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Sample records for absolute molecular weight

  1. Determination of the absolute molecular weight averages and molecular weight distributions of alginates used as ice cream stabilizers by using multiangle laser light scattering measurements.

    PubMed

    Turquois, T; Gloria, H

    2000-11-01

    High-performance size exclusion chromatography with multiangle laser light scattering detection (HPSEC-MALLS) was used for characterizing complete molecular weight distributions for a range of commercial alginates used as ice cream stabilizers. For the samples investigated, molecular weight averages were found to vary between 115 000 and 321 700 g/mol and polydispersity indexes varied from 1. 53 to 3.25. These samples displayed a high content of low molecular weights. Thus, the weight percentage of material below 100 000 g/mol ranged between 6.9 and 54.4%.

  2. Absolute molecular weight determination of hypromellose acetate succinate by size exclusion chromatography: use of a multi angle laser light scattering detector and a mixed solvent.

    PubMed

    Chen, Raymond; Ilasi, Nicholas; Sekulic, Sonja S

    2011-12-05

    Molecular weight distribution is an important quality attribute for hypromellose acetate succinate (HPMCAS), a pharmaceutical excipient used in spray-dried dispersions. Our previous study showed that neither relative nor universal calibration method of size exclusion chromatography (SEC) works for HPMCAS polymers. We here report our effort to develop a SEC method using a mass sensitive multi angle laser light scattering detector (MALLS) to determine molecular weight distributions of HPMCAS polymers. A solvent screen study reveals that a mixed solvent (60:40%, v/v 50mM NaH(2)PO(4) with 0.1M NaNO(3) buffer: acetonitrile, pH* 8.0) is the best for HPMCAS-LF and MF sub-classes. Use of a mixed solvent creates a challenging condition for the method that uses refractive index detector. Therefore, we thoroughly evaluated the method performance and robustness. The mean weight average molecular weight of a polyethylene oxide standard has a 95% confidence interval of (28,443-28,793) g/mol vs. 28,700g/mol from the Certificate of Analysis. The relative standard deviations of average molecular weights for all polymers are 3-6%. These results and the Design of Experiments study demonstrate that the method is accurate and robust. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. Molecular Weight and Molecular Weight Distributions in Synthetic Polymers.

    ERIC Educational Resources Information Center

    Ward, Thomas Carl

    1981-01-01

    Focuses on molecular weight and molecular weight distributions (MWD) and models for predicting MWD in a pedagogical way. In addition, instrumental methods used to characterize MWD are reviewed with emphasis on physical chemistry of each, including end-group determination, osmometry, light scattering, solution viscosity, fractionation, and…

  4. Apparatus for molecular weight separation

    DOEpatents

    Smith, Richard D.; Liu, Chuanliang

    2001-01-01

    The present invention relates generally to an apparatus and method for separating high molecular weight molecules from low molecular weight molecules. More specifically, the invention relates to the use of microdialysis for removal of the salt (low molecular weight molecules) from a nucleotide sample (high molecular weight molecules) for ESI-MS analysis. The dialysis or separation performance of the present invention is improved by (1) increasing dialysis temperature thereby increasing desalting efficiency and improving spectrum quality; (2) adding piperidine and imidazole to the dialysis buffer solution and reducing charge states and further increasing detection sensitivity for DNA; (3) using low concentrations (0-2.5 mM NH4OAc) of dialysis buffer and shifting the DNA negative ions to higher charge states, producing a nearly 10-fold increase in detection sensitivity and a slightly decreased desalting efficiency, (4) conducting a two-stage separation or (5) any combination of (1), (2), (3) and (4).

  5. Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals

    NASA Astrophysics Data System (ADS)

    Ge, Qinghui; Mao, Yuezhi; Head-Gordon, Martin

    2018-02-01

    An energy decomposition analysis (EDA) scheme is developed for understanding the intermolecular interaction involving molecules in their excited states. The EDA utilizes absolutely localized molecular orbitals to define intermediate states and is compatible with excited state methods based on linear response theory such as configuration interaction singles and time-dependent density functional theory. The shift in excitation energy when an excited molecule interacts with the environment is decomposed into frozen, polarization, and charge transfer contributions, and the frozen term can be further separated into Pauli repulsion and electrostatics. These terms can be added to their counterparts obtained from the ground state EDA to form a decomposition of the total interaction energy. The EDA scheme is applied to study a variety of systems, including some model systems to demonstrate the correct behavior of all the proposed energy components as well as more realistic systems such as hydrogen-bonding complexes (e.g., formamide-water, pyridine/pyrimidine-water) and halide (F-, Cl-)-water clusters that involve charge-transfer-to-solvent excitations.

  6. The Molecular Weight Distribution of Polymer Samples

    ERIC Educational Resources Information Center

    Horta, Arturo; Pastoriza, M. Alejandra

    2007-01-01

    Various methods for the determination of the molecular weight distribution (MWD) of different polymer samples are presented. The study shows that the molecular weight averages and distribution of a polymerization completely depend on the characteristics of the reaction itself.

  7. Effect of molecular weight on polymer processability

    SciTech Connect

    Karg, R.F.

    1983-01-01

    Differences in rheological behavior due to the polymer molecular weight and molecular weight distribution have been shown with the MPT. SBR polymers having high molecular weight fractions develop higher stress relaxation time values due to the higher degree of polymer entanglements. Tests conducted at increasing temperatures show the diminishing influence of the polymer entanglements upon stress relaxation time. EPDM polymers show stress relaxation time and head pressure behavior which correlates with mill processability. As anticipated, compounded stock of EPDM have broad molecular weight distribution has higher stress relaxation time values than EPDM compounds with narrow molecular weight distribution.

  8. Ultrahigh molecular weight aromatic siloxane polymers

    NASA Technical Reports Server (NTRS)

    Ludwick, L. M.

    1982-01-01

    The condensation of a diol with a silane in toluene yields a silphenylene-siloxane polymer. The reaction of stiochiometric amounts of the diol and silane produced products with molecular weights in the range 2.0 - 6.0 x 10 to the 5th power. The molecular weight of the product was greatly increased by a multistep technique. The methodology for synthesis of high molecular weight polymers using a two step procedure was refined. Polymers with weight average molecular weights in excess of 1.0 x 10 to the 6th power produced by this method. Two more reactive silanes, bis(pyrrolidinyl)dimethylsilane and bis(gamma butyrolactam)dimethylsilane, are compared with the dimethyleminodimethylsilane in ability to advance the molecular weight of the prepolymer. The polymers produced are characterized by intrinsic viscosity in tetrahydrofuran. Weight and number average molecular weights and polydispersity are determined by gel permeation chromatography.

  9. Effect of molecular weight on polyphenylquinoxaline properties

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.

    1991-01-01

    A series of polyphenyl quinoxalines with different molecular weight and end-groups were prepared by varying monomer stoichiometry. Thus, 4,4'-oxydibenzil and 3,3'-diaminobenzidine were reacted in a 50/50 mixture of m-cresol and xylenes. Reaction concentration, temperature, and stir rate were studied and found to have an effect on polymer properties. Number and weight average molecular weights were determined and correlated well with viscosity data. Glass transition temperatures were determined and found to vary with molecular weight and end-groups. Mechanical properties of films from polymers with different molecular weights were essentially identical at room temperature but showed significant differences at 232 C. Diamine terminated polymers were found to be much less thermooxidatively stable than benzil terminated polymers when aged at 316 C even though dynamic thermogravimetric analysis revealed only slight differences. Lower molecular weight polymers exhibited better processability than higher molecular weight polymers.

  10. Production of high molecular weight polylactic acid

    DOEpatents

    Bonsignore, P.V.

    1995-11-28

    A degradable high molecular weight poly(lactic acid) is described. The poly(lactic acid) has a terminal end group of one of carboxyl or hydroxyl groups with low molecular weight poly(lactic acid) units coupled with linking agents of di-isocyanates, bis-epoxides, bis-oxazolines and bis-ortho esters. The resulting high molecular weight poly(lactic acid) can be used for applications taking advantage of the improved physical properties.

  11. Production of high molecular weight polylactic acid

    DOEpatents

    Bonsignore, Patrick V.

    1995-01-01

    A degradable high molecular weight poly(lactic acid). A poly(lactic acid) has a terminal end group of one of carboxyl or hydroxyl groups with low molecular weight poly(lactic acid) units coupled with linking agents of di-isocyanates, bis-epoxides, bis-oxazolines and bis-ortho esters. The resulting high molecular weight poly(lactic acid) can be used for applications taking advantage of the improved physical properties.

  12. Absolute molecular sieve separation of ethylene/ethane mixtures with silver zeolite A.

    PubMed

    Aguado, Sonia; Bergeret, Gérard; Daniel, Cecile; Farrusseng, David

    2012-09-12

    Absolute ethylene/ethane separation is achieved by ethane exclusion on silver-exchanged zeolite A adsorbent. This molecular sieving type separation is attributed to the pore size of the adsorbent, which falls between ethylene and ethane kinetic diameters.

  13. SEDFIT-MSTAR: Molecular weight and molecular weight distribution analysis of polymers by sedimentation equilibrium in the ultracentrifuge

    PubMed Central

    Schuck, Peter; Gillis, Richard B.; Besong, Tabot M.D.; Almutairi, Fahad; Adams, Gary G.; Rowe, Arthur J.; Harding, Stephen E.

    2014-01-01

    Sedimentation equilibrium (analytical ultracentrifugation) is one of the most inherently suitable methods for the determination of average molecular weights and molecular weight distributions of polymers, because of its absolute basis (no conformation assumptions) and inherent fractionation ability (without the need for columns or membranes and associated assumptions over inertness). With modern instrumentation it is also possible to run up to 21 samples simultaneously in a single run. Its application has been severely hampered because of difficulties in terms of baseline determination (incorporating estimation of the concentration at the air/solution meniscus) and complexity of the analysis procedures. We describe a new method for baseline determination based on a smart-smoothing principle and built into the highly popular platform SEDFIT for the analysis of the sedimentation behavior of natural and synthetic polymer materials. The SEDFIT-MSTAR procedure – which takes only a few minutes to perform - is tested with four synthetic data sets (including a significantly non-ideal system) a naturally occurring protein (human IgG1) and two naturally occurring carbohydrate polymers (pullulan and λ–carrageenan) in terms of (i) weight average molecular weight for the whole distribution of species in the sample (ii) the variation in “point” average molecular weight with local concentration in the ultracentrifuge cell and (iii) molecular weight distribution. PMID:24244936

  14. Microdialysis unit for molecular weight separation

    DOEpatents

    Smith, Richard D.; Liu, Chuanliang

    1999-01-01

    The present invention relates generally to an apparatus and method for separating high molecular weight molecules from low molecular weight molecules. More specifically, the invention relates to the use of microdialysis for removal of the salt (low molecular weight molecules) from a nucleotide sample (high molecular weight molecules) for ESI-MS analysis. The dialysis or separation performance of the present invention is improved by (1) increasing dialysis temperature thereby increasing desalting efficiency and improving spectrum quality; (2) adding piperidine and imidazole to the dialysis buffer solution and reducing charge states and further increasing detection sensitivity for DNA; (3) using low concentrations (0-2.5 mM NH4OAc) of dialysis buffer and shifting the DNA negative ions to higher charge states, producing a nearly 10-fold increase in detection sensitivity and a slightly decreased desalting efficiency, or (4) any combination of (1), (2), and (3).

  15. Age-specific absolute and relative organ weight distributions for B6C3F1 mice.

    PubMed

    Marino, Dale J

    2012-01-01

    The B6C3F1 mouse is the standard mouse strain used in toxicology studies conducted by the National Cancer Institute (NCI) and the National Toxicology Program (NTP). While numerous reports have been published on growth, survival, and tumor incidence, no overall compilation of organ weight data is available. Importantly, organ weight change is an endpoint used by regulatory agencies to develop toxicity reference values (TRVs) for use in human health risk assessments. Furthermore, physiologically based pharmacokinetic (PBPK) models, which utilize relative organ weights, are increasingly being used to develop TRVs. Therefore, all available absolute and relative organ weight data for untreated control B6C3F1 mice were collected from NCI/NTP studies in order to develop age-specific distributions. Results show that organ weights were collected more frequently in NCI/NTP studies at 2-wk (60 studies), 3-mo (147 studies), and 15-mo (40 studies) intervals than at other intervals, and more frequently from feeding and inhalation than drinking water studies. Liver, right kidney, lung, heart, thymus, and brain weights were most frequently collected. From the collected data, the mean and standard deviation for absolute and relative organ weights were calculated. Results show age-related increases in absolute liver, right kidney, lung, and heart weights and relatively stable brain and right testis weights. The results suggest a general variability trend in absolute organ weights of brain < right testis < right kidney < heart < liver < lung < spleen < thymus. This report describes the results of this effort.

  16. Low-molecular-weight heparin for thromboprophylaxis.

    PubMed

    Camporese, Giuseppe; Bernardi, Enrico

    2009-09-01

    Venous thromboembolism represents a potentially threatening complication in surgical and medical patients. Thromboprophylaxis showed a significant reduction of venous thromboembolic events, and low-molecular-weight heparins have been considered the standardized prophylactic regimen for a long time. The purpose of this review is to provide updated evidence on the use of low-molecular-weight heparins for prevention of venous thromboembolism after the publication of the latest American College of Chest Physicians Evidence-Based Clinical Practice Guidelines on antithrombotic and thrombolytic therapy. Low-molecular-weight heparins, used as comparator or investigational drug, have been investigated in several studies not included in the analysis of the latest American College of Chest Physicians Guidelines on Antithrombotic and Thrombolytic Therapy. Data gathered from studies published from December 2007 up to May 2009 dealing with surgical and medical patients have been collected and discussed. Low-molecular-weight heparins are expanding their application, but progressively they will be replaced by other new antithrombotics for the prophylaxis of venous thromboembolism. Surgical patients undergo a more concerted approach to thromboprophylaxis than medical patients. Future research should aim at improving prophylaxis in the latter setting in order to significantly reduce the rate of venous thromboembolic events.

  17. Ultrahigh Molecular Weight Aromatic Siloxane Polymers

    NASA Technical Reports Server (NTRS)

    Ludwick, L. M.

    1983-01-01

    Silphenylene-siloxane polymers can be prepared by a condensation reaction of a diol 1,4-bis(hydroxydimethylsilyl)benzene and a silane bis(dimethylamino)dimethylsilane. Using a stepwise condensation technique, a polymer (R=CH3) with a molecular weight in excess of 1.0 x 1 million has been produced. The polymer exhibits increased thermal stability, compared to a methyl siloxane polymer without the aromatic phenyl ring in the backbone. The use of bis(dimethylamino)methylvinylsilane should allow for ready crosslinking at the vinyl sites (R=-CH=CH2) introduced into the backbone. However, under the conditions of the reaction system a high molecular weight polymer was not obtained or the polymer underwent a crosslinking process during the synthesis.

  18. a Chiral Tagging Strategy for Determining Absolute Configuration and Enantiomeric Excess by Molecular Rotational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Evangelisti, Luca; Caminati, Walther; Patterson, David; Thomas, Javix; Xu, Yunjie; West, Channing; Pate, Brooks

    2017-06-01

    The introduction of three wave mixing rotational spectroscopy by Patterson, Schnell, and Doyle [1,2] has expanded applications of molecular rotational spectroscopy into the field of chiral analysis. Chiral analysis of a molecule is the quantitative measurement of the relative abundances of all stereoisomers of the molecule and these include both diastereomers (with distinct molecular rotational spectra) and enantiomers (with equivalent molecular rotational spectra). This work adapts a common strategy in chiral analysis of enantiomers to molecular rotational spectroscopy. A "chiral tag" is attached to the molecule of interest by making a weakly bound complex in a pulsed jet expansion. When this tag molecule is enantiopure, it will create diastereomeric complexes with the two enantiomers of the molecule being analyzed and these can be differentiated by molecule rotational spectroscopy. Identifying the structure of this complex, with knowledge of the absolute configuration of the tag, establishes the absolute configuration of the molecule of interest. Furthermore, the diastereomer complex spectra can be used to determine the enantiomeric excess of the sample. The ability to perform chiral analysis will be illustrated by a study of solketal using propylene oxide as the tag. The possibility of using current methods of quantum chemistry to assign a specific structure to the chiral tag complex will be discussed. Finally, chiral tag rotational spectroscopy offers a "gold standard" method for determining the absolute configuration of the molecule through determination of the substitution structure of the complex. When this measurement is possible, rotational spectroscopy can deliver a quantitative three dimensional structure of the molecule with correct stereochemistry as the analysis output. [1] David Patterson, Melanie Schnell, John M. Doyle, Nature 497, 475 (2013). [2] David Patterson, John M. Doyle, Phys. Rev. Lett. 111, 023008 (2013).

  19. Polymer Molecular Weight Analysis by [Superscript 1]H NMR Spectroscopy

    ERIC Educational Resources Information Center

    Izunobi, Josephat U.; Higginbotham, Clement L.

    2011-01-01

    The measurement and analysis of molecular weight and molecular weight distribution remain matters of fundamental importance for the characterization and physical properties of polymers. Gel permeation chromatography (GPC) is the most routinely used method for the molecular weight determination of polymers whereas matrix-assisted laser…

  20. Determinations of molecular weight and molecular weight distribution of high polymers by the rheological properties

    NASA Technical Reports Server (NTRS)

    Huang, J. Y.; Hou, T. H.; Tiwari, S. N.

    1989-01-01

    Several methods are reviewed by which the molecular weight (MW) and the molecular weight distribution (MWD) of polymeric material were determined from the rheological properties. A poly(arylene ether) polymer with six different molecular weights was used in this investigation. Experimentally measured MW and MWD were conducted by GPC/LALLS (gel permeation chromatography/low angle laser light scattering), and the rheological properties of the melts were measured by a Rheometric System Four rheometer. It was found that qualitative information of the MW and MWD of these polymers could be derived from the viscoelastic properties, with the methods proposed by Zeichner and Patel, and by Dormier et al., by shifting the master curves of the dynamic storage modulus, G', and the loss modulus, G'', along the frequency axis. Efforts were also made to calculate quantitative profiles of MW and MWD for these polymers from their rheological properties. The technique recently proposed by Wu was evaluated. It was found that satisfactory results could only be obtained for polymers with single modal distribution in the molecular weight.

  1. Unexpected molecular weight effect in polymer nanocomposites

    DOE PAGES

    Cheng, Shiwang; Holt, Adam P.; Wang, Huiqun; ...

    2016-01-22

    Here, the properties of the interfacial layer between the polymer matrix and nanoparticles largely determine the macroscopic properties of polymer nanocomposites (PNCs). Although the static thickness of the interfacial layer was found to increase with the molecular weight (MW), the influence of MW on segmental relaxation and the glass transition in this layer remains to be explored. In this Letter, we show an unexpected MW dependence of the interfacial properties in PNC with attractive polymer-nanoparticle interactions: the thickness of the interfacial layer with hindered segmental relaxation decreases as MW increases, in sharp constrast to theoretical predictions. Further analyses reveal amore » reduction in mass density of the interfacial layer with increasing MW, which can explain these unexpected dynamic effects. Our observations call for a significant revision of the current understandings of PNCs and suggest interesting ways to tailor their properties.« less

  2. Absolute and relative densities of fast-food versus other restaurants in relation to weight status: Does restaurant mix matter?

    PubMed

    Polsky, Jane Y; Moineddin, Rahim; Dunn, James R; Glazier, Richard H; Booth, Gillian L

    2016-01-01

    Given the continuing epidemic of obesity, policymakers are increasingly looking for levers within the local retail food environment as a means of promoting healthy weights. To examine the independent and joint associations of absolute and relative densities of restaurants near home with weight status in a large, urban, population-based sample of adults. We studied 10,199 adults living in one of four cities in southern Ontario, Canada, who participated in the Canadian Community Health Survey (cycles 2005, 2007/08, 2009/10). Multivariate models assessed the association of weight status (obesity and body mass index) with absolute densities (numbers) of fast-food, full-service and other restaurants, and the relative density (proportion) of fast-food restaurants (FFR) relative to all restaurants within ~10-minute walk of residential areas. Higher numbers of restaurants of any type were inversely related to excess weight, even in models adjusting for a range of individual covariates and area deprivation. However, these associations were no longer significant after accounting for higher walkability of areas with high volumes of restaurants. In contrast, there was a direct relationship between the proportion of FFR relative to all restaurants and excess weight, particularly in areas with high volumes of FFR (e.g., odds ratio for obesity=2.55 in areas with 5+ FFR, 95% confidence interval: 1.55-4.17, across the interquartile range). Policies aiming to promote healthy weights that target the volume of certain retail food outlets in residential settings may be more effective if they also consider the relative share of outlets serving more and less healthful foods. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Molecular Weight Effects on the Viscoelastic Response of a Polyimide

    NASA Technical Reports Server (NTRS)

    Nicholson, Lee M.; Whitley, Karen S.; Gates, Thomas S.

    2000-01-01

    The effect of molecular weight on the viscoelastic performance of an advanced polymer (LaRC -SI) was investigated through the use of creep compliance tests. Testing consisted of short-term isothermal creep and recovery with the creep segments performed under constant load. The tests were conducted at three temperatures below the glass transition temperature of each material with different molecular weight. Through the use of time-aging-time superposition procedures, the material constants, material master curves and aging-related parameters were evaluated at each temperature for a given molecular weight. The time-temperature superposition technique helped to describe the effect of temperature on the timescale of the viscoelastic response of each molecular weight. It was shown that the low molecular weight materials have increased creep compliance and creep compliance rate, and are more sensitive to temperature than the high molecular weight materials. Furthermore, a critical molecular weight transition was observed to occur at a weight-average molecular weight of approximately 25000 g/mol below which, the temperature sensitivity of the time-temperature superposition shift factor increases rapidly.

  4. Cytogenetic and molecular aspects of absolute teratozoospermia: comparison between polymorphic and monomorphic forms.

    PubMed

    Brahem, Sonia; Elghezal, Hatem; Ghédir, Houda; Landolsi, Hanène; Amara, Abdelbacett; Ibala, Samira; Gribaa, Moez; Saad, Ali; Mehdi, Meriem

    2011-12-01

    To compare the results of cytogenetic and molecular analysis between absolute polymorphic and monomorphic teratozoospermia. The semen samples from patients with polymorphic teratozoospermia (n = 20), globozoospermia (n = 8), or macrocephalic sperm head syndrome (n = 12), and healthy fertile men (n = 20) were analyzed according to the World Health Organization criteria. The constitutional blood karyotype of the patients was performed on cultured lymphocytes, according to standard techniques. Microdeletion analysis of the Y chromosomes used a sequence tagged site-polymerase chain reaction technique. Triple-color fluorescent in situ hybridization for chromosomes X, Y, and 18 were used to analyze the meiotic segregation. DNA fragmentation was detected using the terminal desoxynucleotidyl transferase-mediated deoxyuridine triphosphate biotin nick-end labeling assay. Whatever the type of teratozoospermia, a normal karyotype and an absence of Y chromosome microdeletion were shown for all patients. A significant increase in the sperm aneuploidy rate and DNA fragmentation were shown, regardless of the type of teratozoospermia. Spermatozoa of the patients with globozoospermia carry an abnormal chromosomal constitution and DNA damage rate with the same frequency as that found in the sperm of patients with absolute polymorphic teratozoospermia. However, a greater sperm aneuploidy rate and DNA fragmentation were found in patients whose teratozoospermia was mainly characterized by increased rates of spermatozoa with macrocephalic head and multiple flagella. Our data have demonstrated that DNA fragmentation and sperm aneuploidy are critical tests in teratozoospermic men, because the results could negatively affect the intracytoplasmic sperm injection outcomes and might play an important role in the counseling of couples considering intracytoplasmic sperm injection. Copyright © 2011 Elsevier Inc. All rights reserved.

  5. Redetermined structure, inter-molecular inter-actions and absolute configuration of royleanone.

    PubMed

    Fun, Hoong-Kun; Chantrapromma, Suchada; Salae, Abdul Wahab; Razak, Ibrahim Abdul; Karalai, Chatchanok

    2011-05-01

    The structure of the title diterpenoid, C(20)H(28)O(3), {systematic name: (4bS,8aS)-3-hy-droxy-2-isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octa-hydro-phenanthrene-1,4-dione} is confirmed [Eugster et al. (1993 ▶). Private communication (refcode HACGUN). CCDC, Union Road, Cambridge] and its packing is now described. Its absolute structure was established by refinement against data collected with Cu radiation: the two stereogenic centres both have S configurations. One cyclo-hexane ring adopts a chair conformation whereas the other cyclo-hexane ring is in a half-chair conformation and the benzoquinone ring is slightly twisted. An intra-molecular O-H⋯O hydrogen bond generates an S(5) ring motif. In the crystal, mol-ecules are linked into chains along [010] by O-H⋯O hydrogen bonds and weak C-H⋯O inter-actions. The packing also features C⋯O [3.131 (3) Å] short contacts.

  6. Low molecular weight species in humic and fulvic fractions

    USGS Publications Warehouse

    Wilson, M.A.; Collin, P.J.; Malcolm, R.L.; Perdue, E. Michael; Cresswell, P.

    1988-01-01

    Fourier transform solution 1H nuclear magnetic resonance (NMR) spectrometry with homogated water peak irradiation is a useful method for detecting low molecular weight substances in humic extracts. Succinate, acetate, methanol, formate, lactate and some aryl methoxyl compounds have been detected in extracts from a wide range of sources. In view of the controversy over whether low molecular weight substances are contaminants in humic extracts introduced by the concentration procedure, we report that some of these materials are not contaminants since 1H-NMR can be used to follow their formation from higher molecular weight species. ?? 1988.

  7. Do Low Molecular Weight Agents Cause More Severe Asthma than High Molecular Weight Agents?

    PubMed

    Meca, Olga; Cruz, María-Jesús; Sánchez-Ortiz, Mónica; González-Barcala, Francisco-Javier; Ojanguren, Iñigo; Munoz, Xavier

    2016-01-01

    The aim of this study was to analyse whether patients with occupational asthma (OA) caused by low molecular weight (LMW) agents differed from patients with OA caused by high molecular weight (HMW) with regard to risk factors, asthma presentation and severity, and response to various diagnostic tests. Seventy-eight patients with OA diagnosed by positive specific inhalation challenge (SIC) were included. Anthropometric characteristics, atopic status, occupation, latency periods, asthma severity according to the Global Initiative for Asthma (GINA) control classification, lung function tests and SIC results were analysed. OA was induced by an HMW agent in 23 patients (29%) and by an LMW agent in 55 (71%). A logistic regression analysis confirmed that patients with OA caused by LMW agents had a significantly higher risk of severity according to the GINA classification after adjusting for potential confounders (OR = 3.579, 95% CI 1.136-11.280; p = 0.029). During the SIC, most patients with OA caused by HMW agents presented an early reaction (82%), while in patients with OA caused by LMW agents the response was mainly late (73%) (p = 0.0001). Similarly, patients with OA caused by LMW agents experienced a greater degree of bronchial hyperresponsiveness, measured as the difference in the methacholine dose-response ratio (DRR) before and after SIC (1.77, range 0-16), compared with patients with OA caused by HMW agents (0.87, range 0-72), (p = 0.024). OA caused by LMW agents may be more severe than that caused by HMW agents. The severity of the condition may be determined by the different mechanisms of action of these agents.

  8. Determination of the absolute binding free energies of HIV-1 protease inhibitors using non-equilibrium molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Ngo, Son Tung; Nguyen, Minh Tung; Nguyen, Minh Tho

    2017-05-01

    The absolute binding free energy of an inhibitor to HIV-1 Protease (PR) was determined throughout evaluation of the non-bonded interaction energy difference between the two bound and unbound states of the inhibitor and surrounding molecules by the fast pulling of ligand (FPL) process using non-equilibrium molecular dynamics (NEMD) simulations. The calculated free energy difference terms help clarifying the nature of the binding. Theoretical binding affinities are in good correlation with experimental data, with R = 0.89. The paradigm used is able to rank two inhibitors having the maximum difference of ∼1.5 kcal/mol in absolute binding free energies.

  9. Low molecular weight salts combined with fluorinated solvents for electrolytes

    SciTech Connect

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

    2015-11-10

    Provided are electrochemical cells and electrolytes used to build such cells. An electrolyte includes at least one salt having a molecular weight less than about 250. Such salts allow forming electrolytes with higher salt concentrations and ensure high conductivity and ion transport in these electrolytes. The low molecular weight salt may have a concentration of at least about 0.5M and may be combined with one or more other salts, such as linear and cyclic imide salts and/or methide salts. The concentration of these additional salts may be less than that of the low molecular weight salt, in some embodiments, twicemore » less. The additional salts may have a molecular weight greater than about 250. The electrolyte may also include one or more fluorinated solvents and may be capable of maintaining single phase solutions at between about -30.degree. C. to about 80.degree. C.« less

  10. High Molecular Weight Polymers in the New Chemicals Program

    EPA Pesticide Factsheets

    There are three categories or types of High Molecular Weight (HMW, 10,000 daltons) polymers typically reviewed by the New Chemicals Program: Soluble, insoluble, and water absorbing. Each of the three types are treated differently.

  11. Phase Behavior of Binary Blends of High Molecular Weight Diblock Copolymers with a Low Molecular Weight Triblock

    SciTech Connect

    Mickiewicz, Rafal A.; Ntoukas, Eleftherios; Avgeropoulos, Apostolos

    2009-08-26

    Binary blends of four different high molecular weight poly(styrene-b-isoprene) (SI) diblock copolymers with a lower molecular weight poly(styrene-b-isoprene-b-styrene) (SIS) triblock copolymer were prepared, and their morphology was characterized by transmission electron microscopy and ultra-small-angle X-ray scattering. All the neat block copolymers have nearly symmetric composition and exhibit the lamellar morphology. The SI diblock copolymers had number-average molecular weights, Mn, in the range 4.4 x 10{sup 5}--1.3 x 10{sup 6} g/mol and volume fractions of poly(styrene), {Phi}{sub PS}, in the range 0.43--0.49, and the SIS triblock had a molecular weight of Mn 6.2 x 10{sup 4} g/mol with {Phi}{sub PS} =more » 0.41. The high molecular weight diblock copolymers are very strongly segregating, with interaction parameter values, {chi}N, in the range 470--1410. A morphological phase diagram in the parameter space of molecular weight ratio (R = M{sub n}{sup diblock}/1/2M{sub n}{sup triblock}) and blend composition was constructed, with R values in the range between 14 and 43, which are higher than previously reported. The phase diagram revealed a large miscibility gap for the blends, with macrophase separation into two distinct types of microphase-separated domains for weight fractions of SI, w{sub SI} < 0.9, implying virtually no solubility of the much higher molecular weight diblocks in the lower molecular weight triblock. For certain blend compositions, above R 30, morphological transitions from the lamellar to cylindrical and bicontinuous structures were also observed.« less

  12. Evaluation of a Viscosity-Molecular Weight Relationship.

    ERIC Educational Resources Information Center

    Mathias, Lon J.

    1983-01-01

    Background information, procedures, and results are provided for a series of graduate/undergraduate polymer experiments. These include synthesis of poly(methylmethacrylate), viscosity experiment (indicating large effect even small amounts of a polymer may have on solution properties), and measurement of weight-average molecular weight by light…

  13. Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure

    DOE PAGES

    Doughty, Benjamin; Goverapet Srinivasan, Sriram; Bryantsev, Vyacheslav S.; ...

    2017-06-12

    The initial mechanistic steps underlying heterogeneous chemical catalysis can be described in a framework where the composition, structure, and orientation of molecules adsorbed to reactive interfaces are known. However, extracting this vital information is the limiting step in most cases due in part to challenges in probing the interfacial monolayer with enough chemical specificity to characterize the surface molecular constituents. These challenges are exacerbated at complex or spatially heterogeneous interfaces where competing processes and a distribution of local environments can uniquely drive chemistry. To address these limitations, this work presents a distinctive combination of materials synthesis, surface specific optical experiments,more » and theory to probe and understand molecular structure at catalytic interfaces. Specifically, isopropanol was adsorbed to surfaces of the model CeO 2 catalyst that were synthesized with only the (100) facet exposed. Vibrational sum-frequency generation was used to probe the molecular monolayer, and with the guidance of density functional theory calculations, was used to extract the structure and absolute molecular orientation of isopropanol at the CeO 2 (100) surface. Our results show that isopropanol is readily deprotonated at the surface, and through the measured absolute molecular orientation of isopropanol, we obtain new insight into the selectivity of the (100) surface to form propylene. Our findings reveal key insight into the chemical and physical phenomena taking place at pristine interfaces thereby pointing to intuitive structural arguments to describe catalytic selectivity in more complex systems.« less

  14. Absolute Molecular Orientation of Isopropanol at Ceria (100) Surfaces: Insight into Catalytic Selectivity from the Interfacial Structure

    SciTech Connect

    Doughty, Benjamin; Goverapet Srinivasan, Sriram; Bryantsev, Vyacheslav S.

    The initial mechanistic steps underlying heterogeneous chemical catalysis can be described in a framework where the composition, structure, and orientation of molecules adsorbed to reactive interfaces are known. However, extracting this vital information is the limiting step in most cases due in part to challenges in probing the interfacial monolayer with enough chemical specificity to characterize the surface molecular constituents. These challenges are exacerbated at complex or spatially heterogeneous interfaces where competing processes and a distribution of local environments can uniquely drive chemistry. To address these limitations, this work presents a distinctive combination of materials synthesis, surface specific optical experiments,more » and theory to probe and understand molecular structure at catalytic interfaces. Specifically, isopropanol was adsorbed to surfaces of the model CeO 2 catalyst that were synthesized with only the (100) facet exposed. Vibrational sum-frequency generation was used to probe the molecular monolayer, and with the guidance of density functional theory calculations, was used to extract the structure and absolute molecular orientation of isopropanol at the CeO 2 (100) surface. Our results show that isopropanol is readily deprotonated at the surface, and through the measured absolute molecular orientation of isopropanol, we obtain new insight into the selectivity of the (100) surface to form propylene. Our findings reveal key insight into the chemical and physical phenomena taking place at pristine interfaces thereby pointing to intuitive structural arguments to describe catalytic selectivity in more complex systems.« less

  15. Microbial detection with low molecular weight RNA.

    PubMed

    Kourentzi, K D; Fox, G E; Willson, R C

    2001-12-01

    The need to monitor microorganisms in the environment has increased interest in assays based on hybridization probes that target nucleic acids (e.g., rRNA). We report the development of liquid-phase assays for specific bacterial 5S rRNA sequences or similarly sized artificial RNAs (aRNAs) using molecular beacon technology. These beacons fluoresce only in the presence of specific target sequences, rendering as much as a 27-fold fluorescence enhancement. The assays can be used with both crude cell lysates and purified total RNA preparations. Minimal sample preparation (e.g., heating to promote leakage from cells) is sufficient to detect many Gram-negative bacteria. Using this approach it was possible to detect an aRNA-labeled Escherichia coli strain in the presence of a large background of an otherwise identical E. coli strain. Finally, by using a longer wavelength carboxytetramethylrhodamine beacon it was possible to reduce the fraction of the signal due to cellular autofluorescence to below 0.5%.

  16. Microbial detection with low molecular weight RNA

    NASA Technical Reports Server (NTRS)

    Kourentzi, K. D.; Fox, G. E.; Willson, R. C.

    2001-01-01

    The need to monitor microorganisms in the environment has increased interest in assays based on hybridization probes that target nucleic acids (e.g., rRNA). We report the development of liquid-phase assays for specific bacterial 5S rRNA sequences or similarly sized artificial RNAs (aRNAs) using molecular beacon technology. These beacons fluoresce only in the presence of specific target sequences, rendering as much as a 27-fold fluorescence enhancement. The assays can be used with both crude cell lysates and purified total RNA preparations. Minimal sample preparation (e.g., heating to promote leakage from cells) is sufficient to detect many Gram-negative bacteria. Using this approach it was possible to detect an aRNA-labeled Escherichia coli strain in the presence of a large background of an otherwise identical E. coli strain. Finally, by using a longer wavelength carboxytetramethylrhodamine beacon it was possible to reduce the fraction of the signal due to cellular autofluorescence to below 0.5%.

  17. Host-Guest Assembly of a Molecular Reporter with Chiral Cyanohydrins for Assignment of Absolute Stereochemistry.

    PubMed

    Gholami, Hadi; Anyika, Mercy; Zhang, Jun; Vasileiou, Chrysoula; Borhan, Babak

    2016-06-27

    The absolute stereochemistry of cyanohydrins, derived from ketones and aldehydes, is obtained routinely, in a microscale and derivatization-free manner, upon their complexation with Zn-MAPOL, a zincated porphyrin host with a binding pocket comprised of a biphenol core. The host-guest complex leads to observable exciton-coupled circular dichroism (ECCD), the sign of which is easily correlated to the absolute stereochemistry of the bound cyanohydrin. A working model, based on the ECCD signal of cyanohydrins with known configuration, is proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Endogenous ethanol affects biopolyester molecular weight in recombinant Escherichia coli.

    PubMed

    Hiroe, Ayaka; Hyakutake, Manami; Thomson, Nicholas M; Sivaniah, Easan; Tsuge, Takeharu

    2013-11-15

    In biopolyester synthesis, polyhydroxyalkanoate (PHA) synthase (PhaC) catalyzes the polymerization of PHA in bacterial cells, followed by a chain transfer (CT) reaction in which the PHA polymer chain is transferred from PhaC to a CT agent. Accordingly, the frequency of CT reaction determines PHA molecular weight. Previous studies have shown that exogenous alcohols are effective CT agents. This study aimed to clarify the effect of endogenous ethanol as a CT agent for poly[(R)-3-hydroxybutyrate] [P(3HB)] synthesis in recombinant Escherichia coli, by comparing with that of exogenous ethanol. Ethanol supplementation to the culture medium reduced P(3HB) molecular weights by up to 56% due to ethanol-induced CT reaction. NMR analysis of P(3HB) polymers purified from the culture supplemented with (13)C-labeled ethanol showed the formation of a covalent bond between ethanol and P(3HB) chain at the carboxyl end. Cultivation without ethanol supplementation resulted in the reduction of P(3HB) molecular weight with increasing host-produced ethanol depending on culture aeration. On the other hand, production in recombinant BW25113(ΔadhE), an alcohol dehydrogenase deletion strain, resulted in a 77% increase in molecular weight. Analysis of five E. coli strains revealed that the estimated number of CT reactions was correlated with ethanol production. These results demonstrate that host-produced ethanol acts as an equally effective CT agent as exogenous ethanol, and the control of ethanol production is important to regulate the PHA molecular weight.

  19. Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances

    USGS Publications Warehouse

    Chin, Y.-P.; Aiken, G.; O'Loughlin, E.

    1994-01-01

    The number- and weight-averaged molecular weights of a number of aquatic fulvic acids, a commercial humic acid, and unfractionated organic matter from four natural water samples were measured by high-pressure size exclusion chromatography (HPSEC). Molecular weights determined in this manner compared favorably with those values reported in the literature. Both recent literature values and our data indicate that these substances are smaller and less polydisperse than previously believed. Moreover, the molecular weights of the organic matter from three of the four natural water samples compared favorably to the fulvic acid samples extracted from similar environments. Bulk spectroscopic properties of the fulvic substances such as molar absorptivity at 280 nm and the E4/E6 ratio were also measured. A strong correlation was observed between molar absorptivity, total aromaticity, and the weight average molecular weights of all the humic substances. This observation suggests that bulk spectroscopic properties can be used to quickly estimate the size of humic substances and their aromatic contents. Both parameters are important with respect to understanding humic substance mobility and their propensity to react with both organic and inorganic pollutants. ?? 1994 American Chemical Society.

  20. Interactions between pyrazole derived enantiomers and Chiralcel OJ: Prediction of enantiomer absolute configurations and elution order by molecular dynamics simulations.

    PubMed

    Hu, Guixiang; Huang, Meilan; Luo, Chengcai; Wang, Qi; Zou, Jian-Wei

    2016-05-01

    The separation of enantiomers and confirmation of their absolute configurations is significant in the development of chiral drugs. The interactions between the enantiomers of chiral pyrazole derivative and polysaccharide-based chiral stationary phase cellulose tris(4-methylbenzoate) (Chiralcel OJ) in seven solvents and under different temperature were studied using molecular dynamics simulations. The results show that solvent effect has remarkable influence on the interactions. Structure analysis discloses that the different interactions between two isomers and chiral stationary phase are dependent on the nature of solvents, which may invert the elution order. The computational method in the present study can be used to predict the elution order and the absolute configurations of enantiomers in HPLC separations and therefore would be valuable in development of chiral drugs. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Absolute vacuum ultraviolet photoabsorption cross section studies of atomic and molecular species: Techniques and observational data

    NASA Technical Reports Server (NTRS)

    Judge, D. L.; Wu, C. Y. R.

    1990-01-01

    Absorption of a high energy photon (greater than 6 eV) by an isolated molecule results in the formation of highly excited quasi-discrete or continuum states which evolve through a wide range of direct and indirect photochemical processes. These are: photoionization and autoionization, photodissociation and predissociation, and fluorescence. The ultimate goal is to understand the dynamics of the excitation and decay processes and to quantitatively measure the absolute partial cross sections for all processes which occur in photoabsorption. Typical experimental techniques and the status of observational results of particular interest to solar system observations are presented.

  2. Easy Absolute Values? Absolutely

    ERIC Educational Resources Information Center

    Taylor, Sharon E.; Mittag, Kathleen Cage

    2015-01-01

    The authors teach a problem-solving course for preservice middle-grades education majors that includes concepts dealing with absolute-value computations, equations, and inequalities. Many of these students like mathematics and plan to teach it, so they are adept at symbolic manipulations. Getting them to think differently about a concept that they…

  3. Low Molecular Weight Polymethacrylates as Multi-Functional Lubricant Additives

    DOE PAGES

    Cosimbescu, Lelia; Vellore, Azhar; Shantini Ramasamy, Uma; ...

    2018-04-24

    In this study, low molecular weight, moderately polar polymethacrylate polymers are explored as potential multi-functional lubricant additives. The performance of these novel additives in base oil is evaluated in terms of their viscosity index, shear stability, and friction-and-wear. The new compounds are compared to two benchmarks, a typical polymeric viscosity modifier and a fully-formulated oil. Results show that the best performing of the new polymers exhibit viscosity index and friction comparable to that of both benchmarks, far superior shear stability to either benchmark (as much as 15x lower shear loss), and wear reduction significantly better than a typical viscosity modifiermore » (lower wear volume by a factor of 2-3). The findings also suggest that the polarity and molecular weight of the polymers affect their performance which suggests future synthetic strategies may enable this new class of additives to replace multiple additives in typical lubricant formulations.« less

  4. Molecular physiology of weight regulation in mice and humans

    PubMed Central

    Leibel, RL

    2009-01-01

    Evolutionary considerations relating to efficiency in reproduction, and survival in hostile environments, suggest that body energy stores are sensed and actively regulated, with stronger physiological and behavioral responses to loss than gain of stored energy. Many physiological studies support this inference, and suggest that a critical axis runs between body fat and the hypothalamus. The molecular cloning of leptin and its receptor—projects based explicitly on the search for elements in this axis—confirmed the existence of this axis and provided important tools with which to understand its molecular physiology. Demonstration of the importance of this soma-brain reciprocal connection in body weight regulation in humans has been pursued using both classical genetic approaches and studies of physiological responses to experimental weight perturbation. This paper reviews the history of the rationale and methodology of the cloning of leptin (Lep) and the leptin receptor (Lepr), and describes some of the clinical investigation characterizing this axis. PMID:19136999

  5. Drying Affects the Fiber Network in Low Molecular Weight Hydrogels

    PubMed Central

    2017-01-01

    Low molecular weight gels are formed by the self-assembly of a suitable small molecule gelator into a three-dimensional network of fibrous structures. The gel properties are determined by the fiber structures, the number and type of cross-links and the distribution of the fibers and cross-links in space. Probing these structures and cross-links is difficult. Many reports rely on microscopy of dried gels (xerogels), where the solvent is removed prior to imaging. The assumption is made that this has little effect on the structures, but it is not clear that this assumption is always (or ever) valid. Here, we use small angle neutron scattering (SANS) to probe low molecular weight hydrogels formed by the self-assembly of dipeptides. We compare scattering data for wet and dried gels, as well as following the drying process. We show that the assumption that drying does not affect the network is not always correct. PMID:28631478

  6. Low Molecular Weight Polymethacrylates as Multi-Functional Lubricant Additives

    SciTech Connect

    Cosimbescu, Lelia; Vellore, Azhar; Shantini Ramasamy, Uma

    In this study, low molecular weight, moderately polar polymethacrylate polymers are explored as potential multi-functional lubricant additives. The performance of these novel additives in base oil is evaluated in terms of their viscosity index, shear stability, and friction-and-wear. The new compounds are compared to two benchmarks, a typical polymeric viscosity modifier and a fully-formulated oil. Results show that the best performing of the new polymers exhibit viscosity index and friction comparable to that of both benchmarks, far superior shear stability to either benchmark (as much as 15x lower shear loss), and wear reduction significantly better than a typical viscosity modifiermore » (lower wear volume by a factor of 2-3). The findings also suggest that the polarity and molecular weight of the polymers affect their performance which suggests future synthetic strategies may enable this new class of additives to replace multiple additives in typical lubricant formulations.« less

  7. Low-molecular-weight heparins: differential characterization/physical characterization.

    PubMed

    Guerrini, Marco; Bisio, Antonella

    2012-01-01

    Low-molecular-weight heparins (LMWHs), derived from unfractionated heparin (UFH) through different depolymerization processes, have advantages with respect to the parent heparin in terms of pharmacokinetics, convenience of administration, and reduced side effects. Each LMWH can be considered as an independent drug with its own activity profile, placing significance on their biophysical characterization, which will also enable a better understanding of their structure-function relationship. Several chemical and physical methods, some involving sample modification, are now available and are reviewed.

  8. High molecular weight polysaccharide that binds and inhibits virus

    SciTech Connect

    Konowalchuk, Thomas W.; Konowalchuk, Jack

    This invention provides a high molecular weight polysaccharide capable of binding to and inhibiting virus and related pharmaceutical formulations and methods of inhibiting viral infectivity and/or pathogenicity, as well as immunogenic compositions. The invention further includes methods of inhibiting the growth of cancer cells and of ameliorating a symptom of aging. Additionally, the invention provides methods of detecting and/or quantifying and/or isolating viruses.

  9. High molecular weight polysaccharide that binds and inhibits virus

    SciTech Connect

    Konowalchuk, Thomas W

    This invention provides a high molecular weight polysaccharide capable of binding to and inhibiting virus and related pharmaceutical formulations and methods on inhibiting viral infectivity and/or pathogenicity, as well as immunogenic compositions. The invention further methods of inhibiting the growth of cancer cells and of ameliorating a symptom of aging. Additionally, the invention provides methods of detecting and/or quantifying and/or isolating viruses.

  10. Molecular weights and subunit structure of LamB proteins.

    PubMed

    Nakae, T; Ishii, J N

    1982-01-01

    Phage lambda-receptor proteins of Escherichia coli, LamB proteins, form oligomeric aggregates to build transmembrane diffusion pores selective for maltose and maltodextrins. The molecular weights (MW) of functional oligomers as well as dissociated monomers were determined by sedimentation equilibrium analysis in homogeneous non-ionic surfactant and deuterium oxide and in 6 M guanidine-HCl, respectively. The MW of oligomers and monomers appeared as 135 600 and 45 900, respectively. Thus, functional Lamb proteins consisted of three identical subunits.

  11. Physical Properties of Low-Molecular Weight Polydimethylsiloxane Fluids

    SciTech Connect

    Roberts, Christine Cardinal; Graham, Alan; Nemer, Martin

    Physical property measurements including viscosity, density, thermal conductivity, and heat capacity of low-molecular weight polydimethylsiloxane (PDMS) fluids were measured over a wide temperature range (-50°C to 150°C when possible). Properties of blends of 1 cSt and 20 cSt PDMS fluids were also investigated. Uncertainties in the measurements are cited. These measurements will provide greater fidelity predictions of environmental sensing device behavior in hot and cold environments.

  12. Comparison of antimicrobial activities of newly obtained low molecular weight scorpion chitosan and medium molecular weight commercial chitosan.

    PubMed

    Kaya, Murat; Asan-Ozusaglam, Meltem; Erdogan, Sevil

    2016-06-01

    In this study the antimicrobial activity of low molecular weight (3.22 kDa) chitosan, obtained for the first time from a species belonging to the Scorpiones, was screened against nine pathogenic microorganisms (seven bacteria and two yeasts) and compared with that of medium molecular weight commercial chitosan (MMWCC). It was observed that the antimicrobial activity of the low molecular weight scorpion chitosan (LMWSC) was specific to bacterial species in general rather than gram-negative or gram-positive bacterial groups. It was also determined that LMWSC had a stronger inhibitory effect than the MMWCC, particularly on the bacterium Listeria monocytogenes and the yeast Candida albicans, which are important pathogens for public health. In addition, it was recorded that the MMWCC had a greater inhibitory effect on Bacillus subtilis than LMWSC. According to the results obtained by the disc diffusion method, the antibacterial activity of both LMWSC and MMWCC against B. subtilis and Salmonella enteritidis was higher than the widely used antibiotic Gentamicin (CN, 10 μg/disc). Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  13. Influence of Molecular Weight on the Mechanical Performance of a Thermoplastic Glassy Polyimide

    NASA Technical Reports Server (NTRS)

    Nicholson, Lee M.; Whitley, Karen S.; Gates, Thomas S.; Hinkley, Jeffrey A.

