPP by empirically incorporating sun-induced chlorophyll fluorescence into a coupled photosynthesis-fluorescence model

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Guanter, L.; Van der Tol, C.; Joiner, J.; Berry, J. A.

    2015-12-01

    Global sun-induced chlorophyll fluorescence (SIF) retrievals are currently available from several satellites. SIF is intrinsically linked to photosynthesis, so the new data sets allow to link remotely-sensed vegetation parameters and the actual photosynthetic activity of plants. In this study, we used space measurements of SIF together with the Soil-Canopy Observation of Photosynthesis and Energy (SCOPE) balance model in order to simulate regional photosynthetic uptake of croplands in the US corn belt. SCOPE couples fluorescence and photosynthesis at leaf and canopy levels. To do this, we first retrieved a key parameter of photosynthesis model, the maximum rate of carboxylation (Vcmax), from field measurements of CO2 and water flux during 2007-2012 at some crop eddy covariance flux sites in the Midwestern US. Then we empirically calibrated Vcmax with apparent fluorescence yield which is SIF divided by PAR. SIF retrievals are from the European GOME-2 instrument onboard the MetOp-A platform. The resulting apparent fluorescence yield shows a stronger relationship with Vcmax during the growing season than widely-used vegetation index, EVI and NDVI. New seasonal and regional Vcmax maps were derived based on the calibration model for the cropland of the corn belt. The uncertainties of Vcmax were also estimated through Gaussian error propagation. With the newly derived Vcmax maps, we modeled regional cropland GPP during the growing season for the Midwestern USA, with meteorological data from MERRA reanalysis data and LAI from MODIS product (MCD15A2). The results show the improvement in the seasonal and spatial patterns of cropland productivity in comparisons with both flux tower and agricultural inventory data.

  18. 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.

  19. Study of Brij Micelles Using Dynamic Light Scattering Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wilson, Karen; Lekan, Mike; Streletzky, Kiril

    2007-10-01

    We studied properties of Brij-35 surfactant micelles using Dynamic Light Scattering (DLS) and Optical Probe Diffusion method. Aqueous solutions of Brij-35 with concentrations ranging from 2 to 100g/L were prepared, both with and without polystyrene latex probes of diameters 24, 50, 282, and 792nm. Solutions were studied at four temperatures of 10, 25, 40, and 70^oC with DLS to obtain micelle and probe diffusion coefficients (Dm, Dp). Using both diffusion coefficients we deduced micelle radius (am), micelle water content (δ), and number of surfactant molecules per micelle (N) using two different models. First, we used the hard sphere model of micelle/probe interaction to analyze the data by two methods. In this model, am is obtained from Stokes-Einstein equation using the intercept of Dm(c). The first method of the model uses the slope of Dm(c) and the size of probes to determine N and δ. The second method of the model uses the linear least-squares fit of Dp(c) for different probe sizes to determine N and δ. Both methods reveal that with solution temperature increase, am increases by 10%, N increases and δ decreases by a factor of 2. Two hard sphere methods yield somewhat different trends, but overall agree with published data on Brij micelles. The second model treats micelles as core-shell particles and uses Dm(c) to determine not only am, δ, and N, but also micelle corona radius ac.

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    PubMed

    Kröner, Dominik; Götze, Jan Philipp

    2012-04-02

    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. Copyright © 2011 Elsevier B.V. All rights reserved.

  2. 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

  3. 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

  4. In vivo imaging of a new indocyanine green micelle formulation in an animal model of laser-induced choroidal neovascularization.

    PubMed

    Meyer, Johanna; Cunea, Alexander; Sonntag-Bensch, Dagmar; Welker, Pia; Licha, Kai; Holz, Frank G; Schmitz-Valckenberg, Steffen

    2014-09-04

    We investigated a novel formulation of indocyanine green (ICG/HS 15) in an animal model of laser-induced choroidal neovascularization (CNV). The ICG was formulated with the nonionic solubilizer and emulsifying agent Kolliphor HS 15 to create ICG/HS 15 to improve the chemical stability and fluorescence efficacy. In vivo imaging was performed in rats that had undergone laser photocoagulation. Retinal uptake and fluorescence intensity of ICG and ICG/HS 15 were compared following intravenous injection of 3 dosages (0.05, 0.1, and 0.15 mg/kg body weight) at 7, 14, and 21 days following laser treatment. Postmortem analysis included histology with frozen sections and flat mounts. Immediately following injection of ICG or ICG/HS 15, a strong fluorescence was visible in the retinal vasculature and at the site of laser lesions. Pixel intensity was higher for ICG/HS 15 compared to conventional ICG at 8 minutes after injection for all different injection days and dosages. Over time, a continuous decrease of the fluorescent signal was observed for up to 60 minutes to baseline level. Flow cytometry data showed an increased uptake of micellar dye of macrophages and endothelial cells. Histology revealed an accumulation of the micellar dye within the laser lesion. Micelle formulated ICG can be visualized in the retinal vasculature and laser-induced CNV in vivo and ex vivo. Micellar ICG/HS 15 showed in vivo stronger signal intensity when compared to ICG for all tested dosages. Following further investigations, ICG/HS 15 may be evaluated in patients with retinal and choroidal diseases for more refined diagnosis. Copyright 2014 The Association for Research in Vision and Ophthalmology, Inc.

  5. Chlorophyll Fluorescence and Dynamic Xanthophyll Reflectance as Methods to Estimate Photosynthesis with Remote Sensors - A Modelling Approach

    NASA Astrophysics Data System (ADS)

    Vilfan, N.; Van der Tol, C.; Verhoef, W.

    2016-12-01

    Chlorophyll fluorescence (ChlF) has been proven valuable in studying the dynamics of photosynthesis: together with the photochemical reflectance index (PRI), which reflects the changes in reflectance around 535 nm due to the xanthophyll cycle effect, it offers a powerful way to non-destructively quantify plant photosynthetic and dissipation activity from leaf to potentially global scale. We present an extended simulation model, Fluspect, for the transfer of light within the leaf as a function of its pigment contents and structure. Output of the model are reflectance and transmittance spectra of the leaf as well as ChlF spectra. From ChlF spectra, fluorescence quantum efficiency parameters (η) of photosystems I and II can be retrieved. Moreover, we extended and parameterized Fluspect by including a physically based description of the dynamic xanthophyll reflectance (XR). We introduced a new, retrievable parameter, V2Z, for the status of the XR. Finally, we combined the model Fluspect with a simple enzyme kinetics model of photosynthesis. In this study, we explore the combined model by using relations among photochemical quenching (PQ), non-photochemical quenching (NPQ), V2Z and η. We explore these relationships by using multiple available datasets, where measurements were by different combinations of the following methods: (1) hyperspectral leaf reflectance in visible to NIR region together with ChlF spectra, (2) gas exchange, and (3) Pulse Amplitude Modulated (PAM) fluorescence. The aim of the study is to explore the relationships between the two fundamentally different components, namely the transfer of light within the leaf and the enzyme kinetics of photosynthesis. Moreover, it is now possible to simulate dynamic xanthophyll reflectance and chlorophyll fluorescence quenching simultaneously, which is relevant for the remote sensing of photosynthesis.

  6. An Integrative Observing and Modeling Approach for the Physiological Understanding of Sun-Induced Chlorophyll Fluorescence in Japan

    NASA Astrophysics Data System (ADS)

    Kobayashi, H.; Kato, T.; Saitoh, Y.; Noda, H.; Kikosaka, K.; Ichii, K.; Nasahara, K. N.

    2016-12-01

    Satellite-derived sun-induced chlorophyll fluorescence (SIF) is expected to provides a pathway to link leaf level photosynthesis to global GPP. Existing studies have stressed how well the satellite-derived SIF is correlated with the eddy covariance and/or modeled GPPs. There are some challenges in SIF interpretation because the satellite-derived SIF is a mixture of fluorescence emission from sunlit and shaded leaves and multiple scatterings of fluorescence within plant canopies. In this presentation, we show observation and modeling results around Japan and discuss how the integrative observing and modeling approach potentially overcomes the gaps in-between satellite SIF and photosynthesis reaction within leaves. We have analyzed ground-based SIF monitoring systems "Phenological Eye Network (PEN)". PEN covers several eddy flux sites in Japan and is equipped with spectroradiometer (MS-700) since 2003 (at an earliest site). The computed seasonal SIF variations in the different ecosystems show environmental dependency of SIF and GPP. Another ground-based system we are now developing is the vegetation lidar system named LIFS (Laser-Induced Fluorescence Spectrum), which can offer eco-physiological information of plants. LIFS is consisted of a pulsed UV (355 nm) laser, a telescope, a spectrometer/filter, and a gated image-intensified CCD detector. This system has been using to remotely monitor tree growth status, chlorophyll contents in leaves and so on. The physical and physiological theories are necessary for understanding the observed SIF under various environmental conditions. We have been developing leaf to plant canopy scale photosynthesis and SIF models as precise as possible. The developed model has been used to understand how the leaf-level SIF emission can be related to the canopy scale SIF, which enables to investigate the top of canopy SIF observed from ground-based and satellite-derived SIF measurements.

  7. Using infrared spectroscopy of a nitrile labeled phenylalanine and tryptophan fluorescence to probe the α-MSH peptide's side-chain interactions with a micelle model membrane

    NASA Astrophysics Data System (ADS)

    Gonzalez, Javier D.; Levonyak, Nicholas S.; Schneider, Sydney C.; Smith, Matthew J.; Cremeens, Matthew E.

    2014-01-01

    The interactions of α-MSH (Ac-SYSMEHFRWGKPV-NH2) side-chains were biophysically characterized with a micelle model membrane and in model intracellular bacterial conditions using infrared (IR) spectroscopy of a nitrile labeled α-MSH analogue, circular dichroism (CD), and tryptophan fluorescence. Local changes detected by the tryptophan and a nitrile-labeled phenylalanine using fluorescence and infrared spectroscopies, respectively, suggest that the Trp9 side-chain in the conserved core (HisPheArgTrp) of α-MSH is buried in an SDS micellar environment, while Phe(CN)7 does not appear to be buried.

  8. [Three wavelengths factor model of chlorophyll concentrations inversion based on different spectral dominating factors for inland lake].

    PubMed

    Shi, Kun; Li, Yun-Mei; Liu, Zhong-Hua; Xu, Yi-Fan; Xu, Xini; Wu, Chuan-Qing; Zhu, Li

    2010-12-01

    A hierarchical cluster analysis is applied to the data set of R(rs) spectra. Combing the inherent optical and measured water color characteristics, we determine factors of the variability for each class of R(rs) spectra. The R(rs) measured from Lake Taihu, Chaohu, Dianchi and Three Gorges Reservoir can be divided into three spectrally distinct classes: class 1, class 2 and class 3. Class 1 is associated with water optical property dominated by total suspended matter and phytoplankton. Class 2 is associated with water optical property dominated by phytoplankton. And Class 3 is associated with water optical property dominated by total suspended matter. The three wavelengths factor Chlorophyll a concentration inversion models were developed according to different class water optical characteristics, which means relative error and RMSE are 23.8% and 8.5 mg/m3, and have higher accuracy than the model developed without classification.

  9. Data assimilation of physical and chlorophyll a observations in the California Current System using two biogeochemical models

    NASA Astrophysics Data System (ADS)

    Mattern, Jann Paul; Song, Hajoon; Edwards, Christopher A.; Moore, Andrew M.; Fiechter, Jerome

    2017-01-01

    Biogeochemical numerical models coupled to physical ocean circulation models are commonly combined with data assimilation in order to improve the models' state or parameter estimates. Yet much still needs to be learned about important aspects of biogeochemical data assimilation, such as the effect of model complexity and the importance of more realistic model formulations on assimilation results. In this study, 4D-Var-based state estimation is applied to two biogeochemical ocean models: a simple NPZD model with 4 biogeochemical variables (including 1 phytoplankton, 1 zooplankton) and the more complex NEMURO model, containing 11 biogeochemical variables (including 2 phytoplankton, 3 zooplankton). Both models are coupled to a 3-dimensional physical ocean circulation model of the U.S. west coast based on the Regional Ocean Modelling System (ROMS). Chlorophyll satellite observations and physical observations are assimilated into the model, yielding substantial improvements in state estimates for the observed physical and biogeochemical variables in both model formulations. In comparison to the simpler NPZD model, NEMURO shows a better overall fit to the observations. The assimilation also results in small improvements for simulated nitrate concentrations in both models and no apparent degradation of the output for other unobserved variables. The forecasting skill of the biogeochemical models is strongly linked to model performance without data assimilation: for both models, the improved fit obtained through assimilation degrades at similar relative rates, but drops to different absolute levels. Despite the better performance of NEMURO in our experiments, the choice of model and desired level of complexity should depend on the model application and the data available for assimilation.

  10. An assessment of phytoplankton primary productivity in the Arctic Ocean from satellite ocean color/in situ chlorophyll-a based models.

    PubMed

    Lee, Younjoo J; Matrai, Patricia A; Friedrichs, Marjorie A M; Saba, Vincent S; Antoine, David; Ardyna, Mathieu; Asanuma, Ichio; Babin, Marcel; Bélanger, Simon; Benoît-Gagné, Maxime; Devred, Emmanuel; Fernández-Méndez, Mar; Gentili, Bernard; Hirawake, Toru; Kang, Sung-Ho; Kameda, Takahiko; Katlein, Christian; Lee, Sang H; Lee, Zhongping; Mélin, Frédéric; Scardi, Michele; Smyth, Tim J; Tang, Shilin; Turpie, Kevin R; Waters, Kirk J; Westberry, Toby K

    2015-09-01

    We investigated 32 net primary productivity (NPP) models by assessing skills to reproduce integrated NPP in the Arctic Ocean. The models were provided with two sources each of surface chlorophyll-a concentration (chlorophyll), photosynthetically available radiation (PAR), sea surface temperature (SST), and mixed-layer depth (MLD). The models were most sensitive to uncertainties in surface chlorophyll, generally performing better with in situ chlorophyll than with satellite-derived values. They were much less sensitive to uncertainties in PAR, SST, and MLD, possibly due to relatively narrow ranges of input data and/or relatively little difference between input data sources. Regardless of type or complexity, most of the models were not able to fully reproduce the variability of in situ NPP, whereas some of them exhibited almost no bias (i.e., reproduced the mean of in situ NPP). The models performed relatively well in low-productivity seasons as well as in sea ice-covered/deep-water regions. Depth-resolved models correlated more with in situ NPP than other model types, but had a greater tendency to overestimate mean NPP whereas absorption-based models exhibited the lowest bias associated with weaker correlation. The models performed better when a subsurface chlorophyll-a maximum (SCM) was absent. As a group, the models overestimated mean NPP, however this was partly offset by some models underestimating NPP when a SCM was present. Our study suggests that NPP models need to be carefully tuned for the Arctic Ocean because most of the models performing relatively well were those that used Arctic-relevant parameters.

  11. Photo-responsive polymeric micelles.

    PubMed

    Huang, Yu; Dong, Ruijiao; Zhu, Xinyuan; Yan, Deyue

    2014-09-07

    Photo-responsive polymeric micelles have received increasing attention in both academic and industrial fields due to their efficient photo-sensitive nature and unique nanostructure. In view of the photo-reaction mechanism, photo-responsive polymeric micelles can be divided into five major types: (1) photoisomerization polymeric micelles, (2) photo-induced rearrangement polymeric micelles, (3) photocleavage polymeric micelles, (4) photo-induced crosslinkable polymeric micelles, and (5) photo-induced energy conversion polymeric micelles. This review highlights the recent advances of photo-responsive polymeric micelles, including the design, synthesis and applications in various biomedical fields. Especially, the influence of different photo-reaction mechanisms on the morphology, structure and properties of the polymeric micelles is emphasized. Finally, the possible future directions and perspectives in this emerging area are briefly discussed.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Substrate-binding model of the chlorophyll biosynthetic magnesium chelatase BchH subunit.

    PubMed

    Sirijovski, Nickolche; Lundqvist, Joakim; Rosenbäck, Matilda; Elmlund, Hans; Al-Karadaghi, Salam; Willows, Robert D; Hansson, Mats

    2008-04-25

    Photosynthetic organisms require chlorophyll and bacteriochlorophyll to harness light energy and to transform water and carbon dioxide into carbohydrates and oxygen. The biosynthesis of these pigments is initiated by magnesium chelatase, an enzyme composed of BchI, BchD, and BchH proteins, which catalyzes the insertion of Mg(2+) into protoporphyrin IX (Proto) to produce Mg-protoporphyrin IX. BchI and BchD form an ATP-dependent AAA(+) complex that transiently interacts with the Proto-binding BchH subunit, at which point Mg(2+) is chelated. In this study, controlled proteolysis, electron microscopy of negatively stained specimens, and single-particle three-dimensional reconstruction have been used to probe the structure and substrate-binding mechanism of the BchH subunit to a resolution of 25A(.) The apo structure contains three major lobe-shaped domains connected at a single point with additional densities at the tip of two lobes termed the "thumb" and "finger." With the independent reconstruction of a substrate-bound BchH complex (BchH.Proto), we observed a distinct conformational change in the thumb and finger subdomains. Prolonged proteolysis of native apo-BchH produced a stable C-terminal fragment of 45 kDa, and Proto was shown to protect the full-length polypeptide from degradation. Fitting of a truncated BchH polypeptide reconstruction identified the N- and C-terminal domains. Our results show that the N- and C-terminal domains play crucial roles in the substrate-binding mechanism.

  19. 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

  20. Performance of a two-leaf light use efficiency model for mapping gross primary productivity against remotely sensed sun-induced chlorophyll fluorescence data.

    PubMed

    Zan, Mei; Zhou, Yanlian; Ju, Weimin; Zhang, Yongguang; Zhang, Leiming; Liu, Yibo

    2017-09-21

    Estimating terrestrial gross primary production is an important task when studying the carbon cycle. In this study, the ability of a two-leaf light use efficiency model to simulate regional gross primary production in China was validated using satellite Global Ozone Monitoring Instrument - 2 sun-induced chlorophyll fluorescence data. The two-leaf light use efficiency model was used to estimate daily gross primary production in China's terrestrial ecosystems with 500-m resolution for the period from 2007 to 2014. Gross primary production simulated with the two-leaf light use efficiency model was resampled to a spatial resolution of 0.5° and then compared with sun-induced chlorophyll fluorescence. During the study period, sun-induced chlorophyll fluorescence and gross primary production simulated by the two-leaf light use efficiency model exhibited similar spatial and temporal patterns in China. The correlation coefficient between sun-induced chlorophyll fluorescence and monthly gross primary production simulated by the two-leaf light use efficiency model was significant (p<0.05, n=96) in 88.9% of vegetated areas in China (average value 0.78) and varied among vegetation types. The interannual variations in monthly sun-induced chlorophyll fluorescence and gross primary production simulated by the two-leaf light use efficiency model were similar in spring and autumn in most vegetated regions, but dissimilar in winter and summer. The spatial variability of sun-induced chlorophyll fluorescence and gross primary production simulated by the two-leaf light use efficiency model was similar in spring, summer, and autumn. The proportion of spatial variations of sun-induced chlorophyll fluorescence and annual gross primary production simulated by the two-leaf light use efficiency model explained by ranged from 0.76 (2011) to 0.80 (2013) during the study period. Overall, the two-leaf light use efficiency model was capable of capturing spatial and temporal variations in gross

  1. 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.

  2. FluorWPS: A Monte Carlo ray-tracing model to compute sun-induced chlorophyll fluorescence of three-dimensional canopy

    USDA-ARS?s Scientific Manuscript database

    A model to simulate radiative transfer (RT) of sun-induced chlorophyll fluorescence (SIF) of three-dimensional (3-D) canopy, FluorWPS, was proposed and evaluated. The inclusion of fluorescence excitation was implemented with the ‘weight reduction’ and ‘photon spread’ concepts based on Monte Carlo ra...

  3. Assimilation of seasonal chlorophyll and nutrient data into an adjoint three-dimensional ocean carbon cycle model: Sensitivity analysis and ecosystem parameter optimization

    NASA Astrophysics Data System (ADS)

    Tjiputra, Jerry F.; Polzin, Dierk; Winguth, Arne M. E.

    2007-03-01

    An adjoint method is applied to a three-dimensional global ocean biogeochemical cycle model to optimize the ecosystem parameters on the basis of SeaWiFS surface chlorophyll observation. We showed with identical twin experiments that the model simulated chlorophyll concentration is sensitive to perturbation of phytoplankton and zooplankton exudation, herbivore egestion as fecal pellets, zooplankton grazing, and the assimilation efficiency parameters. The assimilation of SeaWiFS chlorophyll data significantly improved the prediction of chlorophyll concentration, especially in the high-latitude regions. Experiments that considered regional variations of parameters yielded a high seasonal variance of ecosystem parameters in the high latitudes, but a low variance in the tropical regions. These experiments indicate that the adjoint model is, despite the many uncertainties, generally capable to optimize sensitive parameters and carbon fluxes in the euphotic zone. The best fit regional parameters predict a global net primary production of 36 Pg C yr-1, which lies within the range suggested by Antoine et al. (1996). Additional constraints of nutrient data from the World Ocean Atlas showed further reduction in the model-data misfit and that assimilation with extensive data sets is necessary.

  4. 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

  5. A model of chlorophyll a fluorescence induction kinetics with explicit description of structural constraints of individual photosystem II units.

    PubMed

    Xin, Chang-Peng; Yang, Jin; Zhu, Xin-Guang

    2013-11-01

    Chlorophyll a fluorescence induction (FI) kinetics, in the microseconds to the second range, reflects the overall performance of the photosynthetic apparatus. In this paper, we have developed a novel FI model, using a rule-based kinetic Monte Carlo method, which incorporates not only structural and kinetic information on PSII, but also a simplified photosystem I. This model has allowed us to successfully simulate the FI under normal or different treatment conditions, i.e., with different levels of measuring light, under 3-(3',4'-dichlorophenyl)-1,1-dimethylurea treatment, under 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone treatment, and under methyl viologen treatment. Further, using this model, we have systematically studied the mechanistic basis and factors influencing the FI kinetics. The results of our simulations suggest that (1) the J step is caused by the two-electron gate at the Q B site; (2) the I step is caused by the rate limitation of the plastoquinol re-oxidation in the plastoquinone pool. This new model provides a framework for exploring impacts of modifying not only kinetic but also structural parameters on the FI kinetics.

  6. Water soluble chlorophyll binding protein of higher plants: a most suitable model system for basic analyses of pigment-pigment and pigment-protein interactions in chlorophyll protein complexes.

    PubMed

    Renger, G; Pieper, J; Theiss, C; Trostmann, I; Paulsen, H; Renger, T; Eichler, H J; Schmitt, F-J

    2011-08-15

    This short review paper describes spectroscopic studies on pigment-pigment and pigment-protein interactions of chlorophyll (Chl) a and b bound to the recombinant protein of class IIa water soluble chlorophyll protein (WSCP) from cauliflower. Two Chls form a strongly excitonically coupled open sandwich dimer within the tetrameric protein matrix. In marked contrast to the mode of excitonic coupling of Chl and bacterio-Chl molecules in light harvesting complexes and reaction centers of all photosynthetic organisms, the unique structural pigment array in the Chl dimer of WSCP gives rise to an upper excitonic state with a large oscillator strength. This property opens the way for thorough investigations on exciton relaxation processes in Chl-protein complexes. Lifetime measurements of excited singlet states show that the unusual stability towards photodamage of Chls bound to WSCP, which lack any protective carotenoid molecule, originates from a high diffusion barrier to interaction of molecular dioxygen with Chl triplets. Site selective spectroscopic methods provide a wealth of information on the interactions of the Chls with the protein matrix and on the vibronic structure of the pigments. The presented data and discussions illustrate the great potential of WSCP as a model system for systematic experimental and theoretical studies on the functionalizing of Chls by the protein matrix. It opens the way for further detailed analyses and a deeper understanding of the properties of pigment protein complexes. Copyright © 2011 Elsevier GmbH. All rights reserved.

  7. Contribution of subsurface chlorophyll maxima to primary production in the coastal Beaufort Sea (Canadian Arctic): A model assessment

    NASA Astrophysics Data System (ADS)

    Martin, Johannie; Dumont, Dany; Tremblay, Jean-Éric

    2013-11-01

    Previous comprehensive investigations of the Canadian Arctic revealed that subsurface chlorophyll maxima (SCM) are widespread and long-lived structures that can contribute significantly to daily primary production in the water column. However, estimating the annual contribution of SCM to production with in situ or remote-sensing approaches is challenging in the high Arctic. For this reason and to estimate the impacts of fluctuating or changing environmental conditions on SCM, a numerical approach combining a turbulence model and an ecosystem model was implemented for the coastal Beaufort Sea. An ensemble analysis of simulations suggested that SCM contribute 65-90% of total annual primary production and that this proportion is weakly affected by ice regime, winter nitrogen (N) concentration, parameter values determining phytoplankton growth and decay or the physical forcing imposed, all varying within realistic values. Due to the persistent association between the SCM and the shallow nitracline, the pelagic ecosystem of the coastal Beaufort Sea is apparently characterized by a high ratio of new to total production, contrasting with the common assumption that oligotrophic systems are predominantly supported by recycled N and regenerated production. This study demonstrated that the use of a simple model in combination with in situ data leads to novel insights into biogeochemical processes that are otherwise very difficult to measure and track.

  8. Effects of micelles and vesicles on the oximolysis of p-nitrophenyl diphenyl phosphate: A model system for surfactant-based skin-defensive formulations against organophosphates.

    PubMed

    Gonçalves, Larissa Martins; Kobayakawa, Talita Guedes; Zanette, Dino; Chaimovich, Hernan; Cuccovia, Iolanda Midea

    2009-03-01

    The rates of oximolysis of p-nitrophenyl diphenyl phosphate (PNPDPP) by Acetophenoxime; 10-phenyl-10-hydroxyiminodecanoic acid; 4-(9-carboxynonanyl)-1-(9-carboxy-1-hydroyiminononanyl) benzene; 1-dodecyl-2-[(hydroxyimino)methyl]-pyridinium chloride (IV) and N-methylpyridinium-2-aldoxime chloride were determined in micelles of N-hexadecyl-N,N,N-trimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethylammonium propanesulfonate and dioctadecyldimethylammonium chloride (DODAC) vesicles. The effects of CTAC micelles and DODAC vesicles on the rates of oxymolysis of O,O-Diethyl O-(4-nitrophenyl) phosphate (paraoxon) by oxime IV were also determined. Analysis of micellar and vesicular effects on oximolysis of PNPDPP, using pseudophase or pseudophase with explicit consideration of ion exchange models, required the determination of the aggregate's effects on the pK(a) of oximes and on the rates of PNPDPP hydrolysis. All aggregates increased the rate of oximolysis of PNPDPP and the results were analyzed quantitatively. In particular, DODAC vesicles catalyzed the reaction and increased the rate of oximolysis of PNPDPP by IV several million fold at pH's compatible with pharmaceutical formulations. The rate increase produced by DODAC vesicles on the rate of oximolysis paraoxon by IV demonstrates the pharmaceutical potential of this system, since the substrate is used as an agricultural defensive agent and the surfactant is extensively employed in cosmetic formulations.

  9. Supramolecular structure of the casein micelle.

    PubMed

    McMahon, D J; Oommen, B S

    2008-05-01

    The supramolecular structure of colloidal casein micelles in milk was investigated by using a sample preparation protocol based on adsorption of proteins onto a poly-l-lysine and parlodion-coated copper grid, staining of proteins and calcium phosphate by uranyl oxalate, instantaneous freezing, and drying under a high vacuum. High-resolution transmission electron microscopy stereo-images were obtained showing the interior structure of casein micelles. On the basis of our interpretation of these images, an interlocked lattice model was developed in which both casein-calcium phosphate aggregates and casein polymer chains act together to maintain casein micelle integrity. The caseins form linear and branched chains (2 to 5 proteins long) interlocked by the casein-stabilized calcium phosphate nanoclusters. This model suggests that stabilization of calcium phosphate nanoclusters by phosphoserine domains of alpha(s1)-, alpha(s2)-, or beta-casein, or their combination, would orient their hydrophobic domains outward, allowing interaction and binding to other casein molecules. Other interactions between the caseins, such as calcium bridging, could also occur and further stabilize the supramolecule. The combination of having an interlocked lattice structure and multiple interactions results in an open, sponge-like colloidal supramolecule that is resistant to spatial changes and disintegration. Hydrophobic interactions between caseins surrounding a calcium phosphate nanocluster would prevent complete dissociation of casein micelles when the calcium phosphate nanoclusters are solubilized. Likewise, calcium bridging and other electrostatic interactions between caseins would prevent dissociation of the casein micelles into casein-calcium phosphate nanocluster aggregates when milk is cooled or urea is added to milk, and hydrophobic interactions are reduced. The appearance of both polymer chains and small aggregate particles during milk synthesis would also be expected based on

  10. Modeling the Footprint and Equivalent Radiance Transfer Path Length for Tower-Based Hemispherical Observations of Chlorophyll Fluorescence.

    PubMed

    Liu, Xinjie; Liu, Liangyun; Hu, Jiaochan; Du, Shanshan

    2017-05-16

    The measurement of solar-induced chlorophyll fluorescence (SIF) is a new tool for estimating gross primary production (GPP). Continuous tower-based spectral observations together with flux measurements are an efficient way of linking the SIF to the GPP. Compared to conical observations, hemispherical observations made with cosine-corrected foreoptic have a much larger field of view and can better match the footprint of the tower-based flux measurements. However, estimating the equivalent radiation transfer path length (ERTPL) for hemispherical observations is more complex than for conical observations and this is a key problem that needs to be addressed before accurate retrieval of SIF can be made. In this paper, we first modeled the footprint of hemispherical spectral measurements and found that, under convective conditions with light winds, 90% of the total radiation came from an FOV of width 72°, which in turn covered 75.68% of the source area of the flux measurements. In contrast, conical spectral observations covered only 1.93% of the flux footprint. Secondly, using theoretical considerations, we modeled the ERTPL of the hemispherical spectral observations made with cosine-corrected foreoptic and found that the ERTPL was approximately equal to twice the sensor height above the canopy. Finally, the modeled ERTPL was evaluated using a simulated dataset. The ERTPL calculated using the simulated data was about 1.89 times the sensor's height above the target surface, which was quite close to the results for the modeled ERTPL. Furthermore, the SIF retrieved from atmospherically corrected spectra using the modeled ERTPL fitted well with the reference values, giving a relative root mean square error of 18.22%. These results show that the modeled ERTPL was reasonable and that this method is applicable to tower-based hemispherical observations of SIF.