    1999-01-01

    Mechanical Testing of an advanced thermoplastic polyimide (LaRC-TM-SI) with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. The physical characterization, elastic properties and notched tensile strength were all determined as a function of molecular weight and test temperature. It was shown that notched tensile strength is a strong function of both temperature and molecular weight, whereas stiffness is only a strong function of temperature. A critical molecular weight (Mc) was observed to occur at a weight-average molecular weight (Mw) of approx. 22000 g/mol below which, the notched tensile strength decreases rapidly. This critical molecular weight transition is temperature-independent. Furthermore, inelastic analysis showed that low molecular weight materials tended to fail in a brittle manner, whereas high molecular weight materials exhibited ductile failure. The microstructural images supported these findings.

  14. Statistical Analysis on the Performance of Molecular Mechanics Poisson–Boltzmann Surface Area versus Absolute Binding Free Energy Calculations: Bromodomains as a Case Study

    PubMed Central

    2017-01-01

    Binding free energy calculations that make use of alchemical pathways are becoming increasingly feasible thanks to advances in hardware and algorithms. Although relative binding free energy (RBFE) calculations are starting to find widespread use, absolute binding free energy (ABFE) calculations are still being explored mainly in academic settings due to the high computational requirements and still uncertain predictive value. However, in some drug design scenarios, RBFE calculations are not applicable and ABFE calculations could provide an alternative. Computationally cheaper end-point calculations in implicit solvent, such as molecular mechanics Poisson–Boltzmann surface area (MMPBSA) calculations, could too be used if one is primarily interested in a relative ranking of affinities. Here, we compare MMPBSA calculations to previously performed absolute alchemical free energy calculations in their ability to correlate with experimental binding free energies for three sets of bromodomain–inhibitor pairs. Different MMPBSA approaches have been considered, including a standard single-trajectory protocol, a protocol that includes a binding entropy estimate, and protocols that take into account the ligand hydration shell. Despite the improvements observed with the latter two MMPBSA approaches, ABFE calculations were found to be overall superior in obtaining correlation with experimental affinities for the test cases considered. A difference in weighted average Pearson () and Spearman () correlations of 0.25 and 0.31 was observed when using a standard single-trajectory MMPBSA setup ( = 0.64 and = 0.66 for ABFE; = 0.39 and = 0.35 for MMPBSA). The best performing MMPBSA protocols returned weighted average Pearson and Spearman correlations that were about 0.1 inferior to ABFE calculations: = 0.55 and = 0.56 when including an entropy estimate, and = 0.53 and = 0.55 when including explicit water molecules. Overall, the study suggests that ABFE calculations are indeed the

  15. Statistical Analysis on the Performance of Molecular Mechanics Poisson-Boltzmann Surface Area versus Absolute Binding Free Energy Calculations: Bromodomains as a Case Study.

    PubMed

    Aldeghi, Matteo; Bodkin, Michael J; Knapp, Stefan; Biggin, Philip C

    2017-09-25

    Binding free energy calculations that make use of alchemical pathways are becoming increasingly feasible thanks to advances in hardware and algorithms. Although relative binding free energy (RBFE) calculations are starting to find widespread use, absolute binding free energy (ABFE) calculations are still being explored mainly in academic settings due to the high computational requirements and still uncertain predictive value. However, in some drug design scenarios, RBFE calculations are not applicable and ABFE calculations could provide an alternative. Computationally cheaper end-point calculations in implicit solvent, such as molecular mechanics Poisson-Boltzmann surface area (MMPBSA) calculations, could too be used if one is primarily interested in a relative ranking of affinities. Here, we compare MMPBSA calculations to previously performed absolute alchemical free energy calculations in their ability to correlate with experimental binding free energies for three sets of bromodomain-inhibitor pairs. Different MMPBSA approaches have been considered, including a standard single-trajectory protocol, a protocol that includes a binding entropy estimate, and protocols that take into account the ligand hydration shell. Despite the improvements observed with the latter two MMPBSA approaches, ABFE calculations were found to be overall superior in obtaining correlation with experimental affinities for the test cases considered. A difference in weighted average Pearson ([Formula: see text]) and Spearman ([Formula: see text]) correlations of 0.25 and 0.31 was observed when using a standard single-trajectory MMPBSA setup ([Formula: see text] = 0.64 and [Formula: see text] = 0.66 for ABFE; [Formula: see text] = 0.39 and [Formula: see text] = 0.35 for MMPBSA). The best performing MMPBSA protocols returned weighted average Pearson and Spearman correlations that were about 0.1 inferior to ABFE calculations: [Formula: see text] = 0.55 and [Formula: see text] = 0.56 when including

  16. Utility of inverse probability weighting in molecular pathological epidemiology.

    PubMed

    Liu, Li; Nevo, Daniel; Nishihara, Reiko; Cao, Yin; Song, Mingyang; Twombly, Tyler S; Chan, Andrew T; Giovannucci, Edward L; VanderWeele, Tyler J; Wang, Molin; Ogino, Shuji

    2018-04-01

    As one of causal inference methodologies, the inverse probability weighting (IPW) method has been utilized to address confounding and account for missing data when subjects with missing data cannot be included in a primary analysis. The transdisciplinary field of molecular pathological epidemiology (MPE) integrates molecular pathological and epidemiological methods, and takes advantages of improved understanding of pathogenesis to generate stronger biological evidence of causality and optimize strategies for precision medicine and prevention. Disease subtyping based on biomarker analysis of biospecimens is essential in MPE research. However, there are nearly always cases that lack subtype information due to the unavailability or insufficiency of biospecimens. To address this missing subtype data issue, we incorporated inverse probability weights into Cox proportional cause-specific hazards regression. The weight was inverse of the probability of biomarker data availability estimated based on a model for biomarker data availability status. The strategy was illustrated in two example studies; each assessed alcohol intake or family history of colorectal cancer in relation to the risk of developing colorectal carcinoma subtypes classified by tumor microsatellite instability (MSI) status, using a prospective cohort study, the Nurses' Health Study. Logistic regression was used to estimate the probability of MSI data availability for each cancer case with covariates of clinical features and family history of colorectal cancer. This application of IPW can reduce selection bias caused by nonrandom variation in biospecimen data availability. The integration of causal inference methods into the MPE approach will likely have substantial potentials to advance the field of epidemiology.

  17. Impact resistance and fractography in ultra high molecular weight polyethylenes.

    PubMed

    Puértolas, J A; Pascual, F J; Martínez-Morlanes, M J

    2014-02-01

    Highly crosslinked ultra high molecular weight polyethylenes (UHMWPE) stabilized by a remelting process or by the addition of an antioxidant are highly wear resistant and chemically stable. However, these polyethylenes currently used in total joint replacements suffer a loss of mechanical properties, especially in terms of fracture toughness. In this study we analyze the impact behavior of different polyethylenes using an instrumented double notch Izod test. The materials studied are three resins: GUR1050, GUR1020 with 0.1wt% of vitamin E, and MG003 with 0.1wt% of vitamin E. These resins were gamma irradiated at 90kGy, and pre and post-irradiation remelting processes were applied to GUR1050 for two different time periods. Microstructural data were determined by means of differential scanning calorimetry and transmission electron microscopy. Fractography carried out on the impact fracture surfaces and images obtained by scanning electron microscopy after etching indicated the existence of a fringe structure formed by consecutive ductile-brittle and brittle-ductile transitions, which is related to the appearance of discontinuities in the load-deflection curves. A correlation has been made of the macroscopic impact strength results and the molecular chain and microstructural characteristics of these aforementioned materials, with a view to designing future resins with improved impact resistance. The use of UHMWPE resins with low molecular weight or the application of a remelting treatment could contribute to obtain a better impact strength behavior. © 2013 Published by Elsevier Ltd.

  18. Low-molecular-weight heparins: pharmacologic profile and product differentiation.

    PubMed

    Fareed, J; Jeske, W; Hoppensteadt, D; Clarizio, R; Walenga, J M

    1998-09-10

    The interchangeability of low-molecular-weight heparins (LMWHs) has been the subject of discussion since these products were first introduced for the prophylaxis of deep vein thrombosis. Experimental evidence now exists to show that LMWHs differ from each other in a number of characteristics. Products have been differentiated on the basis of molecular weight and biologic properties, but only limited information derived from the clinical setting is available. Potency has been described on the basis of anti-Factor Xa activity, but at equivalent anti-Xa activities, the anti-Factor IIa activity of different products shows marked variations. At the relatively small doses used for the management of postsurgical deep vein thrombosis, the effect of these interproduct differences may be relatively minor, but as LMWHs are developed for therapeutic use at much higher doses, such differences may become clinically important. Variations in safety and efficacy reported in clinical trials of LMWHs may reflect the known differences in their molecular composition and pharmacologic properties.

  19. Resonant Raman scattering of controlled molecular weight polyacetylene

    NASA Astrophysics Data System (ADS)

    Schen, M. A.; Chien, J. C. W.; Perrin, E.; Lefrant, S.; Mulazzi, E.

    1988-12-01

    Polyacetylene, (CH)x, films of 500, 5300, 10 500, and 100 000 Daltons number average molecular weights (Mn ) were synthesized using the titanium tetra-n-butoxide/triethyl aluminum-catalyst/cocatalyst system and examined using resonant Raman scattering techniques. Before isomerization, trans segments are found to exist mainly as short, isolated sequences independent of Mn. After thermal isomerization, theoretical analysis of the RRS spectra using the Brivio, Mulazzi model indicate the ratio of long trans conjugated segments (N≥30) to short trans conjugated segments (N≤30) is significantly larger for 100 000 Dalton polymer in comparison to polymer of 10 500 Mn and below. For samples below 10 500 Daltons, no clear relationship between actual polymer molecular weight and G is observed. Optimization of the isomerization conditions for 100 000 Dalton polymer results in trans-(CH)x with a G=0.80. These results suggest that not until very long molecular chains are obtained can samples composed principally of long conjugated segments be obtained. It is proposed that defects which arise during and after the polymerization limit the content of long segments. Ambient, short term oxidation of 100 000 Mn polymer shows a decrease in G from 0.80 to 0.70. Low level chain oxidation or doping is shown to preferentially occur within long conjugated segments.

  20. Absolute vs. Weight-Related Maximum Oxygen Uptake in Firefighters: Fitness Evaluation with and without Protective Clothing and Self-Contained Breathing Apparatus among Age Group

    PubMed Central

    Perroni, Fabrizio; Guidetti, Laura; Cignitti, Lamberto; Baldari, Carlo

    2015-01-01

    During fire emergencies, firefighters wear personal protective devices (PC) and a self-contained breathing apparatus (S.C.B.A.) to be protected from injuries. The purpose of this study was to investigate the differences of aerobic level in 197 firefighters (age: 34±7 yr; BMI: 24.4±2.3 kg.m-2), evaluated by a Queen’s College Step field Test (QCST), performed with and without fire protective garments, and to analyze the differences among age groups (<25 yr; 26-30 yr, 31-35 yr, 36-40 yr and >40 yr). Variance analysis was applied to assess differences (p < 0.05) between tests and age groups observed in absolute and weight-related values, while a correlation was examined between QCST with and without PC+S.C.B.A. The results have shown that a 13% of firefighters failed to complete the test with PC+S.C.B.A. and significant differences between QCST performed with and without PC+S.C.B.A. in absolute (F(1,169) = 42.6, p < 0.0001) and weight-related (F(1,169) = 339.9, p < 0.0001) terms. A better correlation has been found in L•min-1 (r=0.67) than in ml•kg-1•min-1 (r=0.54). Moreover, we found significant differences among age groups both in absolute and weight-related values. The assessment of maximum oxygen uptake of firefighters in absolute term can be a useful tool to evaluate the firefighters' cardiovascular strain. PMID:25764201

  1. Synthesis of high molecular weight PEO using non-metal initiators

    DOEpatents

    Yang, Jin; Sivanandan, Kulandaivelu; Pistorino, Jonathan; Eitouni, Hany Basam

    2015-05-19

    A new synthetic method to prepare high molecular weight poly(ethylene oxide) with a very narrow molecular weight distribution (PDI<1.5) is described. The method involves a metal free initiator system, thus avoiding dangerous, flammable organometallic compounds.

  2. Conformations of low-molecular-weight lignin polymers in water

    DOE PAGES

    Petridis, Loukas; Smith, Jeremy C.

    2016-01-13

    Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a criticalmore » degree of polymerization, N c=15, the polymer adopts less spherical conformations than above N c. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. As a result, an implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures.« less

  3. Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals for Large-Scale Density Functional Theory Calculations in Drug Design.

    PubMed

    Phipps, M J S; Fox, T; Tautermann, C S; Skylaris, C-K

    2016-07-12

    We report the development and implementation of an energy decomposition analysis (EDA) scheme in the ONETEP linear-scaling electronic structure package. Our approach is hybrid as it combines the localized molecular orbital EDA (Su, P.; Li, H. J. Chem. Phys., 2009, 131, 014102) and the absolutely localized molecular orbital EDA (Khaliullin, R. Z.; et al. J. Phys. Chem. A, 2007, 111, 8753-8765) to partition the intermolecular interaction energy into chemically distinct components (electrostatic, exchange, correlation, Pauli repulsion, polarization, and charge transfer). Limitations shared in EDA approaches such as the issue of basis set dependence in polarization and charge transfer are discussed, and a remedy to this problem is proposed that exploits the strictly localized property of the ONETEP orbitals. Our method is validated on a range of complexes with interactions relevant to drug design. We demonstrate the capabilities for large-scale calculations with our approach on complexes of thrombin with an inhibitor comprised of up to 4975 atoms. Given the capability of ONETEP for large-scale calculations, such as on entire proteins, we expect that our EDA scheme can be applied in a large range of biomolecular problems, especially in the context of drug design.

  4. Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films.

    PubMed

    Gentekos, Dillon T; Jia, Junteng; Tirado, Erika S; Barteau, Katherine P; Smilgies, Detlef-M; DiStasio, Robert A; Fors, Brett P

    2018-04-04

    We report a method for tuning the domain spacing ( D sp ) of self-assembled block copolymer thin films of poly(styrene- block-methyl methacrylate) (PS- b-PMMA) over a large range of lamellar periods. By modifying the molecular weight distribution (MWD) shape (including both the breadth and skew) of the PS block via temporal control of polymer chain initiation in anionic polymerization, we observe increases of up to 41% in D sp for polymers with the same overall molecular weight ( M n ≈ 125 kg mol -1 ) without significantly changing the overall morphology or chemical composition of the final material. In conjunction with our experimental efforts, we have utilized concepts from population statistics and least-squares analysis to develop a model for predicting D sp based on the first three moments of the MWDs. This statistical model reproduces experimental D sp values with high fidelity (with mean absolute errors of 1.2 nm or 1.8%) and provides novel physical insight into the individual and collective roles played by the MWD moments in determining this property of interest. This work demonstrates that both MWD breadth and skew have a profound influence over D sp , thereby providing an experimental and conceptual platform for exploiting MWD shape as a simple and modular handle for fine-tuning D sp in block copolymer thin films.

  5. Development of haplotype-specific molecular markers for the low-molecular-weight glutenin subunits

    USDA-ARS?s Scientific Manuscript database

    Low-molecular-weight glutenin subunits (LMW-GSs) are one of the major components of gluten and their allelic variation has been widely associated with numerous wheat end-use quality parameters. These proteins are encoded by multigene families located at the orthologous Glu-3 loci (Glu-A3, Glu-B3 and...

  6. Free Energy Perturbation Hamiltonian Replica-Exchange Molecular Dynamics (FEP/H-REMD) for Absolute Ligand Binding Free Energy Calculations.

    PubMed

    Jiang, Wei; Roux, Benoît

    2010-07-01

    Free Energy Perturbation with Replica Exchange Molecular Dynamics (FEP/REMD) offers a powerful strategy to improve the convergence of free energy computations. In particular, it has been shown previously that a FEP/REMD scheme allowing random moves within an extended replica ensemble of thermodynamic coupling parameters "lambda" can improve the statistical convergence in calculations of absolute binding free energy of ligands to proteins [J. Chem. Theory Comput. 2009, 5, 2583]. In the present study, FEP/REMD is extended and combined with an accelerated MD simulations method based on Hamiltonian replica-exchange MD (H-REMD) to overcome the additional problems arising from the existence of kinetically trapped conformations within the protein receptor. In the combined strategy, each system with a given thermodynamic coupling factor lambda in the extended ensemble is further coupled with a set of replicas evolving on a biased energy surface with boosting potentials used to accelerate the inter-conversion among different rotameric states of the side chains in the neighborhood of the binding site. Exchanges are allowed to occur alternatively along the axes corresponding to the thermodynamic coupling parameter lambda and the boosting potential, in an extended dual array of coupled lambda- and H-REMD simulations. The method is implemented on the basis of new extensions to the REPDSTR module of the biomolecular simulation program CHARMM. As an illustrative example, the absolute binding free energy of p-xylene to the nonpolar cavity of the L99A mutant of T4 lysozyme was calculated. The tests demonstrate that the dual lambda-REMD and H-REMD simulation scheme greatly accelerates the configurational sampling of the rotameric states of the side chains around the binding pocket, thereby improving the convergence of the FEP computations.

  7. MALDI matrices for low molecular weight compounds: an endless story?

    PubMed

    Calvano, Cosima Damiana; Monopoli, Antonio; Cataldi, Tommaso R I; Palmisano, Francesco

    2018-04-23

    Since its introduction in the 1980s, matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) has gained a prominent role in the analysis of high molecular weight biomolecules such as proteins, peptides, oligonucleotides, and polysaccharides. Its application to low molecular weight compounds has remained for long time challenging due to the spectral interferences produced by conventional organic matrices in the low m/z window. To overcome this problem, specific sample preparation such as analyte/matrix derivatization, addition of dopants, or sophisticated deposition technique especially useful for imaging experiments, have been proposed. Alternative approaches based on second generation (rationally designed) organic matrices, ionic liquids, and inorganic matrices, including metallic nanoparticles, have been the object of intense and continuous research efforts. Definite evidences are now provided that MALDI MS represents a powerful and invaluable analytical tool also for small molecules, including their quantification, thus opening new, exciting applications in metabolomics and imaging mass spectrometry. This review is intended to offer a concise critical overview of the most recent achievements about MALDI matrices capable of specifically address the challenging issue of small molecules analysis. Graphical abstract An ideal Book of matrices for MALDI MS of small molecules.

  8. Advantages of Molecular Weight Identification during Native MS Screening.

    PubMed

    Khan, Ahad; Bresnick, Anne; Cahill, Sean; Girvin, Mark; Almo, Steve; Quinn, Ronald

    2018-05-09

    Native mass spectrometry detection of ligand-protein complexes allowed rapid detection of natural product binders of apo and calcium-bound S100A4 (a member of the metal binding protein S100 family), T cell/transmembrane, immunoglobulin (Ig), and mucin protein 3, and T cell immunoreceptor with Ig and ITIM (immunoreceptor tyrosine-based inhibitory motif) domains precursor protein from extracts and fractions. Based on molecular weight common hits were detected binding to all four proteins. Seven common hits were identified as apigenin 6- C - β - D -glucoside 8- C - α - L -arabinoside, sweroside, 4',5-dihydroxy-7-methoxyflavanone-6- C -rutinoside, loganin acid, 6- C -glucosylnaringenin, biochanin A 7- O -rutinoside and quercetin 3- O -rutinoside. Mass guided isolation and NMR identification of hits confirmed the mass accuracy of the ligand in the ligand-protein MS complexes. Thus, molecular weight ID from ligand-protein complexes by electrospray ionization Fourier transform mass spectrometry allowed rapid dereplication. Native mass spectrometry using electrospray ionization Fourier transform mass spectrometry is a tool for dereplication and metabolomics analysis. Georg Thieme Verlag KG Stuttgart · New York.

  9. Determination of molecular weight distributions in native and pretreated wood.

    PubMed

    Leskinen, Timo; Kelley, Stephen S; Argyropoulos, Dimitris S

    2015-03-30

    The analysis of native wood components by size-exclusion chromatography (SEC) is challenging. Isolation, derivatization and solubilization of wood polymers is required prior to the analysis. The present approach allowed the determination of molecular weight distributions of the carbohydrates and of lignin in native and processed woods, without preparative component isolation steps. For the first time a component selective SEC analysis of sawdust preparations was made possible by the combination of two selective derivatization methods, namely; ionic liquid assisted benzoylation of the carbohydrate fraction and acetobromination of the lignin in acetic acid media. These were optimized for wood samples. The developed method was thus used to examine changes in softwood samples after degradative mechanical and/or chemical treatments, such as ball milling, steam explosion, green liquor pulping, and chemical oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The methodology can also be applied to examine changes in molecular weight and lignin-carbohydrate linkages that occur during wood-based biorefinery operations, such as pretreatments, and enzymatic saccharification. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Purification of a low molecular weight fucoidan for SPECT molecular imaging of myocardial infarction.

    PubMed

    Saboural, Pierre; Chaubet, Frédéric; Rouzet, Francois; Al-Shoukr, Faisal; Azzouna, Rana Ben; Bouchemal, Nadia; Picton, Luc; Louedec, Liliane; Maire, Murielle; Rolland, Lydia; Potier, Guy; Guludec, Dominique Le; Letourneur, Didier; Chauvierre, Cédric

    2014-09-23

    Fucoidans constitute a large family of sulfated polysaccharides with several biochemical properties. A commercial fucoidan from brown algae, containing low molecular weight polysaccharidic species constituted of l-fucose, uronic acids and sulfate groups, was simply treated here with calcium acetate solution. This treatment led to a purified fraction with a yield of 45%. The physicochemical characterizations of the purified fucoidan using colorimetric assay, MALLS, dRI, FT-IR, NMR, exhibited molecular weight distributions and chemical profiles similar for both fucoidans whereas the sulfate and l-fucose contents increased by 16% and 71%, respectively. The biodistribution study in rat of both compounds labeled with 99mTc evidenced a predominant renal elimination of the purified fucoidan, but the crude fucoidan was mainly retained in liver and spleen. In rat myocardial ischemia-reperfusion, we then demonstrated the better efficiency of the purified fucoidan. This purified sulfated polysaccharide appears promising for the development of molecular imaging in acute coronary syndrome.

  11. Mechanical Properties of LaRC(tm) SI Polymer for a Range of Molecular Weights

    NASA Technical Reports Server (NTRS)

    Whitley, Karen S.; Gates, Thomas S.; Hinkley, Jeffrey A.; Nicholson, Lee M.

    2000-01-01

    Mechanical testing of an advanced polyimide resin (LaRC(tm)-SI) with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. Elastic and inelastic properties were characterized as a function of molecular weight and test temperature. It was shown that notched tensile strength is a strong function of both temperature and molecular weight, whereas stiffness is only a strong function of temperature. The combined analysis of calculated yield stress and notched tensile strength indicated that low molecular weight materials tended to fail in a brittle manner, whereas high molecular weight materials exhibited ductile failure. The microphotographs of the failure surfaces also supported these findings.

  12. Tuning the superstructure of ultrahigh-molecular-weight polyethylene/low-molecular-weight polyethylene blend for artificial joint application.

    PubMed

    Xu, Ling; Chen, Chen; Zhong, Gan-Ji; Lei, Jun; Xu, Jia-Zhuang; Hsiao, Benjamin S; Li, Zhong-Ming

    2012-03-01

    An easy approach was reported to achieve high mechanical properties of ultrahigh-molecular-weight polyethylene (UHMWPE)-based polyethylene (PE) blend for artificial joint application without the sacrifice of the original excellent wear and fatigue behavior of UHMWPE. The PE blend with desirable fluidity was obtained by melt mixing UHMWPE and low molecular weight polyethylene (LMWPE), and then was processed by a modified injection molding technology-oscillatory shear injection molding (OSIM). Morphological observation of the OSIM PE blend showed LMWPE contained well-defined interlocking shish-kebab self-reinforced superstructure. Addition of a small amount of long chain polyethylene (2 wt %) to LMWPE greatly induced formation of rich shish-kebabs. The ultimate tensile strength considerably increased from 27.6 MPa for conventional compression molded UHMWPE up to 78.4 MPa for OSIM PE blend along the flow direction and up to 33.5 MPa in its transverse direction. The impact strength of OSIM PE blend was increased by 46% and 7% for OSIM PE blend in the direction parallel and vertical to the shear flow, respectively. Wear and fatigue resistance were comparable to conventional compression molded UHMWPE. The superb performance of the OSIM PE blend was originated from formation of rich interlocking shish-kebab superstructure while maintaining unique properties of UHMWPE. The present results suggested the OSIM PE blend has high potential for artificial joint application. © 2012 American Chemical Society

  13. Two-phase thermodynamic model for efficient and accurate absolute entropy of water from molecular dynamics simulations.

    PubMed

    Lin, Shiang-Tai; Maiti, Prabal K; Goddard, William A

    2010-06-24

    Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

  14. Recent developments in separation of low molecular weight heparin anticoagulants.

    PubMed

    Sadowski, Radosław; Gadzała-Kopciuch, Renata; Buszewski, Bogusław

    2017-10-05

    The general function of anticoagulants is to prevent blood clotting and growing of the existing clots in blood vessels. In recent years, there has been a significant improvement in developing methods of prevention as well as pharmacologic and surgical treatment of thrombosis. For over the last two decades, low molecular weight heparins (LMWHs) have found their application in the antithrombotic diseases treatment. These types of drugs are widely used in clinical therapy. Despite the biological and medical importance of LMWHs, they have not been completely characterized in terms of their chemical structure. Due to both, the structural complexity of these anticoagulants and the presence of impurities, their structural characterization requires the employment of advanced analytical techniques. Since separation techniques play the key role in these endeavors, this review will focus on the presentation of recent developments in the separation of LMWH anticoagulants. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  15. Optimising low molecular weight hydrogels for automated 3D printing.

    PubMed

    Nolan, Michael C; Fuentes Caparrós, Ana M; Dietrich, Bart; Barrow, Michael; Cross, Emily R; Bleuel, Markus; King, Stephen M; Adams, Dave J

    2017-11-22

    Hydrogels prepared from low molecular weight gelators (LMWGs) are formed as a result of hierarchical intermolecular interactions between gelators to form fibres, and then further interactions between the self-assembled fibres via physical entanglements, as well as potential branching points. These interactions can allow hydrogels to recover quickly after a high shear rate has been applied. There are currently limited design rules describing which types of morphology or rheological properties are required for a LMWG hydrogel to be used as an effective, printable gel. By preparing hydrogels with different types of fibrous network structures, we have been able to understand in more detail the morphological type which gives rise to a 3D-printable hydrogel using a range of techniques, including rheology, small angle scattering and microscopy.

  16. Apparatus and method of determining molecular weight of large molecules

    DOEpatents

    Fuerstenau, S.; Benner, W.H.; Madden, N.M.; Searles, W.

    1998-06-23

    A mass spectrometer determines the mass of multiply charged high molecular weight molecules. This spectrometer utilizes an ion detector which is capable of simultaneously measuring the charge z and transit time of a single ion as it passes through the detector. From this transit time, the velocity of the single ion may then be derived, thus providing the mass-to-charge ratio m/z for a single ion which has been accelerated through a known potential. Given z and m/z, the mass m of the single ion can then be calculated. Electrospray ions with masses in excess of 1 MDa and charge numbers greater than 425 e{sup {minus}} are readily detected. The on-axis single ion detection configuration enables a duty cycle of nearly 100% and extends the practical application of electrospray mass spectrometry to the analysis of very large molecules with relatively inexpensive instrumentation. 14 figs.

  17. Apparatus and method of determining molecular weight of large molecules

    DOEpatents

    Fuerstenau, Stephen; Benner, W. Henry; Madden, Norman; Searles, William

    1998-01-01

    A mass spectrometer determines the mass of multiply charged high molecular weight molecules. This spectrometer utilizes an ion detector which is capable of simultaneously measuring the charge z and transit time of a single ion as it passes through the detector. From this transit time, the velocity of the single ion may then be derived, thus providing the mass-to-charge ratio m/z for a single ion which has been accelerated through a known potential. Given z and m/z, the mass m of the single ion can then be calculated. Electrospray ions with masses in excess of 1 MDa and charge numbers greater than 425 e.sup.- are readily detected. The on-axis single ion detection configuration enables a duty cycle of nearly 100% and extends the practical application of electrospray mass spectrometry to the analysis of very large molecules with relatively inexpensive instrumentation.

  18. Ultra-high molecular weight silphenylene-siloxane polymers

    NASA Technical Reports Server (NTRS)

    Patterson, W. J.; Hundley, N. H.; Ludwick, L. M.

    1984-01-01

    Silphenylene-siloxane copolymers with molecular weights above one million were prepared using a two stage polymerization technique. The technique was successfully scaled up to produce 50 grams of this high polymer in a single run. The reactive monomer approach was also investigated using the following aminosilanes: bis(dimethylamino)dimethylsilane, N,N-bis(pyrrolidinyl)dimethylsilane and N,N-bis(gamma-butyrolactam)dimethylsilane). Thermal analyses were performed in both air and nitrogen. The experimental polymers decomposed at 540 to 562 C, as opposed to 408 to 426 C for commercial silicones. Differential scanning calorimetry showed a glass transition (Tg) at -50 to -55 C for the silphenylene-siloxane copolymer while the commercial silicones had Tg's at -96 to -112 C.

  19. Ultra high molecular weight polyethylene: Optical features at millimeter wavelengths

    NASA Astrophysics Data System (ADS)

    D'Alessandro, G.; Paiella, A.; Coppolecchia, A.; Castellano, M. G.; Colantoni, I.; de Bernardis, P.; Lamagna, L.; Masi, S.

    2018-05-01

    The next generation of experiments for the measurement of the Cosmic Microwave Background (CMB) requires more and more the use of advanced materials, with specific physical and structural properties. An example is the material used for receiver's cryostat windows and internal lenses. The large throughput of current CMB experiments requires a large diameter (of the order of 0.5 m) of these parts, resulting in heavy structural and optical requirements on the material to be used. Ultra High Molecular Weight (UHMW) polyethylene (PE) features high resistance to traction and good transmissivity in the frequency range of interest. In this paper, we discuss the possibility of using UHMW PE for windows and lenses in experiments working at millimeter wavelengths, by measuring its optical properties: emissivity, transmission and refraction index. Our measurements show that the material is well suited to this purpose.

  20. Soluble, High Molecular Weight Polysilsesquioxanes with Carboxylate Functionalities

    SciTech Connect

    RAHIMIAN,KAMYAR; LOY,DOUGLAS A.; WHEELER,DAVID R.

    2000-07-14

    Trialkoxysilyl-containing monomers of the type (RO){sub 3}Si(CH{sub 2}){sub 3}C(O)OtBu (R = Me, Et) were prepared by hydrosilation of the corresponding vinylic tert-butyl esters CH{sub 3}CHCH{sub 2}C(O)OtBu. Acid- or base-catalyzed polymerization of the monomers leads to very high molecular weight polymers with relatively narrow polydispersities. The polymerization results in complete condensation of the alkoxy groups while the tert-butyl ester functionality remains fully intact. Partial or full deprotection of the tert-butyl group can easily be achieved to yield the corresponding carboxylic acid polymers. The ester and carboxylic acid functionalities of these new materials allow for their potential use in a variety ofmore » applications such as scavenging of heavy metals.« less

  1. Characterization of the Low-Molecular-Weight Human Plasma Peptidome.

    PubMed

    Greening, David W; Simpson, Richard J

    2017-01-01

    The human plasma proteome represents an important secreted sub-proteome. Proteomic analysis of blood plasma with mass spectrometry is a challenging task. The high complexity and wide dynamic range of proteins as well as the presence of several proteins at very high concentrations complicate the profiling of the human plasma proteome. The peptidome (or low-molecular-weight fraction, LMF) of the human plasma proteome is an invaluable source of biological information, especially in the context of identifying plasma-based markers of disease. Peptides are generated by active synthesis and proteolytic processing, often yielding proteolytic fragments that mediate a variety of physiological and pathological functions. As such, degradomic studies, investigating cleavage products via peptidomics and top-down proteomics in particular, have warranted significant research interest. However, due to their molecular weight, abundance, and solubility, issues with identifying specific cleavage sites and coverage of peptide fragments remain challenging. Peptidomics is currently focused toward comprehensively studying peptides cleaved from precursor proteins by endogenous proteases. This protocol outlines a standardized rapid and reproducible procedure for peptidomic profiling of human plasma using centrifugal ultrafiltration and mass spectrometry. Ultrafiltration is a convective process that uses anisotropic semipermeable membranes to separate macromolecular species on the basis of size. We have optimized centrifugal ultrafiltration (cellulose triacetate membrane) for plasma fractionation with respect to buffer and solvent composition, centrifugal force, duration, and temperature to facilitate recovery >95% and enrichment of the human plasma peptidome. This method serves as a comprehensive and facile process to enrich and identify a key, underrepresented sub-proteome of human blood plasma.

  2. [Anaphylactic reactions to low-molecular weight chemicals].

    PubMed

    Nowak, Daria; Panaszek, Bernard

    2015-02-06

    Low-molecular weight chemicals (haptens) include a large group of chemical compounds occurring in work environment, items of everyday use (cleaning products, clothing, footwear, gloves, furniture), jewelry (earrings, bracelets), drugs, especially in cosmetics. They cause type IV hypersensitive reactions. During the induction phase of delayed-type hypersensitivity, haptens form complexes with skin proteins. After internalization through antigen presenting cells, they are bound to MHC class II molecules. Next, they are exposed against specific T-lymphocytes, what triggers activation of Th1 cells mainly. After repeating exposition to that hapten, during effector phase, Th1 induce production of cytokines affecting non-specific inflammatory cells. Usually, it causes contact dermatitis. However, occasionally incidence of immediate generalized reactions after contact with some kinds of haptens is noticed. A question arises, how the hapten does induce symptoms which are typical for anaphylaxis, and what contributes to amplification of this mechanism. It seems that this phenomenon arises from pathomechanism occurring in contact urticaria syndrome in which an anaphylactic reaction may be caused either by contact of sensitized skin with protein antigens, high-molecular weight allergens, or haptens. One of the hypotheses indicates the leading role of basophiles in this process. Their contact with haptens, may cause to release mediators of immediate allergic reaction (histamine, eicosanoids) and to produce cytokines corresponding to Th2 cells profile. Furthermore, Th17 lymphocytes secreting pro-inflammatory interleukin-17 might be engaged into amplifying hypersensitivity into immediate reactions and regulatory T-cells may play role in the process, due to insufficient control of the activity of effector cells.

  3. Permeability of low molecular weight organics through nanofiltration membranes.

    PubMed

    Meylan, Sébastien; Hammes, Frederik; Traber, Jacqueline; Salhi, Elisabeth; von Gunten, Urs; Pronk, Wouter

    2007-09-01

    The removal of natural organic matter (NOM) using nanofiltration (NF) is increasingly becoming an option for drinking water treatment. Low molecular weight (LMW) organic compounds are nevertheless only partially retained by such membranes. Bacterial regrowth and biofilm formation in the drinking water distribution system is favoured by the presence of such compounds, which in this context are considered as the assimilable organic carbon (AOC). In this study, the question of whether NF produces microbiologically stable water was addressed. Two NF membranes (cut-off of about 300Da) were tested with different natural and synthetic water samples in a cross-flow filtration unit. NOM was characterised by liquid chromatography with organic carbon detection (LC-OCD) using a size-exclusion column in addition to specific organic acid measurements, while AOC was measured in a batch growth bioassay. Similarly to high molecular weight organic compounds like polysaccharides or humic substances that have a permeability lower than 1%, charged LMW organic compounds were efficiently retained by the NF membranes tested and showed a permeability lower than 3%. However, LMW neutrals and hydrophobic organic compounds permeate to a higher extent through the membranes and have a permeability of up to 6% and 12%, respectively. Furthermore, AOC was poorly retained by NF and the apparent AOC concentration measured in the permeated water was above the proposed limit for microbiologically stable water. This indicates that the drinking water produced by NF might be biologically unstable in the distribution system. Nevertheless, in comparison with the raw water, NF significantly reduced the AOC concentration.

  4. High Molecular Weight Forms of Mammalian Respiratory Chain Complex II

    PubMed Central

    Nůsková, Hana; Holzerová, Eliška; Vrbacký, Marek; Pecina, Petr; Hejzlarová, Kateřina; Kľučková, Katarína; Rohlena, Jakub; Neuzil, Jiri; Houštěk, Josef

    2013-01-01

    Mitochondrial respiratory chain is organised into supramolecular structures that can be preserved in mild detergent solubilisates and resolved by native electrophoretic systems. Supercomplexes of respiratory complexes I, III and IV as well as multimeric forms of ATP synthase are well established. However, the involvement of complex II, linking respiratory chain with tricarboxylic acid cycle, in mitochondrial supercomplexes is questionable. Here we show that digitonin-solubilised complex II quantitatively forms high molecular weight structures (CIIhmw) that can be resolved by clear native electrophoresis. CIIhmw structures are enzymatically active and differ in electrophoretic mobility between tissues (500 – over 1000 kDa) and cultured cells (400–670 kDa). While their formation is unaffected by isolated defects in other respiratory chain complexes, they are destabilised in mtDNA-depleted, rho0 cells. Molecular interactions responsible for the assembly of CIIhmw are rather weak with the complexes being more stable in tissues than in cultured cells. While electrophoretic studies and immunoprecipitation experiments of CIIhmw do not indicate specific interactions with the respiratory chain complexes I, III or IV or enzymes of the tricarboxylic acid cycle, they point out to a specific interaction between CII and ATP synthase. PMID:23967256

  5. Conformations of Low-Molecular-Weight Lignin Polymers in Water.

    PubMed

    Petridis, Loukas; Smith, Jeremy C

    2016-02-08

    Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a critical degree of polymerization, Nc =15, the polymer adopts less spherical conformations than above Nc. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. An implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Low-molecular-weight heparin in pediatric patients.

    PubMed

    Sutor, Anton Heinz; Chan, Anthony K C; Massicotte, Patricia

    2004-02-01

    The incidence of thromboembolic events (TEs) in childhood is greatly underestimated. Two age groups account for approximately 70% of TEs in childhood: infants and teenagers. There are several predisposing risk factors for newborns such as small vessels, high hematocrit, and a unique neonatal hemostatic system. Central venous lines contribute to 80% of deep vein thrombosis in newborns. Other risk factors for all children are shock syndromes, trauma, surgery, heart and kidney disease, and acquired or hereditary thrombophilias. The best prophylaxis is to recognize, avoid, and remove risk factors if possible. This is particularly relevant in childhood, where risk factors can be found in the majority of TEs. The serious sequelae of TEs (mortality, and short- and long-term morbidity) require therapeutic intervention. Unfractionated heparin (UFH) has the following disadvantages: age-dependent unpredictable pharmacokinetics, the need for intravenous access for therapy and monitoring, delays in achieving therapeutic ranges, bleeding risk, the risk of heparin-induced thrombocytopenia, and osteoporosis with long-term use. Oral anticoagulants, in addition to some of these disadvantages, show considerable variation by diet (especially if there is a change from breast to bottle feeding), medication, and intercurrent illness. Review of case reports and cohort studies on 728 children treated with low-molecular-weight heparin (LMWH) indicate the following advantages over UFH: minimal monitoring, ease of administration (subcutaneous), and possibly equivalent efficacy and safety. Dose recommendations for pediatric patients cannot be directly extrapolated from those for adult patients. If dosages are calculated according to body weight, infants < 3 months (or < 5 kg) need approximately 50% more LMWH than older children or adults to reach prophylactic or therapeutic anti-factor Xa levels. Further studies are necessary to address the following: the importance of risk factors, the

  7. In situ reinforced polymers using low molecular weight compounds

    NASA Astrophysics Data System (ADS)

    Yordem, Onur Sinan

    2011-12-01

    The primary objective of this research is to generate reinforcing domains in situ during the processing of polymers by using phase separation techniques. Low molecular weight compounds were mixed with polymers where the process viscosity is reduced at process temperatures and mechanical properties are improved once the material system is cooled or reacted. Thermally induced phase separation and thermotropic phase transformation of low molar mass compounds were used in isotactic polypropylene (iPP) and poly(ether ether ketone) (PEEK) resins. Reaction induced phase separation was utilized in thermosets to generate anisotropic reinforcements. A new strategy to increase fracture toughness of materials was introduced. Simultaneously, enhancement in stiffness and reduction in process viscosity were also attained. Materials with improved rheological and mechanical properties were prepared by using thermotropic phase transformations of metal soaps in polymers (calcium stearate/iPP). Morphology and thermal properties were studied using WAXS, DSC and SEM. Mechanical and rheological investigation showed significant reduction in process viscosity and substantial improvement in fracture toughness were attained. Effects of molecular architecture of metal soaps were investigated in PEEK (calcium stearate/PEEK and sodium stearate/PEEK). The selected compounds reduced the process viscosity due to the high temperature co-continuous morphology of metal soaps. Unlike the iPP system that incorporates spherical particles, interaction between PEEK and metal soaps resulted in two discrete and co-continuous phases of PEEK and the metal stearates. DMA and melt rheology exhibited that sodium stearate/PEEK composites are stiffer. Effective moduli of secondary metal stearate phase were calculated using different composite theories, which suggested bicontinuous morphology to the metal soaps in PEEK. Use of low molecular weight crystallizable solvents was investigated in reactive systems

  8. Low Molecular Weight Norbornadiene Derivatives for Molecular Solar‐Thermal Energy Storage

    PubMed Central

    Quant, Maria; Lennartson, Anders; Dreos, Ambra; Kuisma, Mikael; Erhart, Paul; Börjesson, Karl

    2016-01-01

    Abstract Molecular solar‐thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193–260 g mol−1) norbornadiene–quadricyclane systems. The molecules feature cyano acceptor and ethynyl‐substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo‐thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396–629 kJ kg−1). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules. PMID:27492997

  9. Low Molecular Weight Norbornadiene Derivatives for Molecular Solar-Thermal Energy Storage.

    PubMed

    Quant, Maria; Lennartson, Anders; Dreos, Ambra; Kuisma, Mikael; Erhart, Paul; Börjesson, Karl; Moth-Poulsen, Kasper

    2016-09-05

    Molecular solar-thermal energy storage systems are based on molecular switches that reversibly convert solar energy into chemical energy. Herein, we report the synthesis, characterization, and computational evaluation of a series of low molecular weight (193-260 g mol(-1) ) norbornadiene-quadricyclane systems. The molecules feature cyano acceptor and ethynyl-substituted aromatic donor groups, leading to a good match with solar irradiation, quantitative photo-thermal conversion between the norbornadiene and quadricyclane, as well as high energy storage densities (396-629 kJ kg(-1) ). The spectroscopic properties and energy storage capability have been further evaluated through density functional theory calculations, which indicate that the ethynyl moiety plays a critical role in obtaining the high oscillator strengths seen for these molecules. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  10. Application of the weibull distribution function to the molecular weight distribution of cellulose

    Treesearch

    A. Broido; Hsiukang Yow

    1977-01-01

    The molecular weight distribution of a linear homologous polymer is usually obtained empirically for any particular sample. Sample-to-sample comparisons are made in terms of the weight- or number-average molecular weights and graphic displays of the distribution curves. Such treatment generally precludes data interpretations in which a distribution can be described in...

  11. 21 CFR 172.820 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... ethylene oxide and water with a mean molecular weight of 200 to 9,500. (2) It contains no more than 0.2 percent total by weight of ethylene and diethylene glycols when tested by the analytical methods... the total ethylene and diethylene glycol content of polyethylene glycols having mean molecular weights...

  12. 21 CFR 178.3750 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... conditions: (a) The additive is an addition polymer of ethylene oxide and water with a mean molecular weight of 200 to 9,500. (b) It contains no more than 0.2 percent total by weight of ethylene and diethylene... ethylene and diethylene glycols if its mean molecular weight is below 350, when tested by the analytical...

  13. Optimization of parameters for coverage of low molecular weight proteins

    PubMed Central

    Müller, Stephan A.; Kohajda, Tibor; Findeiß, Sven; Stadler, Peter F.; Washietl, Stefan; Kellis, Manolis; von Bergen, Martin

    2010-01-01

    Proteins with molecular weights of <25 kDa are involved in major biological processes such as ribosome formation, stress adaption (e.g., temperature reduction) and cell cycle control. Despite their importance, the coverage of smaller proteins in standard proteome studies is rather sparse. Here we investigated biochemical and mass spectrometric parameters that influence coverage and validity of identification. The underrepresentation of low molecular weight (LMW) proteins may be attributed to the low numbers of proteolytic peptides formed by tryptic digestion as well as their tendency to be lost in protein separation and concentration/desalting procedures. In a systematic investigation of the LMW proteome of Escherichia coli, a total of 455 LMW proteins (27% of the 1672 listed in the SwissProt protein database) were identified, corresponding to a coverage of 62% of the known cytosolic LMW proteins. Of these proteins, 93 had not yet been functionally classified, and five had not previously been confirmed at the protein level. In this study, the influences of protein extraction (either urea or TFA), proteolytic digestion (solely, and the combined usage of trypsin and AspN as endoproteases) and protein separation (gel- or non-gel-based) were investigated. Compared to the standard procedure based solely on the use of urea lysis buffer, in-gel separation and tryptic digestion, the complementary use of TFA for extraction or endoprotease AspN for proteolysis permits the identification of an extra 72 (32%) and 51 proteins (23%), respectively. Regarding mass spectrometry analysis with an LTQ Orbitrap mass spectrometer, collision-induced fragmentation (CID and HCD) and electron transfer dissociation using the linear ion trap (IT) or the Orbitrap as the analyzer were compared. IT-CID was found to yield the best identification rate, whereas IT-ETD provided almost comparable results in terms of LMW proteome coverage. The high overlap between the proteins identified with IT

  14. Distribution of molecular weight in glyceride polymerizates or aggregates of them after contact with lunar grains

    NASA Technical Reports Server (NTRS)

    Asunmaa, S. K.; Haack, R.

    1977-01-01

    An attempt is made to report on experiments in which a molecular-weight increase was determined in thin layers of triglyceride-containing glycerides after thin-layer contact for two years with lunar topsoil grains at 25 C without any thermal activation. It is noted that solidification was observed on both dielectric grains and metal-rich areas and that changes in viscosity and molecular weights were first detected by solidification of surface layers. Gel permeation chromatography is described which detected a general shift of the Gaussian distribution of the molecular-weight data toward generally higher molecular weights as well as an increase in mean molecular weight. Reaction mechanisms are considered, and results of spectrographic analysis are cited which support the interpretations of the molecular-weight data.

  15. Purification of a Low Molecular Weight Fucoidan for SPECT Molecular Imaging of Myocardial Infarction

    PubMed Central

    Saboural, Pierre; Chaubet, Frédéric; Rouzet, Francois; Al-Shoukr, Faisal; Ben Azzouna, Rana; Bouchemal, Nadia; Picton, Luc; Louedec, Liliane; Maire, Murielle; Rolland, Lydia; Potier, Guy; Le Guludec, Dominique; Letourneur, Didier; Chauvierre, Cédric

    2014-01-01

    Fucoidans constitute a large family of sulfated polysaccharides with several biochemical properties. A commercial fucoidan from brown algae, containing low molecular weight polysaccharidic species constituted of l-fucose, uronic acids and sulfate groups, was simply treated here with calcium acetate solution. This treatment led to a purified fraction with a yield of 45%. The physicochemical characterizations of the purified fucoidan using colorimetric assay, MALLS, dRI, FT-IR, NMR, exhibited molecular weight distributions and chemical profiles similar for both fucoidans whereas the sulfate and l-fucose contents increased by 16% and 71%, respectively. The biodistribution study in rat of both compounds labeled with 99mTc evidenced a predominant renal elimination of the purified fucoidan, but the crude fucoidan was mainly retained in liver and spleen. In rat myocardial ischemia-reperfusion, we then demonstrated the better efficiency of the purified fucoidan. This purified sulfated polysaccharide appears promising for the development of molecular imaging in acute coronary syndrome. PMID:25251032

  16. Molecular imprinted polymer-coated optical fiber sensor for the identification of low molecular weight molecules.

    PubMed

    Lépinay, Sandrine; Ianoul, Anatoli; Albert, Jacques

    2014-10-01

    A biomimetic optical probe for detecting low molecular weight molecules (maltol, 3-hydroxy-2-methyl-4H-pyran-4-one, molecular weight of 126.11 g/mol), was designed, fabricated, and characterized. The sensor couples a molecular imprinted polymer (MIP) and the Bragg grating refractometry technology into an optical fiber. The probe is fabricated first by inscribing tilted grating planes in the core of the fiber, and then by photopolymerization to immobilize a maltol imprinted MIP on the fiber cladding surface over the Bragg grating. The sensor response to the presence of maltol in different media is obtained by spectral interrogation of the fiber transmission signal. The results showed that the limit of detection of the sensor reached 1 ng/mL in pure water with a sensitivity of 6.3 × 10(8)pm/M. The selectivity of the sensor against other compounds and its reusability were also studied experimentally. Finally, the unambiguous detection of concentrations as little as 10nM of maltol in complex media (real food samples) by the MIP-coated tilted fiber Bragg grating sensor was demonstrated. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Molecular weight dependency of polyrotaxane-cross-linked polymer gel extensibility.