  11. Modeling the Footprint and Equivalent Radiance Transfer Path Length for Tower-Based Hemispherical Observations of Chlorophyll Fluorescence

    PubMed Central

    Liu, Xinjie; Liu, Liangyun; Hu, Jiaochan; Du, Shanshan

    2017-01-01

    The measurement of solar-induced chlorophyll fluorescence (SIF) is a new tool for estimating gross primary production (GPP). Continuous tower-based spectral observations together with flux measurements are an efficient way of linking the SIF to the GPP. Compared to conical observations, hemispherical observations made with cosine-corrected foreoptic have a much larger field of view and can better match the footprint of the tower-based flux measurements. However, estimating the equivalent radiation transfer path length (ERTPL) for hemispherical observations is more complex than for conical observations and this is a key problem that needs to be addressed before accurate retrieval of SIF can be made. In this paper, we first modeled the footprint of hemispherical spectral measurements and found that, under convective conditions with light winds, 90% of the total radiation came from an FOV of width 72°, which in turn covered 75.68% of the source area of the flux measurements. In contrast, conical spectral observations covered only 1.93% of the flux footprint. Secondly, using theoretical considerations, we modeled the ERTPL of the hemispherical spectral observations made with cosine-corrected foreoptic and found that the ERTPL was approximately equal to twice the sensor height above the canopy. Finally, the modeled ERTPL was evaluated using a simulated dataset. The ERTPL calculated using the simulated data was about 1.89 times the sensor’s height above the target surface, which was quite close to the results for the modeled ERTPL. Furthermore, the SIF retrieved from atmospherically corrected spectra using the modeled ERTPL fitted well with the reference values, giving a relative root mean square error of 18.22%. These results show that the modeled ERTPL was reasonable and that this method is applicable to tower-based hemispherical observations of SIF. PMID:28509843

  12. 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.

  13. 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

  14. Chirality-mediated polypeptide micelles for regulated drug delivery.

    PubMed

    Ding, Jianxun; Li, Chen; Zhang, Ying; Xu, Weiguo; Wang, Jincheng; Chen, Xuesi

    2015-01-01

    Two kinds of triblock poly(ethylene glycol)-polyleucine (PEG-PLeu) copolymers were synthesized through the ring-opening polymerization of L-Leu N-carboxyanhydride (NCA), or equivalent D-Leu NCA and L-Leu NCA with amino-terminated PEG as a macroinitiator. The amphiphilic copolymers spontaneously self-assembled into spherical micellar aggregations in an aqueous environment. The micelle with a racemic polypeptide core exhibited smaller critical micelle concentration and diameter compared to those with a levorotatory polypeptide core. A model anthracycline antineoplastic agent, i.e., doxorubicin (DOX), was loaded into micelles through nanoprecipitation, and the PEG-P(D,L-Leu) micelle exhibited higher drug-loading efficacy than that with a P(L-Leu) core-this difference was attributed to the flexible and compact P(L-Leu) core. Sustained in vitro DOX release from micelles with both levorotatory and racemic polypeptide cores was observed, and the DOX-loaded PEG-P(D,L-Leu) micelle exhibited a slower release rate. More interestingly, DOX-loaded micelles exhibited chirality-mediated antitumor efficacy in vitro and in vivo, which are all better than that of free DOX. Furthermore, both enhanced tumor inhibition and excellent security in vivo were confirmed by histopathological or in situ cell apoptosis analyses. Therefore, DOX-loaded PEG-PLeu micelles appear to be an interesting nanoscale polymeric formulation for promising malignancy chemotherapy.

  15. Evaluation and perturbation of micelle-solute interactions

    SciTech Connect

    Armstrong, D.W.; Stine, G.Y.

    1983-10-05

    The partitioning or binding of compounds to micelles is an important phenomena in many areas of study including membrane mimetic chemistry, catalysis, enzyme modeling, chromatography, tertiary oil recovery, spectroscopic analysis, and emulsion polymerization. The interaction of 7 compounds (i.e., naphthol green B, bromophenol blue, alizarin red S, 2-naphthol-6-sulfonic acid, ammonium thiocyanate, sodium 2-naphthalenesulfonate, and sodium nitroferricyanide) with sodium dodecyl sulfate micelles was studied using LC and TLC. All compounds showed unusual chromatographic behavior in that their retention increased when the concentration of micelles in the mobile phase increased. Relatively small changes in the micellar environment or the micelle itself can result in pronounced alteration of micelle-solute interactions. 24 references.

  16. 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.

  17. 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

  18. 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%.

  19. Enhanced antitumor effect of anti-tissue factor antibody-conjugated epirubicin-incorporating micelles in xenograft models

    PubMed Central

    Yamamoto, Yoshiyuki; Hyodo, Ichinosuke; Koga, Yoshikatsu; Tsumura, Ryo; Sato, Ryuta; Obonai, Toshihumi; Fuchigami, Hirobumi; Furuya, Fumiaki; Yasunaga, Masahiro; Harada, Mitsunori; Kato, Yasuki; Ohtsu, Atsushi; Matsumura, Yasuhiro

    2015-01-01

    For the creation of a successful antibody–drug conjugate (ADC), both scientific and clinical evidence has indicated that highly toxic anticancer agents (ACA) should be conjugated to a monoclonal antibody (mAb) to administer a reasonable amount of ADC to patients without compromising the affinity of the mAb. For ordinary ACA, the conjugation of a mAb to ACA-loaded micellar nanoparticles is clinically applicable. Tissue factor (TF) is often overexpressed in various cancer cells and tumor vascular endothelium. Accordingly, anti-TF-NC-6300, consisting of epirubicin-incorporating micelles (NC-6300) conjugated with the F(ab')2 of anti-TF mAb was developed. The in vitro and in vivo efficacy and pharmacokinetics of anti-TF-NC-6300 were compared to NC-6300 using two human pancreatic cancer cell lines, BxPC3 (high TF expression) and SUIT2 (low TF expression), and a gastric cancer cell line, 44As3 (high TF expression). The intracellular uptake of epirubicin was faster and greater in BxPC3 cells treated with anti-TF-NC-6300, compared with NC-6300. Anti-TF-NC-6300 showed a superior antitumor activity in BxPC3 and 44As3 xenografts, compared with NC-6300, while the activities of both micelles were similar in the SUIT2 xenograft. A higher tumor accumulation of anti-TF-NC-6300 compared to NC-6300 was seen, regardless of the TF expression levels. However, anti-TF-NC-6300 appeared to be localized to the tumor cells with high TF expression. These results indicated that the enhanced antitumor effect of anti-TF-NC6300 may be independent of the tumor accumulation but may depend on the selective intratumor localization and the preferential internalization of anti-TF-NC-6300 into high TF tumor cells. PMID:25711681

  20. Enhanced antitumor effect of anti-tissue factor antibody-conjugated epirubicin-incorporating micelles in xenograft models.

    PubMed

    Yamamoto, Yoshiyuki; Hyodo, Ichinosuke; Koga, Yoshikatsu; Tsumura, Ryo; Sato, Ryuta; Obonai, Toshihumi; Fuchigami, Hirobumi; Furuya, Fumiaki; Yasunaga, Masahiro; Harada, Mitsunori; Kato, Yasuki; Ohtsu, Atsushi; Matsumura, Yasuhiro

    2015-05-01

    For the creation of a successful antibody-drug conjugate (ADC), both scientific and clinical evidence has indicated that highly toxic anticancer agents (ACA) should be conjugated to a monoclonal antibody (mAb) to administer a reasonable amount of ADC to patients without compromising the affinity of the mAb. For ordinary ACA, the conjugation of a mAb to ACA-loaded micellar nanoparticles is clinically applicable. Tissue factor (TF) is often overexpressed in various cancer cells and tumor vascular endothelium. Accordingly, anti-TF-NC-6300, consisting of epirubicin-incorporating micelles (NC-6300) conjugated with the F(ab')2 of anti-TF mAb was developed. The in vitro and in vivo efficacy and pharmacokinetics of anti-TF-NC-6300 were compared to NC-6300 using two human pancreatic cancer cell lines, BxPC3 (high TF expression) and SUIT2 (low TF expression), and a gastric cancer cell line, 44As3 (high TF expression). The intracellular uptake of epirubicin was faster and greater in BxPC3 cells treated with anti-TF-NC-6300, compared with NC-6300. Anti-TF-NC-6300 showed a superior antitumor activity in BxPC3 and 44As3 xenografts, compared with NC-6300, while the activities of both micelles were similar in the SUIT2 xenograft. A higher tumor accumulation of anti-TF-NC-6300 compared to NC-6300 was seen, regardless of the TF expression levels. However, anti-TF-NC-6300 appeared to be localized to the tumor cells with high TF expression. These results indicated that the enhanced antitumor effect of anti-TF-NC6300 may be independent of the tumor accumulation but may depend on the selective intratumor localization and the preferential internalization of anti-TF-NC-6300 into high TF tumor cells. © 2015 The Authors. Cancer Science published by Wiley Publishing Asia Pty Ltd on behalf of Japanese Cancer Association.

  1. Micelle Bound Structure and Model Membrane Interaction Studies of the Peptide Hylin a1 from the Arboreal South American Frog Hypsiboas albopunctatus.

    PubMed

    Alves, Eliane S F; Junior, Edson C; Cilli, Eduardo M; Castro, Mariana S; Fontes, Wagner; de Magalhães, Mariana T Q; Lião, Luciano M; de Oliveira, Aline L

    2015-01-01

    Antimicrobial peptides (AMPs) appear as a promising therapeutic candidate against multiresistant pathogens, because they are able to kill microorganisms and have low toxicity of resistance cells. Hylin a1 (Hy-a1, IFGAILPLALGALKNLIK-NH2) is a peptide extracted from the skin secretion of the frog Hypsiboas albopunctatus, which displays antimicrobial and hemolytic activities. We report here structural studies of Hy-a1 using different techniques such as fluorescence, CD and NMR. Our data showed that Hy-a1 acquires a well defined amphipathic α-helix when interacting with a membrane-like environment. Furthermore, Hy-a1 presented different affinity when compared to membranes of zwitterionic or anionic lipid composition. Finally, we proposed a molecular interaction model of this peptide with micelles.

  2. Precipitate-Coacervate Transformation in Polyelectrolyte-Mixed Micelle Systems.

    PubMed

    Comert, Fatih; Nguyen, Duy; Rushanan, Marguerite; Milas, Peker; Xu, Amy Y; Dubin, Paul L

    2017-05-04

    The polycation/anionic-nonionic mixed micelle, poly(diallyldimethylammonium chloride)-sodium dodecyl sulfate/Triton X-100 (PDADMAC-SDS/TX100), is a model polyelectrolyte-colloid system in that the micellar mole fraction of SDS (Y) controls the micelle surface charge density, thus modulating the polyelectrolyte-colloid interaction. The exquisite temperature dependence of this system provides an important additional variable, controlling both liquid-liquid (L-L) and liquid-solid (L-S) phase separation, both of which are driven by the entropy of small ion release. In order to elucidate these transitions, we applied high-precision turbidimetry (±0.1 %), isothermal titration calorimetry, and epifluorescence microscopy which demonstrates preservation of micelle structure under all conditions. The L-S region at large Y including precipitation displays a remarkable linear, inverse Y-dependence of the L-S transition temperature Ts. In sharp contrast, the critical temperature for L-L coacervation Tφ, shows nearly symmetrical effects of positive and negative deviations in Y from the point of soluble complex neutrality, which is controlled in solution by the micelle charge and the number of micelles bound per polymer chain n (Zcomplex = Zpolymer + nZmicelle). In solid-like states, n no longer signifies the number of micelles bound per polymer chain, since the proximity of micelles inverts the host-guest relationship with each micelle binding multiple PE chains. This intimate binding goes hand-in-hand with the entropy of release of micelle-localized charge-compensating ions whose concentration depends on Y. These ions need not be released in L-L coacervation, but during L-S transition their displacement by PE accounts for the inverse dependence of Ts on micelle charge, Y.

  3. 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.

  4. Casein micelles and their internal structure.

    PubMed

    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 6M 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(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(-1) In the nanocluster model, the casein micelle is considered as a (homogeneous) matrix of caseins in which the colloidal calcium phosphate (CCP) nanoclusters are

  5. 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.

  6. Smart wormlike micelles.

    PubMed

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

    2013-09-07

    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.

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

    USDA-ARS?s Scientific Manuscript database

    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. A three-state model for energy trapping and chlorophyll fluorescence in photosystem II incorporating radical pair recombination.

    PubMed Central

    Vredenberg, W J

    2000-01-01

    The multiphasic fluorescence induction kinetics upon a high intensity light pulse have been measured and analyzed at a time resolution of 10 micros in intact leaves of Peperomia metallica and Chenopodium album and in chloroplasts isolated from the latter. Current theories and models on the relation between chlorophyll fluorescence yield and primary photochemistry in photosystem II (PSII) are inadequate to describe changes in the initial phase of fluorescence induction and in the dark fluorescence level F(0) caused by pre-energization of the system with single turnover excitation(s). A novel model is presented, which gives a quantitative relation between the efficiencies of primary photochemistry, energy trapping, and radical pair recombination in PSII. The model takes into account that at least two turnovers are required for stationary closure of a reaction center. An open reaction center is transferred with high efficiency into its semiclosed (-open) state. This state is characterized by Q(A) and P680 in the fully reduced state and a lifetime equal to the inverse of the rate constant of Q(A)(-) oxidation (approx. 250 micros). The fluorescence yield of the system with 100% of the centers in the semiclosed state is 50% of the maximal yield with all centers in the closed state at fluorescence level F(m). A situation with approximately 100% of the centers in the semiclosed state is reached after a single turnover excitation in the presence of 3-(3',4'-dichlorophenyl)-1,1-dimethylurea (DCMU). The lifetime of this state under these conditions is approximately 10 s. Closure of a semiclosed (-open) center occurs with low efficiency in a second turnover. The low(er) efficiency is caused by the rate of P(+) reduction by the secondary donor Y(Z) being competitive with the rate of radical pair recombination in second and following turnovers. The single-turnover-induced alterations in the initial kinetics of the fluorescence concomitantly with a 15-25% increase in F(o) can be

  10. Statistical thermodynamics of amphiphile chains in micelles

    PubMed Central

    Ben-Shaul, A.; Szleifer, I.; Gelbart, W. M.

    1984-01-01

    The probability distribution of amphiphile chain conformations in micelles of different geometries is derived through maximization of their packing entropy. A lattice model, first suggested by Dill and Flory, is used to represent the possible chain conformations in the micellar core. The polar heads of the chains are assumed to be anchored to the micellar surface, with the other chain segments occupying all lattice sites in the interior of the micelle. This “volume-filling” requirement, the connectivity of the chains, and the geometry of the micelle define constraints on the possible probability distributions of chain conformations. The actual distribution is derived by maximizing the chain's entropy subject to these constraints; “reversals” of the chains back towards the micellar surface are explicitly included. Results are presented for amphiphiles organized in planar bilayers and in cylindrical and spherical micelles of different sizes. It is found that, for all three geometries, the bond order parameters decrease as a function of the bond distance from the polar head, in accordance with recent experimental data. The entropy differences associated with geometrical changes are shown to be significant, suggesting thereby the need to include curvature (environmental)-dependent “tail” contributions in statistical thermodynamic treatments of micellization. PMID:16593492

  11. Re-assembled casein micelles improve in vitro bioavailability of vitamin D in a Caco-2 cell model.

    PubMed

    Cohen, Yifat; Levi, Moran; Lesmes, Uri; Margier, Marielle; Reboul, Emmanuelle; Livney, Yoav D

    2017-06-01

    The pandemic of vitamin D (VD) deficiency, and the global rise in obesity stimulate a need for staple low-fat foods and beverages enriched with VD. In light of consumer demand for a clean label, the use of natural endogenous food ingredients as delivery vehicles is of great interest. To this end, re-assembled casein micelles (rCM) have been shown to help retain VD during processing and shelf life and provide high bioavailability in low-fat milk and non-fat yoghurt. This follow-up study focused on the performance of VD-loaded rCM after drying and reconstitution, considering VD retention during simulated digestion, and the subsequent in vitro bioavailability of the vitamin. rCM conferred great protection to VD3 during simulated digestion with a significant increase in vitamin retention for 1 h under gastric conditions. This observation is believed to arise from the vitamin-casein binding and the system's natural gelation (curd formation) near the casein isoelectric point that seclude the vitamin from environmental stressors and couple its release with digestive proteolysis of the rCM matrix. Vitamin absorption by Caco-2 cells from digested rCM was not significantly different from the absorption of the digested free VD. However, thanks to the highly protective effect of the rCM, against VD gastric degradation, the overall effect of the rCM was a 4-fold higher bioavailability, compared to the free VD.

  12. Simvastatin prodrug micelles target fracture and improve healing.

    PubMed

    Jia, Zhenshan; Zhang, Yijia; Chen, Yen Hsun; Dusad, Anand; Yuan, Hongjiang; Ren, Ke; Li, Fei; Fehringer, Edward V; Purdue, P Edward; Goldring, Steven R; Daluiski, Aaron; Wang, Dong

    2015-02-28

    Simvastatin (SIM), a widely used anti-lipidemic 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.

  13. Structural properties of CHAPS micelles, studied by molecular dynamics simulations.

    PubMed

    Herrera, Fernando E; Garay, A Sergio; Rodrigues, Daniel E

    2014-04-10

    Detergents are essential tools to study biological membranes, and they are frequently used to solubilize lipids and integral membrane proteins. Particularly the nondenaturing zwitterionic detergent usually named CHAPS was designed for membrane biochemistry and integrates the characteristics of the sulfobetaine-type detergents and bile salts. Despite the available experimental data little is known about the molecular structure of its micelles. In this work, molecular dynamics simulations were performed to study the aggregation in micelles of several numbers of CHAPS (≤ 18) starting from a homogeneous water dilution. The force field parameters to describe the interactions of the molecule were developed and validated. After 50 ns of simulation almost all the systems result in the formation of stable micelles. The molecular shape (gyration radii, volume, surface) and the molecular structure (RDF, salt bridges, H-bonds, SAS) of the micelles were characterized. It was found that the main interactions that lead to the stability of the micelles are the electrostatic ones among the polar groups of the tails and the OH's from the ring moiety. Unlike micelles of other compounds, CHAPS show a grainlike heterogeneity with hydrophobic micropockets. The results are in complete agreement with the available experimental information from NMR, TEM, and SAXS studies, allowing the modeling of the molecular structure of CHAPS micelles. Finally, we hope that the new force field parameters for this detergent will be a significant contribution to the knowledge of such an interesting molecule.

  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. 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

  16. 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.

  17. 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.

  18. 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.

  19. Iron Oxide Nanoparticle-Micelles (ION-Micelles) for Sensitive (Molecular) Magnetic Particle Imaging and Magnetic Resonance Imaging

    PubMed Central

    Starmans, Lucas W. E.; Burdinski, Dirk; Haex, Nicole P. M.; Moonen, Rik P. M.; Strijkers, Gustav J.; Nicolay, Klaas; Grüll, Holger

    2013-01-01

    Background Iron oxide nanoparticles (IONs) are a promising nanoplatform for contrast-enhanced MRI. Recently, magnetic particle imaging (MPI) was introduced as a new imaging modality, which is able to directly visualize magnetic particles and could serve as a more sensitive and quantitative alternative to MRI. However, MPI requires magnetic particles with specific magnetic properties for optimal use. Current commercially available iron oxide formulations perform suboptimal in MPI, which is triggering research into optimized synthesis strategies. Most synthesis procedures aim at size control of iron oxide nanoparticles rather than control over the magnetic properties. In this study, we report on the synthesis, characterization and application of a novel ION platform for sensitive MPI and MRI. Methods and Results IONs were synthesized using a thermal-decomposition method and subsequently phase-transferred by encapsulation into lipidic micelles (ION-Micelles). Next, the material and magnetic properties of the ION-Micelles were analyzed. Most notably, vibrating sample magnetometry measurements showed that the effective magnetic core size of the IONs is 16 nm. In addition, magnetic particle spectrometry (MPS) measurements were performed. MPS is essentially zero-dimensional MPI and therefore allows to probe the potential of iron oxide formulations for MPI. ION-Micelles induced up to 200 times higher signal in MPS measurements than commercially available iron oxide formulations (Endorem, Resovist and Sinerem) and thus likely allow for significantly more sensitive MPI. In addition, the potential of the ION-Micelle platform for molecular MPI and MRI was showcased by MPS and MRI measurements of fibrin-binding peptide functionalized ION-Micelles (FibPep-ION-Micelles) bound to blood clots. Conclusions The presented data underlines the potential of the ION-Micelle nanoplatform for sensitive (molecular) MPI and warrants further investigation of the FibPep-ION-Micelle platform for

  20. In situ time-resolved SAXS study of the formation of mesostructured organically modified silica through modeling of micelles evolution during surfactant-templated self-assembly.

    PubMed

    Michaux, Florentin; Baccile, Niki; Impéror-Clerc, Marianne; Malfatti, Luca; Folliet, Nicolas; Gervais, Christel; Manet, Sabine; Meneau, Florian; Pedersen, Jan Skov; Babonneau, Florence

    2012-12-18

    The mechanisms of formation of organically modified (phenyl, vinyl, and methyl) silica materials with cubic Pm3n and hexagonal p6m periodic mesostructures obtained in one step in the presence of the cetyltrimethylammonium bromide (CTA(+)B) surfactant are reported in this study. Understanding the way these complex materials form is difficult but undoubtedly necessary for controlling the material structure and its properties because of the combined presence of surface organic groups and large surface areas. Here, the mechanism of formation is clarified on the basis of the modeling of time-resolved in situ small angle X-ray scattering (SAXS) experiments, with a specific focus on the micelle evolution during material formation. Their fast self-assembly is followed for the first time with a quick temporal resolution of a few seconds using a third-generation synchrotron radiation source. To better understand the behavior of the complex organic-containing mesostructure, we perform a comparative study with the corresponding organo-free, isostructural materials obtained from three different surfactants (CTA(+), CTEA(+), and CTPA(+)) having a constant chain length (C(16)) and an increasing polar head volume (met-, et-, and prop-). Numerical modeling of SAXS data was crucial to highlighting a systematic sphere-to-rod micellar transition, otherwise undetected, before the formation of the 2D hexagonal phase in both organo-free and organo-containing systems. Then, two different pathways were found in the formation of the cubic Pm3n mesostructure: either an ordering transition from concentrated flocs of spherical micelles (from CTEA(+) or CTPA(+)) for pure TEOS systems or a structural transformation from an intermediate 2D hexagonal mesophase in organosilane systems (from CTA(+)). Combining the comparison between organo-free and organo-containing systems with numerical modeling, we find that the hexagonal-to-cubic phase transition in the organically modified materials seems to be

  1. Ionization of cationic micelles: effect of the detergent structure

    SciTech Connect

    Zana, R.

    1980-12-01

    Measurements show that the micelle ionization degree decreases upon increasing chain length in the alkyltrimethylammonium bromides series, increases with the size of the ionic head group in the tetradecyltrialkylammonium bromide series, and with the length of the variable alkyl chain in the dodecyldimethylalkylammonium bromide series. These variations have been explained in terms of changes of surface area per head group calculated on the basis of a model which assumes spherical micelles. 34 references.

  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. Structural changes of casein micelles in a calcium gradient film.

    PubMed

    Gebhardt, Ronald; Burghammer, Manfred; Riekel, Christian; Roth, Stephan Volkher; Müller-Buschbaum, Peter

    2008-04-09

    Calcium gradients are prepared by sequentially filling a micropipette with casein solutions of varying calcium concentration and spreading them on glass slides. The casein film is formed by a solution casting process, which results in a macroscopically rough surface. Microbeam grazing incidence small-angle X-ray scattering (microGISAXS) is used to investigate the lateral size distribution of three main components in casein films: casein micelles, casein mini-micelles, and micellar calcium phosphate. At length scales within the beam size the film surface is flat and detection of size distribution in a macroscopic casein gradient becomes accessible. The model used to analyze the data is based on a set of three log-normal distributed particle sizes. Increasing calcium concentration causes a decrease in casein micelle diameter while the size of casein mini-micelles increases and micellar calcium phosphate particles remain unchanged.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Gradient structure-induced temperature responsiveness in styrene/methyl methacrylate gradient copolymers micelles.

    PubMed

    Zheng, Chao; Huang, Haiying; He, Tianbai

    2014-02-01

    In this work, micelles are formed by gradient copolymer of styrene and methyl methacrylate in acetone-water mixture and their temperature responsiveness is investigated in a narrow range near room temperature. Three different kinds of structural transitions could be induced by temperature: unimers to micelle transition, shrinkage/stretching of micelles, and morphological transition from spherical micelles to vesicles. In addition, a model analysis on the interface of gradient copolymer micelle is made to better understand these phenomena. It is found that both position and composition of the interface could alter in response to the change in temperature. According to the experiments and model analysis, it is proposed that temperature responsiveness might be an intrinsic and universal property of gradient copolymer micelles, which only originates from the gradient structure.

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

    PubMed

    Gregg, Watson W; Rousseaux, Cécile S

    2014-09-01

    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.

  10. 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

  11. Molecular dynamics study of micelles properties according to their size.

    PubMed

    Lebecque, S; Crowet, J M; Nasir, M N; Deleu, M; Lins, L

    2017-03-01

    Surfactants are molecules able to spontaneously self-assemble to form aggregates with well-defined properties, such as spherical micelles, planar bilayers, cylindrical micelles or vesicles. Micelles have notably several applications in many domains, such as drug delivery or membrane protein solubilization. In this context, the study of micelle formation in relation with the structural and physico-chemical properties of surfactants is of great interest to better control their use in the different application fields. In this work, we use the MD approach developed by Yoshii et al. and extend it to surfactants with different structures. We aim to systematically investigate different micellar properties as a function of the aggregates size by a molecular dynamics approach, to get an insight into the micellar organization and to collect some relevant descriptors about micelle formation. For this, we perform short MD simulations of preformed micelles of various sizes and analyze three parameters for each micelle size, namely the eccentricity of the micelles, the hydrophobic/hydrophilic surface ratio and the hydrophobic tails hydration. If these parameters are known descriptors of micelles, they were not yet studied in this way by MD. We show that eccentricity, used as "validator" parameter, exhibits minimal values when the aggregate size is close to the experimental aggregation number for surfactants that are known to form spherical micelles. This hence indicates that our methodology gives consistent results. The evolution of the two descriptors follows another scheme, with a sharp increase and decrease, respectively, followed by a leveling-off. The aggregate sizes at which this stabilization starts to occur are close to the respective aggregation number of each surfactant. In our approach, we validate the use of these descriptors to follow micelle formation by MD, from "simple" surfactants to more complex structures, like lipopeptides. Our calculations also suggest that

  12. 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.

  13. Development and characterization of lyophilized diazepam-loaded polymeric micelles.

    PubMed

    Suksiriworapong, Jiraphong; Rungvimolsin, Tanaporn; A-gomol, Atitaya; Junyaprasert, Varaporn Buraphacheep; Chantasart, Doungdaw

    2014-02-01

    Polymeric micelles were studied as delivery carriers of diazepam, a practically insoluble drug in water, for rectal administration. The diazepam-loaded polymeric micelles were developed by using poloxamer 407 (P407), poloxamer 188, and D-α-tocopheryl poly(ethylene glycol) 1000 succinate (TPGS). Among the used polymers, TPGS resulted in polymeric micelles with good characteristics for encapsulation of diazepam which had the small particle size of 8-12 nm and narrow size distribution (PI 0.053-0.275). Additionally, 7.5% w/v of TPGS could entirely entrap the desired concentration of diazepam (5 mg/mL). To improve the physical stability upon lyophilization, an addition of P407 of 1% w/v prevented aggregation, increased physical stability, and maintained chemical stability of the lyophilized powders of diazepam-loaded polymeric micelles for 3 months storage at 4°C. The rate and amount of diazepam release from TPGS polymeric micelles mainly depended on the concentration of TPGS. The release data were fitted to Higuchi's model suggesting that the drug release mechanism was controlled by Fickian diffusion. In conclusion, 10% w/v TPGS and 1% w/v P407 were the optimum formulation of lyophilized diazepam-loaded polymeric micelles.

  14. 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

  15. 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

  16. 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, 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-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

  17. 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

  18. 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.

  19. Chlorophyll-a remote sensing retrieval in Taihu lake using a conceptually optimized model: based on HJ-1 satellite hyperspectral imager data

    NASA Astrophysics Data System (ADS)

    Wu, Chuanqing; Zhu, Li; Wang, Xuelei; Yao, Yanjuan

    2014-11-01

    A conceptual model containing reflectance in three spectral bands in the red and near infrared ranges of the spectrum can be used to retrieve vegetation pigment concentration. Based on this model, the bio-optical properties of Chlorophyll-a (Chl-a), suspended solids, dissolved organic matter and water molecules were analyzed in this paper, by using in-situ spectra data, optical parameters and water quality parameters in Taihu Lake. Under the band range determined by spectral feature analysis, the optimal combination of bands (678 nm, 696 nm and 748 nm) was selected through the iterative method, to compose an optimized band combination in order to build the Chl-a semi-analytical model. Based on hyper-spectral imager (HSI) data carried on the Environmental 1 (HJ-1) satellite, this model was used successfully to retrieve the Chl-a concentration in Taihu Lake.