    PubMed

    Ohmori, Kana; Abu Bin, Imran; Seki, Takahiro; Liu, Chang; Mayumi, Koichi; Ito, Kohzo; Takeoka, Yukikazu

    2016-12-11

    This work investigates the influence of the molecular weight of polyrotaxane (PR) cross-linkers on the extensibility of polymer gels. The polymer gels, which were prepared using PR cross-linkers of three different molecular weights but the same number of cross-linking points per unit volume of gel, have almost the same Young's modulus. By contrast, the extensibility and rupture strength of the polymer gels are substantially increased with increasing molecular weight of the PR cross-linker.

  18. Combustion of High Molecular Weight Hydrocarbon Fuels and JP-8 at Moderate Pressures

    DTIC Science & Technology

    2016-07-26

    SECURITY CLASSIFICATION OF: The objective of this research is to characterize combustion of high molecular weight hydrocarbon fuels and jet- fuels (in...Unlimited UU UU UU UU 26-07-2016 1-May-2012 30-Apr-2016 Final Report: Combustion of High Molecular Weight Hydrocarbon Fuels and JP-8 at Moderate...Report: Combustion of High Molecular Weight Hydrocarbon Fuels and JP-8 at Moderate Pressures (Research Area 1: Mechanical Sciences) Report Title The

  19. A method for determining weights for excess relative risk and excess absolute risk when applied in the calculation of lifetime risk of cancer from radiation exposure.

    PubMed

    Walsh, Linda; Schneider, Uwe

    2013-03-01

    Radiation-related risks of cancer can be transported from one population to another population at risk, for the purpose of calculating lifetime risks from radiation exposure. Transfer via excess relative risks (ERR) or excess absolute risks (EAR) or a mixture of both (i.e., from the life span study (LSS) of Japanese atomic bomb survivors) has been done in the past based on qualitative weighting. Consequently, the values of the weights applied and the method of application of the weights (i.e., as additive or geometric weighted means) have varied both between reports produced at different times by the same regulatory body and also between reports produced at similar times by different regulatory bodies. Since the gender and age patterns are often markedly different between EAR and ERR models, it is useful to have an evidence-based method for determining the relative goodness of fit of such models to the data. This paper identifies a method, using Akaike model weights, which could aid expert judgment and be applied to help to achieve consistency of approach and quantitative evidence-based results in future health risk assessments. The results of applying this method to recent LSS cancer incidence models are that the relative EAR weighting by cancer solid cancer site, on a scale of 0-1, is zero for breast and colon, 0.02 for all solid, 0.03 for lung, 0.08 for liver, 0.15 for thyroid, 0.18 for bladder and 0.93 for stomach. The EAR weighting for female breast cancer increases from 0 to 0.3, if a generally observed change in the trend between female age-specific breast cancer incidence rates and attained age, associated with menopause, is accounted for in the EAR model. Application of this method to preferred models from a study of multi-model inference from many models fitted to the LSS leukemia mortality data, results in an EAR weighting of 0. From these results it can be seen that lifetime risk transfer is most highly weighted by EAR only for stomach cancer. However

  20. Composition and molecular weight distribution of carob germ protein fractions.

    PubMed

    Smith, Brennan M; Bean, Scott R; Schober, Tilman J; Tilley, Michael; Herald, Thomas J; Aramouni, Fadi

    2010-07-14

    Biochemical properties of carob germ proteins were analyzed using a combination of selective extraction, reversed-phase high-performance liquid chromatography (RP-HPLC), size exclusion chromatography (SEC) coupled with multiangle laser light scattering (SEC-MALS), and electrophoretic analysis. Using a modified Osborne extraction procedure, carob germ flour proteins were found to contain approximately 32% albumin and globulin and approximately 68% glutelin with no prolamins detected. The albumin and globulin fraction was found to contain low amounts of disulfide-bonded polymers with relatively low M(w) ranging up to 5 x 10(6) Da. The glutelin fraction, however, was found to contain large amounts of high molecular weight disulfide-bonded polymers with M(w) up to 8 x 10(7) Da. When extracted under nonreducing conditions and divided into soluble and insoluble proteins as typically done for wheat gluten, carob germ proteins were found to be almost entirely ( approximately 95%) in the soluble fraction with only ( approximately 5%) in the insoluble fraction. As in wheat, SEC-MALS analysis showed that the insoluble proteins had a greater M(w) than the soluble proteins and ranged up to 8 x 10(7) Da. The lower M(w) distribution of the polymeric proteins of carob germ flour may account for differences in functionality between wheat and carob germ flour.

  1. Antiaging activity of low molecular weight peptide from Paphia undulate

    NASA Astrophysics Data System (ADS)

    Chen, Xin; Cai, Bingna; Chen, Hua; Pan, Jianyu; Chen, Deke; Sun, Huili

    2013-05-01

    Low molecular weight peptide (LMWP) was prepared from clam Paphia undulate and its antiaging effect on D-galactose-induced acute aging in rats, aged Kunming mice, ultraviolet-exposed rats, and thermally injured rats was investigated. P. undulate flesh was homogenized and digested using papain under optimal conditions, then subjected to Sephadex G-25 chromatography to isolate the LMWP. Administration of LMWP significantly reversed D-galactose-induced oxidative stress by increasing the activities of glutathione peroxidase (GPx) and catalase (CAT), and by decreasing the level of malondialdehyde (MDA). This process was accompanied by increased collagen synthesis. The LMWP prevented photoaging and promoted dermis recovery and remission of elastic fiber hyperplasia. Furthermore, treatment with the LMWP helped to regenerate elastic fibers and the collagen network, increased superoxide dismutase (SOD) in the serum and significantly decreased MDA. Thermal scald-induced inflammation and edema were also relieved by the LWMP, while wound healing in skin was promoted. These results suggest that the LMWP from P. undulate could serve as a new antiaging substance in cosmetics.

  2. Biocompatibility of modified ultra-high-molecular-weight polyethylene

    NASA Astrophysics Data System (ADS)

    Novotná, Z.; Lacmanová, V.; Rimpelová, S.; Juřik, P.; Polívková, M.; Å vorčik, V.

    2016-09-01

    Ultra-high-molecular-weight polyethylene (UHMWPE, PE) is a synthetic polymer used for biomedical applications because of its high impact resistance, ductility and stability in contact with physiological fluids. Therefore this material is being used in human orthopedic implants such as total joint replacements. Surface modification of this material relates to changes of its surface hydrophilicity, energy, microstructure, roughness, and morphology, all influencing its biological response. In our recent work, PE was treated by an Ar+ plasma discharge and then grafted with biologically active polyethylene glycol in order to enhance adhesion and proliferation of mouse fibroblast (L929). The surface properties of pristine PE and its grafted counterparts were studied by goniometry (surface wettability). Furthermore, Atomic Force Microscopy was used to determine the surface morphology and roughness. The biological response of the L929 cell lines seeded on untreated and plasma treated PE matrices was quantified in terms of the cell adhesion, density, and metabolic activity. Plasma treatment leads to the ablation of the polymer surface layers. Plasma treatment and subsequent poly(ethylene glycol) grafting lead to dramatic changes in the polymer surface morphology and roughness. Biological tests, performed in vitro, show increased adhesion and proliferation of cells on modified polymers. Grafting with poly(ethylene glycol) increases cell proliferation compared to plasma treatment.

  3. Fatigue crack propagation behavior of ultrahigh molecular weight polyethylene.

    PubMed

    Connelly, G M; Rimnac, C M; Wright, T M; Hertzberg, R W; Manson, J A

    1984-01-01

    The relative fatigue crack propagation resistance of plain and carbon fiber-reinforced ultrahigh molecular weight polyethylene (UHMWPE) was determined from cyclic loading tests performed on compact tension specimens machined from the tibial components of total knee prostheses. Both materials were characterized by dynamic mechanical spectroscopy, X-ray diffraction, and differential scanning calorimetry. The cyclic tests used loading in laboratory air at 5 Hz using a sinusoidal wave form. Dynamic mechanical spectroscopy showed that the reinforced UHMWPE had a higher elastic storage modulus than the plain UHMWPE, whereas X-ray diffraction and differential scanning calorimetry showed that the percent crystallinity and degree of order in the crystalline regions were similar for the two materials. Fatigue crack propagation in both materials proved to be very sensitive to small changes in the applied cyclic stress intensity range. A 10% increase in stress intensity resulted in approximately an order of magnitude increase in fatigue crack growth rate. The fatigue crack propagation resistance of the reinforced UHMWPE was found to be significantly worse than that of the plain UHMWPE. This result was attributed to poor bonding between the carbon fibers and the UHMWPE matrix and the ductile nature of the matrix itself.

  4. A capillary electrophoretic method for fingerprinting low molecular weight heparins.

    PubMed

    King, J Timothy; Desai, Umesh R

    2008-09-15

    Clinically used low molecular weight heparins (LMWH) are anticoagulants of choice and are phenomenally complex mixtures of millions of distinct natural and unnatural polymeric sequences. The FDA recommends that each LMWH be considered as an independent drug with its own activity profile, placing significant importance on the biophysical characterization of each intact LMWH. We report a robust protocol for fingerprinting these pharmaceutical agents. Capillary electrophoresis of three LMWHs, enoxaparin, tinzaparin, and a Sigma preparation, under reverse polarity conditions in the presence of selected linear alkyl polyamines gives an electrophoretic pattern that is characteristic of the nature of the starting material. The buffers that best provided optimal resolution without compromising sensitivity and speed of analysis were 50 mM sodium phosphate, pH 2.3, and 100 mM ammonium formate, pH 3.5. Resolution was strongly dependent on the structure of polyamine with pentaethylenehexamine being most effective for enoxaparin and Sigma LMWH. In contrast, tinzaparin could be best resolved with tetraethylenepentamine. Cyclic polyamines were ineffective. Resolution was also dependent on the concentration of resolving agents and displayed a narrow window that provides optimal resolution. These features suggest a strong structural origin of the fingerprint pattern. Overall, the simple protocol will find special use in assessing LMWH quality and batch-to-batch variability.

  5. Molecular weight distribution of organic matter by ozonation and biofiltration.

    PubMed

    Lin, Yen-Hui

    2012-01-01

    Molecular weight (MW) distribution of organic matter by ozonation and biofiltration was evaluated using gel chromatography. The MW distribution of organic matter by Sephadex G-25 was observed from groups 2 (MW = 1,029-7,031 g/mol) and 3 (MW = 303-1,029 g/mol) shifted to groups 2, 3 and 4 (MW < 303 g/mol) under ozone doses of 0.1 and 0.4 mg O₃/mg total organic carbon (TOC). The shift in MW increases as ozone dosage increases. Biofiltration effectively degraded the organic molecule of group 2; however, the biofiltration only slightly degraded the organic molecule of group 4. Increased ozone dose destroyed functional groups C═C in phenolic and C-O in alcoholic compounds and increased UV-insensitive biodegradable organic carbon for subsequent biofiltration. Biofiltration effectively degraded organic compounds of alcohols and alkenes at an ozone dose of 0.1 mg O₃/mg TOC. Experimental approaches in this study can be applied to evaluate and diagnose the function of a full-scale process combining ozonation and biofiltration in drinking water treatment plants.

  6. Effect of polymer molecular weight on chitosan-protein interaction.

    PubMed

    Bekale, L; Agudelo, D; Tajmir-Riahi, H A

    2015-01-01

    We present a comprehensive study of the interactions between chitosan nanoparticles (15, 100 and 200 kDa with the same degree of deacetylation 90%) and two model proteins, i.e., bovine (BSA) and human serum albumins (HSA), with the aim of correlating chitosan molecular weight (Mw) and the binding affinity of these naturally occurring polymers to protein. The effect of chitosan on the protein secondary structure and the influence of protein complexation on the shape of chitosan nanoparticles are discussed. A combination of multiple spectroscopic methods, transmission electron microscopy (TEM) and thermodynamic analysis were used to assess the polymer-protein complex formation. Results revealed that the three chitosan nanoparticles interact with BSA to form chitosan-BSA complexes, mainly through hydrophobic contacts with the affinity order: 200>100>15 kDa. However, HSA-chitosan complexation is mainly via electrostatic interactions with the stability order: 100>200>15 kDa. Furthermore, the association between polymer and protein causes a partial protein conformational change by a major reduction of α-helix from 63% (free BSA) to 57% (chitosan-BSA) and 57% (free HSA) to 51% (chitosan-HSA). Finally, TEM micrographs clearly revealed that the binding of serum albumins with chitosan nanoparticles induces a significant change in protein morphology and the shape of the polymer. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Low molecular weight heparin use in unexplained recurrent miscarriage

    PubMed Central

    Yuksel, Halide; Kayatas, Semra; Boza, Aysen Telce; Api, Murat; Ertekin, A. Aktug; Cam, Cetin

    2014-01-01

    Objective: The aim of the study was to investigate whether the use of low molecular weight heparin (LMWH) improve live birth rates when compared with control group in patients with unexplained recurrent miscarriages (URM). Methods: In this prospective observational study 150 women with a history of two or more previous unexplained first trimester pregnancy loss who received LMWH; either enoxaparin (n=50), tinzaparin (n=50) or nothing (n=50) were followed for the pregnancy outcome measures. Only the patients who have used standardized dosage of LMWH (4000 IU/day enoxaparin or 3500 IU/day tinzaparin ) were included to the study. The primary end point was the live birth rate and secondary end points were the side effects, late pregnancy complications and neonatal outcome in the study cohorts. Results: Live birth was achieved 85% of the LMWH group and 66% of the control group (p=0.007). According to the subgroup analysis; live birth rates did not differ significantly between the enoxaparin and tinzaparin group (84% and 86%, respectively). Maternal and neonatal side effects were not statistically significant among the study participants. Conclusion: Thromboprophylaxis with LMWH resulted in a improved live-birth rate in patient with 2 or more consecutive unexplained recurrent pregnancy loss. Nevertheless these findings need to be confirmed in larger randomized trials. PMID:25674114

  8. Source apportionment of soil heavy metals using robust absolute principal component scores-robust geographically weighted regression (RAPCS-RGWR) receptor model.

    PubMed

    Qu, Mingkai; Wang, Yan; Huang, Biao; Zhao, Yongcun

    2018-06-01

    The traditional source apportionment models, such as absolute principal component scores-multiple linear regression (APCS-MLR), are usually susceptible to outliers, which may be widely present in the regional geochemical dataset. Furthermore, the models are merely built on variable space instead of geographical space and thus cannot effectively capture the local spatial characteristics of each source contributions. To overcome the limitations, a new receptor model, robust absolute principal component scores-robust geographically weighted regression (RAPCS-RGWR), was proposed based on the traditional APCS-MLR model. Then, the new method was applied to the source apportionment of soil metal elements in a region of Wuhan City, China as a case study. Evaluations revealed that: (i) RAPCS-RGWR model had better performance than APCS-MLR model in the identification of the major sources of soil metal elements, and (ii) source contributions estimated by RAPCS-RGWR model were more close to the true soil metal concentrations than that estimated by APCS-MLR model. It is shown that the proposed RAPCS-RGWR model is a more effective source apportionment method than APCS-MLR (i.e., non-robust and global model) in dealing with the regional geochemical dataset. Copyright © 2018 Elsevier B.V. All rights reserved.

  9. Degradation mechanisms of bioresorbable polyesters. Part 2. Effects of initial molecular weight and residual monomer.

    PubMed

    Gleadall, Andrew; Pan, Jingzhe; Kruft, Marc-Anton; Kellomäki, Minna

    2014-05-01

    This paper presents an understanding of how initial molecular weight and initial monomer fraction affect the degradation of bioresorbable polymers in terms of the underlying hydrolysis mechanisms. A mathematical model was used to analyse the effects of initial molecular weight for various hydrolysis mechanisms including noncatalytic random scission, autocatalytic random scission, noncatalytic end scission or autocatalytic end scission. Different behaviours were identified to relate initial molecular weight to the molecular weight half-life and to the time until the onset of mass loss. The behaviours were validated by fitting the model to experimental data for molecular weight reduction and mass loss of samples with different initial molecular weights. Several publications that consider initial molecular weight were reviewed. The effect of residual monomer on degradation was also analysed, and shown to accelerate the reduction of molecular weight and mass loss. An inverse square root law relationship was found between molecular weight half-life and initial monomer fraction for autocatalytic hydrolysis. The relationship was tested by fitting the model to experimental data with various residual monomer contents. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  10. Molecular weight dependence of LB morphology of poly(n-hexyl isocyanate) (PHIC).

    PubMed

    Morioka, Takako; Shibata, Osamu; Kawaguchi, Masami

    2010-12-07

    The morphologies of Langmuir-Blodgett (LB) films of two fractionated poly(n-hexyl isocyanate) (PHIC) and those of their binary mixtures were observed by AFM, together with those of an unfractionated PHIC. The low molecular weight PHIC formed random packing of bundles consisting of rigid rods, while the high molecular weight PHIC formed random packing of bundles consisting of hairy rods. Bundle interpenetration was observed only for the latter in the semidilute regime. In the bilayer region, the area occupied by the PHIC bundles in the upper layer was obviously smaller for the high molecular weight PHIC than for the low molecular weight PHIC, suggesting that the bundles of high molecular weight PHIC more easily interpenetrate than those of low molecular weight PHIC. For the blended films composed of both low and high molecular weight PHICs, the characteristic morphologies of the respective PHIC samples were no longer present. Moreover, the morphologies of the blended films appeared to resemble each other at any molar fraction owing to the ideal miscibility of the low molecular weight and high molecular weight PHICs. The morphologies of the blended films were also similar to that of the unfractionated PHIC film in the dilute regime. In the semidilute regime, the blended films became rounded owing to an increase in bundles interpenetration between PHICs as compared to that in the dilute regime, whereas the morphology of unfractionated PHIC films remained unchanged as compared to that in the dilute regime.

  11. Chromatographic molecular weight measurements for heparin, its fragments and fractions, and other glycosaminoglycans.

    PubMed

    Mulloy, Barbara; Hogwood, John

    2015-01-01

    Glycosaminoglycan samples are usually polydisperse, consisting of molecules with differing length and differing sequence. Methods for measuring the molecular weight of heparin have been developed to assure the quality and consistency of heparin products for medicinal use, and these methods can be applied in other laboratory contexts. In the method described here, high-performance gel permeation chromatography is calibrated using appropriate heparin molecular weight markers or a single broad standard calibrant, and used to characterize the molecular weight distribution of polydisperse samples or the peak molecular weight of monodisperse, or approximately monodisperse, heparin fractions. The same technology can be adapted for use with other glycosaminoglycans.

  12. Effect of Sulfation and Molecular Weight on Anticoagulant Activity of Dextran.

    PubMed

    Drozd, N N; Logvinova, Yu S; Torlopov, M A; Udoratina, E V

    2017-02-01

    Sulfation (to 2.8) of dextrans with molecular weight of 150 and 20 kDa was followed by the appearance of anticoagulant activity that increased with decreasing their molecular weight and did not depend on antithrombin, plasma inhibitor of serine proteases of the blood coagulation system. Antithrombin activity of dextran sulfate with a molecular weight of 20 kDa reached 12.6-15.3 U/mg. Dextran sulfates with molecular weights of 20 and 150 kDa did not potentiate ADP-induced human platelet aggregation.

  13. Molecular weight of Escherichia coli β-galactosidase in concentrated solutions of guanidine hydrochloride

    PubMed Central

    Erickson, Robert P.

    1970-01-01

    The molecular weight of Escherichia coli β-galactosidase was determined in 6m- and 8m-guanidine hydrochloride by meniscus-depletion sedimentation equilibrium, sedimentation velocity and viscosity. Sedimentation equilibrium revealed heterogeneity with the smallest component having a molecular weight of about 50000. At lower speeds, the apparent weight-average molecular weight is about 80000. By use of a calculation based on an empirical correlation for proteins that are random coils in 6m-guanidine hydrochloride, sedimentation velocity gave a molecular weight of 91000, and the intrinsic viscosity indicated a viscosity-average molecular weight of 84000. Heating in 6m-guanidine hydrochloride lowered the viscosity of β-galactosidase in a variable manner. PMID:4924171

  14. Characterization and analysis of the molecular weight of lignin for biorefining studies

    SciTech Connect

    Tolbert, Allison; Akinosho, Hannah; Khunsupat, Ratayakorn

    2014-06-04

    The molecular weight of lignin is a fundamental property that infl uences the recalcitrance of biomass and the valorization of lignin. The determination of the molecular weight of lignin in native biomass is dependent on the bioresources used and the isolation and purifi cation procedures employed. The three most commonly employed isolation methods are milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL). Common characterization techniques for determining the molecular weight of lignin will be addressed, with an emphasis on gel permeation chromatography (GPC). This review also examines the mechanisms behind several biological, physical, andmore » chemical pre-treatments and their impact on the molecular weight of lignin. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (D) all vary in magnitude depending on the biomass source, pre-treatment conditions, and isolation method. Additionally, there is a growing body of literature that supports changes in the molecular weight of lignin in response to genetic modifi cations in the lignin biosynthetic pathways. This review summarizes different procedures for obtaining the molecular weight of lignin that have been used in recent years and highlight future opportunities for applications of lignin.« less

  15. Using molecular recognition of beta-cyclodextrin to determine molecular weights of low-molecular-weight explosives by MALDI-TOF mass spectrometry.

    PubMed

    Zhang, Min; Shi, Zhen; Bai, Yinjuan; Gao, Yong; Hu, Rongzu; Zhao, Fenqi

    2006-02-01

    This study presents a novel method for determining the molecular weights of low molecular weight (MW) energetic compounds through their complexes of beta-cyclodextrin (beta-CD) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) in a mass range of 500 to 1700 Da, avoiding matrix interference. The MWs of one composite explosive composed of 2,6-DNT, TNT, and RDX, one propellant with unknown components, and 14 single-compound explosives (RDX, HMX, 3,4-DNT, 2,6-DNT, 2,5-DNT, 2,4,6-TNT, TNAZ, DNI, BTTN, NG, TO, NTO, NP, and 662) were measured. The molecular recognition and inclusion behavior of beta-CD to energetic materials (EMs) were investigated. The results show that (1) the established method is sensitive, simple, accurate, and suitable for determining the MWs of low-MW single-compound explosives and energetic components in composite explosives and propellants; and (2) beta-CD has good inclusion and modular recognition abilities to the above EMs.

  16. Molecular weights and metabolism of rat brain proteins

    PubMed Central

    Vrba, R.; Cannon, Wendy

    1970-01-01

    1. Rats were injected with [U-14C]glucose and after various intervals extracts of whole brain proteins (and in some cases proteins from liver, blood and heart) were prepared by high-speed centrifugation of homogenates in 0.9% sodium chloride or 0.5% sodium deoxycholate. 2. The extracts were subjected to gel filtration on columns of Sephadex G-200 equilibrated with 0.9% sodium chloride or 0.5% sodium deoxycholate. 3. Extracts prepared with both solvents displayed on gel filtration a continuous range of proteins of approximate molecular weights ranging from less than 2×104 to more than 8×105. 4. The relative amount of the large proteins (mol.wt.>8×105) was conspicuously higher in brain and liver than in blood. 5. At 15min after the injection of [U-14C]glucose the smaller protein molecules (mol.wt.<2×104) were significantly radioactive, whereas no 14C could be detected in the larger (mol.wt.>2×104) protein molecules. The labelling of all protein samples was similar within 4h after injection of [U-14C]glucose. Fractionation of brain proteins into distinctly different groups by the methods used in the present work yielded protein samples with a specific radioactivity comparable with that of total brain protein. 6. No evidence could be obtained by the methods used in the present and previous work to indicate the presence of a significant amount of `metabolically inert protein' in the brain. 7. It is concluded that: (a) most or all of the brain proteins are in a dynamic state of equilibrium between continuous catabolism and anabolism; (b) the continuous conversion of glucose into protein is an important part of the maintenance of this equilibrium and of the homoeostasis of brain proteins in vivo. PMID:5435499

  17. [Low molecular weight heparin and non valvular atrial fibrillation].

    PubMed

    Ederhy, S; Di Angelantonio, E; Meuleman, C; Janower, S; Boccara, F; Cohen, A

    2006-12-01

    Low molecular weight heparin (LMWH) are obtained through chemical or enzyme depolymerisation of unfractioned heparins (UFH). LMWHs present several advantages over UFH: they exhibit a smaller interindividual variability of the anticoagulant effect, they have a greater bioavailability, a longer plasma half-life and do not require monitoring of the anticoagulant effect. LMWH have restrictive indications in AF patients, cardioversion (II level C and TEE for ACC/AHA/ESC and 2C for ACCP guidelines) or use as a bridge therapy (IIB, level C for ACC/AHA/ESC). The ACE study (Anticoagulation for cardioversion using enoxaparin), showed a reduction, though not statistically significant, of 42% of the composite end point (embolic event, major bleeding and death) 2.8% under enoxaparin vs. 4.8 % under conventional treatment, relative risk 0.58, CI 95% 0.23-1.46). Other studies, using dalteparin, confirmed that an anticoagulant treatment using LMWH followed by warfarin was at least as good as conventional management. ACUTE II (Assessment of cardioversion using transesophageal echochardiography), a randomized multicenter trial, compared the efficacy and tolerance of enoxaparin (1 mg/kg every 12 hours) and UFH in 155 patients eligible for a TEE-guided cardioversion. These patients were administered LMWH or UFH for 24 hours before TEE or cardioversion. There were no significative differences regarding the incidence of the study end points, in particular stroke and bleeding, and no death occurred. HAEST (Heparin in acute embolic stroke trial), a randomized, placebo-controlled, double blind trial failed to show the LMWH superiority over aspirin in patients with acute ischemic stroke and atrial fibrillation. Finally, LMWH have been proposed as a bridge therapy in patients under chronic VKA prior to surgery or invasive procedures. This strategy resulted in a low rate of thromboembolic events and major bleedings.

  18. Properties of crosslinked ultra-high-molecular-weight polyethylene.

    PubMed

    Lewis, G

    2001-02-01

    Substantially reducing the rate of generation of wear particles at the surfaces of ultra-high-molecular-weight polyethylene (UHMWPE) orthopedic implant bearing components, in vivo, is widely regarded as one of the most formidable challenges in modern arthroplasty. In the light of this, much research attention has been paid to the myriad of endogenous and exogenous factors that have been postulated to affect this wear rate, one such factor being the polymer itself. In recent years, there has been a resurgence of interest in crosslinking the polymer as a way of improving its properties that are considered relevant to its use for fabricating bearing components. Such properties include wear resistance, fatigue life, and fatigue crack propagation rate. Although a large volume of literature exists on the topic on the impact of crosslinking on the properties of UHMWPE, no critical appraisal of this literature has been published. This is one of the goals of the present article, which emphasizes three aspects. The first is the trade-off between improvement in wear resistance and depreciation in other mechanical and physical properties. The second aspect is the presentation of a method of estimating the optimal value of a crosslinking process variable (such as dose in radiation-induced crosslinking) that takes into account this trade-off. The third aspect is the description of a collection of under- and unexplored research areas in the field of crosslinked UHMWPE, such as the role of starting resin on the properties of the crosslinked polymer, and the in vitro evaluation of the wear rate of crosslinked tibial inserts and other bearing components that, in vivo, are subjected to nearly unidirectional motion.

  19. High Molecular Weight Petrogenic and Pyrogenic Hydrocarbons in Aquatic Environments

    NASA Astrophysics Data System (ADS)

    Abrajano, T. A., Jr.; Yan, B.; O'Malley, V.

    2003-12-01

    Geochemistry is ultimately the study of sources, movement, and fate of chemicals in the geosphere at various spatial and temporal scales. Environmental organic geochemistry focuses such studies on organic compounds of toxicological and ecological concern (e.g., Schwarzenbach et al., 1993, 1998; Eganhouse, 1997). This field emphasizes not only those compounds with potential toxicological properties, but also the geological systems accessible to the biological receptors of those hazards. Hence, the examples presented in this chapter focus on hydrocarbons with known health and ecological concern in accessible shallow, primarily aquatic, environments.Modern society depends on oil for energy and a variety of other daily needs, with present mineral oil consumption throughout the 1990s exceeding 3×109 t yr-1 (NRC, 2002). In the USA, e.g., ˜40% of energy consumed and 97% of transportation fuels are derived from oil. In the process of extraction, refinement, transport, use, and waste production, a small but environmentally significant fraction of raw oil materials, processed products, and waste are released inadvertently or purposefully into the environment. Because their presence and concentration in the shallow environments are often the result of human activities, these organic materials are generally referred to as "environmental contaminants." Although such reference connotes some form of toxicological or ecological hazard, specific health or ecological effects of many organic "environmental contaminants" remain to be demonstrated. Some are, in fact, likely innocuous at the levels that they are found in many systems, and simply adds to the milieu of biogenic organic compounds that naturally cycle through the shallow environment. Indeed, virtually all compounds in crude oil and processed petroleum products have been introduced naturally to the shallow environments as oil and gas seepage for millions of years ( NRC, 2002). Even high molecular weight (HMW) polyaromatic

  20. Molecular chaperone properties of the high molecular weight aggregate from aged lens

    NASA Technical Reports Server (NTRS)

    Takemoto, L.; Boyle, D.; Spooner, B. S. (Principal Investigator)

    1994-01-01

    The high molecular weight aggregate (HMWA) fraction was isolated from the water soluble proteins of aged bovine lenses. Its composition and ability to inhibit heat-induced denaturation and aggregation were compared with the lower molecular weight, oligomeric fraction of alpha isolated from the same lens. Although the major components of both fractions were the alpha-A and alpha-B chains, the HMWA fraction possessed a decreased ability to protect other proteins against heat-induced denaturation and aggregation. Immunoelectron microscopy of both fractions demonstrated that alpha particles from the HMWA fraction contained increased amounts of beta and gamma crystallins, bound to a central region of the supramolecular complex. Together, these results demonstrate that alpha crystallins found in the HMWA fraction possess a decreased ability to protect against heat-induced denaturation and aggregation, and suggest that at least part of this decrease could be due to the increased presence of beta and gamma crystallins complexed to the putative chaperone receptor site of the alpha particles.

  1. A Transposon Screen Identifies Genetic Determinants of Vibrio cholerae Resistance to High-Molecular-Weight Antibiotics

    PubMed Central

    Delgado, Fernanda; Umans, Benjamin D.; Gerding, Matthew A.; Davis, Brigid M.

    2016-01-01

    Gram-negative bacteria are notoriously resistant to a variety of high-molecular-weight antibiotics due to the limited permeability of their outer membrane (OM). The basis of OM barrier function and the genetic factors required for its maintenance remain incompletely understood. Here, we employed transposon insertion sequencing to identify genes required for Vibrio cholerae resistance to vancomycin and bacitracin, antibiotics that are thought to be too large to efficiently penetrate the OM. The screen yielded several genes whose protein products are predicted to participate in processes important for OM barrier functions and for biofilm formation. In addition, we identified a novel factor, designated vigA (for vancomycin inhibits growth), that has not previously been characterized or linked to outer membrane function. The vigA open reading frame (ORF) codes for an inner membrane protein, and in its absence, cells became highly sensitive to glycopeptide antibiotics (vancomycin and ramoplanin) and bacitracin but not to other large antibiotics or detergents. In contrast to wild-type (WT) cells, the vigA mutant was stained with fluorescent vancomycin. These observations suggest that VigA specifically prevents the periplasmic accumulation of certain large antibiotics without exerting a general role in the maintenance of OM integrity. We also observed marked interspecies variability in the susceptibilities of Gram-negative pathogens to glycopeptides and bacitracin. Collectively, our findings suggest that the OM barrier is not absolute but rather depends on specific OM-antibiotic interactions. PMID:27216069

  2. 21 CFR 172.820 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... the total ethylene and diethylene glycol content of polyethylene glycols having mean molecular weights... and diethylene glycol content of polyethylene glycols having mean molecular weights below 450. Analytical Method ethylene glycol and diethylene glycol content of polyethylene glycols The analytical method...

  3. Molecular Weight of Deoxyribonucleic Acid Synthesized During Initiation of Chromosome Replication in Escherichia coli

    PubMed Central

    Kuempel, Peter L.

    1972-01-01

    Alkaline sucrose gradients were used to study the molecular weight of deoxyribonucleic acid (DNA) synthesized during the initiation of chromosome replication in Escherichia coli 15 TAU-bar. The experiments were conducted to determine whether newly synthesized, replication origin DNA is attached to higher-molecular-weight parental DNA. Little of the DNA synthesized after readdition of required amino acids to cells previously deprived of the amino acids was present in DNA with a molecular weight comparable to that of the parental DNA. The newly synthesized, low-molecular-weight DNA rapidly appeared in higher-molecular-weight material, but there was an upper limit to the size of this intermediate-molecular-weight DNA. This limit was not observed when exponentially growing cells converted newly synthesized DNA to higher-molecular-weight material. The size of the intermediate-molecular-weight DNA was related to the age of the replication forks, and the size increased as the replication forks moved further from the replication origin. The results indicate that the newly synthesized replication origin DNA is not attached to parental DNA, but it is rapidly attached to the growing strands that extend from the replication fork to the replication origin, or to the other replication fork if replication is bidirectional. Experiments are reported which demonstrate that the DNA investigated was from the vicinity of the replication origin and was not plasmid DNA or DNA from random positions on the chromosome. PMID:4562387

  4. Formation of high molecular weight products from benzene during boundary lubrication

    NASA Technical Reports Server (NTRS)

    Morales, W.

    1985-01-01

    High molecular weight products were detected on the wear track of an iron disk at the end of a sliding friction and wear test using benzene as a lubricant. Size exclusion chromagography in conjunction with UV analysis gave evidence that the high molecular weight products are polyphenyl ether type substances. Organic electrochemistry was used to elucidate the possible surface reaction mechanisms.

  5. Molecular Weight Determination by an Improved Temperature-Monitored Vapor-Density Method.

    ERIC Educational Resources Information Center

    Grider, Douglas J.; And Others

    1988-01-01

    Recommends determining molecular weights of liquids by use of a thermocouple. Utilizing a mathematical gas equation, the molecular weight can be determined from the measurement of the vapor temperature upon complete evaporation. Lists benefits as reduced time and cost, and improved safety factors. (ML)

  6. A Simple, Inexpensive Molecular Weight Measurement for Water-Soluble Polymers Using Microemulsions.

    ERIC Educational Resources Information Center

    Mathias, Lon J.; Moore, D. Roger

    1985-01-01

    Describes an experiment involving use of a microemulsion and its characteristic thermal phase change to determine molecular weights of polyoxyethylene samples. The experiment provides students with background information on polymers and organized media and with experience in evaluating polymer molecular weight by using a unique property of a…

  7. Effects of Hofmeister Anions on the LCST of PNIPAM as a Function of Molecular Weight

    PubMed Central

    Zhang, Yanjie; Furyk, Steven; Sagle, Laura B.; Cho, Younhee; Bergbreiter, David E.; Cremer, Paul S.

    2008-01-01

    The effect of a series of sodium salts on the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide), PNIPAM, was investigated as a function of molecular weight and polymer concentration with a temperature gradient microfluidic device under a dark-field microscope. In solutions containing sufficient concentrations of kosmotropic anions, the phase transition of PNIPAM was resolved into two separate steps for higher molecular weight samples. The first step of this two step transition was found to be sensitive to the polymer’s molecular weight and solution concentration, while the second step was not. Moreover, the binding of chaotropic anions to the polymer was also influenced by molecular weight. Both sets of results could be explained by the formation of intramolecular and intermolecular hydrogen-bonding between polymer chains. By contrast, the hydrophobic hydration of the isopropyl moieties and polymer backbone was found to be unaffected by either the polymer’s molecular weight or solution concentration. PMID:18820735

  8. Low molecular weight carboxylic acids in oxidizing porphyry copper tailings.

    PubMed

    Dold, Bernhard; Blowes, David W; Dickhout, Ralph; Spangenberg, Jorge E; Pfeifer, Hans-Rudolf

    2005-04-15

    The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(III) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances

  9. Bioremediation of Mixtures of High Molecular Weight Polycyclic Aromatic Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Xu, H.; Wu, J.; Shi, X.; Sun, Y.

    2014-12-01

    Although bioremediation has been considered as one of the most promising means to remove polycyclic aromatic hydrocarbons (PAHs) from polluted environments, the efficacy of PAHs bioremediation still remains challenged, especially for high molecular weight PAHs (HMW PAHs) and their mixtures. This study was focused on (a) isolation and characterization of pure strain and mixed microbial communities able to degrade HMW PAHs and (b) further evaluation of the ability of the isolated microbes to degrade HMW PAHs mixtures in the absence and presence of indigenous flora. Fluoranthene, benzo[b]fluoranthene and pyrene were selected as the representative HMW PAHs in this study. A pure bacterial strain, identified as Herbaspirillum chlorophenolicum FA1, was isolated from activated sludge. A mixed bacterial community designated as consortium-4 was isolated from petroleum contaminated soils, containing Pseudomonas sp. FbP1、Enterobacter sp. FbP2、Hydrogenophaga sp. FbP3 and Luteolibacter pohnpeiensis. FbP4. To our knowledge, this is the first study to demonstrate that bacterial strains of Herbaspirillum chlorophenolicum FA1 and Luteolibacter pohnpeiensis. FbP4 can also degrade fluoranthene, benzo[b]fluoranthene and pyrene. Experiment results showed that both strain FA1 and consortium-4 could degrade fluoranthene, benzo[b]fluoranthene and pyrene within a wide range of temperature, pH and initial PAHs concentration. Degradation of HMW PAHs mixtures (binary and ternary) demonstrated the interactive effects that can alter the rate and extent of biodegradation within a mixture. The presence of indigenous flora was found to either increase or decrease the degradation of HMW PAHs, suggesting possible synergistic or competition effects. Biodegradation kinetics of HMW PAHs for sole substrates, binary and ternary systems was evaluated, with the purpose to better characterize and compare the biodegradation process of individual HMW PAH and mixtures of HMW PAHs. Results of this study

  10. Lunch-time food choices in preschoolers: relationships between absolute and relative intake of different food categories, and appetitive characteristics and weight

    PubMed Central

    Carnell, S; Pryor, K; Mais, LA; Warkentin, S; Benson, L; Cheng, R

    2016-01-01

    Children’s appetitive characteristics measured by parent-report questionnaires are reliably associated with body weight, as well as behavioral tests of appetite, but relatively little is known about relationships with food choice. As part of a larger preloading study, we served 4-5y olds from primary school classes five school lunches at which they were presented with the same standardized multi-item meal. Parents completed Child Eating Behavior Questionnaire (CEBQ) sub-scales assessing satiety responsiveness (CEBQ-SR), food responsiveness (CEBQ-FR) and enjoyment of food (CEBQ-EF), and children were weighed and measured. Despite differing preload conditions, children showed remarkable consistency of intake patterns across all five meals with day-to-day intra-class correlations in absolute and percentage intake of each food category ranging from .78 to .91. Higher CEBQ-SR was associated with lower mean intake of all food categories across all five meals, with the weakest association apparent for snack foods. Higher CEBQ-FR was associated with higher intake of white bread and fruits and vegetables, and higher CEBQ-EF was associated with greater intake of all categories, with the strongest association apparent for white bread. Analyses of intake of each food group as a percentage of total intake, treated here as an index of the child’s choice to consume relatively more or relatively less of each different food category when composing their total lunch-time meal, further suggested that children who were higher in CEBQ-SR ate relatively more snack foods and relatively less fruits and vegetables, while children with higher CEBQ-EF ate relatively less snack foods and relatively more white bread. Higher absolute intakes of white bread and snack foods were associated with higher BMI z score. CEBQ sub-scale associations with food intake variables were largely unchanged by controlling for daily metabolic needs. However, descriptive comparisons of lunch intakes with

  11. Lunch-time food choices in preschoolers: Relationships between absolute and relative intakes of different food categories, and appetitive characteristics and weight.

    PubMed

    Carnell, S; Pryor, K; Mais, L A; Warkentin, S; Benson, L; Cheng, R

    2016-08-01

    Children's appetitive characteristics measured by parent-report questionnaires are reliably associated with body weight, as well as behavioral tests of appetite, but relatively little is known about relationships with food choice. As part of a larger preloading study, we served 4-5year olds from primary school classes five school lunches at which they were presented with the same standardized multi-item meal. Parents completed Child Eating Behavior Questionnaire (CEBQ) sub-scales assessing satiety responsiveness (CEBQ-SR), food responsiveness (CEBQ-FR) and enjoyment of food (CEBQ-EF), and children were weighed and measured. Despite differing preload conditions, children showed remarkable consistency of intake patterns across all five meals with day-to-day intra-class correlations in absolute and percentage intake of each food category ranging from 0.78 to 0.91. Higher CEBQ-SR was associated with lower mean intake of all food categories across all five meals, with the weakest association apparent for snack foods. Higher CEBQ-FR was associated with higher intake of white bread and fruits and vegetables, and higher CEBQ-EF was associated with greater intake of all categories, with the strongest association apparent for white bread. Analyses of intake of each food group as a percentage of total intake, treated here as an index of the child's choice to consume relatively more or relatively less of each different food category when composing their total lunch-time meal, further suggested that children who were higher in CEBQ-SR ate relatively more snack foods and relatively less fruits and vegetables, while children with higher CEBQ-EF ate relatively less snack foods and relatively more white bread. Higher absolute intakes of white bread and snack foods were associated with higher BMI z score. CEBQ sub-scale associations with food intake variables were largely unchanged by controlling for daily metabolic needs. However, descriptive comparisons of lunch intakes with

  12. Isolation of a thermophilic bacterium capable of low-molecular-weight polyethylene degradation.

    PubMed

    Jeon, Hyun Jeong; Kim, Mal Nam

    2013-02-01

    A thermophilic bacterium capable of low-molecular-weight polyethylene (LMWPE) degradation was isolated from a compost sample, and was identified as Chelatococcus sp. E1, through sequencing of the 16S rRNA gene. LMWPE was prepared by thermal degradation of commercial PE in a strict nitrogen atmosphere. LMWPE with a weight-average-molecular-weight (Mw) in the range of 1,700-23,700 was noticeably mineralized into CO(2) by the bacterium. The biodegradability of LMWPE decreased as the Mw increased. The low molecular weight fraction of LMWPE decreased significantly as a result of the degradation process, and thereby both the number-average-molecular-weight and Mw increased after biodegradation. The polydispersity of LMWPE was either narrowed or widened, depending on the initial Mw of LMWPE, due to the preferential elimination of the low molecular weight fraction, in comparison to the high molecular weight portion. LMWPE free from an extremely low molecular weight fraction was also mineralized by the strain at a remarkable rate, and FTIR peaks assignable to C-O stretching appeared as a result of microbial action. The FTIR peaks corresponding to alkenes also became more intense, indicating that dehydrogenations occurred concomitantly with microbial induced oxidation.

  13. Enzymatic and acidic degradation of high molecular weight dextran into low molecular weight and its characterizations using novel Diffusion-ordered NMR spectroscopy.

    PubMed

    Iqbal, Samina; Marchetti, Roberta; Aman, Afsheen; Silipo, Alba; Qader, Shah Ali Ul; Molinaro, Antonio

    2017-10-01

    Low molecular weight fractions were derived from native high molecular weight dextran produced by Leuconostoc mesenteroides KIBGE-IB26. Structural characterization of native and low molecular weight fractions obtained after acidic and enzymatic hydrolysis was done using FTIR and NMR spectroscopy. The molecular weight was estimated using Diffusion Ordered NMR spectroscopy. Native dextran (892kDa) is composed of α-(1→6) glycosidic linkage along with α-(1→3) branching. Major proportion of 528kDa dextran was obtained after prolong enzymatic hydrolysis however, an effective acidic treatment at pH-1.4 up to 02 and 04h of exposure resulted in the formation of 77kDa and 57kDa, respectively. The increment in pH from 1.4 to 1.8 lowered the hydrolysis efficiency and resulted in the formation of 270kDa dextran fraction. The results suggest that derived low molecular weight water soluble fractions can be utilized as a drug delivery carrier along with multiple application relating pharmaceutical industries. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Molecular dynamics simulations on the interactions of low molecular weight natural organic acids with C60.

    PubMed

    Sun, Qian; Xie, Hong-Bin; Chen, Jingwen; Li, Xuehua; Wang, Zhuang; Sheng, Lianxi

    2013-07-01

    As an important part of dissolved organic matter (DOM), low molecular weight organic acids (LOAs) may play a key role in the process for DOM stabilizing carbon nanomaterials (e.g. C60) suspensions in aquatic environment. In addition, both LOAs and C60 have been detected in the troposphere and therefore have a chance to interact with each other in the gaseous phase. However, the mechanism for LOAs-C60 interactions and their environmental implications need further investigations. In this study, molecular dynamics (MD) simulation was employed to investigate the interactions between both neutral and ionic LOAs with C60 in vacuum and water. The results showed that the adsorptions of all LOAs on C60 in energy are favorable, and the aromatic acids have stronger interactions with C60 than the aliphatic acids in vacuum and water. The interaction energies (Eint) of the LOA anions with C60 were weaker than those of their corresponding neutral LOA molecules. The models were also developed to predict and interpret Eint based on the results from MD simulations. Dispersion, induction and hydrophobic interactions were found to be the dominating factor in Eint. These findings indicate that cost-efficient MD simulation can be employed as an important tool to predict the adsorption behavior of LOAs on carbon nanomaterials. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

    PubMed

    Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

    2017-03-15

    Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. Molecular weight kinetics and chain scission models for dextran polymers during ultrasonic degradation.

    PubMed

    Pu, Yuanyuan; Zou, Qingsong; Hou, Dianzhi; Zhang, Yiping; Chen, Shan

    2017-01-20

    Ultrasonic degradation of six dextran samples with different initial molecular weights (IMW) has been performed to investigate the degradation behavior and chain scission mechanism of dextrans. The weight-average molecular weight (Mw) and polydispersity index (D value) were monitored by High Performance Gel Permeation Chromatography (HPGPC). Results showed that Mw and D value decreased with increasing ultrasonic time, resulting in a more homologous dextran solution with lower molecular weight. A significant degradation occurred in dextrans with higher IMW, particularly at the initial stage of the ultrasonic treatment. The Malhotra model was found to well describe the molecular weight kinetics for all dextran samples. Experimental data was fitted into two chain scission models to study dextran chain scission mechanism and the model performance was compared. Results indicated that the midpoint scission model agreed well with experimental results, with a linear regression factor of R 2 >0.99. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. How Does the Preparation of Rye Porridge Affect Molecular Weight Distribution of Extractable Dietary Fibers?

    PubMed Central

    Rakha, Allah; Åman, Per; Andersson, Roger

    2011-01-01

    Extractable dietary fiber (DF) plays an important role in nutrition. This study on porridge making with whole grain rye investigated the effect of rest time of flour slurries at room temperature before cooking and amount of flour and salt in the recipe on the content of DF components and molecular weight distribution of extractable fructan, mixed linkage (1→3)(1→4)-β-d-glucan (β-glucan) and arabinoxylan (AX) in the porridge. The content of total DF was increased (from about 20% to 23% of dry matter) during porridge making due to formation of insoluble resistant starch. A small but significant increase in the extractability of β-glucan (P = 0.016) and AX (P = 0.002) due to rest time was also noted. The molecular weight of extractable fructan and AX remained stable during porridge making. However, incubation of the rye flour slurries at increased temperature resulted in a significant decrease in extractable AX molecular weight. The molecular weight of extractable β-glucan decreased greatly during a rest time before cooking, most likely by the action of endogenous enzymes. The amount of salt and flour used in the recipe had small but significant effects on the molecular weight of β-glucan. These results show that whole grain rye porridge made without a rest time before cooking contains extractable DF components maintaining high molecular weights. High molecular weight is most likely of nutritional importance. PMID:21686191

  18. How does the preparation of rye porridge affect molecular weight distribution of extractable dietary fibers?

    PubMed

    Rakha, Allah; Aman, Per; Andersson, Roger

    2011-01-01

    Extractable dietary fiber (DF) plays an important role in nutrition. This study on porridge making with whole grain rye investigated the effect of rest time of flour slurries at room temperature before cooking and amount of flour and salt in the recipe on the content of DF components and molecular weight distribution of extractable fructan, mixed linkage (1→3)(1→4)-β-d-glucan (β-glucan) and arabinoxylan (AX) in the porridge. The content of total DF was increased (from about 20% to 23% of dry matter) during porridge making due to formation of insoluble resistant starch. A small but significant increase in the extractability of β-glucan (P = 0.016) and AX (P = 0.002) due to rest time was also noted. The molecular weight of extractable fructan and AX remained stable during porridge making. However, incubation of the rye flour slurries at increased temperature resulted in a significant decrease in extractable AX molecular weight. The molecular weight of extractable β-glucan decreased greatly during a rest time before cooking, most likely by the action of endogenous enzymes. The amount of salt and flour used in the recipe had small but significant effects on the molecular weight of β-glucan. These results show that whole grain rye porridge made without a rest time before cooking contains extractable DF components maintaining high molecular weights. High molecular weight is most likely of nutritional importance.

  19. Effect of molecular weight profile of sorghum proanthocyanidins on resistant starch formation.

    PubMed

    Barros, Frederico; Awika, Joseph; Rooney, Lloyd W

    2014-04-01

    There is a growing interest to increase resistant starch (RS) in foods through natural modification of starch. Sorghum tannins (proanthocyanidins, PAs) were recently reported to interact with starch, increasing RS. However, there is no information about how the molecular weight profile of PAs affects RS formation. This study investigated how different-molecular-weight PAs from sorghum affected RS formation in different starch models. The levels of RS were higher (331-437 mg g(-1)) when high-amylose starch was cooked with phenolic extracts containing mostly high-molecular-weight PAs compared with extracts containing lower-molecular-weight PAs or monomeric catechin (249-285 mg g(-1)). In general, binding capacity of PAs with amylose increased proportionally with molecular weight. For example, the percentage of PAs bound to amylose increased from 45% (PAs with degree of polymerization (DP) = 6) to 94% (polymeric PAs, DP > 10). The results demonstrate that molecular weight of the PAs directly affects their interaction with starch: the higher the molecular weight, the stronger the binding to amylose and the higher the RS formation. Polymeric PAs from sorghum can naturally modify starch by interacting strongly with amylose and are thus most suitable to produce foods with higher RS. © 2013 Society of Chemical Industry.

  20. Immunostimulative Activity of Low Molecular Weight Chitosans in RAW264.7 Macrophages

    PubMed Central

    Wu, Ning; Wen, Zheng-Shun; Xiang, Xing-Wei; Huang, Yan-Na; Gao, Yang; Qu, You-Le

    2015-01-01

    Chitosan and its derivatives such as low molecular weight chitosans (LMWCs) have been reported to exert many biological activities, such as antioxidant and antitumor effects. However, complex and molecular weight dependent effects of chitosan remain controversial and the mechanisms that mediate these complex effects are still poorly defined. This study was carried out to investigate the immunostimulative effect of different molecular weight chitosan in RAW264.7 macrophages. Our data suggested that two LMWCs (molecular weight of 3 kDa and 50 kDa) both possessed immunostimulative activity, which was dependent on dose and, at the higher doses, also on the molecular weight. LMWCs could significantly enhance the the pinocytic activity, and induce the production of tumor necrosis factor α (TNF-α), interleukin 6 (IL-6), interferon-γ (IFN-γ), nitric oxide (NO) and inducible nitric oxide synthase (iNOS) in a molecular weight and concentration-dependent manner. LMWCs were further showed to promote the expression of the genes including iNOS, TNF-α. Taken together, our findings suggested that LMWCs elicited significantly immunomodulatory response through up-regulating mRNA expression of proinflammatory cytokines and activated RAW264.7 macrophage in a molecular weight- and concentration-dependent manner. PMID:26437419

  1. Perchlorate-induced combustion of organic matter with variable molecular weights: Implications for Mars missions

    NASA Astrophysics Data System (ADS)

    Sephton, Mark A.; Lewis, James M. T.; Watson, Jonathan S.; Montgomery, Wren; Garnier, Carole

    2014-11-01

    Instruments on the Viking landers and Curiosity rover analyzed samples of Mars and detected carbon dioxide and organic compounds of uncertain origin. Mineral-assisted reactions are leading to uncertainty, particularly those involving perchlorate minerals which thermally decompose to produce chlorine and oxygen which can then react with organic matter to generate organochlorine compounds and carbon dioxide. Although generally considered a problem for interpretation, the release profiles of generated gases can indicate the type of organic matter present. We have performed a set of experiments with perchlorate and organic matter of variable molecular weights. Results indicate that organic susceptibility to thermal degradation and mineral-assisted reactions is related to molecular weight. Low molecular weight organic matter reacts at lower temperatures than its high molecular weight counterparts. The natural occurrence and association of organic matter with differing molecular weights helps to discriminate between contamination (usually low molecular weight organic matter only) and indigenous carbon (commonly low and high molecular weight organic matter together). Our results can be used to provide insights into data returning from Mars.

  2. Temperature and molecular-weight dependences of acoustic behaviors of polystyrene studied using Brillouin spectroscopy

    NASA Astrophysics Data System (ADS)

    Oh, Soo Han; Lee, Byoung Wan; Ko, Jae-Hyeon; Lee, Hyeonju; Park, Jaehoon; Ko, Young Ho; Kim, Kwang Joo

    2017-04-01

    The acoustic properties of three polystyrene polymers with different molecular weights were investigated as a function of temperature by using Brillouin light scattering. The longitudinal sound velocity showed a change in the slope, which depended on the molecular weight, at the glass transition temperature. The absorption coefficient exhibited a maximum above the glass transition temperature, and the maximum temperature became higher as the molecular weight was increased. Comparison with previous acoustic studies on polystyrene indicate that a substantial frequency dispersion caused by strong coupling between the longitudinal acoustic waves and the segmental motions exists in the high-temperature range.

  3. Isolation and Characterization of a Toxic Moiety of Low Molecular Weight from Clostridium botulinum Type A

    PubMed Central

    Gerwing, Julia; Dolman, Claude E.; Bains, Hardial S.

    1965-01-01

    Gerwing, Julia (The University of British Columbia, Vancouver, B.C., Canada), Claude E. Dolman, and Hardial S. Bains. Isolation and characterization of a toxic moiety of low molecular weight from Clostridium botulinum type A. J. Bacteriol. 89:1383–1386. 1965.—A toxic moiety of low molecular weight has been isolated from a type A strain of Clostridium botulinum, by a method involving ammonium sulfate precipitation and elution through diethylaminoethyl cellulose at pH 5.6. By means of electrophoresis and ultracentrifugation, the toxic substance was shown to be homogeneous; a molecular weight of 12,200 was calculated. Images PMID:14293025

  4. Origin of change in molecular-weight dependence for polymer surface tension.

    PubMed

    Thompson, R B; Macdonald, J R; Chen, P

    2008-09-01

    Self-consistent-field theory is used to reproduce the behavior of polymer surface tension with molecular-weight for both lower and higher molecular-weight polymers. The change in behavior of the surface tension between these two regimes is shown to be due to the almost total exclusion of polymer from the nonpolymer bulk phase. The predicted two regime surface tension behavior with molecular-weight and the exclusion explanation are shown to be valid for a range of different polymer compressibilities.

  5. Effect of sterilization irradiation on friction and wear of ultrahigh-molecular-weight polyethylene

    NASA Technical Reports Server (NTRS)

    Jones, W. R., Jr.; Hady, W. F.; Crugnola, A.

    1979-01-01

    The effect of sterilization gamma irradiation on the friction and wear properties of ultrahigh molecular weight polyethylene (UHMWPE) sliding against 316L stainless steel in dry air at 23 C was determined. A pin-on-disk apparatus was used. Experimental conditions included a 1-kilogram load, a 0.061- to 0.27-meter-per-second sliding velocity, and a 32000- to 578000-meter sliding distance. Although sterilization doses of 2.5 and 5.0 megarads greatly altered the average molecular weight and the molecular weight distribution, the friction and wear properties of the polymer were not significantly changed.

  6. Effect of PEO molecular weight on the miscibility and dynamics in epoxy/PEO blends.

    PubMed

    Lu, Shoudong; Zhang, Rongchun; Wang, Xiaoliang; Sun, Pingchuan; Lv, Weifeng; Liu, Qingjie; Jia, Ninghong

    2015-11-01

    In this work, the effect of poly(ethylene oxide) (PEO) molecular weight in blends of epoxy (ER) and PEO on the miscibility, inter-chain weak interactions and local dynamics were systematically investigated by multi-frequency temperature modulation DSC and solid-state NMR techniques. We found that the molecular weight (M(w)) of PEO was a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interactions between PEO and ER. A critical PEO molecular weight (M(crit)) around 4.5k was found. PEO was well miscible with ER when the molecular weight was below M(crit), where the chain motion of PEO was restricted due to strong inter-chain hydrogen bonding interactions. However, for the blends with high molecular weight PEO (M(w) > M(crit)), the miscibility between PEO and ER was poor, and most of PEO chains were considerably mobile. Finally, polarization inversion spin exchange at magic angle (PISEMA) solid-state NMR experiment further revealed the different mobility of the PEO in ER/PEO blends with different molecular weight of PEO at molecular level. Based on the DSC and NMR results, a tentative model was proposed to illustrate the miscibility in ER/PEO blends.

  7. Modeling the relationship between body weight and energy intake: A molecular diffusion-based approach

    PubMed Central

    2012-01-01

    Background Body weight is at least partly controlled by the choices made by a human in response to external stimuli. Changes in body weight are mainly caused by energy intake. By analyzing the mechanisms involved in food intake, we considered that molecular diffusion plays an important role in body weight changes. We propose a model based on Fick's second law of diffusion to simulate the relationship between energy intake and body weight. Results This model was applied to food intake and body weight data recorded in humans; the model showed a good fit to the experimental data. This model was also effective in predicting future body weight. Conclusions In conclusion, this model based on molecular diffusion provides a new insight into the body weight mechanisms. Reviewers This article was reviewed by Dr. Cabral Balreira (nominated by Dr. Peter Olofsson), Prof. Yang Kuang and Dr. Chao Chen. PMID:22742862

  8. Enrichment of low-molecular-weight proteins from biofluids for biomarker discovery.

    PubMed

    Chertov, Oleg; Simpson, John T; Biragyn, Arya; Conrads, Thomas P; Veenstra, Timothy D; Fisher, Robert J

    2005-01-01

    The dramatic progress in mass spectrometry-based methods of protein identification has triggered a new quest for disease-associated biomarkers. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and its variant surface-enhanced laser desorption/ionization mass spectrometry, provide effective means to explore the less studied information slice of the human serum proteome -- low-molecular-weight proteins and peptides. These low-molecular-weight proteins and peptides are promising for the detection of important biomarkers. Due to the significant experimental problems imposed by high-abundance and high-molecular-weight proteins, it is important to effectively remove these species prior to mass spectrometry analysis of the low-molecular-weight serum and plasma proteomes. In this review, the advantages afforded by recently introduced methods for prefractionation of serum, as they pertain to the detection and identification of biomarkers, will be discussed.

  9. Fluorescence spectroscopy and molecular weight distribution of extracellular polymers from full-scale activated sludge biomass.

    PubMed

    Esparza-Soto, M; Westerhoff, P K

    2001-01-01

    Two fractions of extracellular polymer substances (EPSs), soluble and readily extractable (RE), were characterised in terms of their molecular weight distributions (MWD) and 3-D excitation-emission-matrix (EEM) fluorescence spectroscopy signatures. The EPS fractions were different: the soluble EPSs were composed mainly of high molecular weight compounds, while the RE EPSs were composed of small molecular weight compounds. Contrary to previous thought, EPS may not be considered only as macromolecular because most organic matter present in both fractions had low molecular weight. Three different fluorophore peaks were identified in the EEM fluorescence spectra. Two peaks were attributed to protein-like fluorophores, and the third to a humic-like fluorophore. Fluorescence signatures were different from other previously published signatures for marine and riverine environments. EEM spectroscopy proved to be a suitable method that may be used to characterise and trace organic matter of bacterial origin in wastewater treatment operations.

  10. Manipulation of Molecular Weight Distribution Shape as a New Strategy to Control Processing Parameters.

    PubMed

    Nadgorny, Milena; Gentekos, Dillon T; Xiao, Zeyun; Singleton, S Parker; Fors, Brett P; Connal, Luke A

    2017-10-01

    Molecular weight and dispersity (Ð) influence physical and rheological properties of polymers, which are of significant importance in polymer processing technologies. However, these parameters provide only partial information about the precise composition of polymers, which is reflected by the shape and symmetry of molecular weight distribution (MWD). In this work, the effect of MWD symmetry on thermal and rheological properties of polymers with identical molecular weights and Ð is demonstrated. Remarkably, when the MWD is skewed to higher molecular weight, a higher glass transition temperature (T g ), increased stiffness, increased thermal stability, and higher apparent viscosities are observed. These observed differences are attributed to the chain length composition of the polymers, easily controlled by the synthetic strategy. This work demonstrates a versatile approach to engineer the properties of polymers using controlled synthesis to skew the shape of MWD. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. EPDM polymers with intermolecular asymmetrical molecular weight, crystallinity and diene distribution

    SciTech Connect

    Datta, S.; Cheremishinoff, N.P.; Kresge, E.N.

    1993-12-31

    Rapid extrusion of EPDM elastomers require low viscosity and thus low molecular weights for the polymer. Efficient vulcanization of these elastomers requires network perfection and thus high molecular weights for the polymer. The benefits of these apparently mutually exclusive goals is important in uses of EPDM elastomers which require extrusion of profiles which are later cured. This paper shows that by introducing simultaneously asymmetry in the distribution of molecular weights, crystallinity and vulcanizable sites these apparently contradictory goals can be resolved. While these polymers cannot be made from a single Ziegler polymerization catalyst, the authors show the synthesis of thesemore » model EPDM polymers by blending polymers with very different molecular weights, ethylene and ENB contents. These blends can be rapidly extruded without melt fracture and can be cured to vulcanizates which have excellent tensile properties.« less

  12. Absolute Intra-Molecular Distance Measurements with Ångström-Resolution using Anomalous Small-Angle X-ray Scattering

    DOE PAGES

    Zettl, Thomas; Mathew, Rebecca S.; Seifert, Sönke; ...

    2016-05-31

    Accurate determination of molecular distances is fundamental to understanding the structure, dynamics, and conformational ensembles of biological macromolecules. Here we present a method to determine the full,distance,distribution between small (~7 Å) gold labels attached to macromolecules with very high-precision(≤1 Å) and on an absolute distance scale. Our method uses anomalous small-angle X-ray scattering close to a gold absorption edge to separate the gold-gold interference pattern from other scattering contributions. Results for 10-30 bp DNA constructs achieve excellent signal-to-noise and are in good agreement with previous results obtained by single-energy,SAXS measurements without requiring the preparation and measurement of single labeled andmore » unlabeled samples. Finally, the use of small gold labels in combination with ASAXS read out provides an attractive approach to determining molecular distance distributions that will be applicable to a broad range of macromolecular systems.« less

  13. [Intensive care of children with DIC syndrome based on the use of low molecular weight heparins].

    PubMed

    Chuprova, A V; Shmakov, A N; Solov'ev, O N; Anokhina, T Iu; Loskutova, S A; Pinegina, Iu S

    2002-01-01

    The first section of this paper presents data on low-molecular-weight heparins: pharmacokinetics and pharmacodynamics, advantages in comparison with common heparin. The second section presents the results of fraxiparin and clivarin use in 43 children aged 9 months to 14 years with acute/subacute DIC syndrome of infectious origin. Therapeutic and maintenance doses, the mode of injection of low-molecular-weight heparins, and methods for laboratory monitoring of their efficiency and safety are presented.

  14. Synthesis and Structural Characterization of New Light Molecular Weight Inorganic Oxidizers and Related Derivatives. Volume: 2

    DTIC Science & Technology

    1993-02-01

    of the strong inductive effect of the five fluorine ligands attached to the tellurium atom. 34 It is prepared under anhydrous conditions according to...MOLECULAR WEIGHT INORGANIC OXIDIZERS AND RELATED DERIVATIVES. VOLUME: II Professor G. J. Schrobilgen McMaster University Department of Chemistry...C: F04611-91-K-0004 Molecular Weight Inorganic Oxidizers and Relative PE: 62302F SDerivatives: Volume II 1PR: 5730 6. AUTHOFR(S) TA: 0*( C

  15. Should Low Molecular Weight PSMA Targeted Ligands Get Bigger and Use Albumin Ligands for PSMA Targeting?

    PubMed

    Huang, Steve S; Heston, Warren D W

    2017-01-01

    Prostate Specific Membrane Antigen (PSMA) is strongly expressed in prostate cancer. Recently a number of low-molecular-weight inhibitors have demonstrated excellent PSMA targeting activity for both imaging as well as Lutecium-177 radiotherapy in human trials. The paper by Choy et al raises the question of whether we can further increase the effectiveness of PSMA targeted therapy by adding an albumin-binding entity to low-molecular-weight agents.

  16. High and low molecular weight hyaluronic acid differentially influence macrophage activation

    PubMed Central

    Rayahin, Jamie E.; Buhrman, Jason S.; Zhang, Yu; Koh, Timothy J.; Gemeinhart, Richard A.

    2015-01-01

    Macrophages exhibit phenotypic diversity permitting wide-ranging roles in maintaining physiologic homeostasis. Hyaluronic acid, a major glycosaminoglycan of the extracellular matrix, has been shown to have differential signaling based on its molecular weight. With this in mind, the main objective of this study was to elucidate the role of hyaluronic acid molecular weight on macrophage activation and reprogramming. Changes in macrophage activation were assessed by activation state selective marker measurement, specifically quantitative real time polymerase chain reaction, and cytokine enzyme-linked immunoassays, after macrophage treatment with differing molecular weights of hyaluronic acid under four conditions: the resting state, concurrent with classical activation, and following inflammation involving either classically or alternatively activated macrophages. Regardless of initial polarization state, low molecular weight hyaluronic acid induced a classically activated-like state, confirmed by up-regulation of pro-inflammatory genes, including nos2, tnf, il12b, and cd80, and enhanced secretion of nitric oxide and TNF-α. High molecular weight hyaluronic acid promoted an alternatively activated-like state, confirmed by up regulation of pro-resolving gene transcription, including arg1, il10, and mrc1, and enhanced arginase activity. Overall, our observations suggest that macrophages undergo phenotypic changes dependent on molecular weight of hyaluronan that correspond to either (1) pro-inflammatory response for low molecular weight HA or (2) pro-resolving response for high molecular weight HA. These observations bring significant further understanding of the influence of extracellular matrix polymers, hyaluronic acid in particular, on regulating the inflammatory response of macrophages. This knowledge can be used to guide the design of HA-containing biomaterials to better utilize the natural response to HAs. PMID:26280020

  17. [The low-molecular weight antioxidants of microorganisms].

    PubMed

    Skorokhod, I O; Kurdysh, I K

    2014-01-01

    Support of optimum redox-homeostasis in the cells of microorganisms plays a substantial role in the processes of DNA synthesis, respiration, providing of immune and protective reactions, activity of enzymes, etc. The changes of the redox-status can be accompanied by the increase of the level of reactive oxygen species (ROS) which predetermine the damage of biologically active molecules. Adjusting of ROS concentrations is a very important process in development of microorganisms. Low-molecular antioxidants are effective inhibitors of free-radical processes. The authors of the review present the description of oxidants and consider the ways of origin and consequences of their influence on the living cells. An accent is done on phenomenological description of low-molecular antioxidants. The basic mechanisms of their action are considered. Special attention is given to the question of synergism between these protectors. The detailed study of mechanisms of functioning of low-molecular antioxidants in the cells of microorganisms will allow using these living objects in different spheres of human activity.

  18. Ultrarapid electrophoretic transfer of high and low molecular weight proteins using heat.

    PubMed

    Kurien, Biji T; Scofield, R Hal

    2009-01-01

    An ultrarapid method for the electrophoretic transfer of high and low molecular weight proteins to nitrocellulose membranes following sodium dodecyl sulfate (SDS) polyacrylamide gel is described here. The transfer was performed with heated (70-75 degrees C) normal transfer buffer from which methanol had been omitted. Complete transfer of high and low molecular weight antigens (molecular weight protein standards, a purified protein, and proteins from a human tissue extract) could be carried out in 10 min for a 7% (0.75 mm) SDS polyacrylamide gel. For 10 and 12.5% gels (0.75 mm) the corresponding time was 15 min. A complete transfer could be carried out in 20 min for 7, 10, and 12.5% gels (1.5 mm gels). The permeability of the gel is increased by heat, such that the proteins trapped in the polyacrylamide gel matrix can be easily transferred to the membrane. The heat mediated transfer method was compared with a conventional transfer protocol, under similar conditions. The conventional method transferred minimal low molecular weight proteins while retaining most of the high molecular weight proteins in the gel. In summary, this procedure is particularly useful for the transfer of high molecular weight proteins, very rapid, and avoids the use of methanol.

  19. Western blotting of high and low molecular weight proteins using heat.

    PubMed

    Kurien, Biji T; Scofield, R Hal

    2015-01-01

    A method for the electrophoretic transfer of high and low molecular weight proteins to nitrocellulose membranes following sodium dodecyl sulfate (SDS) polyacrylamide gel is described here. The transfer was performed with heated (70-75 °C) normal transfer buffer from which methanol had been omitted. Complete transfer of high and low molecular weight antigens (molecular weight protein standards, a purified protein, and proteins from a human tissue extract) could be carried out in 10 min for a 7 % (0.75 mm) SDS polyacrylamide gel. For 10 and 12.5 % gels (0.75 mm) the corresponding time was 15 min. A complete transfer could be carried out in 20 min for 7, 10, and 12.5 % gels (1.5 mm gels). The permeability of the gel is increased by heat, such that the proteins trapped in the polyacrylamide gel matrix can be easily transferred to the membrane. The heat mediated transfer method was compared with a conventional transfer protocol, under similar conditions. The conventional method transferred minimal low molecular weight proteins while retaining most of the high molecular weight proteins in the gel. In summary, this procedure is particularly useful for the transfer of high molecular weight proteins, very rapid, and avoids the use of methanol.

  20. Occurrence of a multimeric high-molecular-weight glyceraldehyde-3-phosphate dehydrogenase in human serum.

    PubMed

    Kunjithapatham, Rani; Geschwind, Jean-Francois; Devine, Lauren; Boronina, Tatiana N; O'Meally, Robert N; Cole, Robert N; Torbenson, Michael S; Ganapathy-Kanniappan, Shanmugasundaram

    2015-04-03

    Cellular glyceraldehyde-3-phosphate dehydrogenase (GAPDH) is a phylogenetically conserved, ubiquitous enzyme that plays an indispensable role in energy metabolism. Although a wealth of information is available on cellular GAPDH, there is a clear paucity of data on its extracellular counterpart (i.e., the secreted or extracellular GAPDH). Here, we show that the extracellular GAPDH in human serum is a multimeric, high-molecular-weight, yet glycolytically active enzyme. The high-molecular-weight multimers of serum GAPDH were identified by immunodetection on one- and two-dimensional gel electrophoresis using multiple antibodies specific for various epitopes of GAPDH. Partial purification of serum GAPDH by DEAE Affigel affinity/ion exchange chromatography further established the multimeric composition of serum GAPDH. In vitro data demonstrated that human cell lines secrete a multimeric, high-molecular-weight enzyme similar to that of serum GAPDH. Furthermore, LC-MS/MS analysis of extracellular GAPDH from human cell lines confirmed the presence of unique peptides of GAPDH in the high-molecular-weight subunits. Furthermore, data from pulse-chase experiments established the presence of high-molecular-weight subunits in the secreted, extracellular GAPDH. Taken together, our findings demonstrate the presence of a high-molecular-weight, enzymatically active secretory GAPDH in human serum that may have a hitherto unknown function in humans.

  1. Hyaluronic Acid Molecular Weight-Dependent Modulation of Mucin Nanostructure for Potential Mucosal Therapeutic Applications.

    PubMed

    Hansen, Irene M; Ebbesen, Morten F; Kaspersen, Liselotte; Thomsen, Troels; Bienk, Konrad; Cai, Yunpeng; Malle, Birgitte Mølholm; Howard, Kenneth A

    2017-07-03

    This study investigates the effects of different molecular weight hyaluronic acids (HAs) on the mucosal nanostructure using a pig stomach mucin hydrogel as a mucosal barrier model. Microparticles (1.0 μm) and nanoparticles (200 nm) were used as probes, and their movement in mucin was studied by a three-dimensional confocal microscopy-based particle tracking technique and by Nanoparticle Tracking Analysis (NTA) after addition of high-molecular weight (900 kDa) and low-molecular weight (33 kDa) HA. This demonstrated a molecular weight-dependent HA modulation of the mucin nanostructure with a 2.5-fold decrease in the mobility of 200 nm nanoparticles. To further investigate these mechanisms and to verify that the natural viscoelastic properties of mucus are not undesirably altered, rheological measurements were performed on mucin hydrogels with or without HA. This suggested the observed particle mobility restriction was not attributed to alterations of the natural mucin cohesive and viscoelastic properties but, instead, indicates that the added high-molecular weight HA primarily modulates the mucin nanostructure and mesh size. This study, hereby, demonstrates how mucus nanostructure can be modulated by the addition of high-molecular weight HA that offers an opportunity to control mucosal pathogenesis and drug delivery.

  2. Improving the accuracy of hyaluronic acid molecular weight estimation by conventional size exclusion chromatography.

    PubMed

    Shanmuga Doss, Sreeja; Bhatt, Nirav Pravinbhai; Jayaraman, Guhan

    2017-08-15

    There is an unreasonably high variation in the literature reports on molecular weight of hyaluronic acid (HA) estimated using conventional size exclusion chromatography (SEC). This variation is most likely due to errors in estimation. Working with commercially available HA molecular weight standards, this work examines the extent of error in molecular weight estimation due to two factors: use of non-HA based calibration and concentration of sample injected into the SEC column. We develop a multivariate regression correlation to correct for concentration effect. Our analysis showed that, SEC calibration based on non-HA standards like polyethylene oxide and pullulan led to approximately 2 and 10 times overestimation, respectively, when compared to HA-based calibration. Further, we found that injected sample concentration has an effect on molecular weight estimation. Even at 1g/l injected sample concentration, HA molecular weight standards of 0.7 and 1.64MDa showed appreciable underestimation of 11-24%. The multivariate correlation developed was found to reduce error in estimations at 1g/l to <4%. The correlation was also successfully applied to accurately estimate the molecular weight of HA produced by a recombinant Lactococcus lactis fermentation. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. From oligomers to molecular giants of soybean oil in supercritical carbon dioxide medium: 1. Preparation of polymers with lower molecular weight from soybean oil.

    PubMed

    Liu, Zengshe; Sharma, Brajendra K; Erhan, Sevim Z

    2007-01-01

    Polymers with a low molecular weight derived from soybean oil have been prepared in a supercritical carbon dioxide medium by cationic polymerization. Boron trifluoride diethyl etherate was used as an initiator. Influences of polymerization temperature, amount of initiator, and carbon dioxide pressure on the molecular weight were investigated. It is shown that the higher polymerization temperature favors polymers with relatively higher molecular weights. Larger amounts of initiator also provide polymers with higher molecular weights. Higher pressure favors polymers with relatively higher molecular weights. The applications of these soy-based materials will be in the lubrication and hydraulic fluid areas.

  4. 21 CFR 172.820 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... ethylene oxide and water with a mean molecular weight of 200 to 9,500. (2) It contains no more than 0.2..., or equivalent) 12 percent in H2O by weight on 60-80 mesh nonacid washed diatomaceous earth... in cylinder equipped with reducing regulator to provide 50 p.s.i.g. to the gas chromatograph...

  5. 21 CFR 172.820 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... ethylene oxide and water with a mean molecular weight of 200 to 9,500. (2) It contains no more than 0.2..., or equivalent) 12 percent in H2O by weight on 60-80 mesh nonacid washed diatomaceous earth... in cylinder equipped with reducing regulator to provide 50 p.s.i.g. to the gas chromatograph...

  6. Use of Kinematic Viscosity Data for the Evaluation of the Molecular Weight of Petroleum Oils

    ERIC Educational Resources Information Center

    Maroto, J. A.; Quesada-Perez, M.; Ortiz-Hernandez, A. J.

    2010-01-01

    A new laboratory procedure for the evaluation of the mean molecular weight (mean relative molecular mass) of petroleum oils with high accuracy is described. The density and dynamic viscosity of three commercial petroleum oils are measured at different temperatures. These experimental data are used to calculate the kinematic viscosity as a function…

  7. Absolute Summ

    NASA Astrophysics Data System (ADS)

    Phillips, Alfred, Jr.

    Summ means the entirety of the multiverse. It seems clear, from the inflation theories of A. Guth and others, that the creation of many universes is plausible. We argue that Absolute cosmological ideas, not unlike those of I. Newton, may be consistent with dynamic multiverse creations. As suggested in W. Heisenberg's uncertainty principle, and with the Anthropic Principle defended by S. Hawking, et al., human consciousness, buttressed by findings of neuroscience, may have to be considered in our models. Predictability, as A. Einstein realized with Invariants and General Relativity, may be required for new ideas to be part of physics. We present here a two postulate model geared to an Absolute Summ. The seedbed of this work is part of Akhnaton's philosophy (see S. Freud, Moses and Monotheism). Most important, however, is that the structure of human consciousness, manifest in Kenya's Rift Valley 200,000 years ago as Homo sapiens, who were the culmination of the six million year co-creation process of Hominins and Nature in Africa, allows us to do the physics that we do. .

  8. Features of Extrusion Processing of Ultrahigh Molecular Weight Polyethylene. Experiment and Theory

    NASA Astrophysics Data System (ADS)

    Skul‧skii, O. I.; Slavnov, E. V.

    2018-05-01

    Experimental studies have been made of the permissible regimes of processing ultrahigh molecular weight polyethylene GUR 2122 with molecular mass of 4.5 million g/moles in a laboratory extruder with an auger diameter 32 mm and a ratio L/D = 20 at temperatures of 155-165oC. On the basis of rotational viscometry, the rheological properties of the melt are described. A mathematical model and a numerical method for calculating the motion of ultrahigh molecular weight polyethylene melt in the auger and in the moulding rigging are proposed. The velocity and stress fields have been determined.

  9. Profiling of the molecular weight and structural isomer abundance of macroalgae-derived phlorotannins.

    PubMed

    Heffernan, Natalie; Brunton, Nigel P; FitzGerald, Richard J; Smyth, Thomas J

    2015-01-16

    Phlorotannins are a group of complex polymers of phloroglucinol (1,3,5-trihydroxybenzene) unique to macroalgae. These phenolic compounds are integral structural components of the cell wall in brown algae, but also play many secondary ecological roles such as protection from UV radiation and defense against grazing. This study employed Ultra Performance Liquid Chromatography (UPLC) with tandem mass spectrometry to investigate isomeric complexity and observed differences in phlorotannins derived from macroalgae harvested off the Irish coast (Fucus serratus, Fucus vesiculosus, Himanthalia elongata and Cystoseira nodicaulis). Antioxidant activity and total phenolic content assays were used as an index for producing phlorotannin fractions, enriched using molecular weight cut-off dialysis with subsequent flash chromatography to profile phlorotannin isomers in these macroalgae. These fractions were profiled using UPLC-MS with multiple reaction monitoring (MRM) and the level of isomerization for specific molecular weight phlorotannins between 3 and 16 monomers were determined. The majority of the low molecular weight (LMW) phlorotannins were found to have a molecular weight range equivalent to 4-12 monomers of phloroglucinol. The level of isomerization within the individual macroalgal species differed, resulting in substantially different numbers of phlorotannin isomers for particular molecular weights. F. vesiculosus had the highest number of isomers of 61 at one specific molecular mass, corresponding to 12 phloroglucinol units (PGUs). These results highlight the complex nature of these extracts and emphasize the challenges involved in structural elucidation of these compounds.

  10. Profiling of the Molecular Weight and Structural Isomer Abundance of Macroalgae-Derived Phlorotannins

    PubMed Central

    Heffernan, Natalie; Brunton, Nigel P.; FitzGerald, Richard J.; Smyth, Thomas J.

    2015-01-01

    Phlorotannins are a group of complex polymers of phloroglucinol (1,3,5-trihydroxybenzene) unique to macroalgae. These phenolic compounds are integral structural components of the cell wall in brown algae, but also play many secondary ecological roles such as protection from UV radiation and defense against grazing. This study employed Ultra Performance Liquid Chromatography (UPLC) with tandem mass spectrometry to investigate isomeric complexity and observed differences in phlorotannins derived from macroalgae harvested off the Irish coast (Fucus serratus, Fucus vesiculosus, Himanthalia elongata and Cystoseira nodicaulis). Antioxidant activity and total phenolic content assays were used as an index for producing phlorotannin fractions, enriched using molecular weight cut-off dialysis with subsequent flash chromatography to profile phlorotannin isomers in these macroalgae. These fractions were profiled using UPLC-MS with multiple reaction monitoring (MRM) and the level of isomerization for specific molecular weight phlorotannins between 3 and 16 monomers were determined. The majority of the low molecular weight (LMW) phlorotannins were found to have a molecular weight range equivalent to 4–12 monomers of phloroglucinol. The level of isomerization within the individual macroalgal species differed, resulting in substantially different numbers of phlorotannin isomers for particular molecular weights. F. vesiculosus had the highest number of isomers of 61 at one specific molecular mass, corresponding to 12 phloroglucinol units (PGUs). These results highlight the complex nature of these extracts and emphasize the challenges involved in structural elucidation of these compounds. PMID:25603345

  11. Increasing molecular weight parameters of a helical polymer through polymerization in a chiral solvent.

    PubMed

    Holder, Simon J; Achilleos, Mariliz; Jones, Richard G

    2006-09-27

    In this communication, we will demonstrate that polymerization in a chiral solvent can affect the molecular weight distribution of the product by perturbing the balance of the P and M helical screw senses of the growing chains. Specifically, for the Wurtz-type synthesis of polymethylphenylsilane (PMPS) in either (R) or (S)-limonene, the weight-average molecular weight of the products (average Mw = 80 000) was twice that of PMPS synthesized in (R/S)-limonene (average Mw = 39 200). Peturbation of the helical segmentation along the polymer chains leads to a reduction in the rate of occurrence of a key termination step. This the first time that a chiral solvent has been demonstrated to have such an effect on a polymerization process in affecting molecular weight parameters in contrast to affecting tacticity.

  12. Adsorption of dissolved organics in lake water by aluminum oxide. Effect of molecular weight

    USGS Publications Warehouse

    Davis, J.A.; Gloor, R.

    1981-01-01

    Dissolved organic compounds in a Swiss lake were fractionated into three molecular size classes by gel exclusion chromatography, and adsorption of each fraction on colloidal alumina was studied as a function of pH. Organic compounds with molecular weight (Mr) greater than 1000 formed strong complexes with the alumina surface, but low molecular weight compounds were weakly adsorbed. Electrophoretic mobility measurements indicated that alumina particles suspended in the original lake water were highly negatively charged because of adsorbed organic matter. Most of the adsorbed organic compounds were in the Mr range 1000 < Mr < 3000. Adsorption of these compounds during the treatment of drinking water by alum coagulation may be responsible for the preferential removal of trihalomethane precursors. Adsorption may also influence the molecular-weight distribution of dissolved organic material in lakes. surface, the present work will focus on the influence of molecular size and pH on the adsorption behavior of dissolved organic material of a Swiss lake. From a geochemical point of view, it is important to know the molecular-weight distribution of adsorbed organic matter so that we may better assess its reactivity with trace elements. The study also serves as a first step in quantifying the role of adsorption in the geochemical cycle of organic carbon in lacustrine environments. For water-treatment practice, we need to determine whether molecular weight fractionation occurs during adsorption by aluminum oxide. Such a fractionation could be significant in the light of recent reports that chloroform and other organochlorine compounds are preferentially produced by particular molecular-weight fractions (25-27). ?? 1981 American Chemical Society.

  13. Application of computer-assisted molecular modeling (CAMM) for immunoassay of low molecular weight food contaminants: A review

    USDA-ARS?s Scientific Manuscript database

    Immunoassay for low molecular weight food contaminants, such as pesticides, veterinary drugs, and mycotoxins is now a well-established technique which meets the demands for a rapid, reliable, and cost-effective analytical method. However, due to limited understanding of the fundamental aspects of i...

  14. Body weight, hemoglobin, and absolute neutrophil count in patients with advanced-stage epithelial ovarian cancer who received chemotherapy: A single-center study

    NASA Astrophysics Data System (ADS)

    Gunawan, Y.; Winarto, H.

    2017-08-01

    The side effects of chemotherapy, a treatment modality of ovarian cancer, can disrupt overall treatment. To date, the clinical and laboratory profiles of ovarian cancer patients during chemotherapy have not been investigated. This study aimed to elucidate the clinical and laboratory profiles of patients with advanced-stage epithelial ovarian cancer who received chemotherapy in Dr. Cipto Mangunkusumo Hospital, including body mass index (BMI), hemoglobin (Hb), and absolute neutrophil count (ANC). To generate these clinical and laboratory profiles, we collected secondary data from the medical records of advanced-stage epithelial ovarian cancer patients who received six cycles of carboplatin and paclitaxel chemotherapy. We enrolled 23 patients with advanced-stage epithelial ovarian cancer patients who received six cycles of chemotherapy. Mean patient BMI before and after chemotherapy was 22.86 kg/m2 and 21.78 kg/m2, respectively. Hb levels before chemotherapy were 8-13 g/dl, with Hb < 10 g/dl in one patient (4.35%) and Hb ≥ 10 g/dl in 22 patients (95.65%). Mean ANC was 5845.6 ± 3325.0. An average of 24.65% of patients experienced anemia after each cycle of chemotherapy. Mean ANC before chemotherapy was 3.5582 ± 3.3250. An average of 26.81% of patients had ANC <1500 after each cycle of chemotherapy; no patients had ANC <1500 before chemotherapy initiation. After six cycles of chemotherapy, three patients (13.04%) had mild neutropenia, four patients (17.39%) had moderate neutropenia, and one patient (4.35%) had severe neutropenia. Of the 22 patients with Hb ≥ 10 g/dl before chemotherapy, 16 (72.72%) experienced a decrease in ANC during chemotherapy. Of the 20 patients (60.87%) with normal BMI or higher, 14 experienced a decrease in ANC during chemotherapy. The mean patient body weight decreased after six cycles of chemotherapy. Hb and ANC were persistently decreased in approximately a quarter of the 23 subjects. The decrease in ANC was not influenced by initial Hb

  15. Low molecular weight squash trypsin inhibitors from Sechium edule seeds.

    PubMed

    Laure, Hélen J; Faça, Vítor M; Izumi, Clarice; Padovan, Júlio C; Greene, Lewis J

    2006-02-01

    Nine chromatographic components containing trypsin inhibitor activity were isolated from Sechium edule seeds by acetone fractionation, gel filtration, affinity chromatography and RP-HPLC in an overall yield of 46% of activity and 0.05% of protein. The components obtained with highest yield of total activity and highest specific activity were sequenced by Edman degradation and their molecular masses determined by mass spectrometry. The inhibitors contained 31, 32 and 27 residues per molecule and their sequences were: SETI-IIa, EDRKCPKILMRCKRDSDCLAKCTCQESGYCG; SETI-IIb, EEDRKCPKILMRCKRDSDCLAKCTCQESGYCG and SETI-V, CPRILMKCKLDTDCFPTCTCRPSGFCG. SETI-IIa and SETI-IIb, which differed by an amino-terminal E in the IIb form, were not separable under the conditions employed. The sequences are consistent with consensus sequences obtained from 37 other inhibitors: CPriI1meCk_DSDCla_C_C_G_CG, where capital letters are invariant amino acid residues and lower case letters are the most preserved in this position. SETI-II and SETI-V form complexes with trypsin with a 1:1 stoichiometry and have dissociation constants of 5.4x10(-11)M and 1.1x10(-9)M, respectively.

  16. Molecular Factors Governing the Liquid and Glassy States Recrystallization of Celecoxib in Binary Mixtures with Excipients of Different Molecular Weights.

    PubMed

    Grzybowska, K; Chmiel, K; Knapik-Kowalczuk, J; Grzybowski, A; Jurkiewicz, K; Paluch, M

    2017-04-03

    Transformation of poorly water-soluble crystalline pharmaceuticals to the amorphous form is one of the most promising strategies to improve their oral bioavailability. Unfortunately, the amorphous drugs are usually thermodynamically unstable and may quickly return to their crystalline form. A very promising way to enhance the physical stability of amorphous drugs is to prepare amorphous compositions of APIs with certain excipients which can be characterized by significantly different molecular weights, such as polymers, acetate saccharides, and other APIs. By using different experimental techniques (broadband dielectric spectroscopy, differential scanning calorimetry, X-ray diffraction) we compare the effect of adding the large molecular weight polymer-polyvinylpyrrolidone (PVP K30)-and the small molecular weight excipient-octaacetylmaltose (acMAL)-on molecular dynamics as well as the tendency to recrystallization of the amorphous celecoxib (CEL) in the amorphous solid dispersions: CEL-PVP and CEL-acMAL. The physical stability investigations of the binary systems were performed in both the supercooled liquid and glassy states. We found that acMAL is a better inhibitor of recrystallization of amorphous CEL than PVP K30 deep in the glassy state (T < T g ). In contrast, PVP K30 is a better crystallization inhibitor of CEL than acMAL in the supercooled liquid state (at T > T g ). We discuss molecular factors governing the recrystallization of amorphous CEL in examined solid dispersions.

  17. An evaluation of the effects of PEO/PEG molecular weights on extruded alumina rods

    NASA Astrophysics Data System (ADS)

    Bolger, Nancy Beth

    1998-12-01

    Alumina rods were piston extruded from bodies containing polyethylene glycols (PEGs) and polyethylene oxides (PEOs) with molecular weights ranging from 1,300 to 3,800,000 g/mol. A blend of aluminas possessing different particle size distributions was evaluated with regard to its extrusion pressure by varying the amount of PEG/PEO addition. Behavior exhibited by the alumina blend was dependent upon the additive that was used. The higher molecular weight binders with average molecular weight of 200,000 g/mol and 3,350,000 g/mol displayed the most severe behaviors of near dilatant and dilatant respectively. Physical properties of the green and fired states, as well as the binder burnout, were investigated with the changing additions. Correlation between the green and fired strengths and the changing molecular weights were examined. The additive present influenced the surface properties of the rods, which affected the green strengths. The highest average molecular weight polyethylene glycols showed higher green strengths, while the lowest green strengths were observed for the high molecular weight polyethylene oxides. Fired strengths generally ranged from approximately 12,000 psi to 16,000 psi for additive batches. Alumina pellets containing twelve separate combinations of polyethylene glycol with polyethylene oxide were dry pressed. Physical properties of the green and fired states were examined. Statistical analysis was performed upon the data and seven combinations of polyethylene glycol with polyethylene oxide were deemed significant. These combinations in conjunction with the same alumina blend were then piston extruded. The addition of polyethylene glycol reduced the near dilatant behavior exhibited by the 200,000 g/mol average molecular weight polyethylene oxide. Dilatant behavior was completely eliminated from the 3,350,000 g/mol average molecular weight polyethylene oxide batches. Physical properties of the green and fired states were again investigated with

  18. Mass spectrometric characterization of membrane integral low molecular weight proteins from photosystem II in barley etioplasts.

    PubMed

    Plöscher, Matthias; Granvogl, Bernhard; Zoryan, Mikael; Reisinger, Veronika; Eichacker, Lutz Andreas

    2009-02-01

    In Photosystem II (PSII), a high number of plastid encoded and membrane integral low molecular weight proteins smaller than 10 kDa, the proteins PsbE, F, H, I, J, K, L, M, N, Tc, Z and the nuclear encoded PsbW, X, Y1, Y2 proteins have been described. Here we show that all low molecular weight proteins of PSII already accumulate in the etioplast membrane fraction in darkness, whereas PsaI and PsaJ of photosystem I (PSI) represent the only low molecular weight proteins that do not accumulate in darkness. We found by BN-PAGE separation of membrane protein complexes and selective MS that the accumulation of one-helix proteins from PSII is light independent and occurs in etioplasts. In contrast, in chloroplasts isolated from light-grown plants, low molecular weight proteins were found to specifically accumulate in PSI and II complexes. Our results demonstrate how plants grown in darkness prepare for the induction of chlorophyll dependent photosystem assembly upon light perception. We anticipate that our investigation will provide the essential means for the analysis of protein assembly in any membrane utilizing low molecular weight protein subunits.

  19. Production of low-molecular weight soluble yeast β-glucan by an acid degradation method.

    PubMed

    Ishimoto, Yuina; Ishibashi, Ken-Ichi; Yamanaka, Daisuke; Adachi, Yoshiyuki; Kanzaki, Ken; Iwakura, Yoichiro; Ohno, Naohito

    2018-02-01

    β-glucan is widely distributed in nature as water soluble and insoluble forms. Both forms of β-glucan are utilized in several fields, especially for functional foods. Yeast β-glucan is a medically important insoluble particle. Solubilization of yeast β-glucan may be valuable for improving functional foods and in medicinal industries. In the present study, we applied an acid degradation method to solubilize yeast β-glucan and found that β-glucan was effectively solubilized to low-molecular weight β-glucans by 45% sulfuric acid treatment at 20°C. The acid-degraded soluble yeast β-glucan (ad-sBBG) was further fractionated into a higher-molecular weight fraction (ad-sBBG-high) and a lower-molecular weight fraction (ad-sBBG-low). Since ad-sBBG-high contained mannan, while ad-sBBG-low contained it only scarcely, it was possible to prepare low-molecular weight soluble β-glucan with higher purity. In addition, ad-sBBG-low bound to dectin-1, which is an innate immunity receptor of β-glucan, and showed antagonistic activity against reactive oxygen production and cytokine synthesis by macrophages. Thus, this acid degradation method is an important procedure for generating immune-modulating, low-molecular weight, soluble yeast β-glucan. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Biological and structural analyses of bovine heparin fractions of intermediate and high molecular weight.

    PubMed

    Nogueira, Alexsandro V; Drehmer, Daiana L; Iacomini, Marcello; Sassaki, Guilherme L; Cipriani, Thales R

    2017-02-10

    Low molecular weight heparin, which is generally obtained by chemical and enzymatic depolymerization of unfractionated heparin, has high bioavailability and can be subcutaneously injected. The aim of the present investigation was to fractionate bovine heparin using a physical method (ultrafiltration through a 10kDa cut-off membrane), avoiding structural modifications that can be caused by chemical or enzymatic treatments. Two fractions with different molecular weights were obtained: the first had an intermediate molecular weight (B-IMWH; Mn=9587Da) and the other had a high molecular weight (B-HMWH; 22,396Da). B-IMWH and B-HMWH have anticoagulant activity of 103 and 154IU/mg respectively, which could be inhibited by protamine. Both fractions inhibited α-thrombin and factor Xa in vitro and showed antithrombotic effect in vivo. Moreover, ex vivo aPTT assay demonstrated that B-IMWH is absorbed by subcutaneous route. The results showed that ultrafiltration can be used to obtain two bovine heparin fractions, which differ on their molecular weights, structural components, anticoagulant potency, and administration routes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. The Role of Molecular Weight and Temperature on the Elastic and Viscoelastic Properties of a Glassy Thermoplastic Polyimide

    NASA Technical Reports Server (NTRS)

    Nicholson, Lee M.; Whitley, Karen S.; Gates, Thomas S.

    2001-01-01

    Mechanical testing of the elastic and viscoelastic response of an advanced thermoplastic polyimide (LaRC-SI) with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. The notched tensile strength was shown to be a strong function of both molecular weight and temperature, whereas stiffness was only a strong function of temperature. A critical molecular weight was observed to occur at a weight average molecular weight of M, approx. 22,000 g/mol below which, the notched tensile strength decreases rapidly. This critical molecular weight transition is temperature-independent. Low, molecular weight materials tended to fail in a brittle manner, whereas high molecular weight materials exhibited ductile failure. Furthermore, low molecular weight materials have increased creep compliance and creep compliance rate, and are more sensitive to temperature than the high molecular weight materials. At long timescales (less than 1100 hours) physical aging serves to significantly decrease the creep compliance and creep rate of all the materials tested. Low molecular weight materials are less influenced by the effects of physical aging.

  2. Complete Molecular Weight Profiling of Low-Molecular Weight Heparins Using Size Exclusion Chromatography-Ion Suppressor-High-Resolution Mass Spectrometry.

    PubMed

    Zaia, Joseph; Khatri, Kshitij; Klein, Joshua; Shao, Chun; Sheng, Yuewei; Viner, Rosa

    2016-11-01

    Low-molecular weight heparins (LMWH) prepared by partial depolymerization of unfractionated heparin are used globally to treat coagulation disorders on an outpatient basis. Patent protection for several LMWH has expired and abbreviated new drug applications have been approved by the Food and Drug Administration. As a result, reverse engineering of LMWH for biosimilar LMWH has become an active global endeavor. Traditionally, the molecular weight distributions of LMWH preparations have been determined using size exclusion chromatography (SEC) with optical detection. Recent advances in liquid chromatography-mass spectrometry methods have enabled exact mass measurements of heparin saccharides roughly up to degree-of-polymerization 20, leaving the high molecular weight half of the LMWH preparation unassigned. We demonstrate a new LC-MS system capable of determining the exact masses of complete LMWH preparations, up to dp30. This system employed an ion suppressor cell to desalt the chromatographic effluent online prior to the electrospray mass spectrometry source. We expect this new capability will impact the ability to define LMWH mixtures favorably.

  3. Quantitative Structure-Cytotoxicity Relationship of Bioactive Heterocycles by the Semi-empirical Molecular Orbital Method with the Concept of Absolute Hardness

    NASA Astrophysics Data System (ADS)

    Ishihara, Mariko; Sakagami, Hiroshi; Kawase, Masami; Motohashi, Noboru

    The relationship between the cytotoxicity of N-heterocycles (13 4-trifluoromethylimidazole, 15 phenoxazine and 12 5-trifluoromethyloxazole derivatives), O-heterocycles (11 3-formylchromone and 20 coumarin derivatives) and seven vitamin K2 derivatives against eight tumor cell lines (HSC-2, HSC-3, HSC-4, T98G, HSG, HepG2, HL-60, MT-4) and a maximum of 15 chemical descriptors was investigated using CAChe Worksystem 4.9 project reader. After determination of the conformation of these compounds and approximation to the molecular form present in vivo (biomimetic) by CONFLEX5, the most stable structure was determined by CAChe Worksystem 4.9 MOPAC (PM3). The present study demonstrates the best relationship between the cytotoxic activity and molecular shape or molecular weight of these compounds. Their biological activities can be estimated by hardness and softness, and by using η-χ activity diagrams.