  20. 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

  1. Novel fluorescent probe as aggregation predictor and micro-polarity reporter for micelles and mixed micelles

    NASA Astrophysics Data System (ADS)

    Shannigrahi, Mrinmoy; Bagchi, Sanjib

    2005-07-01

    Aggregational behaviour of micelles sodium dodecyl sulphate (SDS and Triton X-100, TX-100 both in pure and mixed form) and micelle like aggregates such as polymer-surfactant system [polymer poly(vinyl pyrrolidone), PVP]-SDS have been studied by using fluorescence characteristics of a newly synthesized probe. The critical micelle concentration (CMC) values determined at various surfactant compositions are lower than the ideal values indicating a synergistic effect. The value of the interaction parameter for the surfactant mixture has been determined which agrees well with the value calculated according to molecular thermodynamic theory. The total aggregation number of surfactant in mixed micelle shows a drastic variation in the SDS mole fraction range 0 ≤ α1 ≤ 0.3 and beyond the range it remains practically constant. Molar-based partition coefficients for the dye between the micellar and aqueous phase have been determined and a non-linear variation is obtained for the mixed micellar system. Variations of micro-polarity in the mixed micellar region have been investigated as a function of surfactant composition and results have been explained in terms of a suitable realistic model.

  2. Convection-enhanced delivery of SN-38-loaded polymeric micelles (NK012) enables consistent distribution of SN-38 and is effective against rodent intracranial brain tumor models.

    PubMed

    Zhang, Rong; Saito, Ryuta; Mano, Yui; Sumiyoshi, Akira; Kanamori, Masayuki; Sonoda, Yukihiko; Kawashima, Ryuta; Tominaga, Teiji

    2016-10-01

    Convection-enhanced delivery (CED) of therapeutic agents is a promising local delivery technique that has been extensively studied as a treatment for CNS diseases over the last two decades. One continuing challenge of CED is accurate and consistent delivery of the agents to the target. The present study focused on a new type of therapeutic agent, NK012, a novel SN-38-loaded polymeric micelle. Local delivery profiles of NK012 and SN-38 were studied using rodent brain and intracranial rodent brain tumor models. First, the cytotoxicity of NK012 against glioma cell lines was determined in vitro. Proliferations of glioma cells were significantly reduced after exposure to NK012. Then, the distribution and local toxicity after CED delivery of NK012 and SN-38 were evaluated in vivo. Volume of distribution of NK012 after CED was much larger than that of SN-38. Histological examination revealed minimum brain tissue damage in rat brains after delivery of 40 µg NK012 but severe damage with SN-38 at the same dose. Subsequently, the efficacy of NK012 delivered via CED was tested in 9L and U87MG rodent orthotopic brain tumor models. CED of NK012 displayed excellent efficacy in the 9L and U87MG orthotopic brain tumor models. Furthermore, NK012 and gadolinium diamide were co-delivered via CED to monitor the NK012 distribution using MRI. Volume of NK012 distribution evaluated by histology and MRI showed excellent agreement. CED of NK012 represents an effective treatment option for malignant gliomas. MRI-guided CED of NK012 has potential for clinical application.

  3. [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.

  4. Glycation Reactions of Casein Micelles.

    PubMed

    Moeckel, Ulrike; Duerasch, Anja; Weiz, Alexander; Ruck, Michael; Henle, Thomas

    2016-04-13

    After suspensions of micellar casein or nonmicellar sodium caseinate had been heated, respectively, in the presence and absence of glucose for 0-4 h at 100 °C, glycation compounds were quantitated. The formation of Amadori products as indicators for the "early" Maillard reaction were in the same range for both micellar and nonmicellar caseins, indicating that reactive amino acid side chains within the micelles are accessible for glucose in a comparable way as in nonmicellar casein. Significant differences, however, were observed concerning the formation of the advanced glycation end products (AGEs), namely, N(ε)-carboxymethyllysine (CML), pyrraline, pentosidine, and glyoxal-lysine dimer (GOLD). CML could be observerd in higher amounts in nonmicellar casein, whereas in the micelles the pyrraline formation was increased. Pentosidine and GOLD were formed in comparable amounts. Furthermore, the extent of protein cross-linking was significantly higher in the glycated casein micelles than in the nonmicellar casein samples. Dynamic light scattering and scanning electron microscopy showed that glycation has no influence on the size of the casein micelles, indicating that cross-linking occurs only in the interior of the micelles, but altered the surface morphology. Studies on glycation and nonenzymatic cross-linking can contribute to the understanding of the structure of casein micelles.

  5. Polymer micelles for delayed release of therapeutics from drug-releasing surfaces with nanotubular structures.

    PubMed

    Sinn Aw, Moom; Addai-Mensah, Jonas; Losic, Dusan

    2012-08-01

    A new approach to engineer a local drug delivery system with delayed release using nanostructured surface with nanotube arrays is presented. TNT arrays electrochemically generated on a titanium surface are used as a model substrate. Polymer micelles as drug carriers encapsulated with drug are loaded at the bottom of the TNT structure and their delayed release is obtained by loading blank micelles (without drug) on the top. The delayed and time-controlled drug release is successfully demonstrated by controlling the ratio of blank and drug loaded-micelles. The concept is verified using four different polymer micelles (regular and inverted) loaded with water-insoluble (indomethacin) and water-soluble drugs (gentamicin).

  6. 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. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  7. 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.

  8. MPEG-DSPE polymeric micelle for translymphatic chemotherapy of lymph node metastasis.

    PubMed

    Li, Xue; Dong, Qing; Yan, Zhiqiang; Lu, Weiyue; Feng, Lingling; Xie, Cao; Xie, Zuoxu; Su, Bingxia; Liu, Min

    2015-06-20

    Lymph node metastasis is one of the major pathways for tumor formation and it is difficult to deliver chemotherapeutics at therapeutic concentrations to lymph node metastasis. This study prepared methyl poly(ethylene glycol)-distearoylphosphatidylethanolamine/doxorubicin (MPEG-DSPE/DOX) micelle for the treatment of lymph node metastasis. The MPEG-DSPE/DOX micelle prepared were of spherical morphology with a particle size of 20 ± 5 nm. The uptake rates of DOX and MPEG-DSPE/DOX micelle by A375 cells were 51.2% and 88.7%, respectively. The phagocytosis rate of MPEG-DSPE/Rhodamine B micelle by RAW264.7 cells was 17.2-fold lower than for Rhodamine B alone. After subcutaneous injection, MPEG-DSPE micelle underwent lymphatic absorption and accumulated in popliteal lymph nodes. MPEG-DSPE/DOX micelle significantly alleviated damage to the subcutaneous tissue of the injection sites compared with DOX alone. We established a model of nude mice bearing lymph node metastasis of A375 cells. After subcutaneous injection, the weights of both the popliteal and iliac lymph nodes of the MPEG-DSPE/DOX micelle group were significantly lower than in the saline and DOX groups. MPEG-DSPE/DOX micelle effectively killed the tumor cells in popliteal and iliac lymph nodes. In conclusion, MPEG-DSPE micelle is a promising drug delivery system for the treatment of lymph node metastasis. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. High intensity focused ultrasound-responsive release behavior of PLA-b-PEG copolymer micelles.

    PubMed

    Zhang, Hongji; Xia, Hesheng; Wang, Jie; Li, Yongwen

    2009-10-01

    Poly(lactic acid) (PLA) was synthesized by solution polycondensation of L-lactic acid and further reacted with dihydroxyl poly(ethylene glycol) (PEG) to obtain the amphiphilic block copolymer PLA-b-PEG. The biodegradable PLA-b-PEG copolymer can self-assemble into spherical micelles in aqueous solution. Nile Red, as a payload model, was used to examine the release behavior of the micelles. The hydrophobic Nile Red can be adsolubilized into the hydrophobic inner core of PLA-b-PEG micelles. With the introduction of Nile Red, the size of micelles increased. Moreover, high intensity focused ultrasound (HIFU), as a non-contact and remote control approach, was introduced to control the release behavior of PLA-b-PEG micelles containing Nile Red. The release behavior of Nile Red was monitored by fluorescence emission spectra. The results showed that HIFU can trigger the release of the encapsulated Nile Red from PLA-b-PEG micelles. By adjusting the HIFU time, intensity and location, the release behavior of Nile Red from micelles can be tuned. Base on the results, an irreversible release mechanism under HIFU was proposed. The irreversible release of Nile Red from the PLA-b-PEG micelle was attributed to a chemically breaking process of micelle structure due to the degradation of the PLA-b-PEG chain that resulted from the transient cavitation in the HIFU focal spot.

  10. 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

  11. 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

    2015-03-03

    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.

  12. Pulse amplitude modulated chlorophyll fluorometer

    DOEpatents

    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.

  13. MICELLE, the micelle size effect on the LS counting efficiency

    NASA Astrophysics Data System (ADS)

    Grau Carles, A.

    2007-02-01

    This version extends the computation of the liquid-scintillation counting efficiency to electron-capture radionuclides of 30⩽Z⩽54. The simplified deterministic models of previous versions are replaced by a complete stochastic model, which considers all possible subshells involved in the atomic rearrangement of the atom. The program can simulate samples in the gel phase, including the effects of the micelles on the counting efficiency. These effects have been found to be useful for building nanodosimeters based on gel scintillators. Program summaryTitle of program: MICELLE Catalogue identifier:ACPU_v3_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ACPU_v3_0 Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Licensing previsions: none Computers revisions: any IBM PC compatible with 80386 or higher Intel processors Operating systems under which the program has been tested: MS-DOS and higher systems Programming language used: FORTRAN 77 Memory required to execute with typical data: 235 kword No. of bits in a word: 16 No. of lines in distributed program, including test data, etc.: 16 653 No. of bytes in distributed program, including test data, etc.: 358 166 Distribution format: tar.gz Nature of the physical problem: Both β and electron-capture are decay processes characterized by a large variability in energy. In the first case, one single β-particle is emitted per decay following the Fermi distribution. In the second, several electrons (Auger and/or Coster-Kronig) of very different energies can be ejected simultaneously. The detailed simulation of these two electron release processes has practical interest in two situations: (1) to standardize radionuclides with a liquid-scintillation counter, (2) to compute the absorbed dose in the surroundings of a radiolabeled molecule. Method of solution: Although the application of simplified deterministic models is sufficiently accurate for pure β-ray emitters, the large

  14. Retrieval of chlorophyll in Hangzhou Bay based on hyperspectral satellite

    NASA Astrophysics Data System (ADS)

    Zhu, Qiankun; Huang, Haiqing; Mao, Feng; Hu, Qiliang; Cheng, Qian

    2016-10-01

    Chlorophyll concentration is one of the important parameters of water quality assessment, and the quantitative retrieval of chlorophyll concentration and its distribution is one of the main applications of remote sensing in the coastal waters. Because of its unique geographical position and economic value, Hangzhou Bay has a very important research significance. By hyperspectral remote sensing technology effectively overcomes the effect of turbid coastal for chlorophyll concentration estimates, the researchers by accurate measurement of chlorophyll spectral characteristics of chlorophyll concentration for quantitative retrieval possible. The Hyperion hyperspectral imager for Hangzhou Bay estuary area of chlorophyll remote sensing monitoring data were chlorophyll a concentration in remote sensing inversion model is constructed, and combined with pretreated Hyperion high image data inversion of regional chlorophyll a concentration, and then analyzes the uneven distribution of Hangzhou Bay Estuary chlorophyll content space, near the Yangtze River Estuary and Hangzhou Bay estuarine research area of chlorophyll concentration is lower than that far from the coast in the study area, and the conclusion of regional autumn average CHL concentration is higher than in winter.

  15. Thermodynamics of hexadecyltrimethylammonium bromide micelle formation

    NASA Astrophysics Data System (ADS)

    Velikov, A. A.

    2017-07-01

    The thermodynamic parameters for CTAB micelle formation (Δ H, Δ G, Δ S) are calculated at different temperatures. Critical micelle concentrations CMC1 are determined. The possibility of determining CMC2 is demonstrated.

  16. Achieving micelle control through core crystallinity.

    PubMed

    Glavas, Lidija; Olsén, Peter; Odelius, Karin; Albertsson, Ann-Christine

    2013-11-11

    We have designed a pathway for controlling the critical micelle concentration and micelle size of polyester-based systems. This was achieved by creating an array of different copolymers with semicrystalline or amorphous hydrophobic blocks. The hydrophobic block was constructed through ring-opening polymerization of ε-caprolactone, L-lactide, and ε-decalactone, either as homopolymers or random copolymers, using PEG as both the initiator and the hydrophilic block. Micelles formed with amorphous cores exhibited considerably higher critical micelle concentrations than those with semicrystalline cores. Micelles with amorphous cores also became larger in size with an increased molecular weight of the hydrophobic bock, in contrast to micelles with semicrystalline cores, which displayed the opposite behavior. Hence, core crystallinity was found to be a potent tool for tailoring micelle properties and thereby facilitating the optimization of drug delivery systems. The introduction of PEG-PεDL also proved to be a valuable asset in the tuning of micelle properties.

  17. Achieving Micelle Control through Core Crystallinity

    PubMed Central

    2013-01-01

    We have designed a pathway for controlling the critical micelle concentration and micelle size of polyester-based systems. This was achieved by creating an array of different copolymers with semicrystalline or amorphous hydrophobic blocks. The hydrophobic block was constructed through ring-opening polymerization of ε-caprolactone, l-lactide, and ε-decalactone, either as homopolymers or random copolymers, using PEG as both the initiator and the hydrophilic block. Micelles formed with amorphous cores exhibited considerably higher critical micelle concentrations than those with semicrystalline cores. Micelles with amorphous cores also became larger in size with an increased molecular weight of the hydrophobic bock, in contrast to micelles with semicrystalline cores, which displayed the opposite behavior. Hence, core crystallinity was found to be a potent tool for tailoring micelle properties and thereby facilitating the optimization of drug delivery systems. The introduction of PEG-PεDL also proved to be a valuable asset in the tuning of micelle properties. PMID:24066701

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Theory of liquid crystalline micelles.

    PubMed

    Matsuyama, Akihiko

    2013-01-21

    A theory is introduced to describe self-assembly of liquid crystalline AB diblock copolymers, consisting of a homopolymer (A) and a side-chain liquid crystalline polymer (B). We derive the free energy of the liquid crystalline micellar solutions and examine the equilibrium solution properties: critical micelle concentration (CMC), nematic-isotropic phase transition (NIT) of the rigid side-chains inside the micelle core, and phase separations. It is shown that there is a critical micelle size below which the NIT becomes continuous due to a packing effect. We also find re-entrant micellizations near the NIT temperature. The phase diagrams, including binodal, spinodal, CMC, and NIT curves are also examined on the temperature-concentration plane.

  3. Chlorophyll a reconstruction from in situ measurements: 1. Method description

    NASA Astrophysics Data System (ADS)

    Fründt, B.; Dippner, J. W.; Waniek, J. J.

    2015-02-01

    Understanding the development of primary production is essential for projections of the global carbon cycle in the context of climate change. A chlorophyll a hindcast that serves as a primary production indicator was obtained by fitting in situ measurements of nitrate, chlorophyll a, and temperature. The resulting fitting functions were adapted to a modeled temperature field. The method was applied to observations from the Madeira Basin, in the northeastern part of the oligotrophic North Atlantic Subtropical Gyre and yielded a chlorophyll a field from 1989 to 2008 with a monthly resolution validated with remotely measured surface chlorophyll a data by SeaWiFS. The chlorophyll a hindcast determined with our method resolved the seasonal and interannual variability in the phytoplankton biomass of the euphotic zone as well as the deep chlorophyll maximum. Moreover, it will allow estimation of carbon uptake over long time scales.

  4. Spectroscopic properties of chlorophyll f.

    PubMed

    Li, Yaqiong; Cai, Zheng-Li; Chen, Min

    2013-09-26

    The absorption and fluorescence spectra of chlorophyll f (newly discovered in 2010) have been measured in acetone and methanol at different temperatures. The spectral analysis and assignment are compared with the spectra of chlorophyll a and d under the same experimental conditions. The spectroscopic properties of these chlorophylls have further been studied by the aid of density functional CAM-B3LYP and high-level symmetric adapted coupled-cluster configuration interaction calculations. The main Q and Soret bands and possible sidebands of chlorophylls have been determined. The photophysical properties of chlorophyll f are discussed.

  5. Derivation of original RESP atomic partial charges for MD simulations of the LDAO surfactant with AMBER: applications to a model of micelle and a fragment of the lipid kinase PI4KA.

    PubMed

    Karakas, Esra; Taveneau, Cyntia; Bressanelli, Stéphane; Marchi, Massimo; Robert, Bruno; Abel, Stéphane

    2017-01-01

    In this paper, we describe the derivation and the validation of original RESP atomic partial charges for the N, N-dimethyl-dodecylamine oxide (LDAO) surfactant. These charges, designed to be fully compatible with all the AMBER force fields, are at first tested against molecular dynamics simulations of pure LDAO micelles and with a fragment of the lipid kinase PIK4A (DI) modeled with the QUARK molecular modeling server. To model the micelle, we used two distinct AMBER force fields (i.e. Amber99SB and Lipid14) and a variety of starting conditions. We find that the micelle structural properties (such as the shape, size, the LDAO headgroup hydration, and alkyl chain conformation) slightly depend on the force field but not on the starting conditions and more importantly are in good agreement with experiments and previous simulations. We also show that the Lipid14 force field should be used instead of the Amber99SB one to better reproduce the C(sp3)C(sp3)C(sp3)C(sp3) conformation in the surfactant alkyl chain. Concerning the simulations with LDAO-DI protein, we carried out different runs at two NaCl concentrations (i.e. 0 and 300 mM) to mimic, in the latter case, the experimental conditions. We notice a small dependence of the simulation results with the LDAO parameters and the salt concentration. However, we find that in the simulations, three out of four tryptophans of the DI protein are not accessible to water in agreement with our fluorescence spectroscopy experiments reported in the paper.

  6. 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.

  7. Predicting critical micelle concentration and micelle molecular weight of polysorbate 80 using compendial methods.

    PubMed

    Braun, Alexandra C; Ilko, David; Merget, Benjamin; Gieseler, Henning; Germershaus, Oliver; Holzgrabe, Ulrike; Meinel, Lorenz

    2015-08-01

    This manuscript addresses the capability of compendial methods in controlling polysorbate 80 (PS80) functionality. Based on the analysis of sixteen batches, functionality related characteristics (FRC) including critical micelle concentration (CMC), cloud point, hydrophilic-lipophilic balance (HLB) value and micelle molecular weight were correlated to chemical composition including fatty acids before and after hydrolysis, content of non-esterified polyethylene glycols and sorbitan polyethoxylates, sorbitan- and isosorbide polyethoxylate fatty acid mono- and diesters, polyoxyethylene diesters, and peroxide values. Batches from some suppliers had a high variability in functionality related characteristic (FRC), questioning the ability of the current monograph in controlling these. Interestingly, the combined use of the input parameters oleic acid content and peroxide value - both of which being monographed methods - resulted in a model adequately predicting CMC. Confining the batches to those complying with specifications for peroxide value proved oleic acid content alone as being predictive for CMC. Similarly, a four parameter model based on chemical analyses alone was instrumental in predicting the molecular weight of PS80 micelles. Improved models based on analytical outcome from fingerprint analyses are also presented. A road map controlling PS80 batches with respect to FRC and based on chemical analyses alone is provided for the formulator. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Quenching of chlorophyll fluorescence by quinones.

    PubMed

    Samuilov, V D; Borisov AYu; Barsky, E L; Borisova, O F; Kitashov, A V

    1998-10-01

    Quinones caused quenching of Chl a fluorescence in native and model systems. Menadione quenched twofold the fluorescence of Chl a and BChl a in pea chloroplasts, chromatophores of purple bacteria, and liposomes at concentrations of 50-80 microM. To obtain twofold quenching in Triton X-100 micelles and in ethanol, the addition of 1.3 mM and 11 mM menadione was required, respectively. A proportional decrease in the lifetime and yield of Chl a fluorescence in chloroplasts, observed as the menadione concentration increased, is indicative of the efficient excitation energy transfer from bulk Chl to menadione. The decrease in the lifetime and yield of fluorescence was close to proportional in liposomes, but not in detergent micelles. The insensitivity of the menadione quenching effect to DCMU in chloroplasts, and similarity of its action in chloroplasts and liposomes indicate that menadione in chloroplasts interacts with antenna Chl, i.e., nonphotochemical quenching of fluorescence occurs.

  9. 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.

  10. 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.

  11. Relative binding affinities of chlorophylls in peridinin-chlorophyll-protein reconstituted with heterochlorophyllous mixtures.

    PubMed

    Brotosudarmo, T H P; Mackowski, S; Hofmann, E; Hiller, R G; Bräuchle, C; Scheer, H

    2008-01-01

    Peridinin-chlorophyll-protein (PCP), containing differently absorbing chlorophyll derivatives, are good models with which to study energy transfer among monomeric chlorophylls (Chls) by both bulk and single-molecule spectroscopy. They can be obtained by reconstituting the N-terminal domain of the protein (N-PCP) with peridinin and chlorophyll mixtures. Upon dimerization of these "half-mers", homo- and heterochlorophyllous complexes are generated, that correspond structurally to monomeric protomers of native PCP from Amphidinium carterae. Heterochlorophyllous complexes contain two different Chls in the two halves of the complete structure. Here, we report reconstitution of N-PCP with binary mixtures of Chl a, Chl b, and [3-acetyl]-Chl a. The ratios of the pigments were varied in the reconstitution mixture, and relative binding constants were determined from quantification of these pigments in the reconstituted PCPs. We find higher affinities for both Chl b and [3-acetyl]-Chl a than for the native pigment, Chl a.

  12. Almost fooled again: new insights into cesium dodecyl sulfate micelle structures.

    PubMed

    Lee, Han Seung; Adhimoolam Arunagirinathan, Manickam; Vagias, Apostolos; Lee, Sangwoo; Bellare, Jayesh R; Davis, H Ted; Kaler, Eric W; McCormick, Alon V; Bates, Frank S

    2014-11-04

    Replacing sodium with cesium as the counterion for dodecyl sulfate in aqueous solution results in stronger complexation and charge shielding, which should lead to larger micelles and ultimately to a cylindrical structure (cf. spheres for sodium dodecyl sulfate), but small angle X-ray scattering (SAXS) and small angle neutron scattering patterns previously have been interpreted with ellipsoidal micelle models. We directly image CsDS micelles via cryo-transmission electron microscopy and report large core-shell spherical micelles at low concentrations (≤2 wt %) and cylindrical micelles at higher concentrations (5.0 and 8.1 wt %). These structures are shown to be consistent with SAXS patterns modeled using established form factors. These findings highlight the importance of combining real and reciprocal space imaging techniques in the characterization of self-assembled soft materials.

  13. 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.

  14. Triclosan-loaded Tooth-binding Micelles for Prevention and Treatment of Dental Biofilm

    PubMed Central

    Chen, Fu; Rice, Kelly C.; Liu, Xin-Ming; Reinhardt, Richard A.; Bayles, Kenneth W.; Wang, Dong

    2010-01-01

    The purpose of the present study was to develop tooth-binding micelle formulations and evaluate their ability to both inhibit initial biofilm formation as well as decrease the viability of preformed biofilm using an in vitro dental biofilm model. Alendronate (ALN, a bisphosphonate) was covalently attached to the ends of different Pluronic copolymers to confer tooth-binding ability to the micelles, and triclosan was used as a model drug. Based on different micelle preparation methods, Pluronic copolymers and ALN-terminated Pluronic copolymers were used to prepare triclosan-loaded tooth-binding micelles. The formulation was optimized for triclosan solubility, particle size, hydroxyapatite (HA) binding capacity and kinetics, and in vitro drug release behavior. In vitro biofilm treatment studies demonstrated that the triclosan-loaded tooth-binding micelles were able to inhibit initial biofilm growth of Streptococcus mutans UA159 by 6-log CFU/HA disc compared to the untreated control. These tooth-binding micelles were also capable of reducing the viability of preformed biofilm by 4-log CFU/HA disc compared to untreated control biofilm. In summary, triclosan-loaded tooth-binding micelles have been successfully developed and optimized in this study. These micelles demonstrated promising anti-biofilm capabilities that have the potential for use in the future treatment and prevention of dental diseases. PMID:20387099

  15. 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.

  16. 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).

  17. Extinction coefficient for red-shifted chlorophylls: chlorophyll d and chlorophyll f.

    PubMed

    Li, Yaqiong; Scales, Nicholas; Blankenship, Robert E; Willows, Robert D; Chen, Min

    2012-08-01

    Both chlorophyll f and chlorophyll d are red-shifted chlorophylls in oxygenic photosynthetic organisms, which extend photon absorbance into the near infrared region. This expands the range of light that can be used to drive photosynthesis. Quantitative determination of chlorophylls is a crucial step in the investigation of chlorophyll-photosynthetic reactions in the field of photobiology and photochemistry. No methods have yet been worked out for the quantitative determination of chlorophyll f. There is also no method available for the precise quantitative determination of chlorophyll d although it was discovered in 1943. In order to obtain the extinction coefficients (ε) of chlorophyll f and chlorophyll d, the concentrations of chlorophylls were determined by Inductive Coupled Plasma Mass Spectrometry according to the fact that each chlorophyll molecule contains one magnesium (Mg) atom. Molar extinction coefficient ε(chl f) is 71.11×10(3)Lmol(-1)A(707nm)cm(-1) and ε(chl d) is 63.68×10(3)Lmol(-1)A(697nm)cm(-1) in 100% methanol. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial.

  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. Nanoparticle-Loaded Multifunctional Block Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Bae, Jinhye; Lawrence, Jimmy; Miesch, Caroline; Ribbe, Alexander; Li, Weikun; Emrick, Todd; Zhu, Jintao; Hayward, Ryan

    2012-02-01

    We have studied the incorporation of pre-synthesized hydrophobic inorganic nanoparticles within the cores of amphiphilic polystyrene-block-poly(ethylene oxide) (PS-PEO) diblock copolymer micelles formed through solvent-evaporation-induced interfacial instabilities of emulsion droplets. Using iron oxide, gold, and cadmium selenide nanoparticles coated with native alkane ligands, highly uniform encapsulation is obtained for cylindrical micelles, while spherical micelles can be enriched to ˜ 90 % of loaded micelles through simple magnetic or centrifugal purification steps. Multiple different types of nanoparticles can easily be incorporated into each micelle, yielding multi-functional micelles. The ability to encapsulate both spherical and rod-like particles of different core chemistries and sizes ranging from ˜ 1 to 20 nm, without the necessity of coating particles with specially designed ligands, makes this a versatile route to prepare hybrid micelle structures.

  20. Assessment of degradation and intestinal cell uptake of carotenoids and chlorophyll derivatives from spinach puree using an in vitro digestion and Caco-2 human cell model.

    PubMed

    Ferruzzi, M G; Failla, M L; Schwartz, S J

    2001-04-01

    Although numerous studies have demonstrated the health benefits of chlorophyll derivatives, information regarding the digestion, absorption, and metabolism of these phytochemicals is quite limited. To better understand the digestion of these pigments, green vegetables including fresh spinach puree (FSP), heat- and acid-treated spinach puree (HASP), and ZnCl(2)-treated spinach puree (ZnSP) were subjected to an in vitro digestion method which simulates both the gastric and small intestinal phases of the process. Native chlorophylls were converted to Mg-free pheophytin derivatives during digestion. Conversely, Zn-pheophytins were completely stable during the digestive process. Transfer of lipophilic chlorophyll derivatives, as well as the carotenoids lutein and beta-carotene, into the aqueous micellar fraction from the food matrix was quantified. Micellarization of total chlorophyll derivatives differed significantly (p < 0.05) for FSP (37.6%), HASP (17.2%), and ZnSP (8.7%). Micellarization of chlorophyll a derivatives was determined to be significantly more efficient than chlorophyll b derivatives in FSP and HASP (p < 0.01), but not in ZnSP (p > 0.05). Intestinal cell uptake of micellarized pigments was investigated using HTB-37 (parent) and clonal TC7 lines of human Caco-2 cells. Medium containing the pigment-enriched fraction generated during digestion was added to the apical surface of fully differentiated monolayers for 4 h. Pigments were then extracted from cells and analyzed by C18 HPLC with photodiode array detection. Both Caco-2 HTB-37 and TC7 clone cells accumulated 20-40% and 5-10% of micellarized carotenoid and chlorophyll derivatives, respectively. These results are the first to demonstrate uptake of chlorophyll derivatives by human intestinal cells and to support the potential importance of chlorophylls as health-promoting phytochemicals.

  1. Preparation and characterization of long-circulating PELMD/mPEG-PLGA-mixed micelles for 10-hydroxycamptothecin

    NASA Astrophysics Data System (ADS)

    Yin, Shaoping; Li, Juan; Li, Nannan; Wang, Guangji; Gu, Xiaochen

    2014-02-01

    A novel long-circulating nano-delivery system was constructed using block copolymers of poly monomethoxy-(ethylene glycol)-poly( d,l-lactic- co-glycolic acid)-poly(3( S)-methyl-morpholine-2,5-dione) (PELMD) and poly-monomethoxy (ethylene glycol)-poly-( d,l-lactic- co-glycolic acid) (mPEG-PLGA). The two copolymers possessed satisfactory critical micelle concentration and hemolytic effect. Antitumor compound 10-hydroxycamptothecin (HCPT) was loaded to the mixed micelles to further characterize in vitro and in vivo properties. HCPT-mixed micelles were measured 165-205 nm in particle size, with spherical core-shell structure and uniform-size distribution. The zeta potentials of the mixed micelles ranged 15-20 mV, attributed to the polydesipeptide. Stability of the mixed micelles was improved without complex synthesis. Drug release from the mixed micelles was pH-dependent, which was beneficial for improving specific drug targeting to tumor tissues. HCPT-mixed micelles demonstrated prolonged retention and tissue targeting in animal models. Mean residence time (MRT0→∞) of HCPT-mixed micelles was significantly longer than that of HCPT injection, and biodistribution of the mixed micelles showed specific drug disposition in liver and lungs. The results indicated that PELMD/mPEG-PLGA-mixed micelles could become a potential drug delivery system for anticancer drugs to improve therapeutic efficacy and minimize adverse effects.