  4. Cytotoxicity of polycations: Relationship of molecular weight and the hydrolytic theory of the mechanism of toxicity.

    PubMed

    Monnery, Bryn D; Wright, Michael; Cavill, Rachel; Hoogenboom, Richard; Shaunak, Sunil; Steinke, Joachim H G; Thanou, Maya

    2017-04-15

    The mechanism of polycation cytotoxicity and the relationship to polymer molecular weight is poorly understood. To gain an insight into this important phenomenon a range of newly synthesised uniform (near monodisperse) linear polyethylenimines, commercially available poly(l-lysine)s and two commonly used PEI-based transfectants (broad 22kDa linear and 25kDa branched) were tested for their cytotoxicity against the A549 human lung carcinoma cell line. Cell membrane damage assays (LDH release) and cell viability assays (MTT) showed a strong relationship to dose and polymer molecular weight, and increasing incubation times revealed that even supposedly "non-toxic" low molecular weight polymers still damage cell membranes. The newly proposed mechanism of cell membrane damage is acid catalysed hydrolysis of lipidic phosphoester bonds, which was supported by observations of the hydrolysis of DOPC liposomes. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  5. The development of low-molecular weight hydrogels for applications in cancer therapy

    NASA Astrophysics Data System (ADS)

    Tian, Ran; Chen, Jin; Niu, Runfang

    2014-03-01

    To improve the anti-cancer efficacy and to counteract the side effects of chemotherapy, a variety of drug delivery systems have been invented in past decades, but few of these systems have succeeded in clinical trials due to their respective inherent shortcomings. Recently, low-molecular weight hydrogels of peptides that self-assemble via non-covalent interactions have attracted considerable attention due to their good biocompatibility, low toxicity, inherent biodegradability as well as their convenience of design. Low-molecular weight hydrogels have already shown promise in biomedical applications as diverse as 3D-cell culture, enzyme immobilization, controllable MSC differentiation, wound healing, drug delivery etc. Here we review the recent development in the use of low-molecular weight hydrogels for cancer therapy, which may be helpful in the design of soft materials for drug delivery.

  6. Low Molecular Weight Chitosan–Insulin Polyelectrolyte Complex: Characterization and Stability Studies

    PubMed Central

    Al-Kurdi, Zakieh I.; Chowdhry, Babur Z.; Leharne, Stephen A.; Al Omari, Mahmoud M. H.; Badwan, Adnan A.

    2015-01-01

    The aim of the work reported herein was to investigate the effect of various low molecular weight chitosans (LMWCs) on the stability of insulin using USP HPLC methods. Insulin was found to be stable in a polyelectrolyte complex (PEC) consisting of insulin and LMWC in the presence of a Tris-buffer at pH 6.5. In the presence of LMWC, the stability of insulin increased with decreasing molecular weight of LMWC; 13 kDa LMWC was the most efficient molecular weight for enhancing the physical and chemical stability of insulin. Solubilization of insulin-LMWC polyelectrolyte complex (I-LMWC PEC) in a reverse micelle (RM) system, administered to diabetic rats, results in an oral delivery system for insulin with acceptable bioactivity. PMID:25830681

  7. Tests of potential functional barriers for laminated multilayer food packages. Part II: Medium molecular weight permeants.

    PubMed

    Simal-Gándara, J; Sarria-Vidal, M; Rijk, R

    2000-09-01

    Experiments were performed to characterize the kinetics of the permeation of different medium molecular weight model permeants: bisphenol A, warfarin and anthracene, from liquid paraffin, through a surrogate potential functional barrier (25 microns-thick orientated polypropylene--OPP) into the food simulants olive oil and 3% (w/v) acetic acid. The characterization of permeation kinetics generally observed the permeation models previously reported to explain the experimental permeation results obtained for a low molecular weight group of model permeants. In general, the model permeants exhibited behaviour consistent with their relative molecular weights with respect to (a) the time taken to attain steady-state permeation into the food simulant in which they were more soluble, (b) their subsequent steady-state permeation rates, and (c) their partition between liquid paraffin and the OPP membrane.

  8. Synthetic polycations with controlled charge density and molecular weight as building blocks for biomaterials.

    PubMed

    Kleinberger, Rachelle M; Burke, Nicholas A D; Zhou, Christal; Stöver, Harald D H

    2016-01-01

    A series of polycations prepared by RAFT copolymerization of N-(3-aminopropyl)methacrylamide hydrochloride (APM) and N-(2-hydroxypropyl)methacrylamide, with molecular weights of 15 and 40 kDa, and APM content of 10-75 mol%, were tested as building blocks for electrostatically assembled hydrogels such as those used for cell encapsulation. Complexation and distribution of these copolymers within anionic calcium alginate gels, as well as cytotoxicity, cell attachment, and cell proliferation on surfaces grafted with the copolymers were found to depend on composition and molecular weight. Copolymers with lower cationic charge density and lower molecular weight showed less cytotoxicity and cell adhesion, and were more mobile within alginate gels. These findings aid in designing improved polyelectrolyte complexes for use as biomaterials.

  9. Determination of the presence of hyaluronic acid in preparations containing amino acids: the molecular weight characterization.

    PubMed

    Bellomaria, A; Nepravishta, R; Mazzanti, U; Marchetti, M; Piccioli, P; Paci, M

    2014-10-15

    Several pharmaceutical preparations contain hyaluronic acid in the presence of a large variety of low molecular weight charged molecules like amino acids. In these mixtures, it is particularly difficult to determine the concentration and the molecular weight of the hyaluronic acid fragments. In fact zwitterionic compounds in high concentration behave by masking the hyaluronic acid due to the electrostatic interactions between amino acids and hyaluronic acid. In such conditions the common colorimetric test of the hyaluronic acid determination appears ineffective and in the (1)H NMR spectra the peaks of the polymer disappear completely. By a simple separation procedure the presence of hyaluronic acid was revealed by the DMAB test and (1)H NMR while its average molecular weight in the final product was determined by DOSY NMR spectroscopy alone. The latter determination is very important due to the healthy effects of some sizes of this polymer's fragments. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Characteristics and bioactivities of different molecular weight polysaccharides from camellia seed cake.

    PubMed

    Xu, Zhou; Li, Xu; Feng, Shiling; Liu, Jing; Zhou, Lijun; Yuan, Ming; Ding, Chunbang

    2016-10-01

    Four polysaccharides, namely COP-1, COP-2, COP-3 and COP-4, were ultrafiltrated from crud Camellia oleifera seed cake polysaccharides (COP-c), purified, and characterized, including the determination of antioxidant and antiproliferative activities. Their molecular weights were 7.9, 36, 83 and 225kDa, respectively. All COPs showed the similar FT-IR spectrums, but significant differentials in monosaccharide components. COP-2 exhibited the highest radical scavenging abilities. COP-1 has the strongest metal chelating capabilities. Although with higher molecular weight, COP-4 showed the poorest antioxidant abilities. These results suggested appreciate molecular weight COP possessed a better antioxidant activities. Additionally, all COPs had non-significant antiproliferative abilities in HaLa and HepG2 cells. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. A log-normal distribution model for the molecular weight of aquatic fulvic acids

    USGS Publications Warehouse

    Cabaniss, S.E.; Zhou, Q.; Maurice, P.A.; Chin, Y.-P.; Aiken, G.R.

    2000-01-01

    The molecular weight of humic substances influences their proton and metal binding, organic pollutant partitioning, adsorption onto minerals and activated carbon, and behavior during water treatment. We propose a lognormal model for the molecular weight distribution in aquatic fulvic acids to provide a conceptual framework for studying these size effects. The normal curve mean and standard deviation are readily calculated from measured M(n) and M(w) and vary from 2.7 to 3 for the means and from 0.28 to 0.37 for the standard deviations for typical aquatic fulvic acids. The model is consistent with several types of molecular weight data, including the shapes of high- pressure size-exclusion chromatography (HP-SEC) peaks. Applications of the model to electrostatic interactions, pollutant solubilization, and adsorption are explored in illustrative calculations.The molecular weight of humic substances influences their proton and metal binding, organic pollutant partitioning, adsorption onto minerals and activated carbon, and behavior during water treatment. We propose a log-normal model for the molecular weight distribution in aquatic fulvic acids to provide a conceptual framework for studying these size effects. The normal curve mean and standard deviation are readily calculated from measured Mn and Mw and vary from 2.7 to 3 for the means and from 0.28 to 0.37 for the standard deviations for typical aquatic fulvic acids. The model is consistent with several type's of molecular weight data, including the shapes of high-pressure size-exclusion chromatography (HP-SEC) peaks. Applications of the model to electrostatic interactions, pollutant solubilization, and adsorption are explored in illustrative calculations.

  12. The Vertex Version of Weighted Wiener Number for Bicyclic Molecular Structures

    PubMed Central

    Gao, Wei

    2015-01-01

    Graphs are used to model chemical compounds and drugs. In the graphs, each vertex represents an atom of molecule and edges between the corresponding vertices are used to represent covalent bounds between atoms. We call such a graph, which is derived from a chemical compound, a molecular graph. Evidence shows that the vertex-weighted Wiener number, which is defined over this molecular graph, is strongly correlated to both the melting point and boiling point of the compounds. In this paper, we report the extremal vertex-weighted Wiener number of bicyclic molecular graph in terms of molecular structural analysis and graph transformations. The promising prospects of the application for the chemical and pharmacy engineering are illustrated by theoretical results achieved in this paper. PMID:26640513

  13. Formulation/cure technology for ultrahigh molecular weight silphenylene-siloxane polymers

    NASA Technical Reports Server (NTRS)

    Hundley, N. H.; Patterson, W. J.

    1985-01-01

    Molecular weights above one million were achieved for methylvinylsilphenylene-siloxane terpolymers using a two-stage polymerization technique which was successfully scaled up to 200 grams. The resulting polymer was vulcanized by two different formulations and compared to an identically formulated commercial methylvinyl silicone on the basis of ultimate strength, Young's modulus, percent elongation at failure, and tear strength. Relative thermal/oxidative stabilities of the elastomers were assessed by gradient and isothermal thermogravimetric analyses performed in both air and nitrogen. The experimental elastomer exhibited enhanced thermal/oxidative stability and possed equivalent or superior mechanical properties. The effect of variations in prepolymer molecular weight on mechanical properties was also investigated.

  14. Low molecular weight thermostable {beta}-D-glucosidase from Acidothermus cellulolyticus

    DOEpatents

    Himmel, M.E.; Tucker, M.P.; Adney, W.S.; Nieves, R.A.

    1995-07-11

    A purified low molecular weight {beta}-D-glucosidase is produced from Acidothermus cellulolyticus ATCC 43068. The enzyme is water soluble, possesses activity against pNP-{beta}-D-glucopyranoside, has a high of degree of stability toward heat, exhibits optimal temperature activity at about 65 C at a pH range of from about 2 to about 7, has an inactivation temperature of about 80 C at a pH range of from about 2 to about 7 and has a molecular weight of about 50.5--54.5 kD as determined by SDS-PAGE. 6 figs.

  15. [Intraoperative administration of low-molecular-weight heparins in reconstructive vascular operations].

    PubMed

    Pokrovskiĭ, A V; Demidova, V S; Titova, M I; Gontarenko, V N; Burtseva, E A

    2008-01-01

    The article deals with analysing the outcomes of administering low-molecular-weight heparins (LMWH) by the example of nadroparin ("Fraxiparin") during the intraoperative period in patients diagnosed with atherosclerotic lesions of femoropoplietal-crural segment of the lower-limb arteries as compared with non-fractionated heparin (NFH). Studied were the alterations in the parameters of the plasmatic and thrombocytic links of haemostasis on the background of administering various molecular-weight fractions of heparin. A conclusion was drawn on advantageous use of LMWH in the cohort of the patients involved. Also presented herein is an analysis of the literature data concerning appropriate usage of LMWH during the intraoperative period.

  16. Low molecular weight thermostable .beta.-D-glucosidase from acidothermus cellulolyticus

    DOEpatents

    Himmel, Michael E.; Tucker, Melvin P.; Adney, William S.; Nieves, Rafael A.

    1995-01-01

    A purified low molecular weight .beta.-D-glucosidase is produced from Acidothermus cellulolyticus ATCC 43068. The enzyme is water soluble, possesses activity against pNP-.beta.-D-glucopyranoside, has a high of degree of stability toward heat, exhibits optimal temperature activity at about 65.degree. C. at a pH range of from about 2 to about 7, has an inactivation temperature of about 80.degree. C. at a pH range of from about 2 to about 7 and has a molecular weight of about 50.5-54.5 kD as determineded by SDS-PAGE.

  17. Molecular weight dependence of carrier mobility and recombination rate in neat P3HT films

    DOE PAGES

    Dixon, Alex G.; Visvanathan, Rayshan; Clark, Noel A.; ...

    2017-11-02

    The microstructure dependence of carrier mobility and recombination rates of neat films of poly 3-hexylthyophene (P3HT) were determined for a range of materials of weight-average molecular weights, Mw, ranging from 14 to 331 kDa. This variation has previously been shown to modify the polymer microstructure, with low molecular weights forming a one-phase, paraffinic-like structure comprised of chain-extended crystallites, and higher molecular weights forming a semicrystalline structure with crystalline domains being embedded in an amorphous matrix. Using Charge Extraction by Linearly Increasing Voltage (CELIV), we show here that the carrier mobility in P3HT devices peaks for materials of Mw = 48more » kDa, and that the recombination rate decreases monotonically with increasing molecular weight. This trend is likely due to the development of a semicrystalline, two-phase structure with increasing Mw, which allows for the spatial separation of holes and electrons into the amorphous and crystalline regions, respectively. This separation leads to decreased recombination.« less

  18. Molecular weight dependence of carrier mobility and recombination rate in neat P3HT films

    SciTech Connect

    Dixon, Alex G.; Visvanathan, Rayshan; Clark, Noel A.

    The microstructure dependence of carrier mobility and recombination rates of neat films of poly 3-hexylthyophene (P3HT) were determined for a range of materials of weight-average molecular weights, Mw, ranging from 14 to 331 kDa. This variation has previously been shown to modify the polymer microstructure, with low molecular weights forming a one-phase, paraffinic-like structure comprised of chain-extended crystallites, and higher molecular weights forming a semicrystalline structure with crystalline domains being embedded in an amorphous matrix. Using Charge Extraction by Linearly Increasing Voltage (CELIV), we show here that the carrier mobility in P3HT devices peaks for materials of Mw = 48more » kDa, and that the recombination rate decreases monotonically with increasing molecular weight. This trend is likely due to the development of a semicrystalline, two-phase structure with increasing Mw, which allows for the spatial separation of holes and electrons into the amorphous and crystalline regions, respectively. This separation leads to decreased recombination.« less

  19. Synthesis of the low molecular weight heat shock proteins in plants

    SciTech Connect

    Mansfield, M.A.; Key, J.L.

    1987-08-01

    Heat shock of living tissue induces the synthesis of a unique group of proteins, the heat shock proteins. In plants, the major group of heat shock proteins has a molecular mass of 15 to 25 kilodaltons. Accumulation to these proteins to stainable levels has been reported in only a few species. To examine accumulation of the low molecular weight heat shock proteins in a broader range of species, two-dimensional electrophoresis was used to resolve total protein from the following species: soybean (Glycine max L. Merr., var Wayne), pea (Pisum sativum L., var Early Alaska), sunflower (Helianthus annuus L.), wheat (Triticummore » asetivum L.), rice (Oryza sativa L., cv IR-36), maize (Zea mays L.), pearl millet (Pennisetum americanum L. Leeke, line 23DB), and Panicum miliaceum L. When identified by both silver staining and incorporation of radiolabel, a diverse array of low molecular weight heat shock proteins was synthesized in each of these species. These proteins accumulated to significant levels after three hours of heat shock but exhibited considerable heterogeneity in isoelectric point, molecular weight, stainability, and radiolabel incorporation. Although most appeared to be synthesized only during heat shock, some were detectable at low levels in control tissue. Compared to the monocots, a higher proportion of low molecular weight heat shock proteins was detectable in control tissues from dicots.« less

  20. Increasing the wear resistance of ultra-high molecular weight polyethylene by adding solid lubricating fillers

    SciTech Connect

    Panin, S. V., E-mail: svp@ispms.tsc.ru; Kornienko, L. A.; Poltaranin, M. A.

    2014-11-14

    In order to compare effectiveness of adding solid lubricating fillers for polymeric composites based on ultra-high molecular weight polyethylene (UHMWPE) with graphite, molybdenum disulfide and polytetrafluoroethylene, their tribotechnical characteristics under dry friction, boundary lubrication and abrasive wearing were investigated. The optimal weight fractions of fillers in terms of improving wear resistance have been determined. The supramolecular structure and topography of wear track surfaces of UHMWPE-based composites with different content of fillers have been studied.

  1. Quantitative LC-MS of polymers: determining accurate molecular weight distributions by combined size exclusion chromatography and electrospray mass spectrometry with maximum entropy data processing.

    PubMed

    Gruendling, Till; Guilhaus, Michael; Barner-Kowollik, Christopher

    2008-09-15

    We report on the successful application of size exclusion chromatography (SEC) combined with electrospray ionization mass spectrometry (ESI-MS) and refractive index (RI) detection for the determination of accurate molecular weight distributions of synthetic polymers, corrected for chromatographic band broadening. The presented method makes use of the ability of ESI-MS to accurately depict the peak profiles and retention volumes of individual oligomers eluting from the SEC column, whereas quantitative information on the absolute concentration of oligomers is obtained from the RI-detector only. A sophisticated computational algorithm based on the maximum entropy principle is used to process the data gained by both detectors, yielding an accurate molecular weight distribution, corrected for chromatographic band broadening. Poly(methyl methacrylate) standards with molecular weights up to 10 kDa serve as model compounds. Molecular weight distributions (MWDs) obtained by the maximum entropy procedure are compared to MWDs, which were calculated by a conventional calibration of the SEC-retention time axis with peak retention data obtained from the mass spectrometer. Comparison showed that for the employed chromatographic system, distributions below 7 kDa were only weakly influenced by chromatographic band broadening. However, the maximum entropy algorithm could successfully correct the MWD of a 10 kDa standard for band broadening effects. Molecular weight averages were between 5 and 14% lower than the manufacturer stated data obtained by classical means of calibration. The presented method demonstrates a consistent approach for analyzing data obtained by coupling mass spectrometric detectors and concentration sensitive detectors to polymer liquid chromatography.

  2. The Combined Influence of Molecular Weight and Temperature on the Aging and Viscoelastic Response of a Glassy Thermoplastic Polyimide

    NASA Technical Reports Server (NTRS)

    Nicholson, Lee M.; Whitley, Karen S.; Gates, Thomas S.

    2000-01-01

    The effect of molecular weight on the viscoelastic performance of an advanced polymer (LaRC-SI) was investigated through the use of creep compliance tests. Testing consisted of short-term isothermal creep and recovery with the creep segments performed under constant load. The tests were conducted at three temperatures below the glass transition temperature of five materials of different molecular weight. Through the use of time-aging-time superposition procedures, the material constants, material master curves and aging-related parameters were evaluated at each temperature for a given molecular weight. The time-temperature superposition technique helped to describe the effect of temperature on the timescale of the viscoelastic response of each molecular weight. It was shown that the low molecular weight materials have higher creep compliance and creep rate, and are more sensitive to temperature than the high molecular weight materials. Furthermore, a critical molecular weight transition was observed to occur at a weight-average molecular weight of M (bar) (sub w) 25000 g/mol below which, the temperature sensitivity of the time-temperature superposition shift factor increases rapidly. The short-term creep compliance data were used in association with Struik's effective time theory to predict the long-term creep compliance behavior for the different molecular weights. At long timescales, physical aging serves to significantly decrease the creep compliance and creep rate of all the materials tested.

  3. An agarose gel electrophoretic method for analysis of hyaluronan molecular weight distribution.

    PubMed

    Lee, H G; Cowman, M K

    1994-06-01

    An electrophoretic method is described for determining the molecular weight distribution of hyaluronan (HA). The method involves separation of HA by electrophoresis on a 0.5% agarose gel, followed by detection of HA using the cationic dye Stains-All (3,3'-dimethyl-9-methyl-4,5,4'5'-dibenzothiacarbocyanine). The recommended sample load is 7 micrograms. Calibration of the method with HA standards of known molecular weight has established a linear relationship between electrophoretic mobility and the logarithm of the weight-average molecular weight over the range of approximately 0.2-6 x 10(6). The separated HA pattern may also be visualized after electrotransfer of HA from the agarose gel to a nylon membrane. The membrane may be stained with the dye alcian blue. Alternatively, specific detection of HA from impure samples can be achieved by probing the nylon membrane with biotin-labeled HA-binding protein and subsequent interaction with a streptavidin-linked gold reagent and silver staining for amplification. The electrophoretic method was used to analyze HA in two different liquid connective tissues. Normal human knee joint synovial fluid showed a narrow HA molecular weight distribution, with a peak at 6-7 x 10(6). Owl monkey vitreous HA also showed a narrow molecular weight distribution, with a peak at 5-6 x 10(6). These results agree well with available published data and indicate the applicability of the method to the analysis of impure HA samples which may be available in limited amounts.

  4. The effects of postexercise consumption of high-molecular-weight versus low-molecular-weight carbohydrate solutions on subsequent high-intensity interval-running capacity.

    PubMed

    McGlory, Chris; Morton, James P

    2010-10-01

    The aim of this study was to determine the effects of postexercise ingestion of different-molecular-weight glucose polymer solutions on subsequent high-intensity interval-running capacity. In a repeated-measures design, 6 men ran for 60 min in the morning at 70% VO2max. Immediately post- and at 1 and 2 hr postexercise, participants consumed a 15% low-molecular-weight (LMW) or high-molecular-weight (HMW) carbohydrate solution, at a rate of 1.2 g of carbohydrate/kg body mass, or an equivalent volume of flavored water (WAT). After recovery, participants performed repeated 1-min intervals at 90% VO2max interspersed with 1 min active recovery (walking) until volitional exhaustion. Throughout the 3-hr recovery period, plasma glucose concentrations were higher (p=.002) during the HMW and LMW conditions than with WAT (M 7.0±0.8, 7.5±1.0, and 5.6±0.2 mmol/L, respectively), although there was no difference (p=.723) between HMW and LMW conditions. Exercise capacity was 13 (43±10 min; 95% CI for differences: 8-18; p=.001) and 11 min (41±9 min; 95% CI for differences; 2-18: p=.016) longer with HMW and LMW solutions, respectively, than with WAT (30±9 min). There was no substantial difference (2 min; 95% CI for differences: -5 to 10; p=.709) in exercise capacity between LMW and HMW solutions. Although this magnitude of difference is most likely trivial in nature, the uncertainty allows for a possible small substantial enhancement of physiological significance, and further research is required to clarify the true nature of the effect.

  5. Determination of low molecular weight thiols using monobromobimane fluorescent labeling and high-performance liquid chromatography

    NASA Technical Reports Server (NTRS)

    Fahey, Robert C.; Newton, Gerald L.

    1988-01-01

    Methods are described for the preparation and high-performance liquid chromatography (HPLC) analysis of monobromobimane derivatives of low molecular weight thiols in extracts of biological samples. Typical problems encountered in the development and application of these methods are discussed. Analysis of mung bean extract is used as an example.

  6. Anterograde and retrograde tracing with high molecular weight biotinylated dextran amine through thalamocortical and corticothalamic pathways.

    PubMed

    Zhang, Wenjie; Xu, Dongsheng; Cui, Jingjing; Jing, Xianghong; Xu, Nenggui; Liu, Jianhua; Bai, Wanzhu

    2017-02-01

    Biotinylated dextran amine (BDA) has been used for neural pathway tracing in the central nervous system for many decades, in which high molecular weight BDA appeared to be transported predominantly in the anterograde direction and less in the retrograde direction. In the current study, we reexamined the properties of neural labeling with high molecular weight BDA through a reciprocal neural pathway between thalamus and somatosensory cortex. After injection of BDA into the ventral posteromedial nucleus of thalamus (VPM) in the rat, the BDA labeling was sequentially examined on somatosensory cortex at 3, 5, 7, 10, and 14 survival days. Both of anterogradely labeled axonal terminals and retrogradely labeled neuronal cell bodies were observed simultaneously on the somatosensory cortex. With the increasing of survival times after injection, morphological changes occurred on the labeled axonal arbors and neuronal dendrites, in which the high quality of BDA labeling appeared on the tenth survival day. These results indicate that high molecular weight BDA is not only a sensitive anterograde tracer but also an excellent retrograde marker to be used for tracing through thalamocortical and corticothalamic pathways. And the detailed structure of neural labeling with BDA similar to Golgi-like resolution can be obtained at optimal survival times of animals after the injection of high molecular weight BDA. © 2016 Wiley Periodicals, Inc.

  7. 21 CFR 178.3750 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... used in food-packaging adhesives complying with § 175.105 of this chapter. ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Polyethylene glycol (mean molecular weight 200-9,500). 178.3750 Section 178.3750 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

  8. 21 CFR 178.3750 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... are not applicable to polyethylene glycols used in food-packaging adhesives complying with § 175.105... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Polyethylene glycol (mean molecular weight 200-9,500). 178.3750 Section 178.3750 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

  9. 21 CFR 178.3750 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... are not applicable to polyethylene glycols used in food-packaging adhesives complying with § 175.105... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Polyethylene glycol (mean molecular weight 200-9,500). 178.3750 Section 178.3750 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

  10. Incorporation of high-molecular-weight glutenin subunits into doughs using 2 gram mixograph and extensigraphs

    USDA-ARS?s Scientific Manuscript database

    To study the contributions of high-molecular-weight glutenin subunits (HMW-GS) to the gluten macropolymer and dough properties, wheat HMW-GS (x- and y-types) are synthesized in a bacterial expression system. These subunits are then purified and used to supplement dough mixing and extensigraph experi...

  11. 21 CFR 178.3750 - Polyethylene glycol (mean molecular weight 200-9,500).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... are not applicable to polyethylene glycols used in food-packaging adhesives complying with § 175.105... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Polyethylene glycol (mean molecular weight 200-9,500). 178.3750 Section 178.3750 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND...

  12. A global survey of low-molecular weight carbohydrates in lentils

    USDA-ARS?s Scientific Manuscript database

    Lentils contain a range of low-molecular weight carbohydrates (LMWC); however, those have not been well characterized. The objectives of this study were to (1) determine the concentrations of LMWC in lentils grown in six locations, and (2) identify any genetic and environmental effects on those LMWC...

  13. Changes in Light Absorptivity of Molecular Weight Separated Brown Carbon Due to Photolytic Aging.

    PubMed

    Wong, Jenny P S; Nenes, Athanasios; Weber, Rodney J

    2017-08-01

    Brown carbon (BrC) consists of those organic compounds in atmospheric aerosols that absorb solar radiation and may play an important role in planetary radiative forcing and climate. However, little is known about the production and loss mechanisms of BrC in the atmosphere. Here, we study how the light absorptivity of BrC from wood smoke and secondary BrC generated from the reaction of ammonium sulfate with methylglyoxal changes under photolytic aging by UVA radiation in the aqueous phase. Owing to its chemical complexity, BrC is separated by molecular weight using size exclusion chromatography, and the response of each molecular weight fraction to aging is studied. Photolytic aging induced significant changes in the light absorptivity of BrC for all molecular weight fractions; secondary BrC was rapidly photoblenched, whereas for wood smoke BrC, both photoenhancement and photobleaching were observed. Initially, large biomass burning BrC molecules were rapidly photoenhanced, followed by slow photolysis. As a result, large BrC molecules dominated the total light absorption of aged biomass burning BrC. These experimental results further support earlier observations that large molecular weight BrC compounds from biomass burning can be relatively long-lived components in atmospheric aerosols, thus more likely to have larger impacts on aerosol radiative forcing and could serve as biomass burning tracers.

  14. Reorganization of low-molecular-weight fraction of plasma proteins in the annual cycle of cyprinidae.

    PubMed

    Andreeva, A M; Lamas, N E; Serebryakova, M V; Ryabtseva, I P; Bolshakov, V V

    2015-02-01

    Reorganization of the low-molecular-weight fraction of cyprinid plasma was analyzed using various electrophoretic techniques (disc electrophoresis, electrophoresis in polyacrylamide concentration gradient, in polyacrylamide with urea, and in SDS-polyacrylamide). The study revealed coordinated changes in the low-molecular-weight protein fractions with seasonal dynamics and related reproductive rhythms of fishes. We used cultured species of the Cyprinidae family with sequenced genomes for the detection of these interrelations in fresh-water and anadromous cyprinid species. The common features of organization of fish low-molecular-weight plasma protein fractions made it possible to make reliable identification of their proteins. MALDI mass-spectrometry analysis revealed the presence of the same proteins (hemopexin, apolipoproteins, and serpins) in the low-molecular-weight plasma fraction in wild species and cultured species with sequenced genomes (carp, zebrafish). It is found that the proteins of the first two classes are organized as complexes made of protein oligomers. Stoichiometry of these complexes changes in concordance with the seasonal and reproductive rhythms.

  15. A global survey of low-molecular weight carbohydrates in lentils

    USDA-ARS?s Scientific Manuscript database

    Lentils contain a range of low-molecular weight carbohydrates (LMWC); however, they have not been well characterized. The objectives of this study were to (1) determine the concentrations of LMWC in lentils grown in different environments and (2) identify any genetic and environmental effects on tho...

  16. Oligomeric cationic polymethacrylates: a comparison of methods for determining molecular weight.

    PubMed

    Locock, Katherine E S; Meagher, Laurence; Haeussler, Matthias

    2014-02-18

    This study compares three common laboratory methods, size-exclusion chromatography (SEC), (1)H nuclear magnetic resonance (NMR), and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF), to determine the molecular weight of oligomeric cationic copolymers. The potential bias for each method was examined across a series of polymers that varied in molecular weight and cationic character (both choice of cation (amine versus guanidine) and relative proportion present). SEC was found to be the least accurate, overestimating Mn by an average of 140%, owing to the lack of appropriate cationic standards available, and the complexity involved in estimating the hydrodynamic volume of copolymers. MALDI-TOF approximated Mn well for the highly monodisperse (Đ < 1.1), low molecular weight (degree of polymerization (DP) <50) species but appeared unsuitable for the largest polymers in the series due to the mass bias associated with the technique. (1)H NMR was found to most accurately estimate Mn in this study, differing to theoretical values by only 5.2%. (1)H NMR end-group analysis is therefore an inexpensive and facile, primary quantitative method to estimate the molecular weight of oliogomeric cationic polymethacrylates if suitably distinct end-groups signals are present in the spectrum.

  17. Microfluidics Meets Dilute Solution Viscometry: An Undergraduate Laboratory to Determine Polymer Molecular Weight Using a Microviscometer

    ERIC Educational Resources Information Center

    Pety, Stephen J.; Lu, Hang; Thio, Yonathan S.

    2011-01-01

    This paper describes a student laboratory experiment to determine the molecular weight of a polymer sample by measuring the viscosity of dilute polymer solutions in a PDMS microfluidic viscometer. Sample data are given for aqueous solutions of poly(ethylene oxide) (PEO). A demonstration of shear thinning behavior using the microviscometer is…

  18. Synthesis of Polystyrene and Molecular Weight Determination by [superscript 1]H NMR End-Group Analysis

    ERIC Educational Resources Information Center

    Wackerly, Jay Wm.; Dunne, James F.

    2017-01-01

    A procedure for the solution polymerization of styrene using di-"tert"-butyl peroxide (DTBP) as the initiator is described. The use of DTBP allows for end-group analysis by [superscript 1]H NMR spectroscopy and calculation of the number-average molecular weight of the polymer. This experiment was designed as a laboratory introduction to…

  19. MAPLE deposition of PLGA:PEG films for controlled drug delivery: Influence of PEG molecular weight

    NASA Astrophysics Data System (ADS)

    Paun, Irina Alexandra; Moldovan, Antoniu; Luculescu, Catalin Romeo; Staicu, Angela; Dinescu, Maria

    2012-09-01

    Implantable devices consisting of indomethacin (INC) cores coated with poly(lactide-co-glycolide):polyethylene glycol films (i.e. PLGA:PEG films) deposited by Matrix Assisted Pulsed Laser Evaporation (MAPLE) were produced. To predict their behavior after implantation inside the body, the implants were studied in vitro, in media similar with those encountered inside the body (phosphate buffered saline (PBS) pH 7.4 and blood). The influence of the molecular weight of PEG (i.e. low (1450 Da) versus high (10 kDa) molecular weights) on the characteristics of the implants was investigated, in terms of morphology, blood compatibility and kinetics of the drug release. The use of PEG of high molecular weight resulted in larger pores on the implants surfaces, enhanced blood compatibility of the implants and higher drug delivery rates. For both molecular weights PEGs, sustained release of INC was maintained over a three weeks interval. Theoretical fitting of the drug release data with Higuchi's model indicated that the INC was released mainly by diffusion, most probably through the pores formed in PLGA:PEG films during PBS immersion.

  20. High-molecular-weight polymers for protein crystallization: poly-γ-glutamic acid-based precipitants

    PubMed Central

    Hu, Ting-Chou; Korczyńska, Justyna; Smith, David K.; Brzozowski, Andrzej Marek

    2008-01-01

    Protein crystallization has been revolutionized by the intro­duction of high-throughput technologies, which have led to a speeding up of the process while simultaneously reducing the amount of protein sample necessary. Nonetheless, the chemistry dimension of protein crystallization has remained relatively undeveloped. Most crystallization screens are based on the same set of precipitants. To address this shortcoming, the development of new protein precipitants based on poly-γ-­glutamic acid (PGA) polymers with different molecular-weight ranges is reported here: PGA-LM (low molecular weight) of ∼400 kDa and PGA-HM (high molecular weight) of >1000 kDa. It is also demonstrated that protein precipitants can be expanded further to polymers with much higher molecular weight than those that are currently in use. Furthermore, the modification of PGA-like polymers by covalent attachments of glucosamine substantially improved their solubility without affecting their crystallization properties. Some preliminary PGA-based screens are presented here. PMID:18703844

  1. Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate

    PubMed Central

    2018-01-01

    High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA–PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions. PMID:29805184

  2. Sedimentation Coefficient, Frictional Coefficient, and Molecular Weight: A Preparative Ultracentrifuge Experiment for the Advanced Undergraduate Laboratory.

    ERIC Educational Resources Information Center

    Halsall, H. B.; Wermeling, J. R.

    1982-01-01

    Describes an experiment using a high-speed preparative centrifuge and calculator to demonstrate effects of the frictional coefficient of a macromolecule on its rate of transport in a force field and to estimate molecular weight of the macromolecule using an empirical relationship. Background information, procedures, and discussion of results are…

  3. Methanol-induced chain termination in poly(3-hydroxybutyrate) biopolymers: molecular weight control

    USDA-ARS?s Scientific Manuscript database

    A systematic study was performed to demonstrate the impact of methanol (MeOH) on poly(3-hydroxybutyrate) (PHB) synthesis and molecular weight (MW) control. Glycerine (init. conc. = 1.0%; w/v), was used as the primary carbon source in batch-culture fermentations with varying concentrations (0 to 0.85...

  4. Effect of chitosan molecular weight on rheological behavious of chitosan modified nanoclay at highly hydrated state

    USDA-ARS?s Scientific Manuscript database

    Effect of chitosan molecular weight (M(cs)) on the rheological properties of chitosan modified clay (CMCs) at highly hydrated state was investigated. With special emphasis on its effect on the thixotropy of CMCs, the structure recovery at rest after underwent a pre-shearing process was further perfo...

  5. Novel low-molecular-weight-gelator-based microcapsules with controllable morphology and temperature responsiveness.

    PubMed

    Patel, Ashok R; Remijn, Caroline; Heussen, Patricia C M; den Adel, Ruud; Velikov, Krassimir P

    2013-02-04

    A new type of microcapsules with controllable morphology is presented. They are based on a low-molecular-weight gelator and can be switched from temperature-stable to temperature-responsive by simply modifying the preparation method. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effect of mahlep on molecular weight distribution of cookie flour gluten proteins

    USDA-ARS?s Scientific Manuscript database

    Size Exclusion-High performance Chromatography (SE-HPLC) has been extensively used in molecular weight distribution analysis of wheat proteins. In this study the protein analysis was conducted on different cookie dough blends with different percentages of some ingredients. The mean chromatography ...

  7. Polyacrylamide Molecular Weight and Phosphogypsum Effects on Infiltration and Erosion in Semi-Arid Soils

    USDA-ARS?s Scientific Manuscript database

    Seal formation at the surface of semi-arid soils during rainstorms reduces soil infiltration rate (IR) and causes runoff and erosion. Surface application of dry anionic polyacrylamide (PAM) with high molecular weight (MW) has been found to be effective in stabilizing soil aggregates, and decreasing ...

  8. Polyacrylamide molecular weight and phosphogypsum effects on infiltration and erosion in semi-arid soils

    USDA-ARS?s Scientific Manuscript database

    Seal formation at the surface of semi-arid soils during rainstorms reduces soil infiltration rate (IR) and causes runoff and erosion. Surface application of dry anionic polyacrylamide (PAM) with high molecular weight (MW) has been found to be effective in stabilizing soil aggregates, and decreasing ...

  9. Effect of the molecular weight of a neutral polysaccharide on soy protein gelation.

    PubMed

    Monteiro, Sónia R; Lopes-da-Silva, José A

    2017-12-01

    The effects of galactomannans with different molecular weights on the heat-induced gelation characteristics of soybean protein were investigated using dynamic small-strain rheometry, under conditions where the proteins carry a net negative charge (pH7). Microstructure of the resulting gels was investigated by confocal laser scanning microscopy. Phase-separated systems were obtained with different morphologies and degree of phase separation, depending on both biopolymer concentrations and polysaccharide molecular weight. In general, a gelling enhancing effect on soy proteins was verified, despite extensive phase-separation processes observed at the higher polysaccharide molecular weight. This effect was demonstrated by an increase of the gelation rate, a decrease in the temperature at the onset of gelation, and an increase of gel stiffness and elastic character, with the length of polysaccharide chains. Overall, the results obtained established that the judicious selection of the galactomannan molecular weight may be used to modify the structure and gelation properties of soy proteins, originating a diversity of rheological characteristics and microstructures that will impact on the design of novel food formulations. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Effects of molecular weight on the diffusion coefficient of aquatic dissolved organic matter and humic substances.

    PubMed

    Balch, J; Guéguen, C

    2015-01-01

    In situ measurements of labile metal species using diffusive gradients in thin films (DGT) passive samplers are based on the diffusion rates of individual species. Although most studies have dealt with chemically isolated humic substances, the diffusion of dissolved organic matter (DOM) across the hydrogel is not well understood. In this study, the diffusion coefficient (D) and molecular weight (MW) of 11 aquatic DOM and 4 humic substances (HS) were determined. Natural, unaltered aquatic DOM was capable of diffusing across the diffusive gel membrane with D values ranging from 2.48×10(-6) to 5.31×10(-6) cm(2) s(-1). Humic substances had diffusion coefficient values ranging from 3.48×10(-6) to 6.05×10(-6) cm(2) s(-1), congruent with previous studies. Molecular weight of aquatic DOM and HS samples (∼500-1750 Da) measured using asymmetrical flow field-flow fractionation (AF4) strongly influenced D, with larger molecular weight DOM having lower D values. No noticeable changes in DOM size properties were observed during the diffusion process, suggesting that DOM remains intact following diffusion across the diffusive gel. The influence of molecular weight on DOM mobility will assist in further understanding and development of the DGT technique and the uptake and mobility of contaminants associated with DOM in aquatic environments. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. TOXICOLOGICAL HIGHLIGHT (REDOX REDUX: A CLOSER LOOK AT CONCEPTAL LOW MOLECULAR WEIGHT THIOLS)

    EPA Science Inventory

    Glutathione (GSH) is present as the most abundant low molecular weight thiol (LMWT) in virtually all mitochondria-bearing eucaryotic cells, often at millimolar concentrations (Meister, 1988). Functions of GSH include roles in DNA and protein synthesis, maintenance of cell membra...

  12. Holographic recording medium employing a photoconductive layer and a low molecular weight microcrystalline polymeric layer

    NASA Technical Reports Server (NTRS)

    Gange, Robert Allen (Inventor)

    1977-01-01

    A holographic recording medium comprising a conductive substrate, a photoconductive layer and an electrically alterable layer of a linear, low molecular weight hydrocarbon polymer has improved fatigue resistance. An acrylic barrier layer can be interposed between the photoconductive and electrically alterable layers.

  13. Isoleucine epimerization and amino acid composition in molecular-weight separations of Pleistocene Genyornis eggshell

    NASA Astrophysics Data System (ADS)

    Kaufman, Darrell S.; Miller, Gifford H.

    1995-07-01

    This study explores the geochronological utility and analytical reproducibility of separating the high-molecular-weight fraction (HMW) from eggshells of the extinct late Pleistocene ratite, Genyornis, using disposable, prepacked gel-filtration columns. The superior integrity of ratite eggshell for the retention of amino acids indicates that this biomineral is better suited for this type of investigation than previously studied molluscan shell. To evaluate the reproducibility of the gel-filtration technique, we analyzed triplicate subsamples of three eggshells of different ages. The reproducibility, based on the average intrashell variation (coefficient of variation; CV) in the extent of isoleucine epimerization (aIle/Ile) in the HMW (enriched in molecules ca. >10,000 MW) is 3%, well within the range appropriate for geochronological purposes. The average intrashell variation in the total amino acid concentration (Σ[aa]) of the HMW is 5%, somewhat better than for the total acid hydrolysate (TOTAL) of the same samples (7%). To evaluate the relation between molecular weight and the rate of isoleucine epimerization, three molecular-weight fractions were separated using gel filtration, plus the naturally hydrolyzed free fraction (FREE), for each of four fossil eggshells. AIle/Ile increases with decreasing molecular weight in all shells, with a ca. sixfold to ninefold difference in ratios between the HMW andFREE, and a ca. fivefold difference between the HMW andTOTAL. Although linear correlations between aIle/Ile measured in each molecular-weight fraction and in theTOTAL are all highly significant (r ⩾ 0.951), the relation between the extent of epimerization in the HMW and in the TOTAL is best expressed as an exponential function (r = 0.951). This relation is consistent with the idea that, as the epimerization reaction approaches equilibrium in theTOTAL (ca. aIle/Ile > 1.1), its rate decreases beyond that of the HMW. The amino acid composition (relative percent of

  14. Middle molecules and small-molecular-weight proteins in ESRD: properties and strategies for their removal.

    PubMed

    Clark, William R; Winchester, James F

    2003-10-01

    Molecular weight has traditionally been the parameter most commonly used to classify uremic toxins, with a value of approximately 500 Da frequently used as a demarcation point below which the molecular weights of small nitrogenous waste products fall. This toxin group, the most extensively studied from a clinical perspective, is characterized by a high degree of water solubility and the absence of protein binding. However, uremia is mediated by the retention of a plethora of other compounds having characteristics that differ significantly from those of the previously mentioned group. As opposed to the relative homogeneity of the nitrogenous metabolite class, other uremic toxins collectively are a very heterogeneous group, not only with respect to molecular weight but also other characteristics, such as protein binding and hydrophobicity. A recently proposed classification scheme by the European Uraemic Toxin Work Group subdivides the remainder of molecules into 2 categories: protein-bound solutes and middle molecules. For the latter group, the Work Group proposes a molecular weight range (500-60,000 Da) that incorporates many toxins identified since the original middle molecule hypothesis, for which the upper molecular weight limit was approximately 2,000 Da. In fact, low-molecular-weight peptides and proteins (LMWPs) comprise nearly the entire middle molecule category in the new scheme. The purpose of this article is to provide an overview of the middle molecule class of uremic toxins, with the focus on LMWPs. A brief review of LMWP metabolism under conditions of normal (and in a few cases, abnormal) renal function will be presented. The physical characteristics of several LMWPs will also be presented, including molecular weight, conformation, and charge. Specific LMWPs to be covered will include beta 2-microglobulin, complement proteins (C3a and Factor D), leptin, and proinflammatory cytokines. The article will also include a discussion of the treatment

  15. Melt fracture of linear low-density polyethylenes: Die geometry and molecular weight characteristics

    NASA Astrophysics Data System (ADS)

    Ebrahimi, Marzieh; Tomkovic, Tanja; Liu, Guochang; Doufas, Antonios A.; Hatzikiriakos, Savvas G.

    2018-05-01

    The melt fracture phenomena of three linear low-density polyethylenes are investigated as a function of die geometry (capillary, slit, and annular) and molecular weight and its distribution. The onset of melt fracture instabilities is determined by using capillary rheometry, mainly studying the extrudate appearance using optical microscopy. It is found that the onset of flow instabilities (melt fracture phenomena) is significantly affected by die geometry and molecular weight characteristics of the polymers. Use of annular die eliminates the stick-slip transition (oscillating melt fracture) and delays the onset of sharkskin to higher values of shear rate and shear stress. Moreover, it is shown that the molecular weight characteristics of the polymers are well correlated with critical conditions for the onset of flow instabilities based on a criterion proposed in the literature [A. Allal et al., "Relationships between molecular structure and sharkskin defect for linear polymers," J. Non-Newtonian Fluid Mech. 134, 127-135 (2006) and A. Allal and B. Vergnes, "Molecular design to eliminate sharkskin defect for linear polymers," J. Non-Newtonian Fluid Mech. 146, 45-50 (2007)].

  16. [Correlation of molecular weight and nanofiltration mass transfer coefficient of phenolic acid composition from Salvia miltiorrhiza].

    PubMed

    Li, Cun-Yu; Wu, Xin; Gu, Jia-Mei; Li, Hong-Yang; Peng, Guo-Ping

    2018-04-01

    Based on the molecular sieving and solution-diffusion effect in nanofiltration separation, the correlation between initial concentration and mass transfer coefficient of three typical phenolic acids from Salvia miltiorrhiza was fitted to analyze the relationship among mass transfer coefficient, molecular weight and concentration. The experiment showed a linear relationship between operation pressure and membrane flux. Meanwhile, the membrane flux was gradually decayed with the increase of solute concentration. On the basis of the molecular sieving and solution-diffusion effect, the mass transfer coefficient and initial concentration of three phenolic acids showed a power function relationship, and the regression coefficients were all greater than 0.9. The mass transfer coefficient and molecular weight of three phenolic acids were negatively correlated with each other, and the order from high to low is protocatechualdehyde >rosmarinic acid> salvianolic acid B. The separation mechanism of nanofiltration for phenolic acids was further clarified through the analysis of the correlation of molecular weight and nanofiltration mass transfer coefficient. The findings provide references for nanofiltration separation, especially for traditional Chinese medicine with phenolic acids. Copyright© by the Chinese Pharmaceutical Association.

  17. The pPSU Plasmids for Generating DNA Molecular Weight Markers.

    PubMed

    Henrici, Ryan C; Pecen, Turner J; Johnston, James L; Tan, Song

    2017-05-26

    Visualizing nucleic acids by gel electrophoresis is one of the most common techniques in molecular biology, and reference molecular weight markers or ladders are commonly used for size estimation. We have created the pPSU1 & pPSU2 pair of molecular weight marker plasmids which produce both 100 bp and 1 kb DNA ladders when digested with two common restriction enzymes. The 100 bp ladder fragments have been optimized to migrate appropriately on both agarose and native polyacrylamide, unlike many currently available DNA ladders. Sufficient plasmid DNA can be isolated from 100 ml E. coli cultures for the two plasmids to produce 100 bp or 1 kb ladders for 1000 gels. As such, the pPSU1 and pPSU2 plasmids provide reference fragments from 50 to 10000 bp at a fraction of the cost of commercial DNA ladders. The pPSU1 and pPSU2 plasmids are available without licensing restrictions to nonprofit academic users, affording freely available high-quality, low-cost molecular weight standards for molecular biology applications.

  18. Detection of Diverse and High Molecular Weight Nesprin-1 and Nesprin-2 Isoforms Using Western Blotting.

    PubMed

    Carthew, James; Karakesisoglou, Iakowos

    2016-01-01

    Heavily utilized in cell and molecular biology, western blotting is considered a crucial technique for the detection and quantification of proteins within complex mixtures. In particular, the detection of members of the nesprin (nuclear envelope spectrin repeat protein) family has proven difficult to analyze due to their substantial isoform diversity, molecular weight variation, and the sheer size of both nesprin-1 and nesprin-2 giant protein variants (>800 kDa). Nesprin isoforms contain distinct domain signatures, perform differential cytoskeletal associations, occupy different subcellular compartments, and vary in their tissue expression profiles. This structural and functional variance highlights the need to distinguish between the full range of proteins within the nesprin protein family, allowing for greater understanding of their specific roles in cell biology and disease. Herein, we describe a western blotting protocol modified for the detection of low to high molecular weight (50-1000 kDa) nesprin proteins.

  19. Molecular weight determination and correlation analysis of Dalbergia sissoo polysaccharide with constituent oligosaccharides.