  2. 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

  3. The structure of pH dependent block copolymer micelles: charge and ionic strength dependence

    SciTech Connect

    Pople, John A

    2002-08-06

    We characterize the structures of various polyelectrolyte block copolymer micelles in dilute aqueous solution as a function of pH and ionic strength. The block copolymers carry a common core block 2-(diethylamino) ethyl methacrylate (DEAEMA) and one of three coronal blocks: 2-(dimethylamino) ethyl methacrylate (DMAEMA), polyethylene oxide (PEO), and DMAEMA whose side-chain amine groups are selectively quaternized with benzyl chloride (Q-DMAEMA). The PEO-DEAEMA, DMAEMA-DEAEMA, and Q-DMAEMA-DEAEMA copolymers form micelles with electrostatically neutral, weakly charged, and highly charged coronae, respectively. We adjust the fractional charge a on the DEAEMA and DMAEMA blocks by adjusting the solution pH. For DMAEMA-DEAEMA micelles increasing the fractional charge a swells the micelle corona while decreasing the aggregation number due to electrostatic repulsions. The decrease in aggregation number is also observed with increasing a for the PEO-DEAEMA and Q-DMAEMA-DEAEMA micelles, due to electrostatic repulsions between the hydrophobic DEAEMA blocks. Increasing the ionic strength causes the DMAEMA-DEAEMA micelle corona to shrink as the salt screens electrostatic repulsions within the corona. In all three copolymers increases in the ionic strength causes the micelle aggregation number to increase by screening the electrostatic repulsions between chains. Trends in the corona thickness with varying fractional charge and ionic strength are compared with a number of theoretical models providing additional insight into the micelle structure.

  4. Delivery of the photosensitizer Pc 4 in PEG-PCL micelles for in vitro PDT studies.

    PubMed

    Master, Alyssa M; Rodriguez, Myriam E; Kenney, Malcolm E; Oleinick, Nancy L; Gupta, Anirban Sen

    2010-05-01

    The silicon phthalocyanine Pc 4 is a second-generation photosensitizer that has several properties superior to other photosensitizers currently approved by the FDA, and it has shown significant promise for photodynamic therapy (PDT) in several cancer cells in vitro and model tumor systems in vivo. However, because of the high hydrophobicity of Pc 4, its formulation for in vivo delivery and favorable biodistribution become challenging. To this end, we are studying encapsulation and delivery of Pc 4 in block copolymer micelles. Here, we report the development of biocompatible PEG-PCL micelle nanoparticles, encapsulation of Pc 4 within the micelle core by hydrophobic association with the PCL block, and in vitro PDT studies of the micelle-formulated Pc 4 in MCF-7c3 human breast cancer cells. Our studies demonstrate efficient encapsulation of Pc 4 in the micelles, intracellular uptake of the micelle-formulated Pc 4 in cells, and significant cytotoxic effect of the formulation upon photoirradiation. Quantitative estimation of the extent of Pc 4 loading in the micelles and the photocytotoxicity of the micelle-incorporated Pc 4 demonstrate the promise of our approach to develop a biocompatible nanomedicine platform for tumor-targeted delivery of Pc 4 for site-selective PDT.

  5. Crafting threads of diblock copolymer micelles via flow-enabled self-assembly.

    PubMed

    Li, Bo; Han, Wei; Jiang, Beibei; Lin, Zhiqun

    2014-03-25

    Hierarchically assembled amphiphilic diblock copolymer micelles were exquisitely crafted over large areas by capitalizing on two concurrent self-assembling processes at different length scales, namely, the periodic threads composed of a monolayer or a bilayer of diblock copolymer micelles precisely positioned by flow-enabled self-assembly (FESA) on the microscopic scale and the self-assembly of amphiphilic diblock copolymer micelles into ordered arrays within an individual thread on the nanometer scale. A minimum spacing between two adjacent threads λmin was observed. A model was proposed to rationalize the relationship between the thread width and λmin. Such FESA of diblock copolymer micelles is remarkably controllable and easy to implement. It opens up possibilities for lithography-free positioning and patterning of diblock copolymer micelles for various applications in template fabrication of periodic inorganic nanostructures, nanoelectronics, optoelectronics, magnetic devices, and biotechnology.

  6. Kinetics of formation of bile salt micelles from coarse-grained Langevin dynamics simulations.

    PubMed

    Vila Verde, Ana; Frenkel, Daan

    2016-06-21

    We examine the mechanism of formation of micelles of dihydroxy bile salts using a coarse-grained, implicit solvent model and Langevin dynamics simulations. We find that bile salt micelles primarily form via addition and removal of monomers, similarly to surfactants with typical head-tail molecular structures, and not via a two-stage mechanism - involving formation of oligomers and their subsequent aggregation to form larger micelles - originally proposed for bile salts. The free energy barrier to removal of single bile monomers from micelles is ≈2kBT, much less than what has been observed for head-tail surfactants. Such a low barrier may be biologically relevant: it allows for rapid release of bile monomers into the intestine, possibly enabling the coverage of fat droplets by bile salt monomers and subsequent release of micelles containing fats and bile salts - a mechanism that is not possible for ionic head-tail surfactants of similar critical micellar concentrations.

  7. 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.

  8. Chlorophyll: anatomy of a discovery

    SciTech Connect

    Rebeiz, C.A.

    1982-01-01

    Observations were made that are incompatible with the conventional visualization of the biosynthesis of chlorophyll, such as the pathway proposed by S. Granick. The new discoveries were made possible by techniques developed by the author: cell-free systems capable of synthesizing protochlorophyll and chlorophyll a and b from /delta/-aminolevulinic acid; the use of radio isotopes; and spectrofluorometric techniques. An understanding of the different chlorophyll chemical structures is essential to the technology of capturing solar energy. 53 refs.

  9. CO2, H2O, and chlorophyll fluorescence retrieved from OCO-2 measurements using a fast radiative transfer model approximating multiple scattering effects

    NASA Astrophysics Data System (ADS)

    Reuter, Maximilian; Bovensmann, Heinrich; Buchwitz, Michael; Burrows, John P.; Heymann, Jens; Noël, Stefan; Rozanov, Vladimir; Schneising, Oliver

    2017-04-01

    Carbon dioxide is the most important anthropogenic greenhouse gas. Its global increasing concentration in the Earth's atmosphere is the main driver for global climate change. In spite of its importance, there are still large uncertainties on its global sources and sinks. Satellite measurements have the potential to reduce these surface flux uncertainties. However, the demanding accuracy requirements usually involve the need for precise radiative transfer calculations in a scattering atmosphere. These can be computationally so expensive that hundreds or thousands of CPU cores are need to keep up with the data stream of an instrument like OCO-2. Future instruments will further increase the amount of soundings at least by an order of magnitude. A radiative transfer model has been developed approximating scattering effects by multiple scattering at an optically thin scattering layer reducing the computational costs by several orders of magnitude. The model can be used to simulate the radiance in all three OCO-2 spectral bands allowing the simultaneous retrieval of CO2, H2O, and chlorophyll fluorescence. First retrieval results for OCO-2 data will be presented.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  11. 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. 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.

  13. Proton transfer in ionic and neutral reverse micelles.

    PubMed

    Lawler, Christian; Fayer, Michael D

    2015-05-14

    Proton-transfer kinetics in both ionic and neutral reverse micelles were studied by time-correlated single-photon counting investigations of the fluorescent photoacid 8-hydroxypyrene-1,3,6-trisulfonate (HPTS). Orientational dynamics of dissolved probe molecules in the water pools of the reverse micelles were also investigated by time-dependent fluorescence anisotropy measurements of MPTS, the methoxy derivative of HPTS. These experiments were compared to the same experiments in bulk water. It was found that in ionic reverse micelles (surfactant Aerosol OT, AOT), orientational motion (fluorescence anisotropy decay) of MPTS was relatively unhindered, consistent with MPTS being located in the water core of the reverse micelle away from the water-surfactant interface. In nonionic reverse micelles (surfactant Igepal CO-520, Igepal), however, orientational anisotropy displayed a slow multiexponential decay consistent with wobbling-in-a-cone behavior, indicating MPTS is located at the water-surfactant interface. HPTS proton transfer in ionic reverse micelles followed kinetics qualitatively like those in bulk water, albeit slower, with the long-time power law time dependence associated with recombination of the proton with the dissociated photoacid, suggesting a modified diffusion-controlled process. However, the power law exponents in the ionic reverse micelles are smaller (∼ -0.55) than that in bulk water (-1.1). In neutral reverse micelles, proton-transfer kinetics did not show discernible power law behavior and were best represented by a two-component model with one relatively waterlike population and a population with a faster fluorescence lifetime and negligible proton transfer. We explain the Igepal results on the basis of close association between the probe and the neutral water-surfactant interface, with the probe experiencing a distribution of more and less waterlike environments. In addition, the observation in bulk water of a power law t(-1.1) for diffusion

  14. The gibbs energy, chemical potential, and state parameters of the surface of an ionic micelle in the form of an ellipsoid of revolution

    NASA Astrophysics Data System (ADS)

    Kuznetsov, V. S.; Usol'Tseva, N. V.; Blinov, A. P.

    2008-12-01

    A molecular-thermodynamic model of an ionic micelle in the form of an ellipsoid of revolution was suggested. Equations for the chemical potential of an ellipsoidal micelle, the work of transfer of ions from solution volume into the micelle, and the state parameters of the surface of the micelle (fraction of free hydrophobic surface, surface tension coefficient, and surface charge density) were obtained. The Gibbs energy, chemical potential, work of transfer, and state parameters of an ellipsoidal micelle were determined as depending on the form factor of the corresponding ellipsoid. The model was verified for the example of sodium decyl sulfate micelles. The calculated parameters were close to the thermochemical data on the asymmetrization of spherical micelles in a solution of sodium decyl sulfate. The equilibrium ion-micellar solution composition was estimated.

  15. The Effect of Hydrophilic and Hydrophobic Structure of Amphiphilic Polymeric Micelles on Their Transportation in Rats.

    PubMed

    Deng, Feiyang; Yu, Chao; Zhang, Hua; Dai, Wenbing; He, Bing; Zheng, Ying; Wang, Xueqing; Zhang, Qiang

    2016-01-01

    In the previous study, we have clarified how the hydrophilic and hydrophobic structures of amphiphilic polymers impact the transport of their micelles (PEEP-PCL, PEG-PCL and PEG-DSPE micelles) in epithelial MDCK cells (Biomaterials 2013, 34: 6284-6298). In this study, we attempt to clarify the behavior of the three micelles in rats. Coumarin-6 loaded micelles were injected into different sections of intestine of rats and observed by confocal laser scanning microscope (CLSM) or orally administrated and conducted pharmacokinetic study. All of the three kinds of micelles were able to cross the intestinal epithelial cells and enter blood circulation. The PEEP-PCL micelles demonstrated the fastest distribution mainly in duodenum, while the PEGDSPE micelles showed the longest distribution with the highest proportion in ileum of the three. No significant difference was observed among the pharmacokinetic parameters of the three micelles. The results were consistent in the two analysis methods mentioned above, yet there were some differences between in vivo and in vitro results reported previously. It might be the distinction between the environments in MDCK model and intestine that led to the discrepancy. The hydrophobicity of nanoparticles could both enhance uptake and hinder the transport across the mucus. However, there was no intact mucus in MDCK model, which preferred hydrophobic nanoparticles. PEEP was the most hydrophilic material constructing the micelles in the study and its uptake would be increased in rats compared to that in MDCK model, while DSPE was more hydrophobic than the others and MDCK model would be more ideal for its uptake. Considering the inconsistency of the results in the two models, whether the methods researchers were generally using at present were reasonable needs further investigation.

  16. Depletion Interactions: A New Control Parameter for the Self-Assembly of Diblock Copolymer Micelles

    SciTech Connect

    Abbas, Sayeed; Lodge, Timothy P.

    2007-09-28

    Small angle neutron scattering was performed on disordered mixtures of nonadsorbing homopolymer (A) chains and diblock (A-B) copolymer micelles in an A selective solvent. Increasing the molecular weight or concentration of A led to an increase in the aggregation number, and a decrease in the effective hard-sphere diameter of the micelles. Furthermore an intermicellar attractive force developed, which was successfully modeled by the Asakura-Oosawa depletion potential. Via an alternative model we also extracted information about mesoscopic clusters of micelles formed due to this attractive force.

  17. Simulation of non-ionic surfactant micelle formation across a range of temperature and pressure

    NASA Astrophysics Data System (ADS)

    Custer, Gregory; Das, Payel; Matysiak, Silvina

    Non-ionic surfactants can, at certain concentrations and thermodynamic conditions, aggregate into micelles due to their amphiphilic nature. Our work looks at the formation and behavior of micelles at extremes of temperature and pressure. Due to the large system size and simulation time required to study micelle formation, we have developed a coarse-grained (CG) model of our system. This CG model represents each heavy atom with a single CG bead. We use the multibody Stillinger-Weber potential, which adds a three-body angular penalty to a two-body potential, to emulate hydrogen bonds in the system. We simulate the linear surfactant C12E5 , which has a nonpolar domain of 12 carbons and a polar domain of 5 ethers. Our CG model has been parameterized to match structural properties from all-atom simulations of single and dimer surfactant systems. Simulations were performed using a concentration above the experimental critical micelle concentration at 300K and 1atm. We observe an expected region of stable micelle formation at intermediate temperature, with a breakdown at high and low temperature, as well as at high pressure. The driving forces behind the destabilization of micelles and the mechanism of micelle formation at different thermodynamic conditions will be discussed.

  18. 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.

  19. Molecular Simulation of Reverse Micelles

    NASA Astrophysics Data System (ADS)

    Chowdhary, Janamejaya; Ladanyi, Branka

    2009-03-01

    Reverse micelles (RM) are surfactant assemblies containing a nanosized water pool dissolved in a hydrophobic solvent. Understanding their properties is crucial for insight into the effect of confinement on aqueous structure, dynamics as well as physical processes associated with solutes in confinement. We perform molecular dynamics simulations for the RM formed by the surfactant Aerosol-OT (AOT) in isooctane (2,2,4-trimethyl pentane) in order to study the effect of reverse micelle size on the aqueous phase. The structure of the RM is quantified in terms of the radial and pair density distributions. Dynamics are studied in terms of the mean squared displacements and various orientational time correlation functions in different parts of the RM so as to understand the effect of proximity to the interface on aqueous dynamics. Shape fluctuations of the RM are also analyzed.

  20. 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

  1. The efficacy of nimodipine drug delivery using mPEG-PLA micelles and mPEG-PLA/TPGS mixed micelles.

    PubMed

    Huang, Shuling; Yu, Xiaohong; Yang, Linlin; Song, Fenglan; Chen, Gang; Lv, Zhufen; Li, Tiao; Chen, De; Zhu, Wanhua; Yu, Anan; Zhang, Yongming; Yang, Fan

    2014-10-15

    In order to develop and compare mPEG-PLA micelles and mPEG-PLA/TPGS mixed micelles, with the intention to develop a highly efficient formulation for nimodipine (NIM), NIM-loaded micelles and mixed micelles were made and their pharmacokinetics were studied. Single factor experiments and orthogonal experiments were designed to optimize the final preparation process, characterizations and drug release behaviors were studied. Pharmacokinetics of NIM micelles, NIM mixed micelles were researched and were compared to NIM solution. Micelles and mixed micelles were prepared by solvent evaporation method, with relatively high drug loading efficiency and within nano-particle size range. The CMC value of mPEG-PLA was lower than that of mPEG-PLA/TPGS. The results of FTIR and TEM confirmed the spherical core-shell structure of micelles as well as mixed micelles, and the encapsulation of NIM inside the cores. In vitro release showed that micelles and mixed micelles had sustained release effect in the forms of passive diffusion and dissolution process, respectively. Following intraperitoneal administration (5mg/kg), micelles and mixed micelles were absorbed faster than solution, and with larger MRT(0-t), smaller CLz and larger AUC(0-t) as compared to that of solution, which showed micelles and mixed micelles had higher retention, slower elimination and higher bioavailability. This experiment also showed that mixed micelles released NIM more stably than micelles. By evaluate the bioequivalence, NIM micelles and NIM mixed micelles were testified non-bioequivalent to NIM solution. Micelles and mixed micelles could sustain the NIM concentrations more efficiently in plasma as compared to solution. Mixed micelles were the best ones since they had high loading content and released more stably. Thus, apprehending micelles and mixed micelles were suited as poor aqueous solubility drug carriers, and mixed micelles were better due to their high loading content and more stable release

  2. Hydrolysis-Sensitive Dithiolethione Prodrug Micelles.

    PubMed

    Hasegawa, Urara; Tateishi, Naoya; Uyama, Hiroshi; van der Vlies, André J

    2015-11-01

    Prodrug micelles carrying 5-(4-hydroxyphenyl)-3H-1,2-dithiole-3-thione (ADT-OH), a compound possessing chemopreventive properties, are prepared from amphiphilic block copolymers linking ADT-OH via an ester bond using glycine (PAM-PGlyADT) and isoleucine linkers (PAM-PIleADT). The release of ADT-OH from the PAM-PIleADT micelles is much slower than the PAM-PGlyADT micelles. The PAM-PGlyADT micelles show comparable toxicity with ADT-OH in different cancer cell lines, whereas the PAM-PIleADT micelles are not toxic up to 400 µM. This ADT-ester prodrug micelle approach enables to modulate the release rate of ADT-OH and thus might find application in cancer therapy and prevention. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Deoxycholic acid-modified chitooligosaccharide/mPEG-PDLLA mixed micelles loaded with paclitaxel for enhanced antitumor efficacy.

    PubMed

    Jiang, Chengjun; Wang, Hangxiang; Zhang, Xiaomin; Sun, Zhibin; Wang, Feng; Cheng, Jun; Xie, Haiyang; Yu, Bo; Zhou, Lin

    2014-11-20

    Poly(ethylene glycol) (PEG) as a block in polymeric micelles can prolong circulation life and reduce systemic clearance but decrease the cellular uptake. To overcome this limitation, a mixed micelle composed of deoxycholic acid-modified chitooligosaccharide (COS-DOCA) and methoxy poly(ethylene glycol)-polylactide copolymer (mPEG-PDLLA) was designed to load paclitaxel (PTX). The PTX-loaded mixed micelles was prepared by nanoprecipitation method with high drug-loading efficiency of 8.03% and encapsulation efficiency of 97.09% as well as small size (∼40 nm) and narrow size distribution. COS-DOCA/mPEG-PDLLA mixed micelles exhibited the sustained release property. Due to the positive charge and bioadhesive property of COS-DOCA, the cellular uptake of PTX in mixed micelles was higher in cancer cells but lower in macrophage cells compared to the mPEG-PDLLA micelles. The systemic toxicity of PTX in mixed micelles was much lower than Taxol using zebrafish as a toxicological model. Furthermore, the PTX-loaded COS-DOCA/mPEG-PDLLA mixed micelles can prolong the blood circulation time of PTX and enhance the antitumor efficacy in A549 lung xenograft model. Our findings indicate that COS-DOCA/mPEG-PDLLA mixed micelles could be a potential vehicle for enhanced delivery of anticancer drugs. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Optimizing chlorophyll content in soybean

    USDA-ARS?s Scientific Manuscript database

    Traditionally, leaf chlorophyll content has not been among the target traits for improving crop yield. However, current chlorophyll concentrations may be in excess of the amount that would maximize the season integral of photosynthesis in a crop monoculture, such as soybean, that achieves a high lea...

  5. THE CHLOROPHYLL UNIT IN PHOTOSYNTHESIS

    PubMed Central

    Arnold, William; Kohn, Henry I.

    1934-01-01

    In six species of plants, representing four phyla, the minimum number of chlorophyll molecules present for each molecule of carbon dioxide reduced appears to lie between 2,000 and 3,000. This finding suggests the existence of a chlorophyll unit. PMID:19872820

  6. 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

  7. 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.

  8. Photosynthetic characteristics and organization of chlorophyll in marine dinoflagellates

    PubMed Central

    Prézelin, Barbara B.; Alberte, Randall S.

    1978-01-01

    The photosystem I reaction center complex, the P-700-chlorophyll a-protein, has been isolated from the photosynthetic membranes of two marine dinoflagellates, Gonyaulax polyedra and Glenodinium sp., by detergent solubilization with Triton X-100. The complexes isolated from the two species were indistinguishable, exhibiting identical absorption properties (400-700 nm) at both room (300 K) and low (77 K) temperature. The room temperature, red wavelength maximum was at 675 nm. The absorption properties, kinetics of photobleaching, sodium dodecyl sulfate electrophoretic mobilities, and chlorophyll a/P-700 ratio (50 ± 10) of the P-700-chlorophyll a-protein complexes from the two species also were essentially the same and similar to those properties characterizing P-700-chlorophyll a-protein complexes of higher plants and green algae. Photosynthetic unit sizes were determined for cells grown at 1000 μW/cm2. Both dinoflagellates had unit sizes (total chlorophyll/P-700 ratios) of about 600, even though the distribution of chlorophyll a, chlorophyll c, and peridinin in the light-harvesting components differed in Gonyaulax and Glenodinium. The number of photosynthetic units per cell in the two species correlates directly with their photosynthetic activities. A model is presented for the distribution of chlorophyll in the photosynthetic apparatus of these dinoflagellates which accounts for the known role of the isolated pigment-protein complexes and for the known photoadaptive physiology in pigmentation and photosynthesis for these species. PMID:16592518

  9. Tooth-Binding Micelles for Dental Caries Prevention▿

    PubMed Central

    Chen, Fu; Liu, Xin-Ming; Rice, Kelly C.; Li, Xue; Yu, Fang; Reinhardt, Richard A.; Bayles, Kenneth W.; Wang, Dong

    2009-01-01

    Maintenance of the effective local concentration of antimicrobials on the tooth surface is critical for the management of cariogenic bacteria in the oral cavity. We report on the design of a simple tooth-binding micellar drug delivery platform that would effectively bind to tooth surfaces. To achieve tooth-binding ability, the chain termini of biocompatible Pluronic copolymers were modified with a biomineral-binding moiety (i.e., alendronate). The micelles formulated with this polymer were shown to be able to swiftly (<1 min) bind to hydroxyapatite (HA; a model tooth surface) and gradually release the encapsulated model antimicrobial (farnesol). These tooth-binding micelles were negatively charged and had an average effective hydrodynamic diameter of less than 100 nm. In vitro biofilm inhibition studies demonstrated that the farnesol-containing tooth-binding micelles were able to provide significantly stronger inhibition of Streptococcus mutans UA159 biofilm formation on HA discs than the untreated blank control micelles (P < 0.0001). Upon further optimization, this delivery platform could provide an effective tool for caries prevention and treatment. PMID:19704121

  10. Bioinspired Coordination Micelles Integrating High Stability, Triggered Cargo Release, and Magnetic Resonance Imaging.

    PubMed

    Xin, Keting; Li, Man; Lu, Di; Meng, Xuan; Deng, Jun; Kong, Deling; Ding, Dan; Wang, Zheng; Zhao, Yanjun

    2017-01-11

    Catechol-Fe(3+) coordinated micelles show the potential for achieving on-demand drug delivery and magnetic resonance imaging in a single nanoplatform. Herein, we developed bioinspired coordination-cross-linked amphiphilic polymeric micelles loaded with a model anticancer agent, doxorubicin (Dox). The nanoscale micelles could tolerate substantial dilution to a condition below the critical micelle concentration (9.4 ± 0.3 μg/mL) without sacrificing the nanocarrier integrity due to the catechol-Fe(3+) coordinated core cross-linking. Under acidic conditions (pH 5.0), the release rate of Dox was significantly faster compared to that at pH 7.4 as a consequence of coordination collapse and particle de-cross-linking. The cell viability study in 4T1 cells showed no toxicity regarding placebo cross-linked micelles. The micelles with improved stability showed a dramatically increased Dox accumulation in tumors and hence the enhanced suppression of tumor growth in a 4T1 tumor-bearing mouse model. The presence of Fe(3+) endowed the micelles T1-weighted MRI capability both in vitro and in vivo without the incorporation of traditional toxic paramagnetic contrast agents. The current work presented a simple "three birds with one stone" approach to engineer the robust theranostic nanomedicine platform.

  11. 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.

  12. 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.

  13. Stabilized micelles as delivery vehicles for paclitaxel.

    PubMed

    Yoncheva, Krassimira; Calleja, Patricia; Agüeros, Maite; Petrov, Petar; Miladinova, Ivanka; Tsvetanov, Christo; Irache, Juan M

    2012-10-15

    Paclitaxel is an antineoplastic drug used against a variety of tumors, but its low aqueous solubility and active removal caused by P-glycoprotein in the intestinal cells hinder its oral administration. In our study, new type of stabilized Pluronic micelles were developed and evaluated as carriers for paclitaxel delivery via oral or intravenous route. The pre-stabilized micelles were loaded with paclitaxel by simple solvent/evaporation technique achieving high encapsulation efficiency of approximately 70%. Gastrointestinal transit of the developed micelles was evaluated by oral administration of rhodamine-labeled micelles in rats. Our results showed prolonged gastrointestinal residence of the marker encapsulated into micelles, compared to a solution containing free marker. Further, the oral administration of micelles in mice showed high area under curve of micellar paclitaxel (similar to the area of i.v. Taxol(®)), longer mean residence time (9-times longer than i.v. Taxol(®)) and high distribution volume (2-fold higher than i.v. Taxol(®)) indicating an efficient oral absorption of paclitaxel delivered by micelles. Intravenous administration of micelles also showed a significant improvement of pharmacokinetic parameters of micellar paclitaxel vs. Taxol(®), in particular higher area under curve (1.2-fold), 5-times longer mean residence time and lower clearance, indicating longer systemic circulation of the micelles. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. 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.

  15. Adenine nucleotide translocase greatly increases the partition of trinitrophenyl-ATP into reduced Triton X-100 micelles.

    PubMed Central

    Tummino, P J; Gafni, A

    1992-01-01

    The presence of adenine nucleotide translocase (ANT) was found to greatly enhance the partitioning of the ATP analog 2',3'-O-(2,4,6-trinitrophenyl)-adenosine 5'-triphosphate (TNP-ATP) into reduced Triton X-100 micelles. The protein's effect was studied through the quenching of fluorescence of purified ANT, irreversibly inhibited by carboxyatractyloside (CAT), solubilized in reduced Triton X-100 micelles. The dependence of quenching of the protein's time-resolved tryptophan fluorescence on TNP-ATP concentration was measured and found to follow a Stern-Volmer mechanism. However, the calculated quenching constant was too large to be accounted for by the aqueous TNP-ATP concentration. Experiments were therefore conducted to determine the partitioning of the quencher between the three phases present: aqueous, protein-free micelle, and protein micelle; a system also described by the equation of Omann, G. M., and M. Glaser (1985. Biophys. J. 47:623-627.). By measuring the dependence of the apparent quenching rate constant on the protein concentration and protein/micelle ratios, this equation was used to calculate both the quencher partition coefficient into protein-free micelles (Pm) and into protein-micelles (Ppm), as well as the bimolecular quenching rate constant (kpm) in protein micelles. From the quenching experiments, kpm = 5.0 x 10(8)M-1s-1,Pm = 290 and pyrene quenching experiment to be 325, and by a rapid filtration experiment to be 450. Clearly, the presence of the integral membrane protein ANT-CAT in reduced Triton X-100 micelles greatly increases the partition of TNP-ATP into the micelle. ANT alters the properties and thus, the structure of the detergent micelle, which has direct implications for the use of detergent micelles as a model system for membrane proteins and may indicate that analogous effects occur in the mitochondrial membrane. PMID:1420926

  16. 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.

  17. Identifying efficacious approaches to chemoprevention with chlorophyllin, purified chlorophylls and freeze-dried spinach in a mouse model of transplacental carcinogenesis.

    PubMed

    Castro, David J; Löhr, 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 p.p.m. CHL, 2000 p.p.m. 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, coadministration 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 less lymphoma-dependent mortality (P < 0.001). The degree of protection by CHL, compared with controls dosed with DBP in tricaprylin (TCP) as the vehicle, was less marked, but still significant. Coadministration 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 support a mechanism involving complex-mediated reduction of carcinogen uptake.

  18. Mixed micelles of lipoic acid-chitosan-poly(ethylene glycol) and distearoylphosphatidylethanolamine-poly(ethylene glycol) for tumor delivery.

    PubMed

    Elsaid, Zeeneh; Taylor, Kevin M G; Puri, Sanyogitta; Eberlein, Cath A; Al-Jamal, Khuloud; Bai, Jie; Klippstein, Rebecca; Wang, Julie Tzu-Wen; Forbes, Ben; Chana, Jasminder; Somavarapu, Satyanarayana

    2017-04-01

    Many chemotherapeutics suffer from poor aqueous solubility and tissue selectivity. Distearoylphosphatidylethanolamine-poly(ethylene glycol) (DSPE-PEG) micelles are a promising formulation strategy for the delivery of hydrophobic anticancer drugs. However, storage and in vivo instability restrict their use. The aim of this study was to prepare mixed micelles, containing a novel polymer, lipoic acid-chitosan-poly(ethylene glycol) (LACPEG), and DSPE-PEG, to overcome these limitations and potentially increase cancer cell internalisation. Drug-loaded micelles were prepared with a model tyrosine kinase inhibitor and characterized for size, surface charge, stability, morphology, drug entrapment efficiency, cell viability (A549 and PC-9 cell lines), in vivo biodistribution, ex vivo tumor accumulation and cellular internalisation. Micelles of size 30-130nm with entrapment efficiencies of 46-81% were prepared. LACPEG/DSPE-PEG mixed micelles showed greater interaction with the drug (condensing to half their size following entrapment), greater stability, and a safer profile in vitro compared to DSPE-PEG micelles. LACPEG/DSPE-PEG and DSPE-PEG micelles had similar entrapment efficiencies and in vivo tumor accumulation levels, but LACPEG/DSPE-PEG micelles showed higher tumor cell internalisation. Collectively, these findings suggest that LACPEG/DSPE-PEG mixed micelles provide a promising platform for tumor delivery of hydrophobic drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Effect of high pressure and reversed micelles on the fluorescent proteins.

    PubMed

    Verkhusha, Vladislav V; Pozhitkov, Alexander E; Smirnov, Sergey A; Borst, Jan Willem; van Hoek, Arie; Klyachko, Natalya L; Levashov, Andrey V; Visser, Antonie J W G

    2003-08-22

    Two physico-chemical perturbations were applied to ECFP, EGFP, EYFP and DsRed fluorescent proteins: high hydrostatic pressure and encapsulation in reversed micelles. The observed fluorescence changes were described by two-state model and quantified by thermodynamic formalism. ECFP, EYFP and DsRed exhibited similar reaction volumes under pressure. The changes of the chemical potentials of the chromophore in bis(2-ethylhexyl)sulfosuccinate (AOT) micelles caused apparent chromophore protonation changes resulting in a fluorescence decrease of ECFP and EYFP. In contrast to the remarkable stability of DsRed, the highest sensitivity of EYFP fluorescence under pressure and in micelles is attributed to its chromophore structure.

  20. 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

  1. 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.

  2. Space-borne Chlorophyll Fluorescence, Greenness, Vegetation Models and Interannual Variability of Photosynthetic Activity: Spatio-temporal Patterns, Mechanisms, and Environmental Sensitivities

    NASA Astrophysics Data System (ADS)

    Walther, S.; Guanter, L.; Jung, M.; Frankenberg, C.; Sun, Y.; Forkel, M.; Zhang, Y.; Duveiller, G.; Cescatti, A.; Camps-Valls, G.; Köhler, P.

    2016-12-01

    It is much debated whether respiration or photosynthesis drive net ecosystem productivity andwhich regions contribute strongest to the observed interannual variability (IAV) of the strengthof the land sink. Several studies point to photosynthetic productivity in semi-arid regions as avery important factor influencing atmospheric CO2 variability globally (e.g. Jung et al., 2011;Poulter et al., 2014; Ahlstr ̈ om et al., 2015). Here, we aim at a comprehensive comparison ofthe strength, timing and spatial extent of anomalies of photosynthesis as they are indicated bysatellite observations of greenness, vegetation optical depth, and sun-induced chlorophyll fluo-rescence (SIF). We will compare them to the results of diagnostic, empirical and process-basedvegetation models. Except for the evergreen tropics, the spatio-temporal patterns of monthlydominant vegetation variability are generally consistently shown in semi-arid areas, albeit withdiffering magnitudes between greenness and photosynthesis globally. Relative anomalies (to themean seasonal cycle) are particularly widespread in high northern latitudes. Further researchsteps will include i) the repeated analysis at higher temporal resolution to better refine the dif-ferent time scales of reaction between light-use-efficiency and APAR and between forestedand non-forested ecosystems, ii) investigate on characteristic time scales at which the proxies(dis-)agree and why, iii) study the relative contributions of anomalies in peak and length of thegrowing season to IAV (similar to Xia et al., 2015; Zhou et al., 2016), iv) analyse the proxiesfor possibly differing hydrological sensitivities, and v) vegetation models have long been knownto have very diverse abilities to capture GPP IAV. Our preliminary results confirm this and wewill further study possible limitations and possible ways for improvement of the simulations.

  3. Supramolecular copolymer micelles based on the complementary multiple hydrogen bonds of nucleobases for drug delivery.

    PubMed

    Wang, Dali; Su, Yue; Jin, Chengyu; Zhu, Bangshang; Pang, Yan; Zhu, Lijuan; Liu, Jinyao; Tu, Chunlai; Yan, Deyue; Zhu, Xinyuan

    2011-04-11

    Novel supramolecular copolymer micelles with stimuli-responsive abilities were successfully prepared through the complementary multiple hydrogen bonds of nucleobases and then applied for rapid intracellular release of drugs. First, both adenine-terminated poly(ε-caprolactone) (PCL-A) and uracil-terminated poly(ethylene glycol) (PEG-U) were synthesized. The supramolecular amphiphilic block copolymers (PCL-A:U-PEG) were formed based on multiple hydrogen bonding interactions between PCL-A and PEG-U. The micelles self-assembled from PCL-A:U-PEG were sufficiently stable in water but prone to fast aggregation in acidic condition due to the dynamic and sensitive nature of noncovalent interactions. The low cytotoxicity of supramolecular copolymer micelles was confirmed by MTT assay against NIH/3T3 normal cells. As a hydrophobic anticancer model drug, doxorubicin (DOX) was encapsulated into these supramolecular copolymer micelles. In vitro release studies demonstrated that the release of DOX from micelles was significantly faster at mildly acid pH of 5.0 compared to physiological pH. MTT assay against HeLa cancer cells showed DOX-loaded micelles had high anticancer efficacy. Hence, these supramolecular copolymer micelles based on the complementary multiple hydrogen bonds of nucleobases are very promising candidates for rapid controlled release of drugs.

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

    PubMed Central

    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 (188Re) as a combined radiotherapy and chemotherapy treatment for hepatocellular carcinoma. We investigated the single photon emission computed tomography, biodistribution, antitumor efficacy, and pathology of 188Re-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 188Re-Dox micelles group had significantly longer survival compared with the control, 188ReO4 alone (P<0.005), and Dox micelles alone (P<0.01) groups. Pathohistological analysis revealed that tumors treated with 188Re-Dox micelles had more necrotic features and decreased cell proliferation. Therefore, 188Re-Dox micelles may enable combined radiotherapy and chemotherapy to maximize the effectiveness of treatment for hepatocellular carcinoma. PMID:26719687

  5. 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

  6. Retinal-conjugated pH-sensitive micelles induce tumor senescence for boosting breast cancer chemotherapy.

    PubMed

    Zhang, Yijuan; Li, Ping; Pan, Hong; Liu, Lanlan; Ji, Manyi; Sheng, Nan; Wang, Ce; Cai, Lintao; Ma, Yifan

    2016-03-01

    Evoking tumor cellular senescence, an irreversible status of cell growth quiescence, has been recently proposed as a potential strategy to improve the efficacy of cancer treatment. In the current study, all-trans retinal, the precursor of all-trans retinoic acid, was conjugated to dextran via hydrazone bond to generate amphiphilic dextran-retinal (DR) conjugates, which self-assembled into pH-sensitive DR micelles. Our results showed that DR micelles moderately inhibited MCF-7 breast cancer cell growth through inducing p21-associated cellular senescence, which relied on retinoic acid receptors (RARs) and was accompanied by significant G0/G1 cell cycle arrest. Moreover, DR micelles were capable of encapsulating doxorubicin (DOX) to generate DOX-loaded DD micelles, facilitating the uptake and release of DOX in cancer cells. Compared with free DOX, DD micelles more effectively suppressed tumor growth and prolonged survival time of mouse xenograft model through inducing tumor apoptosis and cellular senescence. However, blocking cellular senescence diminished DD-caused apoptosis in MCF-7 cells by 40-50%. Therefore, pH-sensitive DR micelles not only served as a potent platform for DOX delivery, but also enhanced the anti-tumor effect of DOX by inducing tumor cellular senescence. These data reveal a great potential of evoking tumor senescence with retinal-conjugated micelles for boosting breast cancer chemotherapy. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Relationship between physical properties of casein micelles and rheology of skim milk concentrate.

    PubMed

    Karlsson, A O; Ipsen, R; Schrader, K; Ardö, Y

    2005-11-01

    The properties of casein micelles in milk concentrates are of interest for the use of ultrafiltered (UF) skim milk concentrates in dairy products, and for the general understanding of colloidal stability and behavior of the casein micelle. The rheological behavior of UF skim milk concentrate with a casein concentration of 19.5% (wt/wt) was investigated at different pH and NaCl concentrations by analyzing flow viscometry and small amplitude oscillatory shear measurements. Viscometric flow curves were fitted to the Carreau-Yasuda model with the aim of determining values for the viscosity at infinite high shear rates and thereby estimate the voluminosity of the casein micelles (nu(casein)) in the UF concentrate. The voluminosity of the casein micelles increased with addition of NaCl and decreased when pH was decreased from 6.5 to 5.5. At pH 5.2, nu(casein) increased because of acid-induced aggregation of the casein micelles. The changes in nu(casein) could be interpreted from transmission electron microscopy of freeze-fractured samples of the UF concentrate and partly from dynamic light scattering measurements. Altered interactions between casein micelles due to different pH and NaCl concentrations are proposed to occur due to collapse of the kappa-casein layer, changed ionic strength, and altered distance between casein micelles.

  8. pH triggered doxorubicin delivery of PEGylated glycolipid conjugate micelles for tumor targeting therapy.

    PubMed

    Hu, Fu-Qiang; Zhang, Yin-Ying; You, Jian; Yuan, Hong; Du, Yong-Zhong

    2012-09-04

    The main objective of this study was aimed at tumor microenvironment-responsive vesicle for targeting delivery of the anticancer drug, doxorubicin (DOX). A glucolipid-like conjugate (CS) was synthesized by the chemical reaction between chitosan and stearic acid, and polyethylene glycol (PEG) was then conjugated with CS via a pH-responsive cis-aconityl linkage to produce acid-sensitive PEGylated CS conjugates (PCCS). The conjugates with a critical micelle concentration (CMC) of 181.8 μg/mL could form micelles in aqueous phase, and presented excellent DOX loading capacity with a drug encapsulation efficiency up to 87.6%. Moreover, the PCCS micelles showed a weakly acid-triggered PEG cleavage manner. In vitro drug release from DOX-loaded PCCS micelles indicated a relatively faster DOX release in weakly acidic environments (pH 5.0 and 6.5). The CS micelles had excellent cellular uptake ability, which could be significantly reduced by the PEGylation. However, the cellular uptake ability of PCCS was enhanced comparing with insensitive PEGylated CS (PCS) micelles in weakly acidic condition imitating tumor tissue. Taking PCS micelles as a comparative group, the PCCS drug delivery system was demonstrated to show much more accumulation in tumor tissue, followed by a relatively better performance in antitumor activity together with a security benefit on xenograft tumor model.

  9. 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.

  10. Thermal responsive micelles for dual tumor-targeting imaging and therapy

    NASA Astrophysics Data System (ADS)

    Chen, Haiyan; Li, Bowen; Qiu, Jiadan; Li, Jiangyu; Jin, Jing; Dai, Shuhang; Ma, Yuxiang; Gu, Yueqing

    2013-11-01

    Two kinds of thermally responsive polymers P(FAA-NIPA-co-AAm-co-ODA) and P(FPA-NIPA-co-AAm-co-ODA) containing folate, isopropyl acrylamide and octadecyl acrylate were fabricated through free radical random copolymerization for targeted drug delivery. Then the micelles formed in aqueous solution by self-assembly and were characterized in terms of particle size, lower critical solution temperature (LCST) and a variety of optical spectra. MTT assays demonstrated the low cytotoxicity of the control micelle and drug-loaded micelle on A549 cells and Bel 7402 cells. Then fluorescein and cypate were used as model drugs to optimize the constituents of micelles for drug entrapment efficiency and investigate the release kinetics of micelles in vitro. The FA and thermal co-mediated tumor-targeting efficiency of the two kinds of micelles were verified and compared in detail at cell level and animal level, respectively. These results indicated that the dual-targeting micelles are promising drug delivery systems for tumor-targeting therapy.

  11. 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

  12. 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

  13. Effect of micelles and mixed micelles on efficiency and selectivity of antibiotic-based capillary electrophoretic enantioseparations

    SciTech Connect

    Rundlett, K.L.; Armstrong, D.W.

    1995-07-01

    Vancomycin (an oligophenolic, glycopeptide, macrocyclic antibiotic) has been shown to be a superb chiral selector for anionic and neutral compounds. It was found that adding sodium dodecyl sulfate to the run buffer increased efficiency by over 1 order of magnitude, decreased analysis times, and reversed the elution order of the enantiomers. This allows for control of the retention order as well as the resolution of enantiomers in complex mixtures in a single run. A mechanism is proposed which explains all of the observed effects and is verified experimentally. Since vancomycin is present in both the micelle and in free solution, previously proposed micelle-selector models are, at best, limiting cases. A general equation is derived which can be used to describe all possible interactions, including those with the capillary wall, if needed. Also, it is shown that electrophoretic mobilities and not migration times must be used to calculate binding constants of a solute to the micelle, the chiral selector, or both. Furthermore, it is shown that a neutral marker molecule cannot be used to accurately correct mobilities that have been altered due to changes in solution viscosity. While this work utilizes the practical vancomycin-micelle system, the general conclusions and theory apply to most other analogous CE systems as well. 48 refs., 4 figs., 5 tabs.

  14. 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.

  15. Chlorophyll sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Glenn, D. F.

    1984-06-01

    The photovoltaic properties of the green plant pigment chlorophyll-a (Chl-a) were investigated in photoelectrochemical and solid state solar cells. Both types of cells utilized a thin film of Chl-a electro-deposited on a SnO2 optically transparent electrode. Solid state cells were fabricated by vapor depositing a thin layer of metal on top of the Chl-A to produce a SnO2/Chl-a/metal sandwich cell. Photoelectrochemical cells were assembled by immersing the SnO2/Chl-a electrode in an aqueous electrolyte solution along with a counter electrode. Both types of Chl-a cells were generally characterized by a strong dependence of he photoactivity on the other cell components and a surprisingly large photovoltage. Photoelectrochemical cells of SnO2/l-a/aq.AlCl3 were seen to produce photovoltages as high as 1.1 V and photocurrents of 1.1 micro A/sq cm while a solid state cell of SnO2/Chl-a/Al could produce 1.4 V and an initial photocurrent of 200 micro A/sq cm. This photoactivity was strongly time dependent in both configurations. Despite this fact, these cells are the most powerful Chl-a sensitized solar cells yet reported.

  16. 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

  17. 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.

  18. 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

  19. Design of block-copolymer-based micelles for active and passive targeting

    NASA Astrophysics Data System (ADS)

    Lebouille, Jérôme G. J. L.; Leermakers, Frans A. M.; Cohen Stuart, Martien A.; Tuinier, Remco

    2016-10-01

    A self-consistent field study is presented on the design of active and passive targeting block-copolymeric micelles. These micelles form in water by self-assembly of triblock copolymers with a hydrophilic middle block and two hydrophobic outer blocks. A minority amount of diblock copolymers with the same chemistry is taken to coassemble into these micelles. At the end of the hydrophilic block of the diblock copolymers, a targeting moiety (TM) is present. Assuming that the rotation of the micelle towards the target is sufficiently fast, we can elaborate a single gradient cell model, wherein the micelle is in the center and the receptor (R) substrate exists on the outer plane of the spherical coordinate system. The distribution function of the targeting moiety corresponds to a Landau free energy with local minima and corresponding maxima. The lowest minimum, which is the ground state, shifts from within the micelle to the adsorbing state upon bringing the substrate closer to the micelle, implying a jumplike translocation of the targeting moiety. Equally deep minima represent the binodal of the phase transition, which is, due to the finite chain length, first-order like. The maximum in-between the two relevant minima implies that there is an activation barrier for the targeting moiety to reach the receptor surface. We localize the parameter space wherein the targeting moiety is (when the micelle is far from the target) preferably hidden in the stealthy hydrophilic corona of the micelle, which is desirable to avoid undesired immune responses, and still can jump out of the corona to reach the target quick enough, that is, when the barrier height is sufficiently low. The latter requirement may be identified by a spinodal condition. We found that such hidden TMs can still establish a TM-R contact at distances up to twice the corona size. The translocation transition will work best when the affinity of the TM for the core is avoided and when hydrophilic TMs are selected.

  20. Agarose hydrogels embedded with pH-responsive diblock copolymer micelles for triggered release of substances.

    PubMed

    Jin, Naixiong; Morin, Emily A; Henn, Daniel M; Cao, Yu; Woodcock, Jeremiah W; Tang, Shuangcheng; He, Wei; Zhao, Bin

    2013-08-12

    Hybrid agarose hydrogels embedded with pH-responsive diblock copolymers micelles were developed to achieve functional hydrogels capable of stimulus-triggered drug release. Specifically, a well-defined poly(ethylene oxide) (PEO)-based diblock copolymer, PEO-b-poly(2-(N,N-diisopropylamino)ethyl methacrylate) (PEO(113)-b-PDPAEMA(31), where the subscripts represent the degrees of polymerization of two blocks), was synthesized by atom transfer radical polymerization. PDPAEMA is a pH-responsive polymer with a pKa value of 6.3. The PEO(113)-b-PDPAEMA(31) micelles were formed by a solvent-switching method, and their pH-dependent dissociation behavior was investigated by dynamic light scattering and fluorescence spectroscopy. Both studies indicated that the micelles were completely disassembled at pH = 6.40. The biocompatibility of PEO(113)-b-PDPAEMA(31) micelles was demonstrated by in vitro primary cortical neural culture. Hybrid agarose hydrogels were made by cooling 1.0 wt % agarose solutions that contained various amounts of PEO(113)-b-PDPAEMA(31) micelles at either 2 or 4 °C. Rheological measurements showed that the mechanical properties of gels were not significantly adversely affected by the incorporation of diblock copolymer micelles with a concentration as high as 5.0 mg/g. Using Nile Red as a model hydrophobic drug, its incorporation into the core of diblock copolymer micelles was demonstrated. Characterized by fluorescent spectroscopy, the release of Nile Red from the hybrid hydrogel was shown to be controllable by pH due to the responsiveness of the block copolymer micelles. Based on the prominent use of agarose gels as scaffolds for cell transplantation for neural repair, the hybrid hydrogels embedded with stimuli-responsive block copolymer micelles could allow the controlled delivery of hydrophobic neuroprotective agents to improve survival of transplanted cells in tune with signals from the surrounding pathological environment.

  1. 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)

  2. 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)

  3. 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

  4. Hybridization of Block Copolymer Micelles

    DTIC Science & Technology

    1993-01-01

    J. Macromol. Sci., Part A 1973, 7,601. (10) Tiara, M.; Ramireddy, C.; Webber, S. K; Munk,P. Collect. Czer" (14) 0snford, C. In The Hydrophobic Effect ...equilibrate In the first series of experiments we have studied the within 20 min, similarly as ASA-10 micelles do. However, effect of the copolymer...high. This may happen after a sudden The Johnston-Ogston effect 2’ 6- also may play a role in jump in temperature or in the composition of the mixed

  5. Multiscale coarse graining of diblock copolymer self-assembly: from monomers to ordered micelles.

    PubMed

    Pierleoni, Carlo; Addison, Chris; Hansen, Jean-Pierre; Krakoviack, Vincent

    2006-03-31

    Starting from a microscopic lattice model, we investigate clustering, micellization, and micelle ordering in semidilute solutions of AB diblock copolymers in a selective solvent. To bridge the gap in length scales, from monomers to ordered micellar structures, we implement a two-step coarse-graining strategy, whereby the AB copolymers are mapped onto ultrasoft dumbells with monomer-averaged effective interactions between the centers of mass of the blocks. Monte Carlo simulations of this coarse-grained model yield clear-cut evidence for self-assembly into micelles with a mean aggregation number n approximately 100 beyond a critical concentration. At a slightly higher concentration the micelles spontaneously undergo a disorder-order transition to a cubic phase. We determine the effective potential between these micelles from first principles.

  6. [Spatio-temporal distribution of chlorophyll a concentration and its estimation in Taihu Lake].

    PubMed

    Le, Cheng-Feng; Li, Yun-Mei; Sun, De-Yong; Wang, Hai-Jun; Huang, Chang-Chun

    2008-03-01

    The temporal and spatial distribution of chlorophyll a concentration in Taihu Lake was analyzed using the data measured from January to October in 2005. Otherwise, chlorophyll a retrieval model was built using the synchronous spectrum data obtained in different season to evaluate the effect of chlorophyll a concentration temporal and spatial variation on the retrieval model. Firstly, temporal distribution of chlorophyll a concentration was analyzed. Then, chlorophyll a concentration was induced by Inverse Distance Weight method. Lastly, the chlorophyll a concentration estimation models based on spring, summer, autumn and different trophic states were built. An obvious spatial-temporal distribution was found for chlorophyll a concentration in Taihu. Chlorophyll a concentration had the maximal value in summer and the minimal value in winter,and the average chlorophyll a concentration was 56.29 microg/L, 13.61 microg/L respectively. Due to the effect of autumn, the average chlorophyll a concentration in autumn was higher than that in spring, and the average chlorophyll a concentration was 26.43 microg/L, 34.78 microg/L respectively. Marked spatial difference for chlorophyll a concentration was found in summer,while in winterthe spatial variation was ambiguous. The spatial variation in autumn was greater than that in spring as influenced by summer. Spatially, the variation in north area was greater than those in the other areas and the south area had less variation during the year. Because of the different chlorophyll a concentration, different season had different retrieval model. Band-ratio had better retrieval result in spring and autumn as there were lower concentration and less variation correspondingly. While in summer, because of the high chlorophyll a concentration and great spatial variation, among the arithmetic built in summer, the differential arithmetic was the optimal model, and the difference of Chl-a concentration retrieval model of different trophic

  7. 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.

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

    PubMed

    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.

  10. 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

  11. Nanorod Mobility within Entangled Wormlike Micelle Solutions

    SciTech Connect

    Lee, Jonghun; Grein-Iankovski, Aline; Narayanan, Suresh; Leheny, Robert L.

    2016-12-20

    In the semi-dilute regime, wormlike micelles form an isotropic entangled microstructure that is similar to that of an entangled polymer solution with a characteristic, nanometer-scale entanglement mesh size. We report a combined x-ray photon correlation spectroscopy (XPCS) and rheology study to investigate the translational dynamics of gold nanorods in semi-dilute solutions of entangled wormlike micelles formed by the surfactant cetylpyridinium chloride (CPyCl) and the counter-ion sodium salicylate (NaSal). The CPyCl concentration is varied to tune the entanglement mesh size over a range that spans from approximately equal to the nanorod diameter to larger than the nanorod length. The NaSal concentration is varied along with the CPyCl concentration so that the solutions have the maximum viscosity for given CPyCl concentration. On short time scales the nanorods are localized on a length scale matching that expected from the high-frequency elastic modulus of the solutions as long as the mesh size is smaller than the rod length. On longer time scales, the nanorods undergo free diffusion. At the highest CPyCl concentrations, the nanorod diffusivity approaches the value expected based on the macroscopic viscosity of the solutions, but it increases with decreasing CPyCl concentration more rapidly than expected from the macroscopic viscosity. A recent model by Cai et al. [Cai, L.-H.; Panyukov, S.; Rubinstein, M. Macromolecules 2015, 48, 847-862.] for nanoparticle “hopping” diffusion in entangled polymer solutions accounts quantitatively for this enhanced diffusivity.

  12. Nanorod Mobility within Entangled Wormlike Micelle Solutions

    DOE PAGES

    Lee, Jonghun; Grein-Iankovski, Aline; Narayanan, Suresh; ...

    2016-12-20

    In the semi-dilute regime, wormlike micelles form an isotropic entangled microstructure that is similar to that of an entangled polymer solution with a characteristic, nanometer-scale entanglement mesh size. We report a combined x-ray photon correlation spectroscopy (XPCS) and rheology study to investigate the translational dynamics of gold nanorods in semi-dilute solutions of entangled wormlike micelles formed by the surfactant cetylpyridinium chloride (CPyCl) and the counter-ion sodium salicylate (NaSal). The CPyCl concentration is varied to tune the entanglement mesh size over a range that spans from approximately equal to the nanorod diameter to larger than the nanorod length. The NaSal concentrationmore » is varied along with the CPyCl concentration so that the solutions have the maximum viscosity for given CPyCl concentration. On short time scales the nanorods are localized on a length scale matching that expected from the high-frequency elastic modulus of the solutions as long as the mesh size is smaller than the rod length. On longer time scales, the nanorods undergo free diffusion. At the highest CPyCl concentrations, the nanorod diffusivity approaches the value expected based on the macroscopic viscosity of the solutions, but it increases with decreasing CPyCl concentration more rapidly than expected from the macroscopic viscosity. A recent model by Cai et al. [Cai, L.-H.; Panyukov, S.; Rubinstein, M. Macromolecules 2015, 48, 847-862.] for nanoparticle “hopping” diffusion in entangled polymer solutions accounts quantitatively for this enhanced diffusivity.« less

  13. Prediction of an Autocatalytic Replication Mechanism for Micelle Formation

    NASA Astrophysics Data System (ADS)

    Pool, René; Bolhuis, Peter G.

    2006-07-01

    We report molecular simulations suggesting that the kinetics of surfactant micelle formation can be sped up significantly by a replication mechanism, in which growing micelles become unstable and split into two similar sized micelles. We argue that for certain surfactants types around the critical micelle concentration, such a mechanism becomes more dominant than the commonly accepted nucleation pathway.

  14. 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.

  15. Effect of hydrophobicity of core on the anticancer efficiency of micelles as drug delivery carriers.

    PubMed

    Sun, Chun-Yang; Ma, Yin-Chu; Cao, Zi-Yang; Li, Dong-Dong; Fan, Feng; Wang, Jun-Xia; Tao, Wei; Yang, Xian-Zhu

    2014-12-24

    Recently, micelles, which are self-assembled by amphiphilic copolymers, have attracted tremendous attention as promising drug delivery systems for cancer treatment. Thus, the hydrophobic core of the micelles, which could efficiently encapsulate small molecular drug, will play a significant role for the anticancer efficiency. Unfortunately, the effect of hydrophobicity of micellar core on its anticancer efficiency was rarely reported. Herein, the amphiphilic diblock polymers of poly(ethylene glycol) and polyphosphoester with different side groups (butyl, hexyl, octyl) were synthesized to tune the hydrophobicity of the micellar core. We found that the in vitro cytotoxicity of the DOX-loaded micelles decreased with the increasing hydrophobicity of micellar core due to the drug release rate. However, following systemic delivery, the DOX-loaded micelles with the most hydrophobic core exhibited the most significant inhibition of tumor growth in a MDA-MB-231 tumor model, indicating the importance of hydrophobicity of core on the antitumor efficacy of drug delivery systems.

  16. Application of active-phase plot to the kinetic analysis of lipoxygenase in reverse micelles.

    PubMed Central

    Perez-Gilabert, M; Sanchez-Ferrer, A; Garcia-Carmona, F

    1992-01-01

    A new plot for explaining the complex expression of the enzymic activity in reverse micelles has been developed as an extension of the theoretical model described by our group [Bru, Sánchez-Ferrer & García-Carmona (1990) Biochem. J. 268, 679-684]. The plot describes the changes in the relative volume, amount of enzyme (mumoles), enzyme concentration (microM) and substrate concentration (microM) in the phase where the enzyme is active. To illustrate the usefulness of this plot, the complex activity of soya bean lipoxygenase in reverse micelles acting on its interfacial substrate, octadecadienoic acid, was studied. It showed the key parameters ruling the activity profiles of lipoxygenase with respect to micelle size (omega 0), micelle concentration (theta) and the substrate/surfactant molar ratio (rho), which have never been described before. PMID:1281978

  17. Sampling the kinetic pathways of a micelle fusion and fission transition

    NASA Astrophysics Data System (ADS)

    Pool, René; Bolhuis, Peter G.

    2007-06-01

    The mechanism and kinetics of micellar breakup and fusion in a dilute solution of a model surfactant are investigated by path sampling techniques. Analysis of the path ensemble gives insight in the mechanism of the transition. For larger, less stable micelles the fission/fusion occurs via a clear neck formation, while for smaller micelles the mechanism is more direct. In addition, path analysis yields an appropriate order parameter to evaluate the fusion and fission rate constants using stochastic transition interface sampling. For the small, stable micelle (50 surfactants) the computed fission rate constant is a factor of 10 lower than the fusion rate constant. The procedure opens the way for accurate calculation of free energy and kinetics for, e.g., membrane fusion, and wormlike micelle endcap formation.

  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. Transferrin receptor targeted PLA-TPGS micelles improved efficacy and safety in docetaxel delivery.

    PubMed

    Singh, Rahul Pratap; Sharma, Gunjan; Sonali; Agrawal, Poornima; Pandey, Bajarangprasad L; Koch, Biplob; Muthu, Madaswamy S

    2016-02-01

    The aim of this work was to develop targeted polymeric micelles of poly-lactic acid-D-α-tocopheryl polyethylene glycol 1000 succinate (PLA-TPGS), which are assembled along with D-alpha-tocopheryl polyethylene glycol 1000 succinate-transferrin conjugate (TPGS-Tf), and loaded docetaxel (DTX) as a model drug for enhanced treatment of lung cancer in comparison to non-targeted polymeric micelles and DTX injection (Docel™). A549 human lung cancer cells were employed as an in vitro model to access cytotoxicity study of the DTX loaded polymeric micelles. The safety of DTX formulations were studied by the measurement of alkaline phosphatase (ALP), lactate dehydrogenase (LDH) and total protein levels in bronchoalveolar lavage (BAL) fluid of rats after the treatments. The IC50 values demonstrated that the non-targeted and transferrin receptor targeted polymeric micelles could be 7 and 70 folds more effective than Docel™ after 24 h treatment with the A549 cells. Results suggested that transferrin receptor targeted polymeric micelles have showed better efficacy and safety than the non-targeted polymeric micelles and Docel™.