    PubMed

    Kumar, Vineet; Rana, Vikas; Soni, P L

    2013-01-01

    Mucilaginous polysaccharide extracted from Dalbergia sissoo Roxb. leaves has a number of medicinal applications. Molecular weight studies and correlation analysis of the structure of polysaccharide with oligosaccharides can be helpful for further utilisation, modification and structure-activity relationship for biological applications. To determine molecular weight of medicinally important polysaccharide. To establish an unequivocal correlation of the polysaccharide monosugars with constituting oligosaccharides and glucuronic acid content based on gas-liquid chromatography (GLC) with the spectrophotometric method. Complete and partial hydrolytic studies of pure polysaccharide yielded constituting monosugars and oligosaccharides. The ratio of sugars in polysaccharide and oligosaccharides was studied by preparation of alditol acetates and analysed using GLC. The uronic acid content was studied by GLC analysis and spectrophotometry. Molecular weight of the polysaccharide was determined using the viscometric method. Dalbergia sissoo leaves yielded 14.0% pure polysaccharide, containing 15.7% of glucuronic acid. Complete hydrolysis and GLC analysis of alditol acetate derivatives of reduced and unreduced monosugars indicated the presence of L-rhamnose, D-glucuronic acid, D-galactose and D-glucose in 1.00:1.00:2.00:2.33 molar ratios. Partial hydrolysis followed by monosugar analysis of oligosaccharides established the monosugar ratio in complete agreement with polysaccharide, thereby corroborating the sugar ratio. Similar uronic acid content was obtained by GLC and spectrophotometry. The polysaccharide had an average molecular weight of 1.5 × 10⁵  Da. The study has established an obvious correlation of the structure of polysaccharide with oligosaccharides, leading to unambiguous identification of monosaccharides, which normally is not studied conclusively while reporting the polysaccharide structure. The molecular weight of the polysaccharide was determined

  20. Effects of polymer molecular weight on relative oral bioavailability of curcumin.

    PubMed

    Tsai, Yin-Meng; Chang-Liao, Wan-Ling; Chien, Chao-Feng; Lin, Lie-Chwen; Tsai, Tung-Hu

    2012-01-01

    Polylactic-co-glycolic acid (PLGA) nanoparticles have been used to increase the relative oral bioavailability of hydrophobic compounds and polyphenols in recent years, but the effects of the molecular weight of PLGA on bioavailability are still unknown. This study investigated the influence of polymer molecular weight on the relative oral bioavailability of curcumin, and explored the possible mechanism accounting for the outcome. Curcumin encapsulated in low (5000-15,000) and high (40,000-75,000) molecular weight PLGA (LMw-NPC and HMw-NPC, respectively) were prepared using an emulsification-solvent evaporation method. Curcumin alone and in the nanoformulations was administered orally to freely mobile rats, and blood samples were collected to evaluate the bioavailability of curcumin, LMw-NPC, and HMw-NPC. An ex vivo experimental gut absorption model was used to investigate the effects of different molecular weights of PLGA formulation on absorption of curcumin. High-performance liquid chromatography with diode array detection was used for quantification of curcumin in biosamples. There were no significant differences in particle properties between LMw-NPC and HMw-NPC, but the relative bioavailability of HMw-NPC was 1.67-fold and 40-fold higher than that of LMw-NPC and conventional curcumin, respectively. In addition, the mean peak concentration (C(max)) of conventional curcumin, LMw-NPC, and HMw-NPC was 0.028, 0.042, and 0.057 μg/mL, respectively. The gut absorption study further revealed that the HMw-PLGA formulation markedly increased the absorption rate of curcumin in the duodenum and resulted in excellent bioavailability compared with conventional curcumin and LMw-NPC. Our findings demonstrate that different molecular weights of PLGA have varying bioavailability, contributing to changes in the absorption rate at the duodenum. The results of this study provide the rationale for design of a nanomedicine delivery system to enhance the bioavailability of water

  1. Relationship between molecular weight, monosaccharide composition and immunobiologic activity of Astragalus polysaccharides.

    PubMed

    Jiang, Yiping; Qi, Xiaohui; Gao, Kai; Liu, Wenjun; Li, Na; Cheng, Ningbo; Ding, Gang; Huang, Wenzhe; Wang, Zhenzhong; Xiao, Wei

    2016-10-01

    Four Astragalus polysaccharides (APS1-APS4) were isolated from the water extract of Radix Astragali and purified through ethanol precipitation with 20 %, 40 %, 60 % and 80 % ethanol, respectively. The total sugar content was measured by sulfuric acid-phenol method. Their molecular weight was determined using high performance gel permeation chromatography (HPGPC) and their monosaccharide composition was analyzed by reversed-phase high performance liquid chromatography (HPLC) after pre-column derivatization. Then the immunobiologic activity of APS was evaluated by the experiment of spleen lymphocytes proliferation in vitro. The data suggested that precipitation by different concentration of ethanol will obtain different molecular weight APS, the higher concentration of ethanol the smaller molecular weight for APS. The molecular weights of four APS were 257.7 kDa, 40.1 kDa, 15.3 kDa and 3.2 kDa. Monosaccharide composition analysis indicated that APS1 consisted of glucose only, and APS2 all consisted of arabinose. APS3 consisted of rhamnose, glucose, galactose and arabinose and APS4 consisted of galactose and arabinose, in a molar ratio of 1:10.76:6.55:12 and 3.02:1. The result of immunobiologic activity assay showed that both APS2 and APS3 can effectively stimulate normal spleen lymphocyte proliferation in vitro. Apart from this, the effect of APS2 also showed dose dependent tendency from 6.25 μg/mL to 800 μg/mL. The result of this research indicated that Astragalus polysaccharides, which consist of arabinose and their molecular weight between 15.2 kDa to 40.1 kDa, neither too high nor too low, had significant immune activity.

  2. De facto molecular weight distributions of glucans by size-exclusion chromatography combined with mass/molar-detection of fluorescence labeled terminal hemiacetals.

    PubMed

    Praznik, Werner; Huber, Anton

    2005-09-25

    A major capability of polysaccharides in aqueous media is their tendency for aggregation and dynamic formation of supermolecular structures. Even extended dissolution processes will not eliminate these structures which dominate many analytical approaches, in particular absolute molecular weight determinations referring to light scattering data. An alternative approach for determination of de facto molecular weight for glucans with free terminal hemiacetal functionality (reducing end group) has been adjusted from carbohydrates for midrange and high-dp glucans: quantitative and stabilized labeling as aminopyridyl-derivatives (AP-glucans) and subsequent analysis of SEC-separated elution profiles based on simultaneously monitored mass and molar fractions by refractive index and fluorescence detection. SEC-DRI/FL of AP-glucans proved as an appropriate approach for determination of de facto molecular weight of constituting glucan molecules even in the presence of supermolecular structures for non-branched (pullulan), branched (dextran), narrow distributed and broad distributed and for mixes of compact and loose packed polymer coils (starch glucan hydrolizate).

  3. Low molecular weight chitosan conjugated with folate for siRNA delivery in vitro: optimization studies

    PubMed Central

    Fernandes, Julio C; Qiu, Xingping; Winnik, Francoise M; Benderdour, Mohamed; Zhang, Xiaoling; Dai, Kerong; Shi, Qin

    2012-01-01

    The low transfection efficiency of chitosan is one of its drawbacks as a gene delivery carrier. Low molecular weight chitosan may help to form small-sized polymer-DNA or small interfering RNA (siRNA) complexes. Folate conjugation may improve gene transfection efficiency because of the promoted uptake of folate receptor-bearing cells. In the present study, chitosan was conjugated with folate and investigated for its efficacy as a delivery vector for siRNA in vitro. We demonstrate that the molecular weight of chitosan has a major influence on its biological and physicochemical properties, and very low molecular weight chitosan (below 10 kDa) has difficulty in forming stable complexes with siRNA. In this study, chitosan 25 kDa and 50 kDa completely absorbed siRNA and formed nanoparticles (≤220 nm) at a chitosan to siRNA weight ratio of 50:1. The introduction of a folate ligand onto chitosan decreased nanoparticle toxicity. Compared with chitosan-siRNA, folate-chitosan-siRNA nanoparticles improved gene silencing transfection efficiency. Therefore, folate-chitosan shows potential as a viable candidate vector for safe and efficient siRNA delivery. PMID:23209368

  4. Molecular weight distribution characterization of hydrophobe-modified hydroxyethyl cellulose by size-exclusion chromatography.

    PubMed

    Li, Yongfu; Meunier, David M; Partain, Emmett M

    2014-09-12

    Size-exclusion chromatography (SEC) of hydrophobe-modified hydroxyethyl cellulose (HmHEC) is challenging because polymer chains are not isolated in solution due to association of hydrophobic groups and hydrophobic interaction with column packing materials. An approach to neutralize these hydrophobic interactions was developed by adding β-cyclodextrin (β-CD) to the aqueous eluent. SEC mass recovery, especially for the higher molecular weight chains, increased with increasing concentration of β-CD in the eluent. A β-CD concentration of 0.75wt% in the eluent was determined to be optimal for the HmHEC polymers studied. These conditions enabled precise determinations of apparent molecular weight distributions exhibiting less than 2% relative standard deviation in the measured weight-average molecular weight (MW) for five injections on three studied samples and showed no significant differences in MW determined on two different days. The developed technology was shown to be very robust for characterizing HmHEC having MW from 500kg/mol to 2000kg/mol, and it can be potentially applied to other hydrophobe-modified polymers. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Cellular Viscosity in Prokaryotes and Thermal Stability of Low Molecular Weight Biomolecules.

    PubMed

    Cuecas, Alba; Cruces, Jorge; Galisteo-López, Juan F; Peng, Xiaojun; Gonzalez, Juan M

    2016-08-23

    Some low molecular weight biomolecules, i.e., NAD(P)H, are unstable at high temperatures. The use of these biomolecules by thermophilic microorganisms has been scarcely analyzed. Herein, NADH stability has been studied at different temperatures and viscosities. NADH decay increased at increasing temperatures. At increasing viscosities, NADH decay rates decreased. Thus, maintaining relatively high cellular viscosity in cells could result in increased stability of low molecular weight biomolecules (i.e., NADH) at high temperatures, unlike what was previously deduced from studies in diluted water solutions. Cellular viscosity was determined using a fluorescent molecular rotor in various prokaryotes covering the range from 10 to 100°C. Some mesophiles showed the capability of changing cellular viscosity depending on growth temperature. Thermophiles and extreme thermophiles presented a relatively high cellular viscosity, suggesting this strategy as a reasonable mechanism to thrive under these high temperatures. Results substantiate the capability of thermophiles and extreme thermophiles (growth range 50-80°C) to stabilize and use generally considered unstable, universal low molecular weight biomolecules. In addition, this study represents a first report, to our knowledge, on cellular viscosity measurements in prokaryotes and it shows the dependency of prokaryotic cellular viscosity on species and growth temperature. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  6. Effect of thermal treatment on potato starch evidenced by EPR, XRD and molecular weight distribution.

    PubMed

    Bidzińska, Ewa; Michalec, Marek; Pawcenis, Dominika

    2015-12-01

    Effect of heating of the potato starch on damages of its structure was investigated by quantitative electron paramagnetic resonance (EPR) spectroscopy, X-ray diffraction and determination of the molecular weight distribution. The measurements were performed in the temperature range commonly used for starch modifications optimizing properties important for industrial applications. Upon thermal treatment, because of breaking of the polymer chains, diminishing of the average molecular weights occurred, which significantly influences generation of radicals, evidenced by EPR. For the relatively mild conditions, with heating parameters not exceeding temperature 230 °C and time of heating equal to 30 min a moderate changes of both the number of thermally generated radicals and the mean molecular weight of the starch were observed. After more drastic thermal treatment (e.g. 2 h at 230 °C), a rapid increase in the radical amount occurred, which was accompanied by significant reduction of the starch molecular size and crystallinity. Experimentally established threshold values of heating parameters should not be exceeded in order to avoid excessive damages of the starch structure accompanied by the formation of the redundant amount of radicals. This requirement is important for industrial applications, because significant destruction of the starch matrix might annihilate the positive influence of the previously performed intentional starch modification. Copyright © 2015 John Wiley & Sons, Ltd.

  7. Development and in vivo evaluation of an oral delivery system for low molecular weight heparin based on thiolated polycarbophil.

    PubMed

    Kast, Constantia E; Guggi, Davide; Langoth, Nina; Bernkop-Schnürch, Andreas

    2003-06-01

    It was the purpose of this study to develop a new oral drug delivery system for low molecular weight heparin (LMWH) providing an improved bioavailability and a prolonged therapeutic effect. The permeation enhancing polycarbophil-cysteine conjugate (PCP-Cys) used in this study displayed 111.4 +/- 6.4 microM thiol groups per gram polymer. Permeation studies on freshly excised intestinal mucosa were performed in Ussing chambers demonstrating a 2-fold improved uptake of heparin as a result of the addition of 0.5% (w/v) PCP-Cys and the permeation mediator glutathione (GSH). Tablets containing PCP-Cys, GSH, and 279 IU of LMWH showed a sustained drug release over 4 h. To guarantee the swelling of the polymeric carrier matrix in the small intestine tablets were enteric coated. They were orally given to rats. For tablets being based on the thiomer/GSH system an absolute bioavailability of 19.9 +/- 9.3% (means +/- SD; n = 5) vs. intravenous injection could be achieved. whereas tablets comprising unmodified PCP did not lead to a significant (p < 0.01) heparin concentration in plasma. The permeation enhancing effect and subsequently a therapeutic heparin level was maintained for 24 h after a single dose. Because of the strong and prolonged lasting permeation enhancing effect of the thiomer/GSH system, the oral bioavailability of LMWH could be significantly improved. This new delivery system represents therefore a promising tool for the oral administration of heparin.

  8. Influence of Constraining and Confinement in the Molecular Mobility of Low Molecular Weight Materials

    NASA Astrophysics Data System (ADS)

    Bras, Ana Rita Elias

    Despite the importance that the glassy state has nowadays, the transition from liquid to the glass, glass transition, still remains a matter of debate which constitutes one of the great condensed matter physics challenges. Since this fact is closely related to the cooperativity dynamics, the study of this phenomenon in glass-forming liquids under confinement in the nanometer scale, has recently emerged as a strategy to clarify factors such as the existence of an inherent length scale of the cooperative dynamics that determines the glass transition temperature. In this context, this thesis represents an additional contribution to the study of molecular dynamics of glass-forming liquids under confinement in nanoporous inorganic materials. As target compounds the liquid crystal E7 and the drug Ibuprofen were selected. Since the first exhibit various transitions makes it more sensitive to perturbations and thus appears as the ideal candidate to evaluate confinement effects. The study of ibuprofen is of particular interest because confinement emerges as a method of stabilizing the amorphous phase that is mostly important in pharmaceutical applications. Dielectric Relaxation Spectroscopy (DRS) is the main technique used to obtain detailed information about the molecular mobility in a wide range of frequencies (10-2-109Hz) (Chapter I and II). The first part of the thesis is devoted to the characterization of the two target compounds in the bulk state. The combination of DRS with the specific heat spectroscopy allowed to determine which of the E7 observed relaxation processes (a process in the isotropic phase and two processes in the nematic phase: delta and tumbling) is responsible for the glass transition temperature Tg (tumbling process). Detailed studies of ibuprofen molecular mobility in the liquid, supercooled liquid and glassy states are also presented in this chapter, where four relaxation processes are detected: two secondary processes (gamma and beta), the

  9. Application of computer-assisted molecular modeling for immunoassay of low molecular weight food contaminants: A review.

    PubMed

    Xu, Zhen-Lin; Shen, Yu-Dong; Beier, Ross C; Yang, Jin-Yi; Lei, Hong-Tao; Wang, Hong; Sun, Yuan-Ming

    2009-08-11

    Immunoassay for low molecular weight food contaminants, such as pesticides, veterinary drugs, and mycotoxins is now a well-established technique which meets the demand for a rapid, reliable, and cost-effective analytical method. However, due to limited understanding of the molecular structure of antibody binding sites and antigenic epitopes, as well as the intermolecular binding forces that come into play, the traditional 'trial and error' method used to develop antibodies still remains the method of choice. Therefore, development of enhanced immunochemical techniques for specific- and generic-assays, requires new approaches for antibody design that will improve affinity and specificity of the antibody in a more rapid and economic manner. Computer-assisted molecular modeling (CAMM) has been demonstrated to be a useful tool to help the immunochemist develop immunoassays. CAMM methods can be used to help direct improvements to important antibody features, and can provide insights into the effects of molecular structure on biological activity that are difficult or impossible to obtain in any other way. In this review, we briefly summarize applications of CAMM in immunoassay development, including assisting in hapten design, explaining cross-reactivity, modeling antibody-antigen interactions, and providing insights into the effects of the mouse body temperature on the three-dimensional conformation of a hapten during antibody production. The fundamentals and theory, programs and software, limitations, and prospects of CAMM in immunoassay development were also discussed.

  10. High molecular weight DNA assembly in vivo for synthetic biology applications.

    PubMed

    Juhas, Mario; Ajioka, James W

    2017-05-01

    DNA assembly is the key technology of the emerging interdisciplinary field of synthetic biology. While the assembly of smaller DNA fragments is usually performed in vitro, high molecular weight DNA molecules are assembled in vivo via homologous recombination in the host cell. Escherichia coli, Bacillus subtilis and Saccharomyces cerevisiae are the main hosts used for DNA assembly in vivo. Progress in DNA assembly over the last few years has paved the way for the construction of whole genomes. This review provides an update on recent synthetic biology advances with particular emphasis on high molecular weight DNA assembly in vivo in E. coli, B. subtilis and S. cerevisiae. Special attention is paid to the assembly of whole genomes, such as those of the first synthetic cell, synthetic yeast and minimal genomes.

  11. Evaluating nephrotoxicity of high-molecular-weight organic compounds in drinking water from lignite aquifers

    USGS Publications Warehouse

    Bunnell, J.E.; Tatu, C.A.; Lerch, H.E.; Orem, W.H.; Pavlovic, N.

    2007-01-01

    High-molecular-weight organic compounds such as humic acids and/or fulvic acids that are naturally mobilized from lignite beds into untreated drinking-water supplies were suggested as one possible cause of Balkan endemic nephropathy (BEN) and cancer of the renal pelvis. A lab investigation was undertaken in order to assess the nephrotoxic potential of such organic compounds using an in vitro tissue culture model. Because of the infeasibility of exposing kidney tissue to low concentrations of organics for years in the lab, tangential flow ultrafiltration was employed to hyperconcentrate samples suitable for discerning effects in the short time frames necessitated by tissue culture systems. Effects on HK-2 kidney cells were measured using two different cell proliferation assays (MTT and alamarBlue). Results demonstrated that exposure of kidney tissue to high-molecular-weight organics produced excess cell death or proliferation depending on concentration and duration of exposure. Copyright ?? Taylor & Francis Group, LLC.

  12. Preparation of the low molecular weight serum proteome for mass spectrometry analysis.

    PubMed

    Waybright, Timothy J; Chan, King C; Veenstra, Timothy D; Xiao, Zhen

    2013-01-01

    The discovery of viable biomarkers or indicators of disease states is complicated by the inherent complexity of the chosen biological specimen. Every sample, whether it is serum, plasma, urine, tissue, cells, or a host of others, contains thousands of large and small components, each interacting in multiple ways. The need to concentrate on a group of these components to narrow the focus on a potential biomarker candidate becomes, out of necessity, a priority, especially in the search for immune-related low molecular weight serum biomarkers. One such method in the field of proteomics is to divide the sample proteome into groups based on the size of the protein, analyze each group, and mine the data for statistically significant items. This chapter details a portion of this method, concentrating on a method for fractionating and analyzing the low molecular weight proteome of human serum.

  13. Electrical properties of multilayers from low- and high-molecular-weight polyelectrolytes.

    PubMed

    Radeva, Tsetska; Milkova, Viktoria; Petkanchin, Ivana

    2004-11-15

    The formation of stable multilayer films by using as constituents sodium poly(4-styrene sulfonate) (PSS) and poly(4-vinyl pyridine) (PVP) was studied by electrooptics. A strong increase in basicity of the pyridine rings in the electrical field of the oppositely charged PSS chains was suggested to be the driving force for multilayer film formation. A linear increase in the film thickness was registered after deposition of the first three layers, with no dependence on the polyelectrolyte molecular weight. The electrooptical effect was found to increase with increasing area of each next layer, but depended on the molecular weights of both polymers. Polarization of "condensed" counterions along the chains of the last-adsorbed layer was suggested to explain this dependence. Following the counterion dynamics, we come to the conclusion that the electrical properties of the top layer govern the electrooptical behavior of the PSS/PVP film.

  14. Role of Laccase and Low Molecular Weight Metabolites from Trametes versicolor in Dye Decolorization

    PubMed Central

    Moldes, Diego; Fernández-Fernández, María; Sanromán, M. Ángeles

    2012-01-01

    The studies regarding decolorization of dyes by laccase may not only inform about the possible application of this enzyme for environmental purposes, but also may provide important information about its reaction mechanism and the influence of several factors that could be involved. In this paper, decolorization of crystal violet and phenol red was carried out with different fractions of extracellular liquids from Trametes versicolor cultures, in order to describe the role of laccase in this reaction. Moreover, the possible role of the low molecular weight metabolites (LMWMs) also produced by the fungus was evaluated. The results confirm the existence of a nonenzymatic decolorization factor, since the nonprotein fraction of the extracellular liquids from cultures of T. versicolor has shown decolorization capability. Several experiments were performed in order to identify the main compounds related to this ability, which are probably low molecular weight peroxide compounds. PMID:22566767

  15. Simulated dynamic response of a multi-stage compressor with variable molecular weight flow medium

    NASA Technical Reports Server (NTRS)

    Babcock, Dale A.

    1995-01-01

    A mathematical model of a multi-stage compressor with variable molecular weight flow medium is derived. The modeled system consists of a five stage, six cylinder, double acting, piston type compressor. Each stage is followed by a water cooled heat exchanger which serves to transfer the heat of compression from the gas. A high molecular weight gas (CFC-12) mixed with air in varying proportions is introduced to the suction of the compressor. Condensation of the heavy gas may occur in the upper stage heat exchangers. The state equations for the system are integrated using the Advanced Continuous Simulation Language (ACSL) for determining the system's dynamic and steady state characteristics under varying operating conditions.

  16. Use of electroporation for high-molecular-weight DNA-mediated gene transfer.

    PubMed

    Jastreboff, M M; Ito, E; Bertino, J R; Narayanan, R

    1987-08-01

    Electroporation was used to introduce high-molecular-weight DNA into murine hematopoietic cells and NIH3T3 cells. CCRF-CEM cells were stably transfected with SV2NEO plasmid and the genomic DNA from G-418-resistant clones (greater than 65 kb) was introduced into mouse bone marrow and NIH3T3 cells by electroporation. NEO sequences and expression were detected in the hematopoietic tissues of lethally irradiated mice, with 24% of individual spleen colonies expressing NEO. The frequency of genomic DNA transfer into NIH3T3 cells was 0.25 X 10(-3). Electroporation thus offers a powerful mode of gene transfer not only of cloned genes but also of high-molecular-weight DNA into cells.

  17. Inhibitory Effects of Medium Molecular Weight Heparinyl Amino Acid Derivatives on Ischemic Paw Edema in Mice.

    PubMed

    Takeda, Seiichi; Toda, Takao; Nakamura, Kazuki

    2016-01-01

    We investigated the radical-scavenging effects of heparin (HE), medium molecular weight heparinyl phenylalanine (MHF), and medium molecular weight heparinyl leucine (MHL) using ischemic paw edema in mice. We also examined the activated partial thromboplastin time (APTT) of mice that were administered these compounds as an index of their side-effects. HE had a preventative effect and significant reduced ischemic paw edema. However, its effect was not dose-dependent and the dose-response curve was bell-shaped. The effective dose of HE also exhibited a prolonged APTT. Pretreatment using MHF and MHL were effective against ischemic paw edema without a prolonged APTT. Remarkably, the action of MHF was not only preventively, but also therapeutically active. These results suggest that MHF and MHL are superior to HE as safe radical scavengers in vivo. Copyright © 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  18. Role of laccase and low molecular weight metabolites from Trametes versicolor in dye decolorization.

    PubMed

    Moldes, Diego; Fernández-Fernández, María; Sanromán, M Ángeles

    2012-01-01

    The studies regarding decolorization of dyes by laccase may not only inform about the possible application of this enzyme for environmental purposes, but also may provide important information about its reaction mechanism and the influence of several factors that could be involved. In this paper, decolorization of crystal violet and phenol red was carried out with different fractions of extracellular liquids from Trametes versicolor cultures, in order to describe the role of laccase in this reaction. Moreover, the possible role of the low molecular weight metabolites (LMWMs) also produced by the fungus was evaluated. The results confirm the existence of a nonenzymatic decolorization factor, since the nonprotein fraction of the extracellular liquids from cultures of T. versicolor has shown decolorization capability. Several experiments were performed in order to identify the main compounds related to this ability, which are probably low molecular weight peroxide compounds.

  19. Binding of pyrene to aquatic and commercial humic substances: The role of molecular weight and aromaticity

    USGS Publications Warehouse

    Chin, Y.-P.; Aiken, G.R.; Danielsen, K.M.

    1997-01-01

    The binding of pyrene to a number of humic substances isolated from various aquatic sources and a commercial humic acid was measured using the solubility enhancement method. The humic materials used in this study were characterized by various spectroscopic and liquid chromatography methods. A strong correlation was observed between the pyrene binding coefficient, K(doc), and the molecular weights, molar absorptivities at 280 nm, and aromaticity of the aquatic humic substances. Binding of pyrene to the commercial humic acid, however, was significantly stronger and did not obey the relationships observed between K(doc) and the chemical properties of the aquatic humic substrates. These results suggest that the molecular weight and the aromatic content of the humic substrates exert influences on the binding of nonpolar and planar aromatic molecules and that the physicochemical properties of both humic materials and organic solutes are important in controlling the speciation of nonpolar organic contaminants in natural waters.

  20. Chain-Growth Methods for the Synthesis of High Molecular Weight Conducting and Semiconducting Polymers

    DTIC Science & Technology

    2013-08-25

    to produce the desired polymerization in analogy to the well-known “super glue ” anionic polymerization. Although there are abundant examples of...light (a) and UV light (b). 5 are further functionalized and block polymers formed with polynorborene have elastomeric properties. The...top) and UV (bottom) light show the evolution of the band gap of the polymer with increasing molecular weight. The plot on the right shows the

  1. Generation of Comprehensive Surrogate Kinetic Models and Validation Databases for Simulating Large Molecular Weight Hydrocarbon Fuels

    DTIC Science & Technology

    2012-10-25

    of hydrogen/ carbon molar ratio (H/C), derived cetane number (DCN), threshold sooting index (TSI), and average mean molecular weight (MWave) of...diffusive soot extinction configurations. Matching the “real fuel combustion property targets” of hydrogen/ carbon molar ratio (H/C), derived cetane number...combustion property targets - hydrogen/ carbon molar ratio (H/C), derived cetane number (DCN), threshold sooting index (TSI), and average mean

  2. High molecular weight hyaluronan decreases oxidative DNA damage induced by EDTA in human corneal epithelial cells

    PubMed Central

    Ye, J; Wu, H; Wu, Y; Wang, C; Zhang, H; Shi, X; Yang, J

    2012-01-01

    Purpose To investigate the toxic effects of ethylenediaminetetraacetic acid disodium salt (EDTA), a corneal penetration enhancer in topical ophthalmic formulations, on DNA in human corneal epithelial cells (HCEs), and to investigate whether the effect induced by EDTA can be inhibited by high molecular weight hyaluronan (HA). Methods Cells were exposed to EDTA in concentrations ranging from 0.00001 to 0.01% for 60 min, or 30 min high molecular weight HA pretreatment followed by EDTA treatment. The cell viability was measured by the MTT test. Cell apoptosis was determined with annexin V staining by flow cytometry. The DNA single- and double-strand breaks of HCEs were examined by alkaline comet assay and by immunofluorescence microscope detection of the phosphorylated form of histone variant H2AX (γH2AX) foci, respectively. Reactive oxygen species (ROS) production was assessed by the fluorescent probe, 2′, 7′-dichlorodihydrofluorescein diacetate. Results EDTA exhibited no adverse effect on cell viability and did not induce cell apoptosis in human corneal epithelial cells at concentrations lower than 0.01%. However, a significant increase of DNA single- and double-strand breaks was observed in a dose-dependent manner with all the concentrations of EDTA tested in HCEs. In addition, EDTA treatment led to elevated ROS generation. Moreover, 30 min preincubation with high molecular weight HA significantly decreased EDTA-induced ROS generation and DNA damage. Conclusions EDTA could induce DNA damage in HCEs, probably through oxidative stress. Furthermore, high molecular weight HA was an effective protective agent that had antioxidant properties and decreased DNA damage induced by EDTA. PMID:22595911

  3. Bilateral rectal sheath hematomas after low-molecular weight heparin treatment in uremia.

    PubMed

    Xu, Lu; Liu, Lei; Li, Xinjian

    2017-11-01

    Rectus sheath hematomas (RSHs) are uncommon. They are usually unilateral and rarely bilateral. In this paper, we report the first case of spontaneous bilateral RSHs in a uremic patient after the administration of the first dose of low-molecular weight heparin during hemodialysis. The most interesting aspect of this case is that the main symptom of RSH in our patient was urinary bladder irritation. We highlight the importance of the prompt diagnosis and management of this medical emergency.

  4. Radiation cross-linking in ultra-high molecular weight polyethylene for orthopaedic applications

    NASA Astrophysics Data System (ADS)

    Oral, Ebru; Muratoglu, Orhun K.

    2007-12-01

    The motivation for radiation cross-linking of ultra-high molecular weight polyethylene (UHMWPE) is to increase its wear resistance to be used as bearing surfaces for total joint arthroplasty. However, radiation also leaves behind long-lived residual free radicals in this polymer, the reactions of which can detrimentally affect mechanical properties. In this review, we focus on the radiation cross-linking and oxidative stability of first and second generation highly cross-linked UHMWPEs developed in our laboratory.

  5. [A contribution safety on using low molecular weight heparin in patients with renal failure].

    PubMed

    Gea Rodríguez, E; Barral Viñals, N; Manso Mardones, P; Indo Berges, O

    2004-01-01

    1. To promote safe and appropriate use of low molecular weight heparins in patients with renal failure. 2. To analyze results from a pharmaceutical intervention program. Data from a prospective, 16-month study are presented. The entire adult population of a general hospital with 41,792 stays/year is included. An intensive monitoring program for low molecular weight heparin prescriptions in patients with renal failure is implemented. This program identifies patients using a computerized unit dose system, and is aided by a software able to calculate creatinine clearance using the Cockroft-Gault formula from an interphase between laboratory, pharmacy and admissions data, and by an algorithm to establish a recommended pharmaceutical intervention according to renal failure severity and low molecular weight heparin indication, either with prophylactic or therapeutic purposes. In all, 221 patients were identified, corresponding to 2.9% of admitted patients and 25.5% of patients with renal failure. Answers were assessable for 128 patients (61%). Extent of program acceptance according to physician-accepted pharmaceutical interventions was proportional to renal failure severity and therapy intensiveness. An acceptance of 70% was obtained for treatments with clearance < 30 mL/min, of 41.8% for treatments with 30-60 mL/min, of 31.5% for prophylaxis, and of 21.4% for low-risk patients. 1. Program repercussions improve prescription safety. 2. Scarce literature and a belief in low molecular weight heparin safety account for responses regarding pharmaceutical intervention. 3. Integrated computerized systems are essential for the implementation of intensive pharmaceutical care programs.

  6. Hypoglycemic effect of polysaccharides with different molecular weight of Pseudostellaria heterophylla

    PubMed Central

    2013-01-01

    Abstracts Background The aims of this study were to evaluate the antidiabetic activity and to detect molecular size of Pseudostellaria heterophylla polysaccharide (PHP). Pseudostellaria heterophylla is a medicine extensively used in traditional Chinese medicine formulas to treat diabetes and its complications. Methods Molecular weight of PHP was determined by gel permeation chromatography combined with phenol-sulphuric acid method and the monosaccharides composition was determined by HPLC with a precolumn derivatization. Four polysaccharides with different molecular weight were compared for hypoglycemic active on two animal models both high does alloxan induced type1 diabetic mellitus (T1DM) and high-fat/lower does streptozotocin induced type2 diabetic mellitus (T2DM). Blood sugar, glucose tolerance, and insulin tolerance were detected. Rat serum IL-1β, IL-2, IL-10, Leptin, TNF-α, Acrp30 and CRP were also analyzed by sandwich-ELISA approaches to preliminary probe the hypoglycemic mechanism of PHP. Results The hypoglycemic effects related to molecular size of polysaccharide were more effective against T2DM than T1DM. PHP comprise four monosaccharides of galacturonic acid, glucose, galactose and arabinos. T2DM rats daily receiving oral dose of polysaccharide(100 ~ 400 mg/kg) with 50 ~ 210 kDa molecular weight (PF40) could not only significantly lower blood sugar but also reduce total triglyceride level in serum. PF40 improves in insulin tolerance inhibited the expression of some biomarkers including inflammatory cytokine TNF-α and elevated anti-inflammatory cytokine IL-10, regulated adiponectin Acrp30 and leptin. Conclusions PF40 prevent the cascade of inflammatory events in the treatment of T2DM to block overweight progresses to obesity. PMID:24131482

  7. Stable, concentrated solutions of high molecular weight polyaniline and articles therefrom

    DOEpatents

    Mattes, Benjamin R.; Wang, Hsing-Lin

    1999-11-09

    Stable, concentrated solutions of high molecular weight polyaniline. In order to process high quality fibers and other articles possessing good mechanical properties, it is known that solution concentrations of the chosen polymer should be in the range from 15-30% (w/w). Moreover, it is desirable to use the highest molecular weight consistent with the solubility properties of the polymer. However, such solutions are inherently unstable, forming gels before processing can be achieved. The present invention describes the addition gel inhibitors (GIs) to the polymer solution, thereby permitting high concentrations (between 15% and 30% (w/w)) of high molecular weight ((M.sub.w)>120,000, and (M.sub.n)>30,000) emeraldine base (EB) polyaniline to be dissolved. Secondary amines have been used for this purpose in concentrations which are small compared to those which might otherwise be used in a cosolvent role therefor. The resulting solutions are useful for generating excellent fibers, films, coatings and other objects, since the solutions are stable for significant time periods, and the GIs are present in too small concentrations to cause polymer deterioration. It is demonstrated that the GIs found to be useful do not act as cosolvents, and that gelation times of the solutions are directly proportional to the concentration of GI. In particular, there is a preferred concentration of GI, which if exceeded causes structural and electrical conductivity degradation of resulting articles. Heating of the solutions significantly improves solubility.

  8. Stable, concentrated solutions of high molecular weight polyaniline and articles therefrom

    DOEpatents

    Mattes, Benjamin R.; Wang, Hsing-Lin

    2000-01-01

    Stable, concentrated solutions of high molecular weight polyaniline. In order to process high quality fibers and other articles possessing good mechanical properties, it is known that solution concentrations of the chosen polymer should be in the range from 15-30% (w/w). Moreover, it is desirable to use the highest molecular weight consistent with the solubility properties of the polymer. However, such solutions are inherently unstable, forming gels before processing can be achieved. The present invention describes the addition gel inhibitors (GIs) to the polymer solution, thereby permitting high concentrations (>15% (w/w)) of high molecular weight ((M.sub.w)>120,000, and (M.sub.n)>30,000) emeraldine base (EB) polyaniline to be dissolved. Secondary amines have been used for this purpose in concentrations which are small compared to those which might otherwise be used in a cosolvent role therefor. The resulting solutions are useful for generating excellent fibers, films, coatings and other objects, since the solutions are stable for significant time periods, and the GIs are present in too small concentrations to cause polymer deterioration. It is demonstrated that the GIs found to be useful do not act as cosolvents, and that gelation times of the solutions are directly proportional to the concentration of GI. In particular, there is a preferred concentration of GI, which if exceeded causes structural and electrical conductivity degradation of resulting articles. Heating of the solutions significantly improves solubility.

  9. Low molecular-weight phenols in Tannat wines made by alternative winemaking procedures.

    PubMed

    Favre, Guzmán; Peña-Neira, Álvaro; Baldi, Cecilia; Hernández, Natalia; Traverso, Sofía; Gil, Graciela; González-Neves, Gustavo

    2014-09-01

    Low molecular weight phenols of Tannat red wines produced by Traditional Maceration (TM), Prefermentative Cold Maceration (PCM), Maceration Enzyme (ENZ) and grape-Seed Tannins additions (ST), were performed and discussed. Alternatives to TM increased wine phenolic contents but unequally, ST increased mainly smaller flavans-3-ol, PCM anthocyanins and ENZ proanthocyanidins (up to 2250 mg/L). However low molecular weight flavan-3-ols remained below 9 mg/L in all wines, showing that there is not necessarily a correspondence between wine richness in total tannins and flavan-3-ols contents at low molecular weight. PCM wines had particularly high concentrations of tyrosol and tryptophol, yeast metabolism derived compounds. The use of grape-seed enological tannins did not increase grape seed derived phenolic compounds such as gallic acid. Caftaric acid was found in concentrations much higher than those reported in other grape varieties. Wine phenolic content and composition was considerably affected by the winemaking procedures tested. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Rectus sheath hematoma with low molecular weight heparin administration: a case series.

    PubMed

    Sullivan, Laura E J; Wortham, Dale C; Litton, Kayleigh M

    2014-09-01

    Rectus sheath hematoma is an uncommon but potentially serious bleeding complication that can occur spontaneously or as a result of anticoagulation administration. Case number one: A 62 year old chronically ill Caucasian female develops a rectus sheath hematoma seven days after hospital discharge. The previous hospitalization included low molecular weight heparin administration for deep vein thrombosis prophylaxis. The patient ultimately chooses comfort care and expires due to sepsis and respiratory failure. Case number two: A 79 year old Caucasian male develops a rectus sheath hematoma during hospital admission where LMWH is used for deep vein thrombosis prophylaxis. He is managed conservatively; however, his hematocrit drops from 46 to 25.8%. Case number three: A 44 year old chronically ill Caucasian female is treated with therapeutic low molecular weight heparin for recent deep vein thrombosis during a hospital admission. She develops a large rectus sheath hematoma requiring embolization as well as blood transfusion. We believe this reflects an underreported significant cause of morbidity and mortality with low molecular weight heparin administration. We review the pathophysiology of rectus sheath hematoma as well as its presentation, diagnosis, and treatment. We identify at-risk populations and proposed contributing factors. We also discuss factors leading to underreporting as well as preventive strategies implemented at our institution.

  11. Analysis of low molecular weight compounds by MALDI-FTICR-MS.

    PubMed

    Wang, Hao-Yang; Chu, Xu; Zhao, Zhi-Xiong; He, Xiao-Shuang; Guo, Yin-Long

    2011-05-15

    This review focuses on recent applications of matrix-assisted laser desorption ionization-Fourier-transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS) in qualitative and quantitative analysis of low molecular weight compounds. The scope of the work includes amino acids, small peptides, mono and oligosaccharides, lipids, metabolic compounds, small molecule phytochemicals from medicinal herbs and even the volatile organic compounds from tobacco. We discuss both direct analysis and analysis following derivatization. In addition we review sample preparation strategies to reduce interferences in the low m/z range and to improve sensitivities by derivatization with charge tags. We also present coupling of head space techniques with MALDI-FTICR-MS. Furthermore, omics analyses based on MALDI-FTICR-MS were also discussed, including proteomics, metabolomics and lipidomics, as well as the relative MS imaging for bio-active low molecular weight compounds. Finally, we discussed the investigations on dissociation/rearrangement processes of low molecular weight compounds by MALDI-FTICR-MS. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Hypoglycemic Effect of Chinese Yam (Dioscorea opposita rhizoma) Polysaccharide in Different Structure and Molecular Weight.

    PubMed

    Li, Qian; Li, Wenzhi; Gao, Qunyu; Zou, Yuxiao

    2017-10-01

    Three new Chinese yam polysaccharides (namely HSY, huaishanyao in Chinese) were isolated using the methods of boiled water extraction and stepwise ethanolic precipitation, combined with the tangential flow ultrafiltration membrane system. Their molecular weights were determined by high performance gel permeation chromatography. Three type yam polysaccharides in different molecular weight were isolated: HSY-I (>50 kDa), HSY-II (10 to 50 kDa), HSY-III (<10 kDa). The monosaccharide and glycosidic bond links composition were analyzed with GC and Smith degradation. The structure characteristics were further discussed combined with infrared spectrophotometry. Dexamethasone-induced insulin resistance glucose/lipid metabolism diabetic mice model was established to evaluate the hypoglycemic effect of different concentration of HSY and different molecular weights polysaccharide HSY-I, HSY-II, and HSY-III. The results indicated that the HSY polysaccharide mixture, HSY-I and HSY-II had hypoglycemic effect. Three polysaccharides from Chinese yam tuber were isolated in this study. Their structures were characterized and hypoglycemic effects were evaluated. The result clearly identified the benefits of this plant as a healthy functional food. © 2017 Institute of Food Technologists®.

  13. Externally initiated regioregular P3HT with controlled molecular weight and narrow polydispersity.

    PubMed

    Bronstein, Hugo A; Luscombe, Christine K

    2009-09-16

    The ability of chemists to design and synthesize pi-conjugated organic polymers with precise control remains the key to technological breakthroughs for using polymer materials in electronic and photonic devices. In this communication, the controlled chain-growth polymerization of regioregular poly(3-hexylthiophene) (P3HT) from an external initiator using 1,3-bis(diphenylphosphino)propane (dppp) as a catalyst ligand is reported. The complexes cis-chloro(phenyl)(dppp)nickel(II) and cis-chloro(o-tolyl)(dppp)nickel(II) were synthesized and characterized by (31)P NMR spectroscopy. These complexes served as initiators in the polymerization of 2-bromo-5-chloromagnesio-3-hexylthiophene in THF at room temperature, affording fully regioregular P3HT with controlled molecular weights and narrow molecular weight distributions, as demonstrated by gel-permeation chromatography and (1)H NMR spectroscopy. MALDI-TOF mass spectrometry revealed that the polymers had almost complete incorporation of the initiating aryl group, and when the aryl group was o-tolyl, only Tol/H end groups were observed. Although external initiators have been used previously with a PPh(3) ligand, that methodology led to polymers with broad molecular weight distributions. This is the first example in which complete control over the externally initiated P3HT polymerization has been achieved.

  14. Graphene Nanocomposites with High Molecular Weight Poly(ε-caprolactone) Grafts: Controlled Synthesis and Accelerated Crystallization

    DOE PAGES

    Mondal, Titash; Ashkar, Rana; Butler, Paul; ...

    2016-02-08

    Grafting of high molecular weight polymers to graphitic nanoplatelets is a critical step toward the development of high performance graphene nanocomposites. However, designing such a grafting route has remained a major impediment. Herein, we report a "grafting to" synthetic pathway by which high molecular weight polymer, poly(e-caprolactone) (PCL), is tethered, at high grafting density, to highly anisotropic graphitic nanoplatelets. The efficacy of this tethering route and the resultant structural arrangements within the composite are confirmed by neutron and X-ray scattering measurements in the melt and solution phase. In the semicrystalline state, Xray analysis indicates that chain tethering onto the graphiticmore » nanoplatelets results in conformational changes of the polymer chains, which enhance the nucleation process and aid formation of PCL crystallites. This is corroborated by the superior thermal properties of the composite, manifested in accelerated crystallization kinetics and a significant increase in the thermal degradation temperature. Lastly, in principle, this synthesis route can be extended to a variety of high molecular weight polymers, which can open new avenues to solution-based processing of graphitic nanomaterials and the fabrication of complex 3D patterned graphitic nanocomposites.« less

  15. Synthesis of High-Molecular-Weight Polyhydroxyalkanoates by Marine Photosynthetic Purple Bacteria

    PubMed Central

    Higuchi-Takeuchi, Mieko; Morisaki, Kumiko; Toyooka, Kiminori; Numata, Keiji

    2016-01-01

    Polyhydroxyalkanoate (PHA) is a biopolyester/bioplastic that is produced by a variety of microorganisms to store carbon and increase reducing redox potential. Photosynthetic bacteria convert carbon dioxide into organic compounds using light energy and are known to accumulate PHA. We analyzed PHAs synthesized by 3 purple sulfur bacteria and 9 purple non-sulfur bacteria strains. These 12 purple bacteria were cultured in nitrogen-limited medium containing acetate and/or sodium bicarbonate as carbon sources. PHA production in the purple sulfur bacteria was induced by nitrogen-limited conditions. Purple non-sulfur bacteria accumulated PHA even under normal growth conditions, and PHA production in 3 strains was enhanced by nitrogen-limited conditions. Gel permeation chromatography analysis revealed that 5 photosynthetic purple bacteria synthesized high-molecular-weight PHAs, which are useful for industrial applications. Quantitative reverse transcription polymerase chain reaction analysis revealed that mRNA levels of phaC and PhaZ genes were low under nitrogen-limited conditions, resulting in production of high-molecular-weight PHAs. We conclude that all 12 tested strains are able to synthesize PHA to some degree, and we identify 5 photosynthetic purple bacteria that accumulate high-molecular-weight PHA molecules. Furthermore, the photosynthetic purple bacteria synthesized PHA when they were cultured in seawater supplemented with acetate. The photosynthetic purple bacteria strains characterized in this study should be useful as host microorganisms for large-scale PHA production utilizing abundant marine resources and carbon dioxide. PMID:27513570

  16. Influence of molecular weight on in vitro immunostimulatory properties of instant coffee.

    PubMed

    Passos, Cláudia P; Cepeda, Márcio R; Ferreira, Sónia S; Nunes, Fernando M; Evtuguin, Dmitry V; Madureira, Pedro; Vilanova, Manuel; Coimbra, Manuel A

    2014-10-15

    Instant coffee was prepared and fractionated into higher (>100kDa), medium (5-10, 10-30, 30-100kDa) and lower (1-5, <1kDa) molecular weight fractions. Sugars and linkage composition characteristics of arabinogalactans and galactomannans were recovered in all fractions. Also, amino acid analysis performed after hydrolysis showed similar compositions in all fractions. On the contrary, free chlorogenic acids and caffeine were only detected in the lowest molecular weight fraction (<1kDa). A direct relationship between the melanoidins browning index and the molecular weight was observed. The fractions obtained were incubated in vitro with murine spleen lymphocytes in order to evaluate their possible immunostimulatory abilities. The surface expression of CD69 (early activation marker) on different lymphocyte sub-populations showed that the fraction with 1-5kDa was able to induce activation of B-lymphocytes. This was the only fraction to induce B-lymphocyte activation, since all the other fractions failed, even when higher concentrations were used. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Molecular weight distribution of phosphorus fraction of aquatic dissolved organic matter.

    PubMed

    Ged, Evan C; Boyer, Treavor H

    2013-05-01

    This study characterized dissolved organic phosphorus (DOP) that is discharged from the Everglades Agricultural Area as part of the larger pool of aquatic dissolved organic matter (DOM). Whole water samples collected at the Everglades stormwater treat area 1 West (STA-1 W) were fractionated using a batch ultrafiltration method to separate organic compounds based on apparent molecular weight (AMW). Each AMW fraction of DOM was characterized for phosphorus, carbon, nitrogen, UV absorbance, and fluorescence. The DOP content of the Everglades water matrix was characteristically variable constituting 4-56% of total phosphorus (TP) and demonstrated no correlation with dissolved organic carbon (DOC). Measured values for DOP exceeded 14μgL(-1) in four out of five sampling dates making phosphorus load reductions problematic for the stormwater treatment areas (STAs), which target inorganic phosphorus and have a goal of 10μgL(-1) as TP. The molecular weight distributions revealed 40% of DOP is high molecular weight, aromatic-rich DOM. The results of this research are expected to be of interest to environmental chemists, environmental engineers, and water resources managers because DOP presents a major obstacle to achieving TP levels <10μgL(-1). Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Mesoporous Silica Chips for Selective Enrichment and Stabilization of Low Molecular Weight Proteome

    PubMed Central

    Bouamrani, Ali; Hu, Ye; Tasciotti, Ennio; Li, Li; Chiappini, Ciro; Liu, Xuewu; Ferrari, Mauro

    2010-01-01

    The advanced properties of mesoporous silica have been demonstrated in applications which include chemical sensing, filtration, catalysis, drug-delivery and selective biomolecular uptake. These properties depend on the architectural, physical and chemical properties of the material, which in turn are determined by the processing parameters in evaporation-induced self-assembly. In this study, we introduce a combinatorial approach for the removal of the high molecular weight proteins and for the specific isolation and enrichment of low molecular weight species. This approach is based on Mesoporous Silica Chips able to fractionate, selectively harvest and protect from enzymatic degradation, peptides and proteins present in complex human biological fluids. We present the characterization of the harvesting properties of a wide range of mesoporous chips using a library of peptides and proteins standard and their selectivity on the recovery of serum peptidome. Using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, we established the correlation between the harvesting specificity and the physico-chemical properties of mesoporous silica surfaces. The introduction of this mesoporous material with fine controlled properties will provide a powerful platform for proteomics application offering a rapid and efficient methodology for low molecular weight biomarker discovery. PMID:20013801

  19. High Molecular Weight Isoforms of Growth Hormone In Cells of the Immune System

    PubMed Central

    Weigent, Douglas A.

    2013-01-01

    A substantial body of research exists to support the idea that cells of the immune system produce growth hormone (GH). However, the structure and mechanism of action of lymphocyte-derived GH continues to remain largely unknown. Here we present the results of Western analysis of whole cell extracts showing that different molecular weight isoforms of GH of approximately 100 kDa, 65 kDa, and 48 kDa can be detected in primary mouse cells of the immune system and in the mouse EL4 cell line. The identity of the 65 kDa and 48 kDa isoforms of GH were confirmed by mass spectrometry. The various isoforms were detected in both enriched T and B spleen cell populations. The large molecular weight isoform appears to reside primarily in the cytoplasm whereas the lower molecular weight 65 kDa and 48 kDa isoforms were detected primarily in the nucleus. These results also suggest that GH isoforms are induced by oxidative stress. In EL4 cells overexpressing GH, the expression of luciferase controlled by a promoter containing the antioxidant response element is increased almost three-fold above control. The data suggest that the induction of isoforms of the GH molecule in cells of the immune system may be an important mechanism of adaptation and/or protection of lymphoid cells under conditions of oxidative stress. PMID:21741628

  20. Molecular weight dependent structure and charge transport in MAPLE-deposited poly(3-hexylthiophene) thin films

    DOE PAGES

    Dong, Ban Xuan; Smith, Mitchell; Strzalka, Joseph; ...

    2018-02-06

    In this work, poly(3-hexylthiophene) (P3HT) films prepared using the matrix-assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE-deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side-chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin-cast films, though the MAPLE-deposited films are more disordered. In-planemore » carrier mobilities in the MAPLE-deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE-deposited simples are consistently lower than those in the solvent-cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique.« less

  1. The Effect of Molecular Weight on the Composite Properties of Cured Phenylethynyl Terminated Imide Oligomers

    NASA Technical Reports Server (NTRS)

    Smith, J. G., Jr.; Connell, J. W.; Hergenrother, P. M.

    1997-01-01

    As part of a program to develop high temperature/high performance structural resins for aeronautical applications, imide oligomers containing terminal phenylethynyl groups with calculated number average molecular weights of 1250, 2500 and 5000 g/mol were prepared, characterized, and evaluated as adhesives and composite matrix resins. The goal of this work was to develop resin systems that are processable using conventional processing equipment into void free composites that exhibit high mechanical properties with long term high temperature durability, and are not affected by exposure to common aircraft fluids. The imide oligomers containing terminal phenylethynyl groups were fabricated into titanium adhesive specimens and IM-7 carbon fiber laminates under 0.1 - 1.4 MPa for 1 hr at 350-371 C. The lower molecular weight oligomers exhibited higher cured Tg, better processability, and better retention of mechanical properties at elevated temperature without significantly sacrificing toughness or damage tolerance than the higher molecular weight oligomer. The neat resin, adhesive and composite properties of the cured polymers will be presented.

  2. Systematic Analysis of Polymer Molecular Weight Influence on the Organic Photovoltaic Performance.

    PubMed

    Katsouras, Athanasios; Gasparini, Nicola; Koulogiannis, Chrysanthos; Spanos, Michael; Ameri, Tayebeh; Brabec, Christoph J; Chochos, Christos L; Avgeropoulos, Apostolos

    2015-10-01

    The molecular weight of an electron donor-conjugated polymer is as essential as other well-known parameters in the chemical structure of the polymer, such as length and the nature of any side groups (alkyl chains) positioned on the polymeric backbone, as well as their placement, relative strength, the ratio of the donor and acceptor moieties in the backbone of donor-acceptor (D-A)-conjugated polymers, and the arrangement of their energy levels for organic photovoltaic performance. Finding the "optimal" molecular weight for a specific conjugated polymer is an important aspect for the development of novel photovoltaic polymers. Therefore, it is evident that the chemistry of functional conjugated polymers faces major challenges and materials have to adopt a broad range of specifications in order to be established for high photovoltaic performance. In this review, the approaches followed for enhancing the molecular weight of electron-donor polymers are presented in detail, as well as how this influences the optoelectronic properties, charge transport properties, structural conformation, morphology, and the photovoltaic performance of the active layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Post-translational modification and stability of low molecular weight cyclin E.

    PubMed

    Mull, B B; Cox, J; Bui, T; Keyomarsi, K

    2009-09-03

    Our laboratory has previously described the presence of five tumor-specific low molecular weight isoforms of cyclin E in both tumor cell lines and breast cancer patient biopsies. We have also shown that one of these low forms arises from an alternate start site, whereas the other four appear as two sets of doublets following cleavage through an elastase-like enzyme. However, the origin of both sets of doublets was unknown. Here, we demonstrate that the larger isoform of each doublet is the result of phosphorylation at a key degradation site. Through site-directed mutagenesis of different phosphorylation sites within the cyclin E protein, we discovered that phosphorylation of threonine 395 is responsible for generating the larger isoform of each doublet. Because phosphorylation of threonine 395 has been linked to the proteasome-mediated degradation of full length cyclin E, we examined the stability of T395A phospho-mutants in both non-tumorigenic mammary epithelial cells and tumor cells. The results revealed that the low molecular weight isoforms appear to be stable in both a tumor cell line and a non-tumor forming cell line regardless of the presence of this critical phosphorylation site. The stability of low molecular weight cyclin E may have implications for both tumorigenesis and treatment of tumors expressing them.

  4. Temperature dependence of viscoelasticity of crystalline cellulose with different molecular weights added to silicone elastomer

    NASA Astrophysics Data System (ADS)

    Sugino, Naoto; Nakajima, Shinya; Kameda, Takao; Takei, Satoshi; Hanabata, Makoto

    2017-08-01

    Silicone elastomers ( polydimethylsiloxane _ PDMS) are widely used in the field of imprint lithography and microcontactprinting (μCP). When performing microcontactprinting, the mechanical properties of the PCMS as a base material have a great influence on the performance of the device. Cellulose nanofibers having features of high strength, high elasticity and low coefficient of linear expansion have attracted attention in recent years due to their characteristics. Therefore, three types of crystalline cellulose having different molecular weights were added to PDMS to prepare a composite material, and dynamic viscoelasticity was measured using a rheometer. The PDMS with the highest molecular weight crystalline cellulose added exhibited smaller storage modulus than PDMS with other molecular weight added in all temperature ranges. Furthermore, when comparing PDMS to which crystalline cellulose was added and PDMS which is not added, the storage modulus of PDMS to which cellulose was added in the low temperature region was higher than that of PDMS to which it was not added, but it was reversed in the high temperature region It was a result. When used in a low temperature range (less than 150 ° C.), it can be said that cellulose can function as a reinforcing material for PDMS.

  5. High Sulfation and a High Molecular Weight Are Important for Anti-hepcidin Activity of Heparin

    PubMed Central

    Asperti, Michela; Naggi, Annamaria; Esposito, Emiliano; Ruzzenenti, Paola; Di Somma, Margherita; Gryzik, Magdalena; Arosio, Paolo; Poli, Maura

    2016-01-01

    Heparins are efficient inhibitors of hepcidin expression even in vivo, where they induce an increase of systemic iron availability. Heparins seem to act by interfering with BMP6 signaling pathways that control the expression of liver hepcidin, causing the suppression of SMAD1/5/8 phosphorylation. The anti-hepcidin activity persists also when the heparin anticoagulant property is abolished or reduced by chemical reactions of oxidation/reduction (glycol-split, Gs-Heparins) or by high sulfation (SS-Heparins), but the structural characteristics needed to optimize this inhibitory activity have not been studied in detail. To this aim we analyzed three different heparins (Mucosal Heparin, the Glycol split RO-82, the partially desulfated glycol-split RO-68 and the oversulfated SSLMWH) and separated them in fractions of molecular weight in the range 4–16 kD. Since the distribution of the negative charges in heparins contributes to the activity, we produced 2-O- and 6-O-desulfated heparins. These derivatives were analyzed for the capacity to inhibit hepcidin expression in hepatic HepG2 cells and in mice. The two approaches produced consistent results and showed that the anti-hepcidin activity strongly decreases with molecular weight below 7 kD, with high N-acetylation and after 2-O and 6-O desulfation. The high sulfation and high molecular weight properties for efficient anti-hepcidin activity suggest that heparin is involved in multiple binding sites. PMID:26955355

  6. Developmental co-expression of small molecular weight apolipoprotein B synthesis and triacylglycerol secretion

    SciTech Connect

    Coleman, R.A.; Haynes, E.B.; Sand, T.M.

    1987-05-01

    The development of the liver's ability to coordinately express the synthesis and secretion of the two major components of very low density lipoproteins (VLDL): triacylglycerol (TG) and apolipoprotein B (apo B) was examined in cultured hepatocytes obtained from fetal, suckling and adult rats. Hepatocytes from fetal and suckling rats synthesized and secreted TG at rates lower than that displayed by adult cells. When TG synthesis was equalized by adding oleic acid to the culture medium, fetal cells still secreted only 39% as much TG as did adult cells. To determine the basis for the apparent defect in VLDL assembly/secretion displayedmore » by fetal cells, the synthesis and secretion of (TVS)methionine-labeled apo B was quantified by immunoprecipitation. Although adult and fetal cells synthesized and secreted large molecular weight apo B at similar rates, the synthesis and secretion of small molecular weight apo B was 2-fold greater in adult cells. These data suggest that the ability to assemble/secrete VLDL triacylglycerol varies in parallel with the developmental expression of small molecular weight apo B. Furthermore, these studies show the usefulness of the cultured rat hepatocyte model for examining the ontogeny and regulation of VLDL assembly/secretion.« less

  7. Molecular weight dependent structure and charge transport in MAPLE-deposited poly(3-hexylthiophene) thin films

    SciTech Connect

    Dong, Ban Xuan; Smith, Mitchell; Strzalka, Joseph

    In this work, poly(3-hexylthiophene) (P3HT) films prepared using the matrix-assisted pulsed laser evaporation (MAPLE) technique are shown to possess morphological structures that are dependent on molecular weight (MW). Specifically, the structures of low MW samples of MAPLE-deposited film are composed of crystallites/aggregates embedded within highly disordered environments, whereas those of high MW samples are composed of aggregated domains connected by long polymer chains. Additionally, the crystallite size along the side-chain (100) direction decreases, whereas the conjugation length increases with increasing molecular weight. This is qualitatively similar to the structure of spin-cast films, though the MAPLE-deposited films are more disordered. In-planemore » carrier mobilities in the MAPLE-deposited samples increase with MW, consistent with the notion that longer chains bridge adjacent aggregated domains thereby facilitating more effective charge transport. The carrier mobilities in the MAPLE-deposited simples are consistently lower than those in the solvent-cast samples for all molecular weights, consistent with the shorter conjugation length in samples prepared by this deposition technique.« less

  8. Early Estrogen Action: Stimulation of the Metabolism of High Molecular Weight and Ribosomal RNAs

    PubMed Central

    Luck, Dennis N.; Hamilton, Terrell H.

    1972-01-01

    Samples of RNA, isolated from uteri of ovariectomized adult rats treated with estrogen, have been analyzed on sucrose gradients. Treatment with estrogen either for 20 min or 2 hr increased the specific activity of all classes of uterine RNA, but produced no significant alteration in the distribution of radioactivity in the gradients, when animals received [3H]uridine intraperitoneally 15 min before they were killed. After labeling periods of 30 min, 1 hr, or 2 hr, however, the RNAs isolated from animals treated with estrogen had a smaller percentage of rapidly sedimenting (faster than 28S) species of RNA than did RNA from animals not treated with the hormone. The decreased percentage of high molecular weight RNA correlated with increases in both the specific activity of 28S and 18S RNA and the concentration of RNA in the whole organ. The labeled RNA of high molecular weight was also demonstrated, by the use of actinomycin D in vivo, to have a more rapid turnover rate in the estrogen-stimulated uterus. Our results indicate that estrogen increases not only the rate of synthesis of ribosomal RNA in the uterus of the ovariectomized adult rat, but also the rate or efficiency of processing of precursor RNA species of high molecular weight. PMID:4500546

  9. Mesoporous silica chips for selective enrichment and stabilization of low molecular weight proteome.

    PubMed

    Bouamrani, Ali; Hu, Ye; Tasciotti, Ennio; Li, Li; Chiappini, Ciro; Liu, Xuewu; Ferrari, Mauro

    2010-02-01

    The advanced properties of mesoporous silica have been demonstrated in applications, which include chemical sensing, filtration, catalysis, drug delivery and selective biomolecular uptake. These properties depend on the architectural, physical and chemical properties of the material, which in turn are determined by the processing parameters in evaporation-induced self-assembly. In this study, we introduce a combinatorial approach for the removal of the high molecular weight proteins and for the specific isolation and enrichment of low molecular weight species. This approach is based on mesoporous silica chips able to fractionate, selectively harvest and protect from enzymatic degradation, peptides and proteins present in complex human biological fluids. We present the characterization of the harvesting properties of a wide range of mesoporous chips using a library of peptides and proteins standard and their selectivity on the recovery of serum peptidome. Using MALDI-TOF-MS, we established the correlation between the harvesting specificity and the physicochemical properties of mesoporous silica surfaces. The introduction of this mesoporous material with fine controlled properties will provide a powerful platform for proteomics application offering a rapid and efficient methodology for low molecular weight biomarker discovery.

  10. Enhancement of mechanical properties of 3D printed hydroxyapatite by combined low and high molecular weight polycaprolactone sequential infiltration.

    PubMed

    Suwanprateeb, Jintamai; Thammarakcharoen, Faungchat; Hobang, Nattapat

    2016-11-01

    A new infiltration technique using a combination of low and high molecular weight polycaprolactone (PCL) in sequence was developed as a mean to improve the mechanical properties of three dimensional printed hydroxyapatite (HA). It was observed that using either high (M n ~80,000) or low (M n ~10,000) molecular weight infiltration could only increase the flexural modulus compared to non-infiltrated HA, but did not affect strength, strain at break and energy at break. In contrast, a combination of low and high molecular infiltration in sequence increased the flexural modulus, strength and energy at break compared to those of non-infiltrated HA or infiltrated by high or low molecular weight PCL alone. This overall enhancement was found to be attributed to the densification of low molecular weight PCL and the reinforcement of high molecular PCL concurrently. The combined low and high molecular weight infiltration in sequence also maintained high osteoblast proliferation and differentiation of the composites at the similar level of the HA. Densification was a dominant mechanism for the change in modulus with porosity and density of the infiltrated HA/PCL composites. However, both densification and the reinforcing performance of the infiltration phase were crucial for strength and toughening enhancement of the composites possibly by the defect healing and stress shielding mechanisms. The sequence of using low molecular weight infiltration and followed by high molecular infiltration was seen to provide the greatest flexural properties and highest cells proliferation and differentiation capabilities.

  11. The High and Low Molecular Weight Forms of Hyaluronan Have Distinct Effects on CD44 Clustering*

    PubMed Central

    Yang, Cuixia; Cao, Manlin; Liu, Hua; He, Yiqing; Xu, Jing; Du, Yan; Liu, Yiwen; Wang, Wenjuan; Cui, Lian; Hu, Jiajie; Gao, Feng

    2012-01-01

    CD44 is a major cell surface receptor for the glycosaminoglycan hyaluronan (HA). Native high molecular weight hyaluronan (nHA) and oligosaccharides of hyaluronan (oHA) provoke distinct biological effects upon binding to CD44. Despite the importance of such interactions, however, the feature of binding with CD44 at the cell surface and the molecular basis for functional distinction between different sizes of HA is still unclear. In this study we investigated the effects of high and low molecular weight hyaluronan on CD44 clustering. For the first time, we provided direct evidence for a strong relationship between HA size and CD44 clustering in vivo. In CD44-transfected COS-7 cells, we showed that exogenous nHA stimulated CD44 clustering, which was disrupted by oHA. Moreover, naturally expressed CD44 was distributed into clusters due to abundantly expressed nHA in HK-2 cells (human renal proximal tubule cells) and BT549 cells (human breast cancer cell line) without exogenous stimulation. Our results suggest that native HA binding to CD44 selectively induces CD44 clustering, which could be inhibited by oHA. Finally, we demonstrated that HA regulates cell adhesion in a manner specifically dependent on its size. oHA promoted cell adhesion while nHA showed no effects. Our results might elucidate a molecular- and/or cellular-based mechanism for the diverse biological activities of nHA and oHA. PMID:23118219

  12. Mass spectrometric techniques for characterizing low-molecular-weight resins used as paint varnishes.

    PubMed

    Bonaduce, I; Colombini, M P; Degano, I; Di Girolamo, F; La Nasa, J; Modugno, F; Orsini, S

    2013-01-01

    The molecular structure of three low-molecular-weight resins used as paint varnishes has been characterized by use of an approach based on three different mass spectrometric techniques. We investigated the ketone resin MS2A, the aldehyde resin Laropal A81, and the hydrocarbon resin Regalrez 1094, now commonly used in restoration. To date, the molecular structures of these resins have not been completely elucidated. To improve current knowledge of the chemical composition of these materials, information obtained by gas chromatography-mass spectrometry (GC/MS), pyrolysis-gas chromatography-mass spectrometry (Py/GC/MS), and electrospray ionization mass spectrometry (ESI-Q-ToF) was combined. Analysis, in solution, of the whole polymeric fraction of the resins by flow-injection ESI-Q-ToF, and of the non-polymeric fraction by GC-MS, enabled us to identify previously unreported features of the polymer structures. In addition, the Py-GC/MS profiles that we obtained will help to enhance the databases currently available in the literature. The proposed approach can be extended to other low-molecular-weight resins used as varnishes in conservation.

  13. Screening the low molecular weight fraction of human serum using ATR-IR spectroscopy.

    PubMed

    Bonnier, Franck; Brachet, Guillaume; Duong, Romain; Sojinrin, Tobiloba; Respaud, Renaud; Aubrey, Nicolas; Baker, Matthew J; Byrne, Hugh J; Chourpa, Igor

    2016-10-01

    Vibrational spectroscopic techniques can detect small variations in molecular content, linked with disease, showing promise for screening and early diagnosis. Biological fluids, particularly blood serum, are potentially valuable for diagnosis purposes. The so-called Low Molecular Weight Fraction (LMWF) contains the associated peptidome and metabolome and has been identified as potentially the most relevant molecular population for disease-associated biomarker research. Although vibrational spectroscopy can deliver a specific chemical fingerprint of the samples, the High Molecular Weight Fraction (HMWF), composed of the most abundant serum proteins, strongly dominates the response and ultimately makes the detection of minor spectral variations a challenging task. Spectroscopic detection of potential serum biomarkers present at relatively low concentrations can be improved using pre-analytical depletion of the HMWF. In the present study, human serum fractionation by centrifugal filtration was used prior to analysis by Attenuated Total Reflection infrared spectroscopy. Using a model sample based on glycine spiked serum, it is demonstrated that the screening of the LMWF can be applied to quantify blinded concentrations up to 50 times lower. Moreover, the approach is easily transferable to different bodily fluids which would support the development of more efficient and suitable clinical protocols exploring vibrational spectroscopy based ex-vivo diagnostic tools. Revealing serum LMWF for spectral serological diagnostic applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Novel strategies to construct complex synthetic vectors to produce DNA molecular weight standards.

    PubMed

    Chen, Zhe; Wu, Jianbing; Li, Xiaojuan; Ye, Chunjiang; Wenxing, He

    2009-05-01

    DNA molecular weight standards (DNA markers, nucleic acid ladders) are commonly used in molecular biology laboratories as references to estimate the size of various DNA samples in electrophoresis process. One method of DNA marker production is digestion of synthetic vectors harboring multiple DNA fragments of known sizes by restriction enzymes. In this article, we described three novel strategies-sequential DNA fragment ligation, screening of ligation products by polymerase chain reaction (PCR) with end primers, and "small fragment accumulation"-for constructing complex synthetic vectors and minimizing the mass differences between DNA fragments produced from restrictive digestion of synthetic vectors. The strategy could be applied to construct various complex synthetic vectors to produce any type of low-range DNA markers, usually available commercially. In addition, the strategy is useful for single-step ligation of multiple DNA fragments for construction of complex synthetic vectors and other applications in molecular biology field.

  15. Differentiating low-molecular-weight heparins based on chemical, biological, and pharmacologic properties: implications for the development of generic versions of low-molecular-weight heparins.

    PubMed

    Jeske, Walter P; Walenga, Jeanine M; Hoppensteadt, Debra A; Vandenberg, Curtis; Brubaker, Aleah; Adiguzel, Cafer; Bakhos, Mamdouh; Fareed, Jawed

    2008-02-01

    Low-molecular-weight heparins (LMWHs) are polypharmacologic drugs used to treat thrombotic and cardiovascular disorders. These drugs are manufactured using different chemical and enzymatic methods, resulting in products with distinct chemical and pharmacologic profiles. Generic LMWHs have been introduced in Asia and South America, and several generic suppliers are seeking regulatory approval in the United States and the European Union. For simple small-molecule drugs, generic drugs have the same chemical structure, potency, and bioavailability as the innovator drug. Applying this definition to complex biological products such as the LMWHs has proved difficult. One major issue is defining appropriate criteria to demonstrate bioequivalence; pharmacopoeial specifications alone appear to be inadequate. Whereas available generic versions of LMWHs exhibit similar molecular and pharmacopoeial profiles, marked differences in their biological and pharmacologic behavior have been noted. Preliminary studies have demonstrated differences in terms of anti-Xa activity and tissue factor pathway inhibitor release after subcutaneous administration, as well as antiplatelet and profibrinolytic effects. The current data emphasize the need to consider multiple functional parameters when defining bioequivalence of biologic drugs with complex structures and activities and also underscore the importance of further pharmacologic studies involving animal models and human clinical trials. The U.S. Food and Drug Administration and the European Medicine Evaluation Agency are currently developing guidelines for the acceptance of biosimilar agents including LMWHs. Until such guidelines are complete, generic interchange may not be feasible.

  16. Effects of polymer molecular weight on relative oral bioavailability of curcumin

    PubMed Central

    Tsai, Yin-Meng; Chang-Liao, Wan-Ling; Chien, Chao-Feng; Lin, Lie-Chwen; Tsai, Tung-Hu

    2012-01-01

    Background Polylactic-co-glycolic acid (PLGA) nanoparticles have been used to increase the relative oral bioavailability of hydrophobic compounds and polyphenols in recent years, but the effects of the molecular weight of PLGA on bioavailability are still unknown. This study investigated the influence of polymer molecular weight on the relative oral bioavailability of curcumin, and explored the possible mechanism accounting for the outcome. Methods Curcumin encapsulated in low (5000–15,000) and high (40,000–75,000) molecular weight PLGA (LMw-NPC and HMw-NPC, respectively) were prepared using an emulsification-solvent evaporation method. Curcumin alone and in the nanoformulations was administered orally to freely mobile rats, and blood samples were collected to evaluate the bioavailability of curcumin, LMw-NPC, and HMw-NPC. An ex vivo experimental gut absorption model was used to investigate the effects of different molecular weights of PLGA formulation on absorption of curcumin. High-performance liquid chromatography with diode array detection was used for quantification of curcumin in biosamples. Results There were no significant differences in particle properties between LMw-NPC and HMw-NPC, but the relative bioavailability of HMw-NPC was 1.67-fold and 40-fold higher than that of LMw-NPC and conventional curcumin, respectively. In addition, the mean peak concentration (Cmax) of conventional curcumin, LMw-NPC, and HMw-NPC was 0.028, 0.042, and 0.057 μg/mL, respectively. The gut absorption study further revealed that the HMw-PLGA formulation markedly increased the absorption rate of curcumin in the duodenum and resulted in excellent bioavailability compared with conventional curcumin and LMw-NPC. Conclusion Our findings demonstrate that different molecular weights of PLGA have varying bioavailability, contributing to changes in the absorption rate at the duodenum. The results of this study provide the rationale for design of a nanomedicine delivery system to

  17. Size and shape of soil humic acids estimated by viscosity and molecular weight.

    PubMed

    Kawahigashi, Masayuki; Sumida, Hiroaki; Yamamoto, Kazuhiko

    2005-04-15

    Ultrafiltration fractions of three soil humic acids were characterized by viscometry and high performance size-exclusion chromatography (HPSEC) in order to estimate shapes and hydrodynamic sizes. Intrinsic viscosities under given solute/solvent/temperature conditions were obtained by extrapolating the concentration dependence of reduced viscosities to zero concentration. Molecular mass (weight average molecular weight (M (w)) and number average molecular weight (M (n))) and hydrodynamic radius (R(H)) were determined by HPSEC using pullulan as calibrant. Values of M (w) and M (n) ranged from 15 to 118 x 10(3) and from 9 to 50 x 10(3) (g mol(-1)), respectively. Polydispersity, as indicated by M (w)/M (n), increased with increasing filter size from 1.5 to 2.4. The hydrodynamic radii (R(H)) ranged between 2.2 and 6.4 nm. For each humic acid, M (w) and [eta] were related. Mark-Houwink coefficients calculated on the basis of the M (w)-[eta] relationships suggested restricted flexible chains for two of the humic acids and a branched structure for the third humic acid. Those structures probably behave as hydrated sphere colloids in a good solvent. Hydrodynamic radii of fractions calculated from [eta] using Einstein's equation, which is applicable to hydrated sphere colloids, ranged from 2.2 to 7.1 nm. These dimensions are fit to the size of nanospaces on and between clay minerals and micropores in soil particle aggregates. On the other hand, the good agreement of R(H) values obtained by applying Einstein's equation with those directly determined by HPSEC suggests that pullulan is a suitable calibrant for estimation of molecular mass and size of humic acids by HPSEC.

  18. Teaching Absolute Value Meaningfully

    ERIC Educational Resources Information Center

    Wade, Angela

    2012-01-01

    What is the meaning of absolute value? And why do teachers teach students how to solve absolute value equations? Absolute value is a concept introduced in first-year algebra and then reinforced in later courses. Various authors have suggested instructional methods for teaching absolute value to high school students (Wei 2005; Stallings-Roberts…

  19. Fluorophore-assisted carbohydrate electrophoresis for the determination of molecular mass of heparins and low-molecular-weight (LMW) heparins.

    PubMed

    Buzzega, Dania; Maccari, Francesca; Volpi, Nicola

    2008-11-01

    We report the use of fluorophore-assisted carbohydrate electrophoresis (FACE) to determine the molecular mass (M) values of heparins (Heps) and low-molecular-weight (LMW)-Hep derivatives. Hep are labeled with 8-aminonaphthalene-1,3,6-trisulfonic acid and FACE is able to resolve each fraction as a discrete band depending on their M. After densitometric acquisition, the migration distance of each Hep standard is acquired and the third-grade polynomial calibration standard curve is determined by plotting the logarithms of the M values as a function of migration ratio. Purified Hep samples having different properties, pharmaceutical Heps and various LMW-Heps were analyzed by both FACE and conventional high-performance size-exclusion liquid chromatography (HPSEC) methods. The molecular weight value on the top of the chromatographic peak (Mp), the number-average Mn, weight-average Mw and polydispersity (Mw/Mn) were examined by both techniques and found to be similar. This approach offers certain advantages over the HPSEC method. The derivatization process with 8-aminonaphthalene-1,3,6-trisulfonic acid is complete after 4 h so that many samples may be analyzed in a day also considering that multiple samples can be run simultaneously and in parallel and that a single FACE analysis requires approx. 15 min. Furthermore, FACE is a very sensitive method as it requires approx. 5-10 microg of Heps, about 10-100-fold lower than samples and standards used in HPSEC evaluation. Finally, the utilization of mini-gels allows the use of very low amounts of reagents with neither expensive equipment nor any complicated procedures having to be applied. This study demonstrates that FACE analysis is a sensitive method for the determination of the M values of Heps and LMW-Heps with possible utilization in virtually any kind of research and development such as quality control laboratories due to its rapid, parallel analysis of multiple samples by means of common and simple largely used

  20. Influence of molecular weight of chemically sulfated citrus pectin fractions on their antithrombotic and bleeding effects.

    PubMed

    Cipriani, Thales R; Gracher, Ana Helena P; de Souza, Lauro M; Fonseca, Roberto J C; Belmiro, Celso L R; Gorin, Philip A J; Sassaki, Guilherme L; Iacomini, Marcello

    2009-05-01

    Evaluated were the anticoagulant and antithrombotic activities, and bleeding effect of two chemically sulfated polysaccharides, obtained from citric pectin, with different average molar masses. Both low-molecular-weight (Pec-LWS, 3,600 g/mol) and high-molecular-weight sulfated pectins (Pec-HWS, 12,000 g/mol) had essentially the same structure, consisting of a (1-->4)-linked alpha-D-GalpA chain with almost all its HO-2 and HO-3 groups substituted by sulfate. Both polysaccharides had anticoagulant activity in vitro, although Pec-HWS was a more potent antithrombotic agent in vivo, giving rise to total inhibition of venous thrombosis at a dose of 3.5 mg/kg body weight. Surprisingly, in contrast with heparin, Pec-HWS and Pec-LWS are able to directly inhibit alpha-thrombin and factor Xa by a mechanism independent of antithrombin (AT) and/or heparin co-factor II (HCII). Moreover, Pec-HWS provided a lower risk of bleeding than heparin at a dose of 100% effectiveness against venous thrombosis, indicating it to be a promising antithrombotic agent.

  1. Effects of aerobic exercise on lipid profiles and high molecular weight adiponectin in Japanese workers.

    PubMed

    Guo, Wei; Kawano, Hiroaki; Piao, Lianhua; Itoh, Nana; Node, Koichi; Sato, Takeshi

    2011-01-01

    The metabolic syndrome is characterized by the accumulation of several metabolic risk factors. It is important to improve physical activity and dietary habits to reduce the risk of cardiovascular disease in humans. The study participants participated in a weekly aerobic exercise program that included a session composed of a brief meeting, warm-up exercises, and primary exercises (low and high impact, stretch, muscle training, and cooling down). To evaluate the effect of this intervention we measured body fat composition, holding power, and quality of life assessment. Blood tests were also carried out before and every 3 months during the study. Of the 37 participants enrolled in the exercise group, 31 (83.8%) completed the 12-week program. The control group consisted of 42 subjects, 36 (85.7%) of whom were available for follow-up at the end of the 12-week study period. In the exercise group, weight, body fat percentage, waist circumference, the World Health Organization quality of life 26 (WHO-QOL 26) score, triglyceride, total cholesterol, high density lipoprotein cholesterol and low density lipoprotein cholesterol had improved significantly at the end of three months. The high molecular weight adiponectin concentration of the participants in the exercise group increased during the 9-month period of the study, although this change did not reach statistical significance compared with pre-exercise. Aerobic exercise led to an improvement in body composition and lipid profiles. High molecular weight adiponectin concentrations tended to improve compared with pre-aerobic exercise levels.

  2. Dextran: Influence of Molecular Weight in Antioxidant Properties and Immunomodulatory Potential.

    PubMed

    Soeiro, Vinicius C; Melo, Karoline R T; Alves, Monique G C F; Medeiros, Mayara J C; Grilo, Maria L P M; Almeida-Lima, Jailma; Pontes, Daniel L; Costa, Leandro S; Rocha, Hugo A O

    2016-08-19

    Dextrans (α-d-glucans) extracted from Leuconostoc mesenteroides, with molecular weights (MW) of 10 (D10), 40 (D40) and 147 (D147) kDa, were evaluated as antioxidant, anticoagulant and immunomodulatory drugs for the first time. None presented anticoagulant activity. As for the antioxidant and immunomodulatory tests, a specific test showed an increase in the dextran activity that was proportional to the increase in molecular weight. In a different assay, however, activity decreased or showed no correlation to the MW. As an example, the reducing power assay showed that D147 was twice as potent as other dextrans. On the other hand, all three samples showed similar activity (50%) when it came to scavenging the OH radical, whereas only the D10 sample showed sharp activity (50%) when it came to scavenging the superoxide ion. D40 was the single dextran that presented with immunomodulatory features since it stimulated the proliferation (~50%) of murine macrophages (RAW 264.7) and decreased the release of nitric oxide (~40%) by the cells, both in the absence and presence of lipopolysaccharides (LPS). In addition, D40 showed a greater scavenging activity (50%) for the hydrogen peroxide, which caused it to also be the more potent dextran when it came to inhibiting lipid peroxidation (70%). These points toward dextrans with a 40 kDa weight as being ideal for antioxidant and immunomodulatory use. However, future studies with the D40 and other similarly 40 kDa dextrans are underway to confirm this hypothesis.

  3. Dextran: Influence of Molecular Weight in Antioxidant Properties and Immunomodulatory Potential

    PubMed Central

    Soeiro, Vinicius C.; Melo, Karoline R. T.; Alves, Monique G. C. F.; Medeiros, Mayara J. C.; Grilo, Maria L. P. M.; Almeida-Lima, Jailma; Pontes, Daniel L.; Costa, Leandro S.; Rocha, Hugo A. O.

    2016-01-01

    Dextrans (α-d-glucans) extracted from Leuconostoc mesenteroides, with molecular weights (MW) of 10 (D10), 40 (D40) and 147 (D147) kDa, were evaluated as antioxidant, anticoagulant and immunomodulatory drugs for the first time. None presented anticoagulant activity. As for the antioxidant and immunomodulatory tests, a specific test showed an increase in the dextran activity that was proportional to the increase in molecular weight. In a different assay, however, activity decreased or showed no correlation to the MW. As an example, the reducing power assay showed that D147 was twice as potent as other dextrans. On the other hand, all three samples showed similar activity (50%) when it came to scavenging the OH radical, whereas only the D10 sample showed sharp activity (50%) when it came to scavenging the superoxide ion. D40 was the single dextran that presented with immunomodulatory features since it stimulated the proliferation (~50%) of murine macrophages (RAW 264.7) and decreased the release of nitric oxide (~40%) by the cells, both in the absence and presence of lipopolysaccharides (LPS). In addition, D40 showed a greater scavenging activity (50%) for the hydrogen peroxide, which caused it to also be the more potent dextran when it came to inhibiting lipid peroxidation (70%). These points toward dextrans with a 40 kDa weight as being ideal for antioxidant and immunomodulatory use. However, future studies with the D40 and other similarly 40 kDa dextrans are underway to confirm this hypothesis. PMID:27548151

  4. Enrichment of low molecular weight serum proteins using acetonitrile precipitation for mass spectrometry based proteomic analysis.

    PubMed

    Kay, Richard; Barton, Chris; Ratcliffe, Lucy; Matharoo-Ball, Balwir; Brown, Pamela; Roberts, Jane; Teale, Phil; Creaser, Colin

    2008-10-01

    A rapid acetonitrile (ACN)-based extraction method has been developed that reproducibly depletes high abundance and high molecular weight proteins from serum prior to mass spectrometric analysis. A nanoflow liquid chromatography/tandem mass spectrometry (nano-LC/MS/MS) multiple reaction monitoring (MRM) method for 57 high to medium abundance serum proteins was used to characterise the ACN-depleted fraction after tryptic digestion. Of the 57 targeted proteins 29 were detected and albumin, the most abundant protein in serum and plasma, was identified as the 20th most abundant protein in the extract. The combination of ACN depletion and one-dimensional nano-LC/MS/MS enabled the detection of the low abundance serum protein, insulin-like growth factor-I (IGF-I), which has a serum concentration in the region of 100 ng/mL. One-dimensional sodium dodecyl sulfate/polyacrylamide gel electrophoresis (SDS-PAGE) analysis of the depleted serum showed no bands corresponding to proteins of molecular mass over 75 kDa after extraction, demonstrating the efficiency of the method for the depletion of high molecular weight proteins. Total protein analysis of the ACN extracts showed that approximately 99.6% of all protein is removed from the serum. The ACN-depletion strategy offers a viable alternative to the immunochemistry-based protein-depletion techniques commonly used for removing high abundance proteins from serum prior to MS-based proteomic analyses.

  5. Lead-binding capacity of calcium pectates with different molecular weight.

    PubMed

    Khotimchenko, Maksim; Makarova, Ksenia; Khozhaenko, Elena; Kovalev, Valeri

    2017-04-01

    Nowadays, heavy metal contamination of environment is considered as a serious threat to public health because of toxicity of these pollutants and the lack of effective materials with metal-binding properties. Some biopolymers such as pectins were proposed for removal of metal ions from industrial water disposals. Chemical structure of pectins is quite variable and substantially affects their metal binding properties. In this work, relationship between molecular weight and Pb(II)-binding capacity of calcium pectates was investigated in a batch sorption system. The results showed that all pectate samples are able to form complexes with Pb(II) ions. The effects of contact time, pH of the media and equilibrium metal concentration on metal-binding process were tested in experiments. The equilibrium time min required for uptake of Pb(II) by pectate compounds was found to be 60min. Langmuir and Freundlich models were applied for description of interactions between pectates and metal ions. Binding capacity of low molecular pectate was highest among all the samples tested. Langmuir model was figured out to be the best fit within the whole range of pH values. These results demonstrate that calcium pectate with low molecular weight is more promising agent for elimination of Pb(II) ions from contaminated wastewaters. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Determination of the low molecular weight fraction of food-grade carrageenans.

    PubMed

    Spichtig, Véronique; Austin, Sean

    2008-01-01

    Recently there has been some debate regarding the presence and associated health risk of low molecular weight carrageenan in foodstuffs. Unfortunately measurement of the low molecular weight tail (LMT) of food-grade carrageenans (defined here as the carrageenan having relative molecular mass (Mr) below 50,000) is not trivial, largely due to its low abundance. So far methods employing light scattering have been unsuccessful in producing reproducible results, probably due to the poor detector response at low masses. In this work a method based on high performance size exclusion chromatography coupled to a refractive index detector (HPSEC-RI) has been used for the measurement of the LMT in food-grade carrageenan ingredients and in a carrageenan-containing finished product (a jelly). Over the course of half a year, 19 measurements were made on a reference carrageenan; the results demonstrated that the method had excellent reproducibility. Applied to a number of different carrageenan ingredients, it was found that, in general, the LMT represents less than 8% of the total carrageenan in ingredients, and under the correct conditions increases little during food processing. The data also indicated that pH appears to be a critical factor during food processing and pH levels below 4.0 should be avoided.

  7. Correlation between human maternal-fetal placental transfer and molecular weight of PCB and dioxin congeners/isomers.

    PubMed

    Mori, Chisato; Nakamura, Noriko; Todaka, Emiko; Fujisaki, Takeyoshi; Matsuno, Yoshiharu; Nakaoka, Hiroko; Hanazato, Masamichi

    2014-11-01

    Establishing methods for the assessment of fetal exposure to chemicals is important for the prevention or prediction of the child's future disease risk. In the present study, we aimed to determine the influence of molecular weight on the likelihood of chemical transfer from mother to fetus via the placenta. The correlation between molecular weight and placental transfer rates of congeners/isomers of polychlorinated biphenyls (PCBs) and dioxins was examined. Twenty-nine sample sets of maternal blood, umbilical cord, and umbilical cord blood were used to measure PCB concentration, and 41 sample sets were used to analyze dioxins. Placental transfer rates were calculated using the concentrations of PCBs, dioxins, and their congeners/isomers within these sample sets. Transfer rate correlated negatively with molecular weight for PCB congeners, normalized using wet and lipid weights. The transfer rates of PCB or dioxin congeners differed from those of total PCBs or dioxins. The transfer rate for dioxin congeners did not always correlate significantly with molecular weight, perhaps because of the small sample size or other factors. Further improvement of the analytical methods for dioxin congeners is required. The findings of the present study suggested that PCBs, dioxins, or their congeners with lower molecular weights are more likely to be transferred from mother to fetus via the placenta. Consideration of chemical molecular weight and transfer rate could therefore contribute to the assessment of fetal exposure. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Controlling Internal Organization of Multilayer Poly(methacrylic acid) Hydrogels with Polymer Molecular Weight

    SciTech Connect

    Kozlovskaya, Veronika; Zavgorodnya, Oleksandra; Ankner, John F.

    Here, we report on tailoring the internal architecture of multilayer-derived poly(methacrylic acid) (PMAA) hydrogels by controlling the molecular weight of poly(N-vinylpyrrolidone) (PVPON) in hydrogen-bonded (PMAA/PVPON) layer-by-layer precursor films. The hydrogels are produced by cross-linking PMAA in the spin-assisted multilayers followed by PVPON release. We found that the thickness, morphology, and architecture of hydrogen-bonded films and the corresponding hydrogels are significantly affected by PVPON chain length. For all systems, an increase in PVPON molecular weight from M w = 2.5 to 1300 kDa resulted in increased total film thickness. We also show that increasing polymer M w smooths the hydrogen-bonded filmmore » surfaces but roughens those of the hydrogels. Using deuterated dPMAA marker layers in neutron reflectometry measurements, we found that hydrogen-bonded films reveal a high degree of stratification which is preserved in the cross-linked films. We observed dPMAA to be distributed more widely in the hydrogen-bonded films prepared with small M w PVPON due to the greater mobility of short-chain PVPON. Furthermore, these variations in the distribution of PMAA are erased after cross-linking, resulting in a distribution of dPMAA over about two bilayers for all M w but being somewhat more widely distributed in the films templated with higher M w PVPON. Finally, our results yield new insights into controlling the organization of nanostructured polymer networks using polymer molecular weight and open opportunities for fabrication of thin films with well-organized architecture and controllable function.« less

  9. Antarctic snow: metals bound to high molecular weight dissolved organic matter.

    PubMed

    Calace, Nicoletta; Nardi, Elisa; Pietroletti, Marco; Bartolucci, Eugenia; Pietrantonio, Massimiliana; Cremisini, Carlo

    2017-05-01

    In this paper we studied some heavy metals (Cu, Zn, Cd, Pb, As, U) probably associated to high molecular weight organic compounds present in the Antarctic snow. Snow-pit samples were collected and analysed for high molecular weight fraction and heavy metals bound to them by means of ultrafiltration treatment. High molecular weight dissolved organic matter (HMW-DOM) recovered by ultrafiltration showed a dissolved organic carbon concentration (HMW-DOC) of about 18-83% of the total dissolved organic carbon measured in Antarctic snow. The characterisation of HMW-DOM fraction evidenced an ageing of organic compounds going from surface layers to the deepest ones with a shift from aliphatic compounds and proteins/amino sugars to more high unsaturated character and less nitrogen content. The heavy metals associated to HMW-DOM fraction follows the order: Zn > Cu > Pb > Cd ∼ As ∼ U. The percentage fraction of metals bound to HMW-DOM respect to total metal content follows the order: Cu > Pb > Zn, Cd in agreement with humic substance binding ability (Irwing-William series). Going down to depth of trench, all metals except arsenic, showed a high concentration peak corresponding to 2.0-2.5 m layer. This result was attributed to particular structural characteristic of organic matter able to form different type of complexes (1:1, 1:2, 1:n) with metals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Capture, enrichment, and mass spectrometric detection of low-molecular-weight biomarkers with nanoporous silicon microparticles.

    PubMed

    Tan, Jie; Zhao, Wei-Jie; Yu, Jie-Kai; Ma, Sai; Sailor, Michael J; Wu, Jian-Min

    2012-11-01

    Mining the disease information contained in the low-molecular-weight range of a proteomic profile is becoming of increasing interest in cancer research. This work evaluates the ability of nanoporous silicon microparticles (NPSMPs) to capture, enrich, protect, and detect low-molecular-weight peptides (LMWPs) sieved from a pool of highly abundant plasma proteins. The average pore size and porosity of NPSMPs are controlled by the electrochemical preparation conditions, and the critical parameters for admission or exclusion of protein with a definite molecular weight are determined by reflectometric-interference Fourier transform spectroscopy (RIFTS). Sodium dodecyl sulfate polyacrylamide-gel electrophoresis (SDS-PAGE) and matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) analysis of the proteins captured by the NPSMPs show that the chemical nature of the NPSMPs surface and the solution pH also play vital roles in determining the affinity of NPSMPs for target analytes. It is found that carboxyl-terminated porous microparticles with a porosity of 26% (pore diameter around 9.0 nm) specifically fractionate, enrich and protect LMWPs sieved from either simulated samples or human serum samples. Moreover, NPSMPs containing captured peptides can be directly spotted onto a MALDI plate. When placed in a conventional MALDI matrix, laser irradiation of the particles results in the release of the target peptides confined in the nanopores, which are then ionized and detected in the MALDI experiment. As a proof-of-principle test case, mass spectra of NPSMPs prepared using serum from colorectal cancer patients and from control patients can be clearly distinguished by statistical analysis. The work demonstrates the utility of the method for discovery of biomarkers in the untapped LMWP fraction of human serum, which can be of significant value in the early diagnosis and management of diseases. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Controlling Internal Organization of Multilayer Poly(methacrylic acid) Hydrogels with Polymer Molecular Weight

    DOE PAGES

    Kozlovskaya, Veronika; Zavgorodnya, Oleksandra; Ankner, John F.; ...

    2015-11-16

    Here, we report on tailoring the internal architecture of multilayer-derived poly(methacrylic acid) (PMAA) hydrogels by controlling the molecular weight of poly(N-vinylpyrrolidone) (PVPON) in hydrogen-bonded (PMAA/PVPON) layer-by-layer precursor films. The hydrogels are produced by cross-linking PMAA in the spin-assisted multilayers followed by PVPON release. We found that the thickness, morphology, and architecture of hydrogen-bonded films and the corresponding hydrogels are significantly affected by PVPON chain length. For all systems, an increase in PVPON molecular weight from M w = 2.5 to 1300 kDa resulted in increased total film thickness. We also show that increasing polymer M w smooths the hydrogen-bonded filmmore » surfaces but roughens those of the hydrogels. Using deuterated dPMAA marker layers in neutron reflectometry measurements, we found that hydrogen-bonded films reveal a high degree of stratification which is preserved in the cross-linked films. We observed dPMAA to be distributed more widely in the hydrogen-bonded films prepared with small M w PVPON due to the greater mobility of short-chain PVPON. Furthermore, these variations in the distribution of PMAA are erased after cross-linking, resulting in a distribution of dPMAA over about two bilayers for all M w but being somewhat more widely distributed in the films templated with higher M w PVPON. Finally, our results yield new insights into controlling the organization of nanostructured polymer networks using polymer molecular weight and open opportunities for fabrication of thin films with well-organized architecture and controllable function.« less

  12. Diabetes reversal by inhibition of the low molecular weight tyrosine phosphatase

    PubMed Central

    Stanford, Stephanie M; Aleshin, Alexander E; Zhang, Vida; Ardecky, Robert J; Hedrick, Michael P; Zou, Jiwen; Ganji, Santhi R.; Bliss, Matthew R; Yamamoto, Fusayo; Bobkov, Andrey A.; Kiselar, Janna; Liu, Yingge; Cadwell, Gregory W; Khare, Shilpi; Yu, Jinghua; Barquilla, Antonio; Chung, Thomas DY; Mustelin, Tomas; Schenk, Simon; Bankston, Laurie A; Liddington, Robert C; Pinkerton, Anthony B; Bottini, Nunzio

    2017-01-01

    Obesity-associated insulin resistance plays a central role in type 2 diabetes. As such, tyrosine phosphatases that dephosphorylate the insulin receptor (IR) are potential therapeutic targets. The low molecular weight protein tyrosine phosphatase (LMPTP) is a proposed IR phosphatase, yet its role in insulin signaling in vivo has not been defined. Here we show that global and liver-specific LMPTP deletion protects mice from high-fat diet-induced diabetes without affecting body weight. To examine the role of the catalytic activity of LMPTP, we developed a small-molecule inhibitor with a novel uncompetitive mechanism, a unique binding site at the opening of the catalytic pocket, and exquisite selectivity over other phosphatases. This inhibitor is orally bioavailable, increases liver IR phosphorylation in vivo, and reverses high-fat diet induced diabetes. Our findings suggest that LMPTP is a key promoter of insulin resistance and that LMPTP inhibitors would be beneficial for treating type 2 diabetes. PMID:28346406

  13. [Low-molecular-weight autoregulatory factors in bacteria Thioalkalivibrio versutus and Thioalkalimicrobium aerophilum].

    PubMed

    Loĭko, N G; Kozlova, A N; Osipov, G A; El'-Registan, G I

    2002-01-01

    The haloalkaliphilic, lithoautotrophic, sulfur-oxidizing gram-negative bacteria Thioalkalivibrio versutus and Thioalkalimicrobium aerophilum were found to possess a special system for the autoregulation of their growth. The system includes the extracellular autoinducers of anabiosis (the d1 factor) and autolysis (the d2 factor). The principal components of the d1 factor are alkylhydroxybenzenes. The principal components of the d2 factor are free unsaturated fatty acids dominated by oleic acid isomers. Like the respective autoregulators of neutrophilic bacteria, the d1 factor of haloalkaliphilic bacteria presumably controls their growth and transition to a anabiotic state, while the d2 factor controls autolytic processes. Alkylhydroxybenzenes of both microbial and chemical origin were found to influence bacterial respiration. The low-molecular-weight osmoprotectant glycine betaine enhanced the thermostability of trypsin. This suggests that glycine betaine, like the d1 factor, serves as a molecular chaperone.

  14. Detection of high molecular weight proteins by MALDI imaging mass spectrometry.

    PubMed

    Mainini, Veronica; Bovo, Giorgio; Chinello, Clizia; Gianazza, Erica; Grasso, Marco; Cattoretti, Giorgio; Magni, Fulvio

    2013-06-01

    MALDI imaging mass spectrometry (IMS) is a unique technology to explore the spatial distribution of biomolecules directly on tissues. It allows the in situ investigation of a large number of small proteins and peptides. Detection of high molecular weight proteins through MALDI IMS still represents an important challenge, as it would allow the direct investigation of the distribution of more proteins involved in biological processes, such as cytokines, enzymes, neuropeptide precursors and receptors. In this work we compare the traditional method performed with sinapinic acid with a comparable protocol using ferulic acid as the matrix. Data show a remarkable increase of signal acquisition in the mass range of 20k to 150k Th. Moreover, we report molecular images of biomolecules above 70k Th, demonstrating the possibility of expanding the application of this technology both in clinical investigations and basic science.