  20. Preparation of core-crosslinked linear-dendritic copolymer micelles with enhanced stability and their application for drug solubilisation.

    PubMed

    Zhou, Zhengyuan; Forbes, Robert T; D'Emanuele, Antony

    2017-05-15

    In this study we explore the preparation of core-crosslinked micelles of linear-dendritic methoxy-poly(ethylene glycol) (MPEG)-co-poly(ester-sulfide) (PES) polymers to improve the stability of such polymeric micelle systems against premature disintegration and drug release. A series of MPEG-PES copolymers were synthesised via stepwise reactions of acetylation and thiol-ene photoreaction. Surface tension measurement showed that the copolymers with ethenyl surface groups could self-associate in dilute aqueous solutions to form micelles. Crosslinking within the micelle cores in the presence of dithioerythritol (DTT) linker was initiated under UV radiation. The formation of core-crosslinked micelles was confirmed by HPLC in combination with charged aerosol detection (CAD). The copolymers were found to readily hydrolyse under acidic conditions due to the ester-containing dendrons. Drug solubilisation capacities of the micellar solutions were determined using griseofulvin as a poorly water-soluble model drug. The solubility of griseofulvin showed a 10-fold enhancement in 1% w/v micelle solution and increased with the concentration of the copolymers. Drug release studies indicated that a more sustained release of griseofulvin was achieved for the core-crosslinked micelles compared to the non-crosslinked micelles, attributable to greater stability of the crosslinked core structure. The findings of this study present a new pathway towards developing biodegradable polymeric nanocarriers. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Photothermal Ablation of in Situ Renal Tumor by PEG-IR780-C13 Micelles and Near-Infrared Irradiation.

    PubMed

    Qiu, Xuefeng; Xu, Linfeng; Zhang, Yanting; Yuan, Ahu; Wang, Kaikai; Zhao, Xiaozhi; Wu, Jinhui; Guo, Hongqian; Hu, Yiqiao

    2016-03-07

    PEG-IR780-C13 micelles have been demonstrated to be a novel photothermal agent with tumor-targeting property. This study was designed to explore the feasibility of applying PEG-IR780-C13 micelles and near-infrared (NIR) irradiation for thermal ablation of renal tumor by using an in situ tumor model. In addition, the potential thermal injury to normal renal tissue was evaluated. PEG-IR780-C13 micelles were intended to accumulate in renal tumor after systemic delivery. In vitro results revealed that PEG-IR780-C13 micelles were uptaken by RENCA cells mainly through caveola-mediated endocytosis and mainly distributed in late endosomes and lysosomes. Upon NIR irradiation, PEG-IR780-C13 micelles generated heat effectively both in vitro and in vivo, exhibiting a promising photothermal therapeutic property. The photothermal effect of PEG-IR780-C13 micelles could effectively destroy RENCA cells in vitro and adequately inhibit growth of in situ renal tumor in vivo. Meanwhile, PEG-IR780-C13 micelles mediated photothermal therapy (PTT) resulting in only limited injury to normal renal tissue surrounding tumor sites. Our data indicated that PEG-IR780-C13 micelles mediating PTT could generate tumor-specific heat for destruction of renal tumor in a minimally invasive way, providing a novel strategy for thermal ablation of renal tumor.

  2. Cationic amphiphilic drugs self-assemble to the core-shell interface of PEGylated phospholipid micelles and stabilize micellar structure.

    PubMed

    Wang, Jing; Xing, Xueqing; Fang, Xiaocui; Zhou, Chang; Huang, Feng; Wu, Zhonghua; Lou, Jizhong; Liang, Wei

    2013-10-13

    Since polymeric micelles are promising and have potential in drug delivery systems, people have become more interested in studying the compatibility of polymeric carriers and drugs, which might help them to simplify the preparation method and increase the micellar stability. In this article, we report that cationic amphiphilic drugs can be easily encapsulated into PEGylated phospholipid (PEG-PE) micelles by self-assembly method and that they show high encapsulation efficiency, controllable drug release and better micellar stability than empty micelles. The representative drugs are doxorubicin and vinorelbine. However, gemcitabine and topotecan are not suitable for PEG-PE micelles due to lack of positive charge or hydrophobicity. Using a series of experiments and molecular modelling, we figured out the assembly mechanism, structure and stability of drug-loaded micelles, and the location of drugs in micelles. Integrating the above information, we explain the effect of the predominant force between drugs and polymers on the assembly mechanism and drug release behaviour. Furthermore, we discuss the importance of pKa and to evaluate the compatibility of drugs with PEG-PE in self-assembly preparation method. In summary, this work provides a scientific understanding for the reasonable designing of PEG-PE micelle-based drug encapsulation and might enlighten the future study on drug-polymer compatibility for other polymeric micelles.

  3. 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

  4. 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.

  5. 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.

    1980-01-01

    Chlorophyll gradient maps of large ocean areas were generated from U-2/OCS data obtained over test sites in the Pacific and the 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 the ocean surface can be properly modeled by using a measurement made at 778 nm. The calculation of atmospheric radiance was performed by using a method developed by Dave. An estimation of the chlorophyll concentration is performed by properly ratioing radiances measured at 472 and 548 nm after removing the atmospheric effects. The correlation between the remotely sensed data and the in situ surface chlorophyll measurements has been 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.

  6. Three dimensional (3D) distribution calculation of chlorophyll in rice based on infrared imaging technique

    NASA Astrophysics Data System (ADS)

    Li, Zong-nan; Xie, Jing; Zhang, Jian

    2014-11-01

    Chlorophyll content and distribution in leaf can reflect the plant health and nutrient status of the plant indirectly. It is meaningful to monitor the 3D distribution of chlorophyll in plant science. It can be done by the method in this paper: Firstly, the chlorophyll contents at different point in leaf are measured with the SPAD-502 chlorophyll meter, and the RGN images composed by the channel R, G and NIR are captured with the imaging system. Secondly, the 3D model is built from the RGN images and the RGN texture map containing all the information of R, G and NIR is generated. Thirdly, the regression model between chlorophyll content and color characteristics is established. Finally, the 3D distribution of chlorophyll in rice is captured by mapping the 2D distribution map of chlorophyll calculated by the regression model to the 3D model. This methodology achieves the combination of phenotype and physiology, it can calculated the 3D distribution of chlorophyll in rice well. The color characteristic g is good indicator of chlorophyll content which can be used to measure the 3D distribution of chlorophyll quickly. Moreover, the methodology can be used to high throughout analyze the rice.

  7. Ultrafast Dynamics in Reverse Micelles

    NASA Astrophysics Data System (ADS)

    Levinger, Nancy E.; Swafford, Laura A.

    2009-05-01

    Recent advances in ultrafast laser technology have spurred investigations of microheterogeneous solutions. In particular, researchers have explored details of reverse micelles (RMs), which present isolated droplets of polar solvent sequestered from a continuous nonpolar phase by a surfactant layer. This review explores recent studies utilizing a variety of ultrafast laser techniques to uncover details about structure and dynamics in various RMs. Using ultrafast vibrational spectroscopy, researchers have probed hydrogen-bond dynamics and vibrational energy relaxation in RMs. These studies have developed our understanding of reverse micellar structure, identifying varying water environments in the RMs. In a plethora of experiments employing probe molecules, researchers have explored the confined environment presented by RMs and their impact on a range of chemical reactions. These studies have shown that confinement, rather than the specific interactions with surfactants, is an important factor determining the impact of the reverse micellar environment on the chemistry.

  8. Antimicrobial peptide RP-1 structure and interactions with anionic versus zwitterionic micelles.

    PubMed

    Bourbigot, Sarah; Dodd, Erin; Horwood, Chrystal; Cumby, Nichole; Fardy, Liam; Welch, William H; Ramjan, Zachary; Sharma, Shantanu; Waring, Alan J; Yeaman, Michael R; Booth, Valerie

    2009-01-01

    Topologically, platelet factor-4 kinocidins consist of distinct N-terminal extended, C-terminal helical, and interposing gamma-core structural domains. The C-terminal alpha-helices autonomously confer direct microbicidal activity, and the synthetic antimicrobial peptide RP-1 is modeled upon these domains. In this study, the structure of RP-1 was assessed using several complementary techniques. The high-resolution structure of RP-1 was determined by NMR in anionic sodium dodecyl sulfate (SDS) and zwitterionic dodecylphosphocholine (DPC) micelles, which approximate prokaryotic and eukaryotic membranes, respectively. NMR data indicate the peptide assumes an amphipathic alpha-helical backbone conformation in both micelle environments. However, small differences were observed in the side-chain orientations of lysine, tyrosine, and phenylalanine residues in SDS versus DPC environments. NMR experiments with a paramagnetic probe indicated differences in positioning of the peptide within the two micelle types. Molecular dynamics (MD) simulations of the peptide in both micelle types were also performed to add insight into the peptide/micelle interactions and to assess the validity of this technique to predict the structure of peptides in complex with micelles. MD independently predicted RP-1 to interact only peripherally with the DPC micelle, leaving its spherical shape intact. In contrast, RP-1 entered deeply into and significantly distorted the SDS micelle. Overall, the experimental and MD results support a preferential specificity of RP-1 for anionic membranes over zwitterionic membranes. This specificity likely derives from differences in RP-1 interaction with distinct lipid systems, including subtle differences in side chain orientations, rather than gross changes in RP-1 structure in the two lipid environments.

  9. 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.

  10. Biodegradable hybrid polymer micelles for combination drug therapy in ovarian cancer.

    PubMed

    Desale, Swapnil S; Cohen, Samuel M; Zhao, Yi; Kabanov, Alexander V; Bronich, Tatiana K

    2013-11-10

    The co-delivery of drug combination at a controlled ratio via the same vehicle to the cancer cells is offering the advantages such as spatial-temporal synchronization of drug exposure, synergistic therapeutic effects and increased therapeutic potency. In an attempt to develop such multidrug vehicle this work focuses on functional biodegradable and biocompatible polypeptide-based polymeric micelles. Triblock copolymers containing the blocks of ethylene glycol, glutamic acid and phenylalanine (PEG-PGlu-PPhe) were successfully synthesized via NCA-based ring-opening copolymerization and their composition was confirmed by (1)H NMR. Self-assembly behavior of PEG-PGlu90-PPhe25 was utilized for the synthesis of hybrid micelles with PPhe hydrophobic core, cross-linked ionic PGlu intermediate shell layer, and PEG corona. Cross-linked (cl) micelles were about 90nm in diameter (ξ-potential=-20mV), uniform (narrow size distribution), and exhibited nanogels-like behavior. Degradation of cl-micelles was observed in the presence of proteolytic enzymes (cathepsin B). The resulting cl-micelles can incorporate the combination of drugs with very different physical properties such as cisplatin (15 w/w% loading) and paclitaxel (9 w/w% loading). Binary drug combination in cl-micelles exhibited synergistic cytotoxicity against human ovarian A2780 cancer cells and exerted a superior antitumor activity by comparison to individual drug-loaded micelles or free cisplatin in cancer xenograft model in vivo. Tunable composition and stability of these hybrid biodegradable micelles provide platform for drug combination delivery in a broad range of cancers. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Reversal of doxorubicin resistance in breast cancer by mitochondria-targeted pH-responsive micelles.

    PubMed

    Yu, Pengcheng; Yu, Haijun; Guo, Chengyue; Cui, Zhirui; Chen, Xianzhi; Yin, Qi; Zhang, Pengcheng; Yang, Xiangliang; Cui, Honggang; Li, Yaping

    2015-03-01

    Chemotherapy is an important approach for clinical cancer treatment. However, the success of chemotherapy is usually hindered by the occurrence of intrinsic or acquired multidrug resistance of cancer cells. Herein, we reported an effective approach to overcome doxorubicin (DOX) resistance in MCF-7/ADR breast cancer using DOX-loaded pH-responsive micelles. The micelles were prepared from a pH-responsive diblock copolymer, poly(ethylene glycol)-block-poly(2-(diisopropylamino)ethyl methacrylate) (PEG-b-PDPA), and a vitamin E derivate (D-α-tocopheryl polyethylene glycol 1000 succinate, TPGS) (denoted as PDPA/TPGS micelles). At neutral pH of 7.4, DOX was loaded into the hydrophobic core of PDPA/TPGS micelles via a film sonication method. After cellular uptake, the DOX payload was released in early endosomes by acidic pH-triggered micelle dissociation. Meanwhile, the TPGS component synergistically improved the cytotoxicity of DOX by targeting mitochondrial organelles and reducing the mitochondrial transmembrane potential. In vitro cell culture experiments using DOX-resistant MCF-7/ADR cells demonstrated that PDPA/TPGS micelles reduced the IC50 of DOX by a sixfold magnitude. In vivo animal studies showed that DOX-loaded PDPA/TPGS micelles (PDPA/TPGS@DOX) inhibited tumor growth more efficiently than free DOX in a nude mouse model bearing orthotopic MCF-7/ADR tumor. All these results imply that the mitochondria-targeted pH-responsive PDPA/TPGS micelles have significant potential for efficiently combating DOX resistance in breast cancer cells. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  12. Micelle confined mechanistic pathway for 4-nitrophenol reduction.

    PubMed

    Roy, Anindita; Debnath, Biplab; Sahoo, Ramkrishna; Aditya, Teresa; Pal, Tarasankar

    2017-05-01

    The model 4-nitrophenol reduction has been carried out by different groups in presence of metallic or even non-metallic catalyst elaborating different mechanistic aspects. In the present investigation, we have thoroughly studied the hydrogenation of 4-nitrophenol in a completely metal free homogeneous condition. The introduction of a non-fluorescent probe unequivocally generates a fluorescent molecule that indirectly justifies the anion radical stabilization in the micelle. The reduction mechanism under metal-free condition was proposed and the concept of stabilization of anion radical transition state of 4-nitrophenol at the positively charged Stern layer of anionic micelle was established. The plausible reduction mechanism has also enlightened the graphene-like conducting property of Stern layer of the homogeneous micellar system. Furthermore, the confinement effect for catalysis has also been authenticated by supporting experimental evidences. The borrowed concept of catalysis in confinement drives the catalytic study to a new era of catalysis.

  13. 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

  14. 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

  15. 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.

  16. 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)

  17. Detection of hydrogen peroxide with chemiluminescent micelles.

    PubMed

    Lee, Dongwon; Erigala, Venkata R; Dasari, Madhuri; Yu, Junhua; Dickson, Robert M; Murthy, Niren

    2008-01-01

    The overproduction of hydrogen peroxide is implicated in the progress of numerous life-threatening diseases and there is a great need for the development of contrast agents that can detect hydrogen peroxide in vivo. In this communication, we present a new contrast agent for hydrogen peroxide, termed peroxalate micelles, which detect hydrogen peroxide through chemiluminescence, and have the physical/chemical properties needed for in vivo imaging applications. The peroxalate micelles are composed of amphiphilic peroxalate based copolymers and the fluorescent dye rubrene, they have a 'stealth' polyethylene glycol (PEG) corona to evade macrophage phagocytosis, and a diameter of 33 nm to enhance extravasation into permeable tissues. The peroxalate micelles can detect nanomolar concentrations of hydrogen peroxide (>50 nM) and thus have the sensitivity needed to detect physiological concentrations of hydrogen peroxide. We anticipate numerous applications of the peroxalate micelles for in vivo imaging of hydrogen peroxide, given their high sensitivity, small size, and biocompatible PEG corona.

  18. Gas hydrate formation in reversed micelles

    SciTech Connect

    Nguyen, H.; Rao, A.M.; Phillips, J.B.; John, V.T.; Reed, W.F.

    1991-12-31

    We describe a technique to modify protein solubility and optimize enzyme activity in reversed micellar solutions. The technique is based on the ability of hydrates of natural gas to form in the microaqueous phase. Clathrate hydrates are crystalline inclusions of water and gas, and their formation in bulk water has traditionally been studied with relevance to natural gas recovery. We have found that hydrates can form in the environment of the microaqueous pools of reversed micelles, and that their extent of formation can be well controlled through the thermodynamic variables of temperature and pressure. Additionally, formation of hydrates affects the size and aggregation number of the micelles, and thus influences the solubility and conformation of encapsulated proteins. We demonstrate how the concept can be used in two applications: (1) protein extraction into reversed micelles and subsequent recovery, and (2) optimization of enzyme activity in reversed micelles.

  19. 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)

  20. 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

  1. Nonionic reverse micelles near the critical point.

    PubMed

    Shrestha, Lok Kumar; Shrestha, Rekha Goswami

    2013-01-01

    We report shape, size, and internal cross-sectional structure of diglycerol monomyristate (C₁₄G₂) reverse micelles in n-hexadecane near the critical point using small-angle X-ray scattering (SAXS). Pair-distance distribution function, p(r), which gives structural information in real-space, was obtained by indirect Fourier transformation (IFT) method. The p(r) showed a clear picture of rodlike micelles at higher temperatures well above the critical point (micellar solution phase separates into two immiscible liquids at ~ 48°C). At a fixed surfactant concentration (5% C₁₄G₂), decrease in temperature increases the micellar size monotonously and surprisingly shape of the p(r) curve at 50°C; close to the critical point, mimics the shape of the two dimensional disk-like micelles indicating the onset of critical fluctuations (attractive interactions among rodlike micelles forming a weak network). A similar behavior has been observed with normal micelles in aqueous system near the critical point. When the system is heated to 60°C, shape of the p(r) curve regains rodlike structure. At fixed temperature of 60°C, increase in C₁₄G₂ concentration induced one dimensional micellar growth. Maximum length of micelles increases from ca. 23.5 to 46.0 nm upon increasing concentration from 1 to 12% keeping cross section diameter apparently unchanged at ca. 4.0 nm.

  2. 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.

  3. Polymeric Micelles for Acyclovir Drug Delivery

    PubMed Central

    Sawdon, Alicia J.; Peng, Ching-An

    2014-01-01

    Polymeric prodrug micelles for delivery of acyclovir (ACV) were synthesized. First, ACV was used directly to initiate ring-opening polymerization of ε-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. 1H 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 200 nm and the CMCs of ACV-PCLMPEG and ACV-PCL-chitosan were 2.0 mg L−1 and 6.6 mg L−1, respectively. The drug release kinetics of ACV was investigated and cytotoxicity assay demonstrates that ACV-tagged polymeric micelles were non-toxic. PMID:25193154

  4. Tomato seeds maturity detection system based on chlorophyll fluorescence

    NASA Astrophysics Data System (ADS)

    Li, Cuiling; Wang, Xiu; Meng, Zhijun

    2016-10-01

    Chlorophyll fluorescence intensity can be used as seed maturity and quality evaluation indicator. Chlorophyll fluorescence intensity of seed coats is tested to judge the level of chlorophyll content in seeds, and further to judge the maturity and quality of seeds. This research developed a detection system of tomato seeds maturity based on chlorophyll fluorescence spectrum technology, the system included an excitation light source unit, a fluorescent signal acquisition unit and a data processing unit. The excitation light source unit consisted of two high power LEDs, two radiators and two constant current power supplies, and it was designed to excite chlorophyll fluorescence of tomato seeds. The fluorescent signal acquisition unit was made up of a fluorescence spectrometer, an optical fiber, an optical fiber scaffolds and a narrowband filter. The data processing unit mainly included a computer. Tomato fruits of green ripe stage, discoloration stage, firm ripe stage and full ripe stage were harvested, and their seeds were collected directly. In this research, the developed tomato seeds maturity testing system was used to collect fluorescence spectrums of tomato seeds of different maturities. Principal component analysis (PCA) method was utilized to reduce the dimension of spectral data and extract principal components, and PCA was combined with linear discriminant analysis (LDA) to establish discriminant model of tomato seeds maturity, the discriminant accuracy was greater than 90%. Research results show that using chlorophyll fluorescence spectrum technology is feasible for seeds maturity detection, and the developed tomato seeds maturity testing system has high detection accuracy.

  5. 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.

  6. 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.

  7. Using DLS Spectroscopy and Optical Probe Diffusion to examine structure of Brij Micelles

    NASA Astrophysics Data System (ADS)

    Wilson, Karen; Lekan, Mike; Streletzky, Kiril

    2008-03-01

    We studied properties of Brij-35 surfactant micelles in solution using Dynamic Light Scattering (DLS) Spectroscopy and Optical Probe Diffusion method. Aqueous solutions of Brij-35 with concentrations ranging from 2 to 100g/L were prepared, both with and without polystyrene latex probes of diameters 24, 50, 186, 282 and 792nm. Solutions were studied at four temperatures of 10, 25, 40 and 70^oC with DLS to obtain micelle and probe diffusion coefficients (Dm, Dp). Using both diffusion coefficients we deduced micelle radius (am), micelle water content (δ), and number of surfactant molecules per micelle (N) using two different models. First, hard sphere model of micelles/probe interaction was used to analyze the data by two methods, after am was obtained from intercept of Dm(c). The first method uses the slope of Dm(c) and size of probes to determine N and δ. The second method uses the linear least-squares fit of Dp(c) for different probe sizes to determine N and δ. Both methods reveal that with increase in solution temperature am increases by 10%, N increases and δ decreases by a factor of 2. The second model treats micelles as core-shell particles with corona radius (ac). This model used two different approaches based on linear least-squares fits of Dm(c) and Dp(c). We found am to be 4-4.5nm and ac-am to be 1nm without relying on Stokes-Einstein equation. Results for N and δg were also consistent.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Understanding chlorophylls: central magnesium ion and phytyl as structural determinants.

    PubMed

    Fiedor, Leszek; Kania, Agnieszka; Myśliwa-Kurdziel, Beata; Orzeł, Łukasz; Stochel, Grazyna

    2008-12-01

    Phytol, a C20 alcohol esterifying the C-17(3) propionate, and Mg2+ ion chelated in the central cavity, are conservative structural constituents of chlorophylls. To evaluate their intramolecular structural effects we prepared a series of metal- and phytyl-free derivatives of bacteriochlorophyll a and applied them as model chlorophylls. A detailed spectroscopic study on the model pigments reveals meaningful differences in the spectral characteristics of the phytylated and non-phytylated pigments. Their analysis in terms of solvatochromism and axial coordination shows how the central Mg and phytyl residue shape the properties of the pigment. Surprisingly, the presence/absence of the central Mg has no effect on the solvatochromism of (bacterio)chlorophyll pi-electron system and the hydrophobicity of phytyl does not interfere with the first solvation shell of the chromophore. However, both residues significantly influence the conformation of the pigment macrocycle and the removal of either residue increases the macrocycle flexibility. The chelation of Mg has a flattening effect on the macrocycle whereas bulky phytyl residue seems to control the conformation of the chromophore via steric interactions with ring V and its substituents. The analysis of spectroscopic properties of bacteriochlorophyllide (free acid) shows that esterification of the C-17(3) propionate is necessary in chlorophylls because the carboxyl group may act as a strong chelator of the central Mg. These observations imply that the truncated chlorophylls used in theoretical studies are not adequate as models of native chromophores, especially when fine effects are to be modeled.

  13. Premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions: deprotonation of dye in ion pair micelles.

    PubMed

    Gohain, Biren; Dutta, Robin K

    2008-07-15

    The premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions monitored by surface tension and spectroscopic measurements has been described. The measurements have been made for three anionic sulfonephthalein dyes and cationic surfactants of different chain lengths, head groups, and counterions. The observations have been attributed to the formation of closely packed dye surfactant ion pairs which is similar to nonionic surfactants in very dilute concentrations of the surfactant. These ion pairs dominate in the monolayer at the air-water interface of the aqueous dye surfactant solutions below the CMC of the pure surfactant. It has been shown that the dye in the ion pair deprotonates on micelle formation by the ion pair surfactants at near CMC but submicellar surfactant concentrations. The results of an equilibrium study at varying pH agree with the model of deprotonated 1:1 dye-surfactant ion pair formation in the near CMC submicellar solutions. At concentrations above the CMC of the cationic surfactant the dye is solubilized in normal micelles and the monolayer at the air-water interface consists of the cationic surfactant alone even in the presence of the dyes.

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  16. 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.

  17. Dependence of Micelle Size and Shape on Detergent Alkyl Chain Length and Head Group

    PubMed Central

    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. PMID:23667481

  18. A theoretical study on the expression of enzymic activity in reverse micelles.

    PubMed Central

    Bru, R; Sánchez-Ferrer, A; Garcia-Carmona, F

    1989-01-01

    The present work deals with a theoretical model of catalysis by enzymes entrapped in reverse micelles. Three aspects of the enzyme-reverse-micelle system have been considered: structure, dynamics and enzyme distribution and catalysis in reverse micelles. A proposed structural model of reverse micelles [El Seoud (1984) in Reverse Micelles (Luisi, P. L. & Straub, B. E., eds.), p. 81, Plenum Press, New York] consists of three domains: surfactant apolar tails, bound water and free water. Dynamics are based on a dynamic equilibrium of association-dissociation that lead one to consider the dispersed polar phase as a pseudo-continuous phase [Luisi, Giomini, Pileni & Robinson (1988) Biochim. Biophys. Acta 947, 207-246]. Enzyme is distributed among the reverse-micelle domains and it expresses a catalytic constant for each one of them. The overall activity is calculated taking into account the volume in which enzyme is solubilized, and expressed as a function of the whole volume (V). The characteristic parameters of reverse micelles, omega 0 (= [H2O]/[surfactant]) and theta (= % water, v/v), were investigated as modulators of enzymic activity. Three basic patterns of modulation by omega 0 were found depending on which domain the enzyme expressed the highest catalytic constant. Combinations of those basic patterns lead to other modulation types that can be found experimentally, such as superactivation. Other combinations predict behaviour patterns not described to date, such as superinhibition. Dependence of catalytic activity on theta was only stated at omega 0 values around a critical value, which coincides with the appearance of free water. PMID:2719652

  19. Folic acid-functionalized drug delivery platform of resveratrol based on Pluronic 127/D-α-tocopheryl polyethylene glycol 1000 succinate mixed micelles.

    PubMed

    Hao, Jifu; Tong, Tiantian; Jin, Kai; Zhuang, Qiannan; Han, Te; Bi, Yanping; Wang, Jianzhu; Wang, Xiaodan

    2017-01-01

    A folic acid (FA)-functionalized drug vehicle platform based on Pluronic 127 (P127)/D-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) mixed micelles was orchestrated for an effective delivery of the model drug resveratrol in order to address the problem of poor water solubility and rapid metabolism of resveratrol and improve its targeted accumulation at tumor site. The FA-decorated mixed micelles were prepared using thin-film hydration method and optimized by central composite design approach. The micelles were also characterized in terms of size and morphology, drug entrapment efficiency and in vitro release profile. In addition, the cytotoxicity and cell uptake of the micelles were evaluated in folate receptor-overexpressing MCF-7 cell line. In vivo pharmacokinetic and biodistribution studies were also performed. The average size of the micelles was ~20 nm with a spherical shape and high encapsulation efficiency (99.67%). The results of fluorescence microscopy confirmed the targeting capability of FA-conjugated micelles in MCF-7 cells. FA-modified micelles exhibited superior pharmacokinetics in comparison with that of solution. Further, the low accumulation of resveratrol-loaded FA micelles formulation in the heart and kidney avoided toxicity of these vital organs. It could be concluded that folate-modified P127/TPGS mixed micelles might serve as a potential delivery platform for resveratrol.

  20. Folic acid-functionalized drug delivery platform of resveratrol based on Pluronic 127/D-α-tocopheryl polyethylene glycol 1000 succinate mixed micelles

    PubMed Central

    Hao, Jifu; Tong, Tiantian; Jin, Kai; Zhuang, Qiannan; Han, Te; Bi, Yanping; Wang, Jianzhu; Wang, Xiaodan

    2017-01-01

    A folic acid (FA)-functionalized drug vehicle platform based on Pluronic 127 (P127)/D-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) mixed micelles was orchestrated for an effective delivery of the model drug resveratrol in order to address the problem of poor water solubility and rapid metabolism of resveratrol and improve its targeted accumulation at tumor site. The FA-decorated mixed micelles were prepared using thin-film hydration method and optimized by central composite design approach. The micelles were also characterized in terms of size and morphology, drug entrapment efficiency and in vitro release profile. In addition, the cytotoxicity and cell uptake of the micelles were evaluated in folate receptor-overexpressing MCF-7 cell line. In vivo pharmacokinetic and biodistribution studies were also performed. The average size of the micelles was ~20 nm with a spherical shape and high encapsulation efficiency (99.67%). The results of fluorescence microscopy confirmed the targeting capability of FA-conjugated micelles in MCF-7 cells. FA-modified micelles exhibited superior pharmacokinetics in comparison with that of solution. Further, the low accumulation of resveratrol-loaded FA micelles formulation in the heart and kidney avoided toxicity of these vital organs. It could be concluded that folate-modified P127/TPGS mixed micelles might serve as a potential delivery platform for resveratrol. PMID:28392687

  1. 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

    NASA Astrophysics Data System (ADS)

    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.

  2. 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

    2015-05-05

    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.

  3. 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).

  4. Effects of temperature on the rheological behavior of worm-like micelles in a mixed nonionic surfactant system.

    PubMed

    Hashizaki, Kaname; Taguchi, Hiroyuki; Saito, Yoshihiro

    2009-01-01

    We examined the effects of temperature on the rheological behavior of worm-like micelles in a nonionic surfactant system consisting of polyoxyethylene (10) phytosterol (PhyEO(10))/glyceryl monocaprylate (GFA-C(8))/Water. First, the phase diagram of a PhyEO(10)/GFA-C(8)/Water system was examined when the weight ratio, R, of GFA-C(8) to the total surfactants was changed keeping the total concentration of the surfactants at 5 wt%. The formation of worm-like micelles was confirmed over a wide temperature range. Next, the effect of temperature on the rheological properties of the worm-like micelles was examined. From steady-flow viscosity measurements of the worm-like micelles, it was found that the zero-shear viscosity (eta(0)) gave a maximum value more than 1,000 times greater than the minimum value in the temperature range 20-50 degrees C. Further, the temperature at which the maximum eta(0) was observed decreased with increasing R value. These results indicate that there is an optimal temperature at which the entanglement of worm-like micelles is at its greatest. From dynamic viscoelasticity measurements, it was shown that the viscoelastic behavior observed for the worm-like micelles was consistent with the Maxwell model, which is the basic model for a viscoelastic body. In addition, the plateau modulus (G(0)), which reflects the volume fraction of entangled worm-like micelles, gradually increased with increasing temperature, while the relaxation time (tau), which reflects the disentanglement time of the worm-like micelles, rapidly decreased with increasing temperature. From these results, it was clarified that, for a nonionic worm-like micelle, tau influences the change in eta(0) more strongly than G(0).

  5. 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

  6. Magnetic resonance imaging-visible and pH-sensitive polymeric micelles for tumor targeted drug delivery.

    PubMed

    Zhang, Zuoquan; Sun, Qiquan; Zhong, Jinglian; Yang, Qihua; Li, Hao; Du, Cheng; Liang, Biling; Shuai, Xintao

    2014-02-01

    Folate-functionalized copolymers of poly(ethylene glycol) and 2-(diisopropylamino) ethylamine grafted poly(L-aspartic acid) are synthesized. The copolymers can self-assemble into nanoscaled micelles encapsulated with hydrophobic model drug Fluorescein Diacetate (FDA) and MRI diagnostic agents superparamagnetic iron oxide nanoparticles (SPIONs) in aqueous solution of a neutral pH resembling physiological environment, whereas disassemble in acidic endosomal/lysosomal compartments of tumor cells to achieve rapid drug release. In vitro drug release study showed that FDA release from the pH-sensitive micelles was much faster at pH 5.0 than at pH 7.4. Clustering of SPIONs inside the hydrophobic core of the micelles resulted in a high spin-spin (T2,) relaxivity for a super MRI sensitivity. Cell culture studies showed that the FDA-SPION-loaded micelles were effectively internalized by human hepatic Bel-7402 cancer cells following a folate receptor-mediated targeting mechanism, and then FDA was rapidly release from micelles inside lysosomal compartments. Micelles encapsulating paclitaxel (PTX) studies showed it can induce more effective cell toxicity. This study demonstrated the great potential of the pH-sensitive micelles as an effective multifunctional nanomedician platform for cancer therapy due to their active tumor targeting, pH-triggered drug release and ultrasensitive MRI responsiveness.

  7. Local and systemic delivery of VEGF siRNA using polyelectrolyte complex micelles for effective treatment of cancer.

    PubMed

    Kim, Sun Hwa; Jeong, Ji Hoon; Lee, Soo Hyeon; Kim, Sung Wan; Park, Tae Gwan

    2008-07-14

    For efficient cancer therapy, small interfering RNA (siRNA) should be stably and efficiently delivered into the target tissue and readily taken up by cancer cells. To address these needs, a polyelectrolyte complex (PEC) micelle-based siRNA delivery system was developed for anti-angiogenic gene therapy. The interaction between poly(ethylene glycol) (PEG)-conjugated vascular endothelial growth factor siRNA (VEGF siRNA-PEG) and polyethylenimine (PEI) led to the spontaneous formation of nanoscale polyelectrolyte complex micelles (VEGF siRNA-PEG/PEI PEC micelles), having a characteristic siRNA/PEI PEC inner core with a surrounding PEG shell layer. Intravenous as well as intratumoral administration of the PEC micelles significantly inhibited VEGF expression at the tumor tissue and suppressed tumor growth in an animal tumor model without showing any detectable inflammatory responses in mice. Upon examination of the PEC micelle distribution and in vivo optical imaging following intravenously injection, enhanced accumulation of the PEC micelles was also observed in the tumor region. This study demonstrates the feasibility of using PEC micelles as a potential carrier for therapeutic siRNAs in local and systemic treatment of cancer.

  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. © 2014 John Wiley & Sons Ltd.

  9. Seedling quality tests: chlorophyll fluoresence

    Treesearch

    Gary Ritchie; Thomas D. Landis

    2005-01-01

    So far in this series we have discussed the most commonly -used seedling quality tests: root growth potential, cold hardiness, and stress resistance. In this issue, we're going to talk about one of the newest test-chlorophyll fluorescence (CF). The technology for measuring CF has been in place for over 50 years but has been applied to tr?e seedling physiology only...

  10. Photochemical and photophysical properties of carotenoid immobilized on a surfactant micellar medium including chlorophyll as an artificial photosynthesis system.

    PubMed

    Fuchino, Yoshiko; Amao, Yutaka

    2006-01-01

    To develop an artificial photosynthesis model, the anionic water-soluble carotenoid dye crocetin was electrostatically immobilized onto the surface of cationic surfactant cetyltrimethylammonium bromide (CTAB) micellar medium including Mg chlorophyll-a and b (MgChl-a and b) (Cro/MgChl), and its photophysical properties were studied using UV-vis absorption and fluorescence spectroscopy. The fluorescence of MgChl-a and b was observed, with the excitation wavelength attributed to the absorption band of crocetin, indicating that photo-induced energy transfer from the photoexcited state of crocetin to MgChl-a and b occurs. The photostability of MgChl-a and b in Cro/MgChl was investigated under continuous irradiation. After 60 min irradiation, the absorbance decreases at 660 nm Cro/MgChl and MgChl-a/b, without crocetin, were 3.0 and 17%, respectively. These results indicate that the photo-bleaching rate of MgChl-a/b in Cro/MgChl on irradiation is suppressed by the crocetin molecule on the surface of micelles.

  11. Antiproliferative activity of tea catechins associated with casein micelles, using HT29 colon cancer cells.

    PubMed

    Haratifar, S; Meckling, K A; Corredig, M

    2014-02-01

    Numerous studies have shown that green tea polyphenols display anticancer activities in many organ sites by using different experimental models in rodents and in cultured cell lines in vitro. The present study tested the ability of casein micelles to deliver biologically active concentrations of polyphenols to HT-29 colon cancer cells. Epigallocatechin gallate (EGCG), the major catechin found in green tea, was used as the model molecule, as it has been shown to have antiproliferative activity on colon cancer cells. In the present work, we hypothesized that due to the binding of caseins with EGCG, casein micelles may be an ideal platform for the delivery of this bioactive molecule and that the binding would not affect the bioaccessibility of EGCG. The cytotoxicity and proliferation behavior of HT-29 colon cancer cells when exposed to free EGCG was compared with that of nanoencapsulated EGCG in casein micelles of skim milk. Epigallocatechin gallate-casein complexes were able to decrease the proliferation of HT-29 cancer cells, demonstrating that bioavailability may not be reduced by the nanoencapsulation. As casein micelles may act as protective carriers for EGCG in foods, it was concluded that nanoencapsulation of tea catechins in casein micelles may not diminish their antiproliferative activity on colon cancer cells compared with free tea catechins.

  12. CHARMM-GUI PACE CG Builder for solution, micelle, and bilayer coarse-grained simulations.

    PubMed

    Qi, Yifei; Cheng, Xi; Han, Wei; Jo, Sunhwan; Schulten, Klaus; Im, Wonpil

    2014-03-24

    Coarse-grained (CG) and multiscale simulations are widely used to study large biological systems. However, preparing the simulation system is time-consuming when the system has multiple components, because each component must be arranged carefully as in protein/micelle or protein/bilayer systems. We have developed CHARMM-GUI PACE CG Builder for building solution, micelle, and bilayer systems using the PACE force field, a united-atom (UA) model for proteins, and the Martini CG force field for water, ions, and lipids. The robustness of PACE CG Builder is validated by simulations of various systems in solution (α3D, fibronectin, and lysozyme), micelles (Pf1, DAP12-NKG2C, OmpA, and DHPC-only micelle), and bilayers (GpA, OmpA, VDAC, MscL, OmpF, and lipid-only bilayers for six lipids). The micelle's radius of gyration, the bilayer thickness, and the per-lipid area in bilayers are comparable to the values from previous all-atom and CG simulations. Most tested proteins have root-mean squared deviations of less than 3 Å. We expect PACE CG Builder to be a useful tool for modeling/refining large, complex biological systems at the mixed UA/CG level.

  13. CD44 Receptor Targeting and Endosomal pH-Sensitive Dual Functional Hyaluronic Acid Micelles for Intracellular Paclitaxel Delivery.

    PubMed

    Liu, Yanhua; Zhou, Chengming; Wang, Wenping; Yang, Jianhong; Wang, Hao; Hong, Wei; Huang, Yu

    2016-12-05

    A novel CD44 receptor targeting and endosome pH-sensitive dual functional hyaluronic acid-deoxycholic acid-histidine (HA-DOCA-His) micellar system was designed for intracellular paclitaxel (PTX) delivery. The HA-DOCA-His micelles exhibited desirable endosome pH (5.0-6.0)-induced aggregation and deformation behavior verified by size distribution, critical micellar concentration, and zeta potential changes. The HA-DOCA-His micelles presented excellent encapsulation efficiency and loading capacity of 90.0% and 18.9% for PTX, respectively. The PTX release from HA-DOCA-His micelles was pH-dependent, with more rapid PTX release at pH 6.0 and 5.0 than those at pH 7.4 and 6.5. The cellular uptake performance of HA-DOCA-His micelles was enhanced comparing with pH-insensitive HA-DOCA micelles by qualitative and quantitative measurements. HA-DOCA-His micelles could be taken up via CD44-receptor mediated endocytosis, transported into endosomes, and triggered drug release to cytoplasm. In vitro cytotoxicity study exhibited PTX-loaded HA-DOCA-His micelles were more active in tumor cell growth inhibition in MCF-7 cells at pH 5.8 than those at pH 6.8 and pH 7.4. A superior antitumor efficacy was demonstrated with HA-DOCA-His micelles in a MCF-7 breast tumor model. These indicated that the dual functional HA-DOCA-His micelles combined targeted intracellular delivery and endosomal release strategies could be developed as a promising nanocarrier for anticancer efficacy improvement of PTX.

  14. A nondestructive method to estimate the chlorophyll content of Arabidopsis seedlings.

    PubMed

    Liang, Ying; Urano, Daisuke; Liao, Kang-Ling; Hedrick, Tyson L; Gao, Yajun; Jones, Alan M

    2017-01-01

    Chlorophyll content decreases in plants under stress conditions, therefore it is used commonly as an indicator of plant health. Arabidopsis thaliana offers a convenient and fast way to test physiological phenotypes of mutations and treatments. However, chlorophyll measurements with conventional solvent extraction are not applicable to Arabidopsis leaves due to their small size, especially when grown on culture dishes. We provide a nondestructive method for chlorophyll measurement whereby the red, green and blue (RGB) values of a color leaf image is used to estimate the chlorophyll content from Arabidopsis leaves. The method accommodates different profiles of digital cameras by incorporating the ColorChecker chart to make the digital negative profiles, to adjust the white balance, and to calibrate the exposure rate differences caused by the environment so that this method is applicable in any environment. We chose an exponential function model to estimate chlorophyll content from the RGB values, and fitted the model parameters with physical measurements of chlorophyll contents. As proof of utility, this method was used to estimate chlorophyll content of G protein mutants grown on different sugar to nitrogen ratios. This method is a simple, fast, inexpensive, and nondestructive estimation of chlorophyll content of Arabidopsis seedlings. This method lead to the discovery that G proteins are important in sensing the C/N balance to control chlorophyll content in Arabidopsis.

  15. A nondestructive method to estimate the chlorophyll content of Arabidopsis seedlings

    DOE PAGES

    Liang, Ying; Urano, Daisuke; Liao, Kang-Ling; ...

    2017-04-14

    Chlorophyll content decreases in plants under stress conditions, therefore it is used commonly as an indicator of plant health. Arabidopsis thaliana offers a convenient and fast way to test physiological phenotypes of mutations and treatments. But, chlorophyll measurements with conventional solvent extraction are not applicable to Arabidopsis leaves due to their small size, especially when grown on culture dishes. We provide a nondestructive method for chlorophyll measurement whereby the red, green and blue (RGB) values of a color leaf image is used to estimate the chlorophyll content from Arabidopsis leaves. The method accommodates different profiles of digital cameras by incorporatingmore » the ColorChecker chart to make the digital negative profiles, to adjust the white balance, and to calibrate the exposure rate differences caused by the environment so that this method is applicable in any environment. We chose an exponential function model to estimate chlorophyll content from the RGB values, and fitted the model parameters with physical measurements of chlorophyll contents. As further proof of utility, this method was used to estimate chlorophyll content of G protein mutants grown on different sugar to nitrogen ratios. Our method is a simple, fast, inexpensive, and nondestructive estimation of chlorophyll content of Arabidopsis seedlings. This method lead to the discovery that G proteins are important in sensing the C/N balance to control chlorophyll content in Arabidopsis.« less

  16. 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

  17. Fmoc-conjugated PEG-vitamin E2 micelles for tumor-targeted delivery of paclitaxel: enhanced drug-carrier interaction and loading capacity.

    PubMed

    Zhang, Yifei; Huang, Yixian; Zhao, Wenchen; Lu, Jianqin; Zhang, Peng; Zhang, Xiaolan; Li, Jiang; Gao, Xiang; Venkataramanan, Raman; Li, Song

    2014-11-01

    The purpose of this study is to develop an improved drug delivery system for enhanced paclitaxel (PTX) loading capacity and formulation stability based on PEG5K-(vitamin E)2 (PEG5K-VE2) system. PEG5K-(fluorenylmethoxycarbonyl)-(vitamin E)2 (PEG5K-FVE2) was synthesized using lysine as the scaffold. PTX-loaded PEG5K-FVE2 micelles were prepared and characterized. Fluorescence intensity of Fmoc in the micelles was measured as an indicator of drug-carrier interaction. Cytotoxicity of the micelle formulations was tested on various tumor cell lines. The therapeutic efficacy and toxicity of PTX-loaded micelles were investigated using a syngeneic mouse model of breast cancer (4T1.2). Our data suggest that the PEG5K-FVE2 micelles have a low CMC value of 4 μg/mL and small sizes (~60 nm). The PTX loading capacity of PEG5K-FVE2 micelles was much higher than that of PEG5K-VE2 micelles. The Fmoc/PTX physical interaction was clearly demonstrated by a fluorescence quenching assay. PTX-loaded PEG5K-FVE2 micelles exerted more potent cytotoxicity than free PTX or Taxol formulation in vitro. Finally, intravenous injection of PTX-loaded PEG5K-FVE2 micelles showed superior anticancer activity compared with PEG5K-VE2 formulation with minimal toxicity in a mouse model of breast cancer. In summary, incorporation of a drug-interactive motif (Fmoc) into PEG5K-VE2 micelles represents an effective strategy to improve the micelle formulation for the delivery of PTX.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  19. Self-assembly of micelles in organic solutions of lecithin and bile salt: Mesoscale computer simulation

    NASA Astrophysics Data System (ADS)

    Markina, A.; Ivanov, V.; Komarov, P.; Khokhlov, A.; Tung, S.-H.

    2016-11-01

    We propose a coarse-grained model for studying the effects of adding bile salt to lecithin organosols by means of computer simulation. This model allows us to reveal the mechanisms of experimentally observed increasing of viscosity upon increasing the bile salt concentration. We show that increasing the bile salt to lecithin molar ratio induces the growth of elongated micelles of ellipsoidal and cylindrical shape due to incorporation of disklike bile salt molecules. These wormlike micelles can entangle into transient network displaying perceptible viscoelastic properties.

  20. Comprehensive theory for star-like polymer micelles; combining classical nucleation and polymer brush theory.

    PubMed

    Sprakel, Joris; Leermakers, Frans A M; Cohen Stuart, Martien A; Besseling, Nicolaas A M

    2008-09-14

    A comprehensive theory is proposed that combines classical nucleation and polymer brush theory to describe star-like polymer micelles. With a minimum of adjustable parameters, the model predicts properties such as critical micelle concentrations and micellar size distributions. The validity of the present theory is evidenced in direct comparison to experiments; this revealed that the proportionality constant in the Daoud-Cotton model is of the order of unity and that the star-limit is valid down to relatively short corona chains. Furthermore, we show that the predicted saddle points in the free energy correspond to those solutions that are accessible with self-consistent field methods for self-assembly.

  1. 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.

  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. Biodegradable stereocomplex micelles based on dextran-block-polylactide as efficient drug deliveries.

    PubMed

    Zhao, Ziwei; Zhang, Zhe; Chen, Li; Cao, Yue; He, Chaoliang; Chen, Xuesi

    2013-10-22

    Biodegradable stereocomplex micelles (SCMs) based on amphiphilic dextran-block-polylactide (Dex-b-PLA) were designed and used for efficient intracellular drug deliveries. The Dex-b-PLA copolymers were successfully synthesized by click reaction. The structures of the resultant copolymers were verified by (1)H NMR and FT-IR spectra. The formation of stable micelles through self-assembly driven by the stereocomplexation between enantiomeric l- and d-PLA blocks was characterized by transmission electron microscopy (TEM), dynamic laser scattering (DLS), and fluorescence techniques. It was interesting to observe that the SCMs showed lower critical micelle concentration values (CMCs) because of the stereocomplex interaction between PLLA and PDLA. Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis provided information on the thermal and crystal properties of the copolymers and SCMs. The improved stability of SCMs should be attractive for intracellular drug delivery. Thus, a model anticancer drug doxorubicin (DOX) was loaded into micelles, and the in vitro drug release in was also studied. The release kinetics of DOX showed DOX-loaded SCMs exhibited slower DOX release. Confocal laser scanning microscopy (CLSM) and flow cytometry studies also showed that the DOX-loaded SCMs exhibited a slower drug release behavior. Meanwhile, the MTT assay demonstrated that DOX-loaded SCMs show lower cellular proliferation inhibition against HepG2. In sum, the micelles through self-assembly driven by stereocomplex interaction would have great potential to be used as stable delivery vehicles for pharmaceutical and biomedical applications.

  4. PEG-Farnesyl Thiosalicylic Acid Telodendrimer Micelles as an Improved Formulation for Targeted Delivery of Paclitaxel

    PubMed Central

    2015-01-01

    We have recently designed and developed a dual-functional drug carrier that is based on poly(ethylene glycol) (PEG)-derivatized farnesylthiosalicylate (FTS, a nontoxic Ras antagonist). PEG5K-FTS2 readily form micelles (20–30 nm) and hydrophobic drugs such as paclitaxel (PTX) could be effectively loaded into these micelles. PTX formulated in PEG5K-FTS2 micelles showed an antitumor activity that was more efficacious than Taxol in a syngeneic mouse model of breast cancer (4T1.2). In order to further improve our PEG-FTS micellar system, four PEG-FTS conjugates were developed that vary in the molecular weight of PEG (PEG2K vs PEG5K) and the molar ratio of PEG/FTS (1/2 vs 1/4) in the conjugates. These conjugates were characterized including CMC, drug loading capacity, stability, and their efficacy in delivery of anticancer drug PTX to tumor cells in vitro and in vivo. Our data showed that the conjugates with four FTS molecules were more effective than the conjugates with two molecules of FTS and that FTS conjugates with PEG5K were more effective than the counterparts with PEG2K in forming stable mixed micelles. PTX formulated in PEG5K-FTS4 micelles was the most effective formulation in inhibiting the tumor growth in vivo. PMID:24987803

  5. Self-assembled gold nanocrystal micelles act as an excellent artificial nanozyme with ribonuclease activity.

    PubMed

    Zhang, Zhiming; Fu, Qiuan; Li, Xiangqiu; Huang, Xin; Xu, Jiayun; Shen, Jiacong; Liu, Junqiu

    2009-06-01

    Water-soluble Au nanocrystal (NC) micelles with an inserted catalytic Cu(II) center that act as excellent nanoenzyme models for imitating ribonuclease were constructed by supramolecular self-assembly. The dodecane-1-thiol-based Au NC was constructed first, and subsequently the cationic surfactant hexadecyltrimethylammonium bromide and the catalytic ligand (N1,N1-bis(2-aminoethyl)-N2-dodecylethane-1,2-diamine) copper(II) were installed on the surface of the Au NC via hydrophobic interaction. The catalytic capability of the Au NC micelles designed was estimated by the cleavage of a typical RNA analogue, 2-hydroxypropyl p-nitrophenyl phosphate (HPNP). The study of the catalytic behavior of Au NC micelle catalysis showed that the Au NC micelles exhibited dramatic ribonuclease-like activity: a high rate acceleration of k(cat)/k(uncat) = 1.10 x 10(5) for the cleavage of HPNP in comparison with the spontaneous cleavage of HPNP (k(uncat)) was observed. The catalytic capability for HPNP cleavage by these functionalized Au NC micelles can be compared with that of covalent Au nanoparticles reported previously as nanozymes under comparable conditions. A detailed investigation of enzymatic kinetics was carried out and a possible mechanism was suggested.

  6. Encapsulation of Sesbania grandiflora extract in polymeric micelles to enhance its solubility, stability, and antibacterial activity.

    PubMed

    Anantaworasakul, Pimporn; Okonogi, Siriporn

    2017-02-01

    Clinical applications of Sesbania grandiflora bark extract (SGE) are limited because of its poor water solubility and stability. SGE was loaded in micelles of Pluronics. In vitro and in vivo antibacterial and toxicity tests were investigated using broth dilution and silkworm model. Aqueous solubility of SGE was improved by these micelles. Activity and toxicity of SGE loaded micelles were dependent on type and concentration of Pluronics. The micelles composed of 1:3 SGE to Pluronic F68 (SGE-PF68-13) showed small size (24.95 ± 0.34 nm), narrow PdI (<0.2), high entrapment efficiency (99.63 ± 0.19%) and negative zeta potential (-41.53 ± 0.15 mV). Stability of SGE in SGE-PF68-13 was 10 times higher than the unentrapped SGE. SGE-PF68-13 showed a dose dependent activity and significantly higher therapeutic effect than the unentrapped SGE. It is concluded that encapsulation of SGE in Pluronic micelles can enhance SGE solubility, stability, and antibacterial activity. SGE-PF68-13 is suitable for further study in mammalian animals.

  7. Novel polymer micelles prepared from chitosan grafted hydrophobic palmitoyl groups for drug delivery.

    PubMed

    Jiang, Gang-Biao; Quan, Daping; Liao, Kairong; Wang, Haihua

    2006-01-01

    Chitosan-based polymer micelles have a splendid outlook for drug delivery owing to the interesting properties, abundance, and low cost of chitosan. A new method of preparation of water-soluble N-palmitoyl chitosan (PLCS) which can form micelles in water is developed in this paper. The preparation of PLCS was carried out by swollen chitosan coupling with palmitic anhydride in dimethyl sulfoxide (DMSO). The degree of substitution (DS) of PLCS was in the range of 1.2-14.2%, and the critical aggregation concentration (CAC) of PLCS micelles was in the range of 2.0 x 10(-3) to 37.2 x 10(-3) mg/mL. The properties of PLCS micelles such as encapsulation capacity and controlled release ability of hydrophobic model drug ibuprofen (IBU) were evaluated. Experimental results indicated that the loading capacity (LC) of PLCS was approximately 10%. The drug release strongly depended on pH and temperature: low pH and high temperature accelerated drug release markedly. Moreover, the IR, 1H NMR, and TEM of PLCS, IBU-loaded PLCS, and a PLCS-IBU physical mixture have been measured to show that IBU is loaded by PLCS micelles.

  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. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Electrical conductivity study on micelle formation of long-chain imidazolium ionic liquids in aqueous solution.

    PubMed

    Inoue, Tohru; Ebina, Hayato; Dong, Bin; Zheng, Liqiang

    2007-10-01

    Electrical conductivity was measured for aqueous solutions of long-chain imidazolium ionic liquids (IL), 1-alkyl-3-methylimidazolium bromides with C(12)-C(16) alkyl chains. The break points appeared in specific conductivity (kappa) vs concentration (c) plot indicates that the molecular aggregates, i.e., micelles, are formed in aqueous solutions of these IL species. The critical micelle concentration (cmc) determined from the kappa vs c plot is somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides with the same hydrocarbon chain length. The electrical conductivity data were analyzed according to the mixed electrolyte model of micellar solution, and the aggregation number, n, and the degree of counter ion binding, beta, were estimated. The n values of the present ILs are somewhat smaller than those reported for alkyltrimethylammonium bromides, which may be attributed to bulkiness of the cationic head group of the IL species. The thermodynamic parameters for micelle formation of the present ILs were estimated using the values of cmc and beta as a function of temperature. The contribution of entropy term to the micelle formation is superior to that of enthalpy term below about 30 degrees C, and it becomes opposite at higher temperature. This coincides with the picture drawn for the micelle formation of conventional ionic surfactants.

  10. 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

    2013-10-02

    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.

  11. Polymeric Micelles for Apoptosis-Targeted Optical Imaging of Cancer and Intraoperative Surgical Guidance

    PubMed Central

    Cho, Hyunah; Cho, Clifford S.; Indig, Guilherme L.; Lavasanifar, Afsaneh; Vakili, Mohammad Reza; Kwon, Glen S.

    2014-01-01

    In a two-step strategy, an intraperitoneal (IP) injection of poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-b-PCL) micelles containing paclitaxel (PTX), cyclopamine (CYP), and gossypol (GSP) at 30, 30, and 30 mg/kg, respectively, debulked tumor tissues by 1.3-fold, based on loss of bioluminescence with <10% body weight change, and induced apoptosis in peritoneal tumors when used as neoadjuvant chemotherapy (NACT) in an ES-2-luc-bearing xenograft model for ovarian cancer. In a second step, a single intravenous (IV) injection of apoptosis-targeting GFNFRLKAGAKIRFGS-PEG-b-PCL micelles containing a near-infrared (NIR) fluorescence probe, DiR (1,1′-dioctadecyltetramethyl indotricarbocyanine iodide), resulted in increased peritoneal DiR accumulation in apoptosis-induced ES-2-luc tumor tissues (ex vivo) by 1.5-fold compared with DiR molecules delivered by methoxy PEG-b-PCL micelles (non-targeted) at 48 h after IV injection in a second step. As a result, a tandem of PEG-b-PCL micelles enabled high-resolution detection of ca. 1 mm diameter tumors, resulting in resection of approximately 90% of tumors, and a low peritoneal cancer index (PCI) of ca. 7. Thus, a tandem of PEG-b-PCL micelles used for NCAT and NIR fluorescence imaging of therapy-induced apoptosis for intraoperative surgical guidance may be a promising treatment strategy for metastatic ovarian cancer. PMID:24587157

  12. 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.

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

    NASA Astrophysics Data System (ADS)

    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

    2016-10-01

    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.

  14. 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

  15. 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

  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.

  17. Spectroscopic studies of interaction of Safranine T with nonionic micelles and mixed micelles

    NASA Astrophysics Data System (ADS)

    Chatterjee, Sujan; Bhattacharya, Subhash Chandra

    2006-05-01

    The visible spectra of Safranine T (ST) in micellar solution of Brij 58, Tween 20 and Tween 40 and mixed micellar solution of Brij 58/Tween 20 and Brij 58/Tween 40 indicate formation of 1:1 charge transfer (CT) complex between acceptor ST and donor nonionic micelles and mixed micelles. The experimental CT transition energies are well correlated (through Mulliken's equation) with the vertical ionization potential of the donors. The solvent parameters, i.e. the intramolecular charge transfer energy ET(30) have been determined from the Stokes spectral shift. Variations of ionization potential and micropolarity in the mixed micellar region have been investigated as a function of surfactant composition and the obtained results in mixed micellar medium has been compared to the normal micelles. The critical micelle concentration (CMC) values determined at various surfactant compositions are lower than the ideal values indicating a synergistic interaction. The interaction parameter ( β) and micellar stability has been calculated using regular solution theory.

  18. Transformation from Globular to Cylindrical Mixed Micelles through Molecular Exchange that Induces Micelle Fusion.

    PubMed

    Jensen, Grethe V; Lund, Reidar; Narayanan, Theyencheri; Pedersen, Jan Skov

    2016-06-02

    Transformations between different micellar morphologies in solution induced by changes in composition, salt, or temperature are well-known phenomena; however, the understanding of the associated kinetic pathways is still limited. Especially for mixed surfactant systems, the micelles can take a very wide range of structures, depending on the surfactant packing parameter and other thermodynamic conditions. Synchrotron-based small-angle X-ray scattering (SAXS) in combination with fast mixing using a stopped-flow apparatus can give direct access to the structural kinetics on a millisecond time scale. Here, this approach is used to study the formation of cylindrical micelles after mixing two solutions with globular micelles of the nonionic surfactant dodecyl maltoside (DDM) and the anionic surfactant sodium dodecyl sulfate (SDS), respectively. Two separate processes were identified: (i) a transition in micellar shell structure, interpreted as exchange of surfactant molecules resulting in mixed globular micelles, and subsequently, (ii) fusion into larger, cylindrical structures.

  19. 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.

  20. Applications of micelle enhancement in luminescence-based analysis.

    PubMed

    Alarfaj, Nawal A; El-Tohamy, Maha F

    2015-02-01

    Micelles are self-assembled aggregates that arrange themselves into spheres in aqueous media. When the surfactant concentration reaches the critical micelle concentration, extensive aggregation of the surfactant monomers occurs to form micelles. A micelle has both a hydrophilic and a hydrophobic part. This allows them to form a spherical shape and for their glycolipid and phospholipid components to form lipid bilayers. The importance of micelles is increasing because of their wide analytical applications. Recently, colloidal carrier systems have received much attention in the field of analytical chemistry, especially in luminescence enhancement applications. Copyright © 2014 John Wiley & Sons, Ltd.

  1. 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.

  2. On the composition fluctuations of reverse micelles.

    PubMed

    Tovstun, Sergey A; Razumov, Vladimir F

    2010-11-15

    The polydispersity of the reverse micelles is determined mainly by the fluctuations of their composition. The composition of the reverse micelle is a two-dimensional random variable whose components are the numbers of water (i) and surfactant (j) molecules. In this study the fluctuations of the composition of the reverse micelles are considered in the Gaussian approximation. It is shown that the standard deviation of the quantity w=i/j may be calculated from the dependence of the water vapor pressure above the microemulsion on the molar ratio W=[water]/[surfactant]. The estimation based on the literature data for microemulsion system sodium bis(2-ethylhexyl)sulfosuccinate/water/isooctane at 37°C in the range W=0-18 has shown that the relative standard deviation of the quantity w is about 10%. It is shown that the value of the composition fluctuations is related to the dependence of average composition on the concentration of reverse micelles at constant parameter W.

  3. Hollow flower micelles from a diblock copolymer

    NASA Astrophysics Data System (ADS)

    Changez, Mohammad; Kang, Nam-Goo; Kim, Dong Woo; Lee, Jae-Suk

    2013-11-01

    A poly(2-vinylpyridine)-block-poly(2-(4-vinylphenyl)pyridine) (P2VP106-b-PVPPy95) coil-coil diblock copolymer forms hollow flower micelles in a mixed solvent of methanol and water (95/5, v/v) in a one step process. The geometry and composition of the micelles allow formation of a Pt-Au bimetallic dendritic nanocatalyst with a Pt leaf at room temperature.A poly(2-vinylpyridine)-block-poly(2-(4-vinylphenyl)pyridine) (P2VP106-b-PVPPy95) coil-coil diblock copolymer forms hollow flower micelles in a mixed solvent of methanol and water (95/5, v/v) in a one step process. The geometry and composition of the micelles allow formation of a Pt-Au bimetallic dendritic nanocatalyst with a Pt leaf at room temperature. Electronic supplementary information (ESI) available: Experimental details. See DOI: 10.1039/c3nr03063f

  4. 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.

  5. Detection of hydrogen peroxide with chemiluminescent micelles

    PubMed Central

    Lee, Dongwon; Erigala, Venkata R; Dasari, Madhuri; Yu, Junhua; Dickson, Robert M; Murthy, Niren

    2008-01-01

    The overproduction of hydrogen peroxide is implicated in the progress of numerous life-threatening diseases and there is a great need for the development of contrast agents that can detect hydrogen peroxide in vivo. In this communication, we present a new contrast agent for hydrogen peroxide, termed peroxalate micelles, which detect hydrogen peroxide through chemiluminescence, and have the physical/chemical properties needed for in vivo imaging applications. The peroxalate micelles are composed of amphiphilic peroxalate based copolymers and the fluorescent dye rubrene, they have a ‘stealth’ polyethylene glycol (PEG) corona to evade macrophage phagocytosis, and a diameter of 33 nm to enhance extravasation into permeable tissues. The peroxalate micelles can detect nanomolar concentrations of hydrogen peroxide (>50 nM) and thus have the sensitivity needed to detect physiological concentrations of hydrogen peroxide. We anticipate numerous applications of the peroxalate micelles for in vivo imaging of hydrogen peroxide, given their high sensitivity, small size, and biocompatible PEG corona. PMID:19337415

  6. 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)

  7. Impact of urea on detergent micelle properties.

    PubMed

    Broecker, Jana; Keller, Sandro

    2013-07-09

    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.

  8. Antibacterial polyelectrolyte micelles for coating stainless steel.

    PubMed

    Falentin-Daudré, Céline; Faure, Emilie; Svaldo-Lanero, Tiziana; Farina, Fabrice; Jérôme, Christine; Van De Weerdt, Cécile; Martial, Joseph; Duwez, Anne-Sophie; Detrembleur, Christophe

    2012-05-08

    In this study, we report on the original synthesis and characterization of novel antimicrobial coatings for stainless steel by alternating the deposition of aqueous solutions of positively charged polyelectrolyte micelles doped with silver-based nanoparticles with a polyanion. The micelles are formed by electrostatic interaction between two oppositely charged polymers: a polycation bearing 3,4-dihydroxyphenylalanine units (DOPA, a major component of natural adhesives) and a polyanion (poly(styrene sulfonate), PSS) without using any block copolymer. DOPA units are exploited for their well-known ability to anchor to stainless steel and to form and stabilize biocidal silver nanoparticles (Ag(0)). The chlorine counteranion of the polycation forms and stabilizes biocidal silver chloride nanoparticles (AgCl). We demonstrate that two layers of micelles (alternated by PSS) doped with silver particles are enough to impart to the surface strong antibacterial activity against gram-negative E. coli. Moreover, micelles that are reservoirs of biocidal Ag(+) can be easily reactivated after depletion. This novel water-based approach is convenient, simple, and attractive for industrial applications.

  9. 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.

  10. 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)

  11. What is inside a nonionic reverse micelle? Probing the interior of Igepal reverse micelles using decavanadate.

    PubMed

    Sedgwick, M A; Crans, D C; Levinger, N E

    2009-05-19

    The interiors of reverse micelles formed using nonionic surfactants to sequester water droplets in a nonpolar environment have been investigated using the decavanadate molecule as a probe. Chemical shifts and line widths of the three characteristic signals in the 51V NMR spectrum of decavanadate, corresponding to vanadium atoms in equatorial peripheral, equatorial interior, and axial locations, measure the local proton concentration and characteristics of the reverse micellar interior near the decavandate probe. All samples investigated indicate deprotonation of the vanadate probe in the reverse micelle environment. However, the relative mobility of the decavanadate molecule depends on the reverse micellar components. Specifically, the 51V NMR signals of the decavandate in reverse micelles formed using only the Igepal CO-520 surfactant display sharp signals indicating that the decavandate molecule tumbles relatively freely while reverse micelles formed from a mixture of Igepal CO-610 and -430 present a more viscous environment for the decavanadate molecule; the nature of the interior of the nonionic reverse water pool varies significantly depending on the specific Igepal. The 51V NMR spectra also indicate that the interior core water pool of the reverse micelles is less acidic than the bulk aqueous solution from which the samples were created. Together, these data provide a description that allows for a comparison of the water pools in these different nonionic reverse micelles.

  12. Aldol reaction catalyzed by a hydrophilic catalyst in aqueous micelle as an enzyme mimic system.

    PubMed

    Zhang, Hefeng; Zhao, Wenshan; Zou, Jun; Liu, Yi; Li, Runtao; Cui, Yuanchen

    2009-05-01

    Chitosan-supported L-proline complex was synthesized and applied as a catalyst for the direct asymmetric aldol reaction in various organic solvents and water as well. It was found that the novel synthesized catalyst was able to efficiently catalyze the aldol reaction in various media. The catalytic capacity and stereoselectivity of the catalyst were obviously improved with the introduction of aqueous micelle, possibly because the micelle functioned as a hydrophobic pocket, like the hydrophobic portion in enzymes. Moreover, the present synthetic catalyst showed performance similar to that of enzymes and could be used as a model of enzyme catalysis to help better understand the mystic mechanism of enzymes.

  13. Synthesis of lipids on the micelle/water interface using inorganic phosphate and an alkene oxide.

    PubMed

    Conde-Frieboes, K; Blöchliger, E

    2001-01-01

    Liposomes can be considered as a model for a protocell in the context of the origin of life. These self-organising systems can self-reproduce under certain experimental conditions. Herein we demonstrate the ability of another lipid aggregate, micelles, to catalyse a reaction leading finally to the formation of new lipids. In contrast to other published work, where the lipids are products of a hydrolysis reaction, here the lipids are built up from simple precursors. In addition, we observe a transformation of micelles into liposomes.

  14. [The influence of nonuniform vertical profiles of chlorophyll concentration on apparent optical properties].

    PubMed

    Xi, Ying; Du, Ke-Ping; Zhang, Li-Hua; Zhongping, Lee; Li, Xiao-Wen

    2010-02-01

    Previous researches on ocean optics and ocean color were based on the assumption that inherent optical properties and optically significant constituents of seawater are homogeneous in the vertical direction. However, oceanographic observations show that the assumption is not always exact and the vertical inhomogeneity of them exists in the upper ocean. The purpose of the present research is to study the effect of nonuniform vertical profiles of chlorophyll concentration on apparent optical properties with radiative transfer model Hydrolight. The vertical profiles of chlorophyll concentration were approximated according to a Gaussian function (Lewis et al, 1983). The apparent optical properties of seawater with nonuniform chlorophyll concentration profiles were simulated with Hydrolight radiative transfer model and case-1 bio-optical model, and then compared with those for homogenous ocean whose chlorophyll concentration was identical to the background chlorophyll concentration of inhomogenous cases. The results reveal that the subsurface maximal chlorophyll concentration increases the remote sensing reflectance at the blue wavelength and decreases it at the green wavelength, nonuniform vertical profiles of chlorophyll concentration change the diffuse attenuation coefficient profiles and the angular structure of the light field in the seawater, and the diffuse attenuation coefficients maximum and average cosines minimum appear at the depth of the maximal chlorophyll concentration.

  15. A novel lanreotide-encoded micelle system targets paclitaxel to the tumors with overexpression of somatostatin receptors.

    PubMed

    Zheng, Nan; Dai, Wenbing; Du, Wenwen; Zhang, Haoran; Lei, Liandi; Zhang, Hua; Wang, Xueqing; Wang, Jiancheng; Zhang, Xuan; Gao, Jinming; Zhang, Qiang

    2012-05-07

    Many tumor cells specifically overexpress somatostatin receptors, in particular, subtype 2 (SSTR2). Lanreotide, a somatostatin analogue with high affinity for SSTR2, can be exploited as a ligand for tumor targeted therapy. In this study, lanreotide was first conjugated to poly(ethylene glycol)-b-poly(ε-caprolactone) (PEG-b-PCL) copolymer, and the active targeting micelles with paclitaxel (lanreotide-PM-PTX) or fluorescent agent were constructed and characterized with various analytical methods. Lanreotide-PM-PTX micelles were spherical in shape with a hydrodynamic diameter of 43.2 ± 0.4 nm, high drug encapsulation (87.1 ± 2.8%) and slow drug release rate. Two cancer cell lines (human lung cancer H446 and human breast cancer MCF-7 cells) with different expression levels of SSTR2 were used in this study. As observed by flow cytometry, confocal microscopy and cytotoxicity studies, lanreotide-encoded PEG-b-PCL micelles demonstrated more specific cell uptake and cytotoxicity in SSTR2-positive tumor cells via a receptor-mediated mechanism over the passive targeting micelles. The active targeting micelles showed higher accumulation in tumor tissue and tumor cells in tumor-bearing mice in vivo by near-infrared fluorescence (NIRF) imaging, high-performance liquid chromatography and confocal microscopy, respectively. Furthermore, treatment with lanreotide-PM-PTX micelles resulted in stronger tumor inhibition, increased life span and enhanced tumor cell apoptosis in SSTR2-overexpressing tumor model in athymic nude mice. The in vivo efficacy test with both H446 and MCF-7 tumor models further demonstrated the involvement of receptor-mediated interaction. Finally, the active targeting micelles exhibited less body weight loss, lower hemolysis and lower myelosuppression, as compared with the control groups. In conclusion, lanreotide can serve as an effective homing peptide, and the lanreotide-modified PEG-b-PCL micelles hold considerable promise in the treatment of SSTR2

  16. 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

  17. 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

  18. 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. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. Antiangiogenic gene therapy of solid tumor by systemic injection of polyplex micelles loading plasmid DNA encoding soluble flt-1.

    PubMed

    Oba, Makoto; Vachutinsky, Yelena; Miyata, Kanjiro; Kano, Mitsunobu R; Ikeda, Sorato; Nishiyama, Nobuhiro; Itaka, Keiji; Miyazono, Kohei; Koyama, Hiroyuki; Kataoka, Kazunori

    2010-04-05

    In this study, a polyplex micelle was developed as a potential formulation for antiangiogenic gene therapy of subcutaneous pancreatic tumor model. Poly(ethylene glycol)-poly(l-lysine) block copolymers (PEG-PLys) with thiol groups in the side chain of the PLys segment were synthesized and applied for preparation of disulfide cross-linked polyplex micelles through ion complexation with plasmid DNA (pDNA) encoding the soluble form of vascular endothelial growth factor (VEGF) receptor-1 (sFlt-1), which is a potent antiangiogenic molecule. Antitumor activity and gene expression of polyplex micelles with various cross-linking rates were evaluated in mice bearing subcutaneously xenografted BxPC3 cell line, derived from human pancreatic adenocarcinoma, and polyplex micelles with optimal cross-linking rate achieved effective suppression of tumor growth. Significant gene expression of this micelle was detected selectively in tumor tissue, and its antiangiogenic effect was confirmed by decreased vascular density inside the tumor. Therefore, the disulfide cross-linked polyplex micelle loading sFlt-1 pDNA has a great potential for antiangiogenic therapy against subcutaneous pancreatic tumor model by systemic application.

  20. In vitro and in vivo toxicity evaluation of cationic PDMAEMA-PCL-PDMAEMA micelles as a carrier of curcumin.

    PubMed

    Tzankova, Virginia; Gorinova, Cvetelina; Kondeva-Burdina, Magdalena; Simeonova, Rumiana; Philipov, Stanislav; Konstantinov, Spiro; Petrov, Petar; Galabov, Dimitar; Yoncheva, Krassimira

    2016-11-01

    Polymeric micelles have attracted significant attention because of their potential application as promising drug-delivery systems. In the present study cationic micelles, based on triblock copolymer poly(dimethylaminoethyl methacrylate) - poly(e-caprolactone) - poly(dimethylaminoethyl methacrylate) were prepared and loaded with curcumin. In vitro cytotoxicity of empty and curcumin loaded polymer micelles was investigated on two cell culture models, human hepatoma cell line HEP G2 and freshly isolated rat hepatocytes, following their viability and lactate dehydrogenase (LDH) leakage. MTT dye reduction assay and LDH release study showed that empty cationic micelles did not cause significant changes in cell viability and membrane integrity at the concentration range from 10.0 to 80.0 μg/ml. Our special attention was focused on the effects of empty and curcumin loaded micelles on oxidative stress markers malondialdehyde (MDA) and reduced glutathione (GSH). The increase in the micelles concentration to 100 μg/ml was accompanied by GSH depletion and increased levels of MDA production in isolated rat hepatocytes. The in vivo toxicity of polymeric micelles was examined in male Wistar rats. The results showed that neither single (7.5 mg/kg, i.p.), nor repeated (3.5 mg/kg, i.p., 14 days) exposure to empty or curcumin loaded polymeric micelles induced any toxicity changes, e.g. hematopoietic and liver tissue damages.

  1. Specific targeting of A54 homing peptide-functionalized dextran-g-poly(lactic-co-glycolic acid) micelles to tumor cells

    PubMed Central

    Situ, Jun-Qing; Ye, Yi-Qing; Zhu, Xiu-Liang; Yu, Ri-Sheng; You, Jian; Yuan, Hong; Hu, Fu-Qiang; Du, Yong-Zhong

    2015-01-01

    The delivery of chemotherapeutics into tumor cells is a fundamental knot for tumor-target therapy to improve the curative effect and avoid side effects. Here, A54 peptide-functionalized poly(lactic-co-glycolic acid)-grafted dextran (A54-Dex-PLGA) was synthesized. The synthesized A54-Dex-PLGA self-assembled to form micelles with a low critical micelle concentration of 16.79 μg·mL−1 and diameter of about 50 nm. With doxorubicin (DOX) base as a model antitumor drug, the drug-encapsulation efficiency of DOX-loaded A54-Dex-PLGA micelles (A54-Dex-PLGA/DOX) reached up to 75%. In vitro DOX release from the A54-Dex-PLGA/DOX was prolonged to 72 hours. The A54-Dex-PLGA micelles presented excellent internalization ability into hepatoma cells (BEL-7402 cell line and HepG2 cell line) in vitro, and the cellular uptake of the micelles by the BEL-7402 cell line was specific, which was demonstrated by the blocking experiment. In vitro antitumor activity studies confirmed that A54-Dex-PLGA/DOX micelles suppressed tumor-cell (BEL-7402 cell) growth more effectively than Dex-PLGA micelles. Furthermore, in vivo biodistribution testing demonstrated that the A54-Dex-PLGA micelles had a higher distribution ability to BEL-7402 tumors than that to HepG2 tumors. PMID:25653517

  2. 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

  3. The photophysics of 7-(N,N'-diethylamino)coumarin-3-carboxylic acid in water/AOT/isooctane reverse micelles: an excitation wavelength dependent study.

    PubMed

    Chatterjee, Aninda; Maity, Banibrata; Seth, Debabrata

    2013-02-14

    In this manuscript we have studied the photophysics of 7-(N,N'-diethylamino)coumarin-3-carboxylic acid (7-DCCA) in water/AOT/isooctane reverse micelles. For this purpose we have used steady state absorption and fluorescence emission spectroscopy and time resolved fluorescence spectroscopy. We have studied the spectral behaviour of 7-DCCA inside the water/AOT/isooctane reverse micelles with variation of excitation wavelength. We have studied the dynamics of solvent and rotational relaxation by using two different excitation wavelengths (λ(exi) = 375 nm and λ(exi) = 405 nm). We have observed the excitation wavelength dependent dynamics of 7-DCCA in the reverse micelles. The fluorescence quantum yield, decay time, solvent relaxation time and rotational relaxation time of 7-DCCA in reverse micelles vary with the excitation wavelength. A two step and wobbling-in-cone model was used to interpret the rotational relaxation dynamics of 7-DCCA in reverse micelles.

  4. Intrinsic Photoprotective Mechanisms in Chlorophylls.

    PubMed

    Kotkowiak, Michał; Dudkowiak, Alina; Fiedor, Leszek

    2017-08-21

    Photosynthetic energy conversion competes with the formation of chlorophyll triplet states and the generation of reactive oxygen species. These may, especially under high light stress, damage the photosynthetic apparatus. Many sophisticated photoprotective mechanisms have evolved to secure a harmless flow of excitation energy through the photosynthetic complexes. Time-resolved laser-induced optoacoustic spectroscopy was used to compare the properties of the T1 states of pheophytin a and its metallocomplexes. The lowest quantum yield of the T1 state is always observed in the Mg complex, which also shows the least efficient energy transfer to O2 . Axial coordination to the central Mg further lowers the yield of both T1 and singlet oxygen. These results reveal the existence of intrinsic photoprotective mechanisms in chlorophylls, embedded in their molecular design, which substantially suppress the formation of triplet states and the efficiency of energy transfer to O2 , each by 20-25 %. Such intrinsic photoprotective effects must have created a large evolutionary advantage for the Mg complexes during their evolution as the principal photoactive cofactors of photosynthetic proteins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. Synthesis and characterization of 3,6-O,O'- dimyristoyl chitosan micelles for oral delivery of paclitaxel.

    PubMed

    Silva, Daniella S; Almeida, Andreia; Prezotti, Fabíola; Cury, Beatriz; Campana-Filho, Sérgio P; Sarmento, Bruno

    2017-04-01

    The aim of the present study was to investigate the potential application of 3,6-O,O'- dimyristoyl chitosan DMCh, an amphiphilic derivative of chitosan, for improving the oral bioavailability of paclitaxel (PTX), a water insoluble anticancer drug. The O-acylation of chitosan with myristoyl chloride was carried out by employing high (≈13.3) or low (2.0) molar excess of chitosan to result in samples DMCh07 and DMCh12, respectively. The successful O-acylation of chitosan was confirmed by FTIR and (1)H NMR spectroscopy, the latter allowing also the determination of average degree of substitution (DS). The critical aggregation concentration (CAC) of samples DMCh07 (DS≈6.8%) and DMCh12 (DS≈12.0%) were 8.9×10(-3)mg/mL and 13.2×10(3)mg/mL, respectively. It was observed by TEM that the DMCh micelles showed spherical shape while DLS measurements allowed the determination of their average size (287nm-490nm) and zeta potential (+32mV to +44mV). Such DMCh micelles were able to encapsulate paclitaxel with high drug encapsulation efficiency (EE), as confirmed by HPLC analyses. Studies on the cytotoxicity of DMCh07 micelles toward Caco-2 and HT29-MTX cells showed that, regardless the PTX loaded, DMCh07 micelles slightly decreased cellular viability at low micelles concentration (≤1μg/mL) while at high concentration (>10μg/mL) PTX-loaded DMCh07 micelles were less toxic toward Caco-2 cells when compared to free PTX. The PTX permeation across Caco-2 monoculture and Caco-2/HT29-MTX co-culture model confirmed the potential of DMCh micelles in improving the intestinal absorption of PTX. These results suggest that DMCh micelles may be a promising carrier to encapsulate PTX aiming cancer therapy. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. 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

  12. Lipid absorption triggers drug supersaturation at the intestinal unstirred water layer and promotes drug absorption from mixed micelles.

    PubMed

    Yeap, Yan Yan; Trevaskis, Natalie L; Porter, Christopher J H

    2013-12-01

    To evaluate the potential for the acidic intestinal unstirred water layer (UWL) to induce drug supersaturation and enhance drug absorption from intestinal mixed micelles, via the promotion of fatty acid absorption. Using a single-pass rat jejunal perfusion model, the absorptive-flux of cinnarizine and (3)H-oleic acid from oleic acid-containing intestinal mixed micelles was assessed under normal acidic microclimate conditions and conditions where the acidic microclimate was attenuated via the co-administration of amiloride. As a control, the absorptive-flux of cinnarizine from micelles of Brij® 97 (a non-ionizable, non-absorbable surfactant) was assessed in the absence and presence of amiloride. Cinnarizine solubility was evaluated under conditions of decreasing pH and decreasing micellar lipid content to assess likely changes in solubilization and thermodynamic activity during micellar passage across the UWL. In the presence of amiloride, the absorptive-flux of cinnarizine and (3)H-oleic acid from mixed micelles decreased 6.5-fold and 3.0-fold, respectively. In contrast, the absorptive-flux of cinnarizine from Brij® 97 micelles remained unchanged by amiloride, and was significantly lower than from the long-chain micelles. Cinnarizine solubility in long-chain micelles decreased under conditions where pH and micellar lipid content decreased simultaneously. The acidic microclimate of the intestinal UWL promotes drug absorption from intestinal mixed micelles via the promotion of fatty acid absorption which subsequently stimulates drug supersaturation. The observations suggest that formulations (or food) containing absorbable lipids (or their digestive precursors) may outperform formulations that lack absorbable components since the latter do not benefit from lipid absorption-induced drug supersaturation.

  13. 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

  14. New self-assembling polyaspartylhydrazide copolymer micelles for anticancer drug delivery.

    PubMed

    Licciardi, Mariano; Cavallaro, Gennara; Di Stefano, Mauro; Pitarresi, Giovanna; Fiorica, Calogero; Giammona, Gaetano

    2010-08-30

    A new amphiphilic copolymer have been synthesized starting from the hydrosoluble polyaspartylhydrazide (PAHy) polymer, by grafting both hydrophilic PEG(2000) chains and hydrophobic palmitic acid (C(16)) moieties on polymer backbone, and the structure of obtained PAHy-PEG(2000)-C(16) copolymer have been characterized by 2D (1)H/(13)C NMR experiments. PAHy-PEG(2000)-C(16) copolymer showed the ability of self-assembling in aqueous media giving a core-shell structure and resulted potentially useful for encapsulating and dissolving hydrophobic drug. The formation of micellar core-shell structure has been investigated by 2D (1)H NMR NOESY experiments. The presence of cross-peaks for protons of C(16) and PAHy portions, indicated that the two domains are in close proximity forming micelle core. The critical aggregation concentration (CAC) values of PAHy-PEG(2000)-C(16) amphiphilic graft copolymer was determined in water by fluorescence technique, and it was demonstrated that PAHy-PEG(2000)-C(16) micelles are well suited to be micellar vehicle of highly hydrophobic molecules. Therefore, anticancer drug tamoxifen, used as a model hydrophobic molecule, was loaded into PAHy-PEG(2000)-C(16) micelles obtaining an increase of drug solubility of about 3000 times. Transmission electron microscopy (TEM) observations showed the spherical morphology of micelles formed by PAHy-PEG(2000)-C(16) copolymer with a mean diameter of about 30nm, as confirmed also by dynamic light scattering (DLS) studies. Finally, in vitro cell viability studies were carried out on human breast cancer cells (MCF-7) testing the pharmacological activity of tamoxifen-loaded PAHy-PEG(2000)-C(16) micelles, in comparison with free tamoxifen at different drug concentrations, demonstrating that tamoxifen-loaded PAHy-PEG(2000)-C(16) micelles exhibited a concentration-dependent cytotoxic activity. Copyright 2010 Elsevier B.V. All rights reserved.

  15. Lysophosphatidylcholine enhances carotenoid uptake from mixed micelles by Caco-2 human intestinal cells.

    PubMed

    Sugawara, T; Kushiro, M; Zhang, H; Nara, E; Ono, H; Nagao, A

    2001-11-01

    Despite the interest in the beneficial roles of dietary carotenoids in human health, little is known about their solubilization from foods to mixed bile micelles during digestion and the intestinal uptake from the micelles. We investigated the absorption of carotenoids solubilized in mixed micelles by differentiated Caco-2 human intestinal cells, which is a useful model for studying the absorption of dietary compounds by intestinal cells. The micelles were composed of 1 micromol/L carotenoids, 2 mmol/L sodium taurocholate, 100 micromol/L monoacylglycerol, 33.3 micromol/L fatty acid and phospholipid (0-200 micromol/L). The phospholipid content of micelles had profound effects on the cellular uptake of carotenoids. Uptake of micellar beta-carotene and lutein was greatly suppressed by phosphatidylcholine (PC) in a dose-dependent manner, whereas lysophosphatidylcholine (lysoPC), the lipolysis product of PC by phospholipase A2 (PLA2), markedly enhanced both beta-carotene and lutein uptake. The addition of PLA2 from porcine pancreas to the medium also enhanced the uptake of carotenoids from micelles containing PC. Caco-2 cells could take up 15 dietary carotenoids, including epoxy carotenoids, such as violaxanthin, neoxanthin and fucoxanthin, from micellar carotenoids, and the uptakes showed a linear correlation with their lipophilicity, defined as the distribution coefficient in 1-octanol/water (log P(ow)). These results suggest that pancreatic PLA2 and lysoPC are important in regulating the absorption of carotenoids in the digestive tract and support a simple diffusion mechanism for carotenoid absorption by the intestinal epithelium.

  16. Novel cyclosporin A formulations using MPEG-hexyl-substituted polylactide micelles: a suitability study.

    PubMed

    Mondon, K; Zeisser-Labouèbe, M; Gurny, R; Möller, M

    2011-01-01

    The immunosuppressive agent Cyclosporin A (CsA) has very poor solubility in water and, in consequence, non-aqueous formulations have been developed for its intravenous administration to treat patients with transplant rejection. In this article, aqueous micelle solutions of novel amphiphilic copolymers based on methoxy-poly(ethylene glycol) (MPEG) and hexyl-substituted poly(lactides) (hexPLA) were studied for possible incorporation and formulation of CsA, and for their biocompatibility towards novel pharmaceutical applications. Above the critical micellar concentration (CMC), MPEG-hexPLA block-copolymers self-assemble into unimodal micelles with diameters of around 30 nm, either unloaded or drug-loaded. The best shelf-life stability of these formulations was observed when stored at 4°C with a drug loss inferior to 7% after 1 year. The polymer and micelle toxicities were evaluated in vitro for three different cell lines and in vivo using the chick embryo chorioallantoic membrane (CAM) model. The hemolytic property was assessed using human blood samples. As the studies revealed, MPEG-hexPLAs are non-toxic and do not show hemolysis; the same was found for the comparable MPEG-PLAs, both as unimers below their CMC and as polymeric micelles up to copolymer concentrations of 20 mg/mL. At this concentration, CsA was efficiently incorporated into MPEG-hexPLA micelles up to 6 mg/mL, which corresponds to a 500-fold increase of its water solubility. The current recommended clinical concentration administered per infusion (0.5-2.5 mg/mL) can be easily achieved and requires four times less copolymer than with the often-used Cremophor®EL surfactant. In this regard, MPEG-hexPLA micelle formulations can be an applicable formulation in transplant rejection treatments as an injectable CsA carrier system. Copyright © 2010 Elsevier B.V. All rights reserved.

  17. 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

  18. Synthesis and characterization of mPEG-PLA prodrug micelles.

    PubMed

    Hans, Meredith; Shimoni, Karin; Danino, Dganit; Siegel, Steven J; Lowman, Anthony

    2005-01-01

    Polymeric prodrugs of mPEG-PLA-haloperidol (methoxypoly(ethylene glycol)-b-poly(lactic acid)) can self-assemble into nanoscale micelle-like structures in aqueous solutions. mPEG-PLA-haloperidol was prepared and characterized using 1H and 13C NMR. The conjugation efficiency was found to be 64.8 +/- 21%. Micelles that form spontaneously upon solubilization of the mPEG-PLA and the polymeric prodrugs in water were characterized using a variety of techniques. The mPEG-PLA and prodrug micelles were found to have diameters of 28.73 +/- 1.45 and 49.67 +/- 4.29 nm, respectively, using dynamic light scattering (DLS). The micelle size and polydispersity were also evaluated with cryogenic transmission electron microscopy (cryo-TEM) and were consistent with the DLS results. Cryo-TEM and proton NMR confirmed that the micelles were spherical in shape. DLS was also used to determine the aggregation numbers of the micelles. The aggregation numbers ranged from 351 to 603. The change in aggregation number was dependent on the total drug incorporation into the micelle core. Critical micelle concentrations were determined for the various micelle/drug formulations and found to range from 3 to 14 microg/mL. Finally, drug was incorporated into the micelle core using the conjugate, free drug with a saturated aqueous phase during production, or a combination of both techniques. Drug incorporation could be increased from 3% to 20% (w/w) using the different formulations.

  19. Structural changes in block copolymer micelles induced by cosolvent mixtures†

    PubMed Central

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

    2013-01-01

    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. PMID:24282441

  20. 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.

  1. 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.

  2. 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 comp