  15. Weighted Distance Functions Improve Analysis of High-Dimensional Data: Application to Molecular Dynamics Simulations.

    PubMed

    Blöchliger, Nicolas; Caflisch, Amedeo; Vitalis, Andreas

    2015-11-10

    Data mining techniques depend strongly on how the data are represented and how distance between samples is measured. High-dimensional data often contain a large number of irrelevant dimensions (features) for a given query. These features act as noise and obfuscate relevant information. Unsupervised approaches to mine such data require distance measures that can account for feature relevance. Molecular dynamics simulations produce high-dimensional data sets describing molecules observed in time. Here, we propose to globally or locally weight simulation features based on effective rates. This emphasizes, in a data-driven manner, slow degrees of freedom that often report on the metastable states sampled by the molecular system. We couple this idea to several unsupervised learning protocols. Our approach unmasks slow side chain dynamics within the native state of a miniprotein and reveals additional metastable conformations of a protein. The approach can be combined with most algorithms for clustering or dimensionality reduction.

  16. Low-molecular-weight heparin use in the obese, elderly, and in renal insufficiency.

    PubMed

    Clark, N P

    2008-01-01

    Superior bioavailability and simple weight-based dosing have made low-molecular-weight heparins (LMWH) the preferred agents for treatment and prevention of venous thromboembolism (VTE) for most indications. Despite improved pharmacokinetics, there remain populations where appropriate LMWH dose intensity and frequency are open to question. Obese patients have a lower proportion of lean body mass as a percentage of total body weight. As a result, LMWH dosing based on total body weight could cause supra-therapeutic anticoagulation. Elderly patients also have less lean body mass in addition to a higher incidence of age-related renal disease and increased risk of bleeding. Renal insufficiency presents a risk of LMWH accumulation as well as increased risk of bleeding. Among LMWH products, only dalteparin labeling recommends a maximum dose. Prospective data call into question the validity of this dose limitation. Additionally, because obese patients are already at higher risk of VTE recurrence, they may be particularly sensitive to subtherapeutic anticoagulation. Prospective data evaluating LMWH use in elderly patients have been limited to in-patient treatment. Few recommendations can be made in this population other than close monitoring. Renal insufficiency is a risk for bleeding during LMWH use. Available evidence supports the potential for enoxaparin accumulation, but not tinzaparin. Enoxaparin dose adjustment, either empiric or based on anti-Xa monitoring, has insufficient data to support widespread implementation. Unfractionated heparin is not reliant on renal elimination and is a sensible option for VTE treatment in patients with a creatinine clearance<30 ml/min.

  17. The preparation and characterization of silk fibroin blended with low molecular weight hydroxypropyl methylcellulose (HPMC)

    NASA Astrophysics Data System (ADS)

    Shetty, G. Rajesha; Rao, B. Lakshmeesha; Gowda, Mahadeva; Shivananda, C. S.; Asha, S.; Sangappa, Y.

    2018-04-01

    In this work, the structure and optical properties of Silk Fibroin (SF), lower molecular weight Hydroxypropyl Methylcellulose (HPMC(L)) and its blend film of SF-HPMC(L) were studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron Microscope (SEM) and UV-Visible spectroscopy (UV-Vis). The results indicates that the homogeneous miscible blend of SF-HPMC(L) has lower crystallite size and lower optical band gap compared to virgin SF and HPMC(L). FTIR study confirms the presence of both SF and HPMC(L) molecules in the prepared blend films.

  18. Study on different molecular weights of chitosan as an immobilization matrix for a glucose biosensor.

    PubMed

    Ang, Lee Fung; Por, Lip Yee; Yam, Mun Fei

    2013-01-01

    Two chitosan samples (medium molecular weight (MMCHI) and low molecular weight (LMCHI)) were investigated as an enzyme immobilization matrix for the fabrication of a glucose biosensor. Chitosan membranes prepared from acetic acid were flexible, transparent, smooth and quick-drying. The FTIR spectra showed the existence of intermolecular interactions between chitosan and glucose oxidase (GOD). Higher catalytic activities were observed on for GOD-MMCHI than GOD-LMCHI and for those crosslinked with glutaraldehyde than using the adsorption technique. Enzyme loading greater than 0.6 mg decreased the activity. Under optimum conditions (pH 6.0, 35°C and applied potential of 0.6 V) response times of 85 s and 65 s were observed for medium molecular weight chitosan glucose biosensor (GOD-MMCHI/PT) and low molecular weight chitosan glucose biosensor (GOD-LMCHI/PT), respectively. The apparent Michaelis-Menten constant ([Formula: see text]) was found to be 12.737 mM for GOD-MMCHI/PT and 17.692 mM for GOD-LMCHI/PT. This indicated that GOD-MMCHI/PT had greater affinity for the enzyme. Moreover, GOD-MMCHI/PT showed higher sensitivity (52.3666 nA/mM glucose) when compared with GOD-LMCHI/PT (9.8579 nA/mM glucose) at S/N>3. Better repeatability and reproducibility were achieved with GOD-MMCHI/PT than GOD-LMCHI/PT regarding glucose measurement. GOD-MMCHI/PT was found to give the highest enzymatic activity among the electrodes under investigation. The extent of interference encountered by GOD-MMCHI/PT and GOD-LMCHI/PT was not significantly different. Although the Nafion coated biosensor significantly reduced the signal due to the interferents under study, it also significantly reduced the response to glucose. The performance of the biosensors in the determination of glucose in rat serum was evaluated. Comparatively better accuracy and recovery results were obtained for GOD-MMCHI/PT. Hence, GOD-MMCHI/PT showed a better performance when compared with GOD-LMCHI/PT. In conclusion

  19. Total internal reflection ellipsometry and SPR detection of low molecular weight environmental toxins

    NASA Astrophysics Data System (ADS)

    Nabok, A. V.; Tsargorodskaya, A.; Hassan, A. K.; Starodub, N. F.

    2005-06-01

    The environmental toxins, such as herbicides simazine and atrazine, and T2 mycotoxin were registered with the optical methods of surface plasmon resonance (SPR) and recently developed total internal reflection ellipsometry (TIRE). The immune assay approach was exploited for in situ registration of the above low molecular weight toxins with specific antibodies immobilised onto the gold surface via (poly)allylamine hydrochloride layer using electrostatic self-assembly (ESA) technique. The comparison of two methods of SPR and TIRE shows a higher sensitivity of the latter.

  20. Modification of polyelectrolyte microcapsules into a container for the low molecular weight compounds

    NASA Astrophysics Data System (ADS)

    Goryacheva, O. A.; Gao, H.; Sukhorukov, G. B.

    2018-04-01

    Polyelectrolyte microcapsules are one of the most successful developments in the direction of target drug delivery. Nevertheless, to encapsulate low molecular weight compounds and to deliver the targeted drugs it is necessary to modify the surface of the microcapsules. Silica nanostructures obtained as result of hydrolysis of (3-Aminopropyl)- triethoxysilane (APTES) were used for the modification of the microcapsules. This material shows no toxic effect on cells and is capable of biodegradation. Amino-groups in the structure of APTES make it possible for further direct bioconjugation.

  1. Rheological Properties of Gels from Pyrene Based Low Molecular Weight Gelators

    SciTech Connect

    Leivo, Kimmo T.; Hahma, Arno P.

    2008-07-07

    Gels of pyrene derived low molecular weight organogelators (LMOGs) in primary alcohols have been characterized by rheometry and scanning electron microscopy. Total gelator concentration was 1-2.7 % w/w depending on the solvent and the gelator, including equimolar amounts of the gelator and 2,4,7-trinitrofluorenone (TNF), which is necessary for gelation. Thermoreversible and strongly shear thinning gels were achieved as the two components interact non-covalently to form a gel network. A qualitative correlation between the rheological properties and the nanoscale gel structure were found.

  2. Rheological Properties of Gels from Pyrene Based Low Molecular Weight Gelators

    NASA Astrophysics Data System (ADS)

    Leivo, Kimmo T.; Hahma, Arno P.

    2008-07-01

    Gels of pyrene derived low molecular weight organogelators (LMOGs) in primary alcohols have been characterized by rheometry and scanning electron microscopy. Total gelator concentration was 1-2.7 % w/w depending on the solvent and the gelator, including equimolar amounts of the gelator and 2,4,7-trinitrofluorenone (TNF), which is necessary for gelation. Thermoreversible and strongly shear thinning gels were achieved as the two components interact non-covalently to form a gel network. A qualitative correlation between the rheological properties and the nanoscale gel structure were found.

  3. An investigation of the preparation of high molecular weight perfluorocarbon polyethers

    NASA Technical Reports Server (NTRS)

    Watts, R. O.; Tarrant, P.

    1972-01-01

    High molecular weight perfluorocarbon polyether gums were obtained by photolysis of perfluorodienes and discyl fluorides containing a perfluorocarbon polyether backbond. The materials obtained are represented by chemical formulas. A method was developed whereby reactive acyl fluoride and trifluorovinyl end groups are converted into inert structures. In order to investigate the possible preparation of difunctional molecules which may be useful in polymer synthesis, the reactions of hexafluoropropene oxide (HFPO) with Grignard and organolithium reagents have been studied. Reactions of various nucleophilic reagents with HFPO were also investigated.

  4. Low-molecular-weight compounds with anticoagulant activity from the scorpion Heterometrus laoticus venom.

    PubMed

    Thien, Tran Vu; Anh, Hoang Ngoc; Trang, Nguyen Thi Thuy; Trung, Phung Van; Khoa, Nguyen Cuu; Osipov, A V; Dubovskii, P V; Ivanov, I A; Arseniev, A S; Tsetlin, V I; Utkin, Yu N

    2017-09-01

    Low-molecular-weight compounds with anticoagulant activity were isolated from the scorpion Heterometrus laoticus venom. The determination of the structure of the isolated compounds by nuclear magnetic resonance and mass spectrometry showed that one of the isolated compounds is adenosine, and the other two are dipeptides leucyl-tryptophan and isoleucyl-tryptophan. The anticoagulant properties of adenosine, which is an inhibitor of platelet aggregation, is well known, but its presence in scorpion venom is shown for the first time. The ability of leucyl-tryptophan and isoleucyl-tryptophan to slow down blood clotting and their presence in scorpion venom are also established for the first time.

  5. Study on Different Molecular Weights of Chitosan as an Immobilization Matrix for a Glucose Biosensor

    PubMed Central

    Ang, Lee Fung; Por, Lip Yee; Yam, Mun Fei

    2013-01-01

    Two chitosan samples (medium molecular weight (MMCHI) and low molecular weight (LMCHI)) were investigated as an enzyme immobilization matrix for the fabrication of a glucose biosensor. Chitosan membranes prepared from acetic acid were flexible, transparent, smooth and quick-drying. The FTIR spectra showed the existence of intermolecular interactions between chitosan and glucose oxidase (GOD). Higher catalytic activities were observed on for GOD-MMCHI than GOD-LMCHI and for those crosslinked with glutaraldehyde than using the adsorption technique. Enzyme loading greater than 0.6 mg decreased the activity. Under optimum conditions (pH 6.0, 35°C and applied potential of 0.6 V) response times of 85 s and 65 s were observed for medium molecular weight chitosan glucose biosensor (GOD-MMCHI/PT) and low molecular weight chitosan glucose biosensor (GOD-LMCHI/PT), respectively. The apparent Michaelis-Menten constant () was found to be 12.737 mM for GOD-MMCHI/PT and 17.692 mM for GOD-LMCHI/PT. This indicated that GOD-MMCHI/PT had greater affinity for the enzyme. Moreover, GOD-MMCHI/PT showed higher sensitivity (52.3666 nA/mM glucose) when compared with GOD-LMCHI/PT (9.8579 nA/mM glucose) at S/N>3. Better repeatability and reproducibility were achieved with GOD-MMCHI/PT than GOD-LMCHI/PT regarding glucose measurement. GOD-MMCHI/PT was found to give the highest enzymatic activity among the electrodes under investigation. The extent of interference encountered by GOD-MMCHI/PT and GOD-LMCHI/PT was not significantly different. Although the Nafion coated biosensor significantly reduced the signal due to the interferents under study, it also significantly reduced the response to glucose. The performance of the biosensors in the determination of glucose in rat serum was evaluated. Comparatively better accuracy and recovery results were obtained for GOD-MMCHI/PT. Hence, GOD-MMCHI/PT showed a better performance when compared with GOD-LMCHI/PT. In conclusion, chitosan membranes shave

  6. Comparison of selected analytical techniques for protein sizing, quantitation and molecular weight determination.

    PubMed

    Goetz, H; Kuschel, M; Wulff, T; Sauber, C; Miller, C; Fisher, S; Woodward, C

    2004-09-30

    Protein analysis techniques are developing fast due to the growing number of proteins obtained by recombinant DNA techniques. In the present paper we compare selected techniques, which are used for protein sizing, quantitation and molecular weight determination: sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE), lab-on-a-chip or microfluidics technology (LoaC), size exclusion chromatography (SEC) and mass spectrometry (MS). We compare advantages and limitations of each technique in respect to different application areas, analysis time, protein sizing and quantitation performance.

  7. Enhanced wear performance of ultra high molecular weight polyethylene crosslinked by organosilane.

    PubMed

    Tang, C Y; Xie, X L; Wu, X C; Li, R K Y; Mai, Y W

    2002-11-01

    Ultra high molecular weight polyethylene (UHMWPE) crosslinked by organosilane was thermal compression molded. The organosilane used was the tri-ethyloxyl vinyl silane. Its gelation, melting behavior, crystallinity, mechanical and wear-resisting properties were systematically investigated. The results showed that the gel ratio of UHMWPE increases with the incorporation of organosilane. At a low content of organosilane, the melting point and crystallinity of the crosslinked UHMWPE increase, and hence the mechanical and wear-resisting properties are improved. However, at a high content of organosilane, these performances of the crosslinked UHMWPE become worse. At 0.4 phr silane, the wear resistance of crosslinked UHMWPE reaches its optimum value.

  8. Release of low molecular weight silicones and platinum from silicone breast implants.

    PubMed

    Lykissa, E D; Kala, S V; Hurley, J B; Lebovitz, R M

    1997-12-01

    We have conducted a series of studies addressing the chemical composition of silicone gels from breast implants as well as the diffusion of low molecular weight silicones (LM-silicones) and heavy metals from intact implants into various surrounding media, namely, lipid-rich medium (soy oil), aqueous tissue culture medium (modified Dulbecco's medium, DMEM), or an emulsion consisting of DMEM plus 10% soy oil. LM-silicones in both implants and surrounding media were detected and quantitated using gas chromatography (GC) coupled with atomic emission (GC-AED) as well as mass spectrometric (GC/MS) detectors, which can detect silicones in the nanogram range. Platinum, a catalyst used in the preparation of silicone gels, was detected and quantitated using inductive argon-coupled plasma/mass spectrometry (ICP-MS), which can detect platinum in the parts per trillion range. Our results indicate that GC-detectable low molecular weight silicones contribute approximately 1-2% to the total gel mass and consist predominantly of cyclic and linear poly-(dimethylsiloxanes) ranging from 3 to 20 siloxane [(CH3)2-Si-O] units (molecular weight 200-1500). Platinum can be detected in implant gels at levels of approximately 700 micrograms/kg by ICP-MS. The major component of implant gels appears to be high molecular weight silicone polymers (HM-silicones) too large to be detected by GC. However, these HM-silicones can be converted almost quantitatively (80% by mass) to LM-silicones by heating implant gels at 150-180 degrees C for several hours. We also studied the rates at which LM-silicones and platinum leak through the intact implant outer shell into the surrounding media under a variety of conditions. Leakage of silicones was greatest when the surrounding medium was lipid-rich, and up to 10 mg/day LM-silicones was observed to diffuse into a lipid-rich medium per 250 g of implant at 37 degrees C. This rate of leakage was maintained over a 7-day experimental period. Similarly, platinum was

  9. ESIprot: a universal tool for charge state determination and molecular weight calculation of proteins from electrospray ionization mass spectrometry data.

    PubMed

    Winkler, Robert

    2010-02-01

    Electrospray ionization (ESI) ion trap mass spectrometers with relatively low resolution are frequently used for the analysis of natural products and peptides. Although ESI spectra of multiply charged protein molecules also can be measured on this type of devices, only average spectra are produced for the majority of naturally occurring proteins. Evaluating such ESI protein spectra would provide valuable information about the native state of investigated proteins. However, no suitable and freely available software could be found which allows the charge state determination and molecular weight calculation of single proteins from average ESI-MS data. Therefore, an algorithm based on standard deviation optimization (scatter minimization) was implemented for the analysis of protein ESI-MS data. The resulting software ESIprot was tested with ESI-MS data of six intact reference proteins between 12.4 and 66.7 kDa. In all cases, the correct charge states could be determined. The obtained absolute mass errors were in a range between -0.2 and 1.2 Da, the relative errors below 30 ppm. The possible mass accuracy allows for valid conclusions about the actual condition of proteins. Moreover, the ESIprot algorithm demonstrates an extraordinary robustness and allows spectral interpretation from as little as two peaks, given sufficient quality of the provided m/z data, without the necessity for peak intensity data. ESIprot is independent from the raw data format and the computer platform, making it a versatile tool for mass spectrometrists. The program code was released under the open-source GPLv3 license to support future developments of mass spectrometry software. Copyright 2010 John Wiley & Sons, Ltd.

  10. Removal of low-molecular weight DBPs and inorganic ions for characterization of high-molecular weight DBPs in drinking water.

    PubMed

    Zhang, Xiangru; Minear, Roger A

    2006-03-01

    High-molecular weight (MW) halogenated disinfection byproducts (DBPs) may cause adverse health effects. In this work several issues related to the better separation and characterization of the high MW halogenated DBPs (MW>500Da) were studied. Ultra-filtration (UF) coupled with a nominal 500-Da membrane was employed to flush out low MW DBPs and inorganic ions. Two procedures, intermittent UF and continuous UF, were used and compared. The results demonstrate that haloacetic acids, chloride and sodium ions could be effectively flushed out, and most of phosphate ions could be flushed out for a given dilution number or sufficient Milli-Q water. The size exclusion chromatograms indicate that haloacetic acids and trihalomethanes were not bound to Suwannee River fulvic acid (SRFA); 2,4,6-trichlorophenol might form some binding with SRFA, but it appeared to be very weak and readily broken up when passing along the size exclusion column. The octanol-water partition coefficients of low MW DBPs and the properties of humic substances seem to play key roles in determining the formation of possible bindings between low MW DBPs and humic substances.

  11. Low-molecular-weight heparin biosimilars: potential implications for clinical practice. Australian Low-Molecular-Weight Heparin Biosimilar Working Group (ALBW).

    PubMed

    Nandurkar, H; Chong, B; Salem, H; Gallus, A; Ferro, V; McKinnon, R

    2014-05-01

    A working group of clinicians and scientists was formed to review the clinical considerations for use of low-molecular-weight heparin (LMWH) biosimilars. LMWH are biological molecules of significant complexity; the full complexity of chemical structure is still to be elucidated. LMWH biosimilars are products that are biologically similar to their reference product and rely on clinical data from a reference product to establish safety and efficacy. The complex nature of LMWH molecules means that it is uncertain whether a LMWH biosimilar is chemically identical to its reference product; this introduces the possibility of differences in activity and immunogenicity. The challenge for regulators and clinicians is to evaluate the level of evidence required to demonstrate that a LMWH is sufficiently similar to the reference product. The consensus opinion of the working group is that prior to clinical use a LMWH biosimilar should have proven efficacy and safety, similar to the reference product with prospective studies, which should be confirmed with a proactive post-marketing pharmacovigilance programme. © 2014 The Authors; Internal Medicine Journal © 2014 Royal Australasian College of Physicians.

  12. Ultrafiltration for the Determination of Cu Complexed with Dissolved Organic Matters of Different Molecular Weight from a Eutrophic River, China.

    PubMed

    Li, Anding; Zhang, Yan; Zhou, Beihai; Xin, Kailing; Gu, Yingnan; Xu, Weijie; Tian, Jie

    2018-05-21

    The molecular weight of dissolved organic matter (DOM) is one of the essential factors controlling the properties of metal complexes. A continuous ultrafiltration experiment was designed to study the properties of Cu complexes with different molecular weights in a river before and after eutrophication. The results showed that the concentration of DOM increased from 26.47 to 38.20 mg/L during the eutrophication process, however, DOM was still dominated by the small molecular weight fraction before and after eutrophication. The amount of Cu-DOM complexes increased with the increasing of molecular weight, however, the amounts of DOM-Cu complexes before eutrophication were higher than those after eutrophication. This is because DOM contained more -COOH and -OH before eutrophication and these functional groups are the active sites complexed with Cu.

  13. Effect of the different chain transfer agents on molecular weight and optical properties of poly(methyl methacrylate)

    NASA Astrophysics Data System (ADS)

    Çetinkaya, Onur; Demirci, Gökhan; Mergo, Paweł

    2017-08-01

    Investigation of molecular weight and optical properties of poly(methyl metacrylate) (PMMA) polymerized in house with different chain transfer agents was studied. Isopropyl alcohol (IPA), n-butyl mercaptan (nBMC) and pentamethyl disilane (PMDS) were used as chain transfer agents. The molecular weight (Mw) of PMMA samples were measured by Ostwald viscometer. Mw of bulk polymer samples were decreased with increase the concentration of chain transfer agents (CTA). Since reactivity of used CTAs is not same, molecular weights of samples which were produced with different type of CTA but same concentration of CTA was varied. Higher concentration of n-BMC showed higher scattering. Transmission of samples could not be correlated with different concentration of CTA. Refractive index of samples was not affected by concentration of CTA nevertheless higher molecular weight of CTA showed higher refractive index.

  14. Effects of the Terminal Structure, Purity, and Molecular Weight of an Amorphous Conjugated Polymer on Its Photovoltaic Characteristics.

    PubMed

    Kuwabara, Junpei; Yasuda, Takeshi; Takase, Naoto; Kanbara, Takaki

    2016-01-27

    The photovoltaic characteristics of an amorphous polymer containing EDOT and fluorene units were investigated. In particular, the effects of the terminal structure, residual amount of Pd, and molecular weight were systematically investigated. Direct arylation polycondensation of EDOT followed by an established purification method readily afforded polymers with different terminal structures, Pd contents, and molecular weights. Of these factors, the terminal structure of the polymer was a crucial factor affecting the photovoltaic characteristics. For example, the polymer with a Br terminal had a PCE of 2.9% in bulk-heterojunction organic photovoltaics (BHJ OPVs) with a fullerene derivative, whereas the polymer without a Br terminal had a PCE of 4.6% in the same cell configuration. The decreased Pd residues and high molecular weights of the polymers increased the long-term stability of the devices. Moreover, BHJ OPVs containing the high-molecular-weight polymer could be fabricated with an environmentally friendly nonhalogenated solvent.

  15. Heat-mediated, ultra-rapid electrophoretic transfer of high and low molecular weight proteins to nitrocellulose membranes.

    PubMed

    Kurien, Biji T; Scofield, R Hal

    2002-08-01

    Here, we report an ultra-rapid method for the transfer of high and low molecular weight proteins to nitrocellulose membranes following sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). In this procedure, the electro-transfer was performed with heated (70-75 degrees C) normal transfer buffer from which methanol had been omitted. Complete transfer of high and low molecular weight proteins (a purified protein, molecular weight protein standards and proteins from a human tissue extract) could be carried out in 10 min for a 0.75-mm, 7% SDS-PAGE gel. For 10% and 12.5% gels (0.75 mm), the corresponding time was 15 min. In the case of 1.5-mm gels, a complete transfer could be carried out in 20 min for 7%, 10% and 12.5% gels. The permeability of the gel is increased by heat, such that the proteins trapped in the polyacrylamide gel matrix can be easily transferred to the membrane. When the heat-mediated transfer method was compared with a conventional transfer protocol, under similar conditions, we found that the latter method transferred minimal low molecular weight proteins while retaining most of the high molecular weight proteins in the gel. In summary, this procedure is very rapid, avoids the use of methanol and is particularly useful for the transfer of high molecular weight proteins.

  16. Effects of Molecular Weight upon Irradiation-Cross-Linked Poly(vinyl alcohol)/Clay Aerogel Properties.

    PubMed

    Chen, Hong-Bing; Zhao, Yan; Shen, Peng; Wang, Jun-Sheng; Huang, Wei; Schiraldi, David A

    2015-09-16

    Facile fabrication of mechanically strong poly(vinyl alcohol) (PVOH)/clay aerogel composites through a combination of increasing polymer molecular weights and gamma irradiation-cross-linking is reported herein. The aerogels produced from high polymer molecular weights exhibit significantly increased compressive moduli, similar to the effect of irradiation-induced cross-linking. The required irradiation dose for fabricating strong PVOH composite aerogels with dense microstructure decreased with increasing polymer molecular weight. Neither thermal stability nor flammability was significantly changed by altering the polymer molecular weight or by modest gamma irradiation, but they were highly dependent upon the polymer/clay ratio in the aerogel. Optimization of the mechanical, thermal, and flammability properties of these composite aerogels could therefore be obtained by using relatively low levels of polymer, with very high polymer molecular weight, or lower molecular weight coupled with moderate gamma irradiation. The facile preparation of strong, low flammability aerogels is an alternative to traditional polymer foams in applications where fire safety is important.

  17. Effects of molecular weight of natural organic matter on cadmium mobility in soil environments and its carbon isotope characteristics.

    PubMed

    Mahara, Y; Kubota, T; Wakayama, R; Nakano-Ohta, T; Nakamura, T

    2007-11-15

    We investigated the role of natural organic matter in cadmium mobility in soil environments. We collected the dissolved organic matter from two different types of natural waters: pond surface water, which is oxic, and deep anoxic groundwater. The collected organic matter was fractionated into four groups with molecular weights (unit: Da (Daltons)) of <1 x 10(3), 1-10 x 10(3), 10-100 x 10(3), and >100 x 10(3). The organic matter source was land plants, based on the carbon isotope ratios (delta(13)C/(12)C). The organic matter in surface water originated from presently growing land plants, based on (14)C dating, but the organic matter in deep groundwater originated from land plants that grew approximately 4000 years ago. However, some carbon was supplied by the high-molecular-weight fraction of humic substances in soil or sediments. Cadmium interacted in a system of siliceous sand, fractionated organic matter, and water. The lowest molecular weight fraction of organic matter (<1 x 10(3)) bound more cadmium than did the higher molecular weight fractions. Organic matter in deep groundwater was more strongly bound to cadmium than was organic matter in surface water. The binding behaviours of organic matter with cadmium depended on concentration, age, molecular weight, and degradation conditions of the organic matter in natural waters. Consequently, the dissolved, low-molecular-weight fraction in organic matter strongly influences cadmium migration and mobility in the environment.

  18. Physical characterization of polyethylene glycols by thermal analytical technique and the effect of humidity and molecular weight.

    PubMed

    Majumdar, R; Alexander, K S; Riga, A T

    2010-05-01

    Polyethylene glycols (PEGs) are well known as excipients in tablet dosage formulations. PEGs are generally known to be inert and have very few interactions with other components in the solid dosage forms. However, the physical nature of PEGs and how they affect the disintegration of tablets is not very well understood for the different molecular weights of PEGs. The knowledge of the effect of molecular weight of PEGs on their physical properties and the effect of humidity on the physical properties of PEGs are important parameters for the choice of a PEG to be acceptable as an excipient in pharmaceutical formulations. This study was done to determine the precision of the DSC physical properties for a wide range of PEGs with varying molecular weights from 194 to 23000 daltons. Nine different molecular weights of PEGs were examined in a DSC controlled Heat-Cool-Heat-Cool-Heat (HCHCH) cycle and the observed reproducible values of melting temperature, heat of fusion, crystallization temperature and the heat of crystallization were compared with values obtained from the literature and the observed percent crystallinity was again cross-checked by X-ray Diffraction (XRD) studies. The comparison values indicated acceptable precision. This study was also done to check the effect of humidity on the DSC physical properties for the entire range of PEGs. The results indicated that humidity probably has a higher effect on the physical properties of the low molecular weight PEGs as compared to the high molecular weight PEGs.

  19. Laser-based methods for the analysis of low molecular weight compounds in biological matrices.

    PubMed

    Kiss, András; Hopfgartner, Gérard

    2016-07-15

    Laser-based desorption and/or ionization methods play an important role in the field of the analysis of low molecular-weight compounds (LMWCs) because they allow direct analysis with high-throughput capabilities. In the recent years there were several new improvements in ionization methods with the emergence of novel atmospheric ion sources such as laser ablation electrospray ionization or laser diode thermal desorption and atmospheric pressure chemical ionization and in sample preparation methods with the development of new matrix compounds for matrix-assisted laser desorption/ionization (MALDI). Also, the combination of ion mobility separation with laser-based ionization methods starts to gain popularity with access to commercial systems. These developments have been driven mainly by the emergence of new application fields such as MS imaging and non-chromatographic analytical approaches for quantification. This review aims to present these new developments in laser-based methods for the analysis of low-molecular weight compounds by MS and several potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. Mass spectrometric profiling of low-molecular-weight volatile compounds--diagnostic potential and latest applications.

    PubMed

    Lechner, Matthias; Rieder, Josef

    2007-01-01

    The theoretical use of mass spectrometric profiling of low-molecular-weight volatile compounds, as one possible method to non-invasively and rapidly diagnose a variety of diseases, such as cancer, infection, and metabolic disorders has greatly raised the profile of this technique over the last ten years. Despite a number of promising results, this technique has not been introduced into common clinical practice yet. The use of mass spectrometric profiling of exhaled air is particularly hampered by various technical problems and basic methodological issues which have only been partially overcome. However, breath analysis aside, recently published studies reveal completely new ideas and concepts on how to establish fast and reliable diagnosis by using this valuable tool. These studies focussed on the headspace screening of various bodily fluids and sample fluids obtained during diagnostic procedures, as well as microbial cell cultures and demonstrated the vast diagnostic potential of this technique in a wide variety of settings, predominantly in vitro. It is the aim of the present review to discuss the most commonly detected low-molecular-weight volatile compounds and to summarize the current potential applications, latest developments and future perspectives of this promising diagnostic approach.

  1. Seasonal Variations of Low Molecular Weight Dicarboxylic Acids in Atmospheric Aerosols at Okinawa Islands, Japan

    NASA Astrophysics Data System (ADS)

    Nakaema, F.; Handa, D.; Tanahara, A.; Arakaki, T.

    2009-04-01

    Low molecular weight dicarboxylic acids are major fraction of water soluble organic compounds in the atmospheric aerosols. Recently, economy of East Asia grows up remarkably, and atmospheric aerosols discharged from this area have been transported to Japan. In this study, we collected aerosol at Cape Hedo (CH) and University of the Ryukyus(UR), and studied the distribution and origin of low molecule dicarboxylic acid. Aerosols were collected on a quartz filter with a high volume air sampler. Low molecular weight dicarboxylic acids extracted by pure water were derivatized to dibutyl esters by reactions with BF3/butanol and were measured by GC-FID. In many samples, oxalic acid showed the highest concentration. Concentration of oxalic acid, malonic acid, succinic acid and malic acid were strongly correlated between the two sampling sites. Oxalic acid occupied on the average 83% and 76% of all the dicarboxylic acid measured for CH samples and UR samples. It is suggested that the aerosols in Okinawa were affected by secondary photochemical reactions, not by the primary emissions from local sources. The seasonal variation of the dicarboxylic acids concentrations in CH and UR showed higher in spring and fall, and a lower in summer. From the back trajectory analysis, dicarboxylic acids concentrations showed higher when an air mass came from East Asia area, and showed lower when it came from Pacific Ocean.

  2. Low molecular weight protamine (LMWP): a nontoxic protamine substitute and an effective cell-penetrating peptide.

    PubMed

    He, Huining; Ye, Junxiao; Liu, Ergang; Liang, Qiuling; Liu, Quan; Yang, Victor C

    2014-11-10

    Low molecular weight protamine (LMWP) is a peptide fragment produced in our laboratory from enzymatic digestion of native protamine. More than 30 papers studying the properties and applications of LMWP have been published by our group in various journals since its initial discovery in 1999. Results have shown that LMWP could completely neutralize the anticoagulant functions of both heparin and low molecular weight heparin (LMWH), with reduced antigenicity and cross-reactivity toward the mice-derived anti-protamine antibodies. Aside from its potential as a heparin/LMWH antagonist, LMWP also shows the ability to retard insulin adsorption by the formation of an insoluble complex, making it a less toxic long-lasting insulin product than the conventional neutral protamine Hagedorn (NPH) insulin for diabetic control. Importantly, LMWP (Sequence: VSRRRRRRGGRRRR), with 10 arginine residues in its structure, could function as a cell-penetrating peptide (CPP), also termed protein transduction domain (PTD), to achieve effective intracellular protein or gene delivery in clinical practice. In this paper, we present a thorough review of our work related to LMWP, with the aim of providing readers an insight into its potential to be a clinical protamine substitute as well as a non-toxic cell penetrating peptide applicable to achieve intracellular protein and gene delivery. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. The integrity of welded interfaces in ultra-high molecular weight polyethylene: Part 2--interface toughness.

    PubMed

    Haughie, David W; Buckley, C Paul; Wu, Junjie

    2006-07-01

    In Part 2 of a study of welding of ultra-high molecular weight polyethylene (UHMWPE), experiments were conducted to measure the interfacial fracture energy of butt welds, for various welding times and temperatures above the melting point. Their toughness was investigated at 37 degrees C in terms of their fracture energy, obtained by adapting the essential work of fracture (EWF) method. However, a proportion of the welded samples (generally decreasing with increasing welding time or temperature) failed in dual ductile/brittle mode, hence invalidating the EWF test. Even those failing in purely ductile mode showed a measurable interface work of fracture only for the highest weld temperature and time: 188 degrees C and 90 min. Results from the model presented in Part 1 show that this corresponds to the maximum reptated molecular weight reaching close to the peak in the molar mass distribution. Hence this work provides the first experimental evidence that the slow rate of self-diffusion in UHMWPE leads to welded interfaces acting as low-toughness crack paths. Since such interfaces exist around every powder particle in processed UHMWPE this problem cannot be avoided, and it must be accommodated in design of hip and knee bearing surfaces made from this polymer.

  4. Insights into the toxicological properties of a low molecular weight fraction from Zoanthus sociatus (Cnidaria).

    PubMed

    Domínguez-Pérez, Dany; Diaz-Garcia, Carlos Manlio; García-Delgado, Neivys; Sierra-Gómez, Yusvel; Castañeda, Olga; Antunes, Agostinho

    2013-08-13

    The phylum Cnidaria is an ancient group of venomous animals, specialized in the production and delivery of toxins. Many species belonging to the class Anthozoa have been studied and their venoms often contain a group of peptides, less than 10 kDa, that act upon ion channels. These peptides and their targets interact with high affinity producing neurotoxic and cardiotoxic effects, and even death, depending on the dose and the administration pathway. Zoanthiniaria is an order of the Subclass Hexacorallia, class Anthozoa, and unlike sea anemone (order Actiniaria), neither its diversity of toxins nor the in vivo effects of the venoms has been exhaustively explored. In this study we assessed some toxicological tests on mice with a low molecular weight fraction obtained by gel filtration in Sephadex G-50 from Zoanthus sociatus crude extract. The gel filtration chromatogram at 280 nm revealed two major peaks, the highest absorbance corresponding to the low molecular weight fraction. The toxicological effects seem to be mostly autonomic and cardiotoxic, causing death in a dose dependent manner with a LD50 of 792 μg/kg. Moreover, at a dose of 600 μg/kg the active fraction accelerated the KCl-induced lethality in mice.

  5. Structure and Activity of a New Low Molecular Weight Heparin Produced by Enzymatic Ultrafiltration

    PubMed Central

    FU, LI; ZHANG, FUMING; LI, GUOYUN; ONISHI, AKIHIRO; BHASKAR, UJJWAL; SUN, PEILONG; LINHARDT, ROBERT J.

    2014-01-01

    The standard process for preparing the low molecular weight heparin (LMWH) tinzaparin, through the partial enzymatic depolymerization of heparin, results in a reduced yield due to the formation of a high content of undesired disaccharides and tetrasaccharides. An enzymatic ultrafiltration reactor for LMWH preparation was developed to overcome this problem. The behavior, of the heparin oligosaccharides and polysaccharides using various membranes and conditions, was investigated to optimize this reactor. A novel product, LMWH-II, was produced from the controlled depolymerization of heparin using heparin lyase II in this optimized ultrafiltration reactor. Enzymatic ultrafiltration provides easy control and high yields (>80%) of LMWH-II. The molecular weight properties of LMWH-II were similar to other commercial LMWHs. The structure of LMWH-II closely matched heparin’s core structural features. Most of the common process artifacts, present in many commercial LWMHs, were eliminated as demonstrated by 1D and 2D nuclear magnetic resonance spectroscopy. The antithrombin III and platelet factor-4 binding affinity of LMWH-II were comparable to commercial LMWHs, as was its in vitro anticoagulant activity. PMID:24634007

  6. Comprehensive Analysis of Low-Molecular-Weight Human Plasma Proteome Using Top-Down Mass Spectrometry.

    PubMed

    Cheon, Dong Huey; Nam, Eun Ji; Park, Kyu Hyung; Woo, Se Joon; Lee, Hye Jin; Kim, Hee Cheol; Yang, Eun Gyeong; Lee, Cheolju; Lee, Ji Eun

    2016-01-04

    While human plasma serves as a great source for disease diagnosis, low-molecular-weight (LMW) proteome (<30 kDa) has been shown to contain a rich source of diagnostic biomarkers. Here we employ top-down mass spectrometry to analyze the LMW proteoforms present in four types of human plasma samples pooled from three healthy controls (HCs) without immunoaffinity depletion and with depletion of the top two, six, and seven high-abundance proteins. The LMW proteoforms were first fractionated based on molecular weight using gel-eluted liquid fraction entrapment electrophoresis (GELFrEE). Then, the GELFrEE fractions containing up to 30 kDa were subjected to nanocapillary-LC-MS/MS, and the high-resolution MS and MS/MS data were processed using ProSightPC 3.0. As a result, a total of 442 LMW proteins and cleaved products, including those with post-translational modifications and single amino acid variations, were identified. From additional comparative analysis of plasma samples without immunoaffinity depletion between HCs and colorectal cancer (CRC) patients via top-down approach, tens of LMW proteoforms, including platelet factor 4, were found to show >1.5-fold changes between the plasma samples of HCs and CRC patients, and six of the LMW proteins were verified by Western blot analysis.

  7. Controllable production of low molecular weight heparins by combinations of heparinase I/II/III.

    PubMed

    Wu, Jingjun; Zhang, Chong; Mei, Xiang; Li, Ye; Xing, Xin-Hui

    2014-01-30

    Enzymatic depolymerization of heparin by heparinases is promising for production of low molecular weight heparins (LMWHs) as anticoagulants, due to its mild reaction conditions and high selectivity. Here, different heparinase combinations were used to depolymerize heparin. Heparinase I and heparinase II can depolymerize heparin more efficiently than heparinase III, respectively, but heparinase III was the best able to protect the anticoagulant activities of LMWHs. Heparinase III and heparinase I/II combinations were able to efficiently depolymerize heparin to LMWHs with higher anticoagulant activity than the LMWHs produced by the respective heparinase I and heparinase II. HepIII and HepI is the best combination for maintaining high anti-IIa activity (75.7 ± 4.21 IU/mg) at the same Mw value. Furthermore, considering both the changes in molecular weight and anticoagulant activity, the action patterns of heparinase I and heparinase II were found not to follow the exolytic and processive depolymerizing mechanism from the reducing end of heparin. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Analysis of sulfates on low molecular weight heparin using mass spectrometry: structural characterization of enoxaparin.

    PubMed

    Gupta, Rohitesh; Ponnusamy, Moorthy P

    2018-05-31

    Structural characterization of low molecular weight heparin (LMWH) is critical to meet biosimilarity standards. In this context, the review focuses on structural analysis of labile sulfates attached to the side-groups of LMWH using mass spectrometry. A comprehensive review of this topic will help readers to identify key strategies for tackling the problem related to sulfate loss. At the same time, various mass spectrometry techniques are presented to facilitate compositional analysis of LMWH, mainly enoxaparin. Areas covered: This review summarizes findings on mass spectrometry application for LMWH, including modulation of sulfates, using enzymology and sample preparation approaches. Furthermore, popular open-source software packages for automated spectral data interpretation are also discussed. Successful use of LC/MS can decipher structural composition for LMWH and help evaluate their sameness or biosimilarity with the innovator molecule. Overall, the literature has been searched using PubMed by typing various search queries such as 'enoxaparin', 'mass spectrometry', 'low molecular weight heparin', 'structural characterization', etc. Expert commentary: This section highlights clinically relevant areas that need improvement to achieve satisfactory commercialization of LMWHs. It also primarily emphasizes the advancements in instrumentation related to mass spectrometry, and discusses building automated software for data interpretation and analysis.

  9. Capillary Electrophoresis-Mass Spectrometry for the Analysis of Heparin Oligosaccharides and Low Molecular Weight Heparin.

    PubMed

    Sun, Xiaojun; Lin, Lei; Liu, Xinyue; Zhang, Fuming; Chi, Lianli; Xia, Qiangwei; Linhardt, Robert J

    2016-02-02

    Heparins, highly sulfated, linear polysaccharides also known as glycosaminoglycans, are among the most challenging biopolymers to analyze. Hyphenated techniques in conjunction with mass spectrometry (MS) offer rapid analysis of complex glycosaminoglycan mixtures, providing detailed structural and quantitative data. Previous analytical approaches have often relied on liquid chromatography (LC)-MS, and some have limitations including long separation times, low resolution of oligosaccharide mixtures, incompatibility of eluents, and often require oligosaccharide derivatization. This study examines the analysis of glycosaminoglycan oligosaccharides using a novel electrokinetic pump-based capillary electrophoresis (CE)-MS interface. CE separation and electrospray were optimized using a volatile ammonium bicarbonate electrolyte and a methanol-formic acid sheath fluid. The online analyses of highly sulfated heparin oligosaccharides, ranging from disaccharides to low molecular weight heparins, were performed within a 10 min time frame, offering an opportunity for higher-throughput analysis. Disaccharide compositional analysis as well as top-down analysis of low molecular weight heparin was demonstrated. Using normal polarity CE separation and positive-ion electrospray ionization MS, excellent run-to-run reproducibility (relative standard deviation of 3.6-5.1% for peak area and 0.2-0.4% for peak migration time) and sensitivity (limit of quantification of 2.0-5.9 ng/mL and limit of detection of 0.6-1.8 ng/mL) could be achieved.

  10. Analysis of low molecular weight metabolites in tea using mass spectrometry-based analytical methods.

    PubMed

    Fraser, Karl; Harrison, Scott J; Lane, Geoff A; Otter, Don E; Hemar, Yacine; Quek, Siew-Young; Rasmussen, Susanne

    2014-01-01

    Tea is the second most consumed beverage in the world after water and there are numerous reported health benefits as a result of consuming tea, such as reducing the risk of cardiovascular disease and many types of cancer. Thus, there is much interest in the chemical composition of teas, for example; defining components responsible for contributing to reported health benefits; defining quality characteristics such as product flavor; and monitoring for pesticide residues to comply with food safety import/export requirements. Covered in this review are some of the latest developments in mass spectrometry-based analytical techniques for measuring and characterizing low molecular weight components of tea, in particular primary and secondary metabolites. The methodology; more specifically the chromatography and detection mechanisms used in both targeted and non-targeted studies, and their main advantages and disadvantages are discussed. Finally, we comment on the latest techniques that are likely to have significant benefit to analysts in the future, not merely in the area of tea research, but in the analytical chemistry of low molecular weight compounds in general.

  11. Structure and activity of a new low-molecular-weight heparin produced by enzymatic ultrafiltration.

    PubMed

    Fu, Li; Zhang, Fuming; Li, Guoyun; Onishi, Akihiro; Bhaskar, Ujjwal; Sun, Peilong; Linhardt, Robert J

    2014-05-01

    The standard process for preparing the low-molecular-weight heparin (LMWH) tinzaparin, through the partial enzymatic depolymerization of heparin, results in a reduced yield because of the formation of a high content of undesired disaccharides and tetrasaccharides. An enzymatic ultrafiltration reactor for LMWH preparation was developed to overcome this problem. The behavior, of the heparin oligosaccharides and polysaccharides using various membranes and conditions, was investigated to optimize this reactor. A novel product, LMWH-II, was produced from the controlled depolymerization of heparin using heparin lyase II in this optimized ultrafiltration reactor. Enzymatic ultrafiltration provides easy control and high yields (>80%) of LMWH-II. The molecular weight properties of LMWH-II were similar to other commercial LMWHs. The structure of LMWH-II closely matched heparin's core structural features. Most of the common process artifacts, present in many commercial LWMHs, were eliminated as demonstrated by 1D and 2D nuclear magnetic resonance spectroscopy. The antithrombin III and platelet factor-4 binding affinity of LMWH-II were comparable to commercial LMWHs, as was its in vitro anticoagulant activity. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  12. Low-Molecular-Weight Plasma Proteome Analysis Using Top-Down Mass Spectrometry.

    PubMed

    Cheon, Dong Huey; Yang, Eun Gyeong; Lee, Cheolju; Lee, Ji Eun

    2017-01-01

    While human plasma has a wealth of diagnostic information regarding the state of the human body in heath and disease, low molecular weight (LMW) proteome (<30 kDa) has been shown to contain a rich source of diagnostic biomarkers. Here we describe a protocol for top-down proteomic analysis to identify and characterize the LMW proteoforms present in four types of human plasma samples without immunoaffinity depletion and with depletion of the top two, six, and seven high-abundance proteins. Each type of plasma sample was first fractionated based on molecular weight using gel-eluted liquid fraction entrapment electrophoresis (GELFrEE). Then, the GELFrEE fractions containing up to 30 kDa were subjected to nanocapillary-LC-MS/MS, and the high-resolution MS and MS/MS data were processed using ProSightPC software. As a result, a total of 442 LMW proteins and cleaved products, including those with posttranslational modifications (PTMs) and single amino acid variations (SAAVs), were identified with a threshold E-value of 1 × 10 -4 from the four types of plasma samples.

  13. Low-molecular-weight hydroxyacids in marine atmospheric aerosol: evidence of a marine microbial origin

    NASA Astrophysics Data System (ADS)

    Miyazaki, Y.; Sawano, M.; Kawamura, K.

    2014-04-01

    Lactic acid (LA) and glycolic acid (GA), which are low-molecular-weight hydroxyacids, were identified in the particle and gas phases within the marine atmospheric boundary layer over the western subarctic North Pacific. Major portion of LA (81%) and GA (57%) were present in the particulate phase, which is consistent with the presence of a hydroxyl group in these molecules leading to the low volatility of the compounds. The average concentration of LA in more biologically influenced marine aerosols (average 33 ± 58 ng m-3) was substantially higher than that in less biologically influenced aerosols (average 11 ± 12 ng m-3). Over the oceacnic region of phytoplankton blooms, the concentration of aerosol LA was comparable to that of oxalic acid, which was the most abundant diacid during the study period. A positive correlation was found between the LA concentrations in more biologically influenced aerosols and chlorophyll a in seawater (r2 = 0.56), suggesting an important production of aerosol LA possibly associated with microbial (e.g., lactobacillus) activity in seawater and/or aerosols. Our finding provides a new insight into the poorly quantified microbial sources of marine organic aerosols (OA) because such low-molecular-weight hydroxyacids are key intermediates for OA formation.

  14. Low-molecular-weight hydroxyacids in marine atmospheric aerosol: evidence of a marine microbial origin

    NASA Astrophysics Data System (ADS)

    Miyazaki, Y.; Sawano, M.; Kawamura, K.

    2014-08-01

    Lactic acid (LA) and glycolic acid (GA), which are low-molecular-weight hydroxyacids, were identified in the particle and gas phases within the marine atmospheric boundary layer over the western subarctic North Pacific. A major portion of LA (81%) and GA (57%) was present in the particulate phase, which is consistent with the presence of a hydroxyl group in these molecules leading to the low volatility of the compounds. The average concentration (±SD) of LA in more biologically influenced marine aerosols (33 ± 58 ng m-3) was substantially higher than that in less biologically influenced aerosols (11 ± 12 ng m-3). Over the oceanic region of phytoplankton blooms, the concentration of aerosol LA was comparable to that of oxalic acid, which was the most abundant diacid during the study period. A positive correlation was found between the LA concentrations in more biologically influenced aerosols and chlorophyll a in seawater (r2 = 0.56), suggesting an important production of aerosol LA possibly associated with microbial (e.g., lactobacillus) activity in seawater and/or aerosols. Our finding provides a new insight into the poorly quantified microbial sources of marine organic aerosols (OAs) because such low-molecular-weight hydroxyacids are key intermediates for OA formation.

  15. The low molecular weight fraction of compounds released from immature wheat pistils supports barley pollen embryogenesis.

    PubMed

    Lippmann, Rico; Friedel, Swetlana; Mock, Hans-Peter; Kumlehn, Jochen

    2015-01-01

    Pollen embryogenesis provides a useful means of generating haploid plants for plant breeding and basic research. Although it is well-established that the efficacy of the process can be enhanced by the provision of immature pistils as a nurse tissue, the origin and compound class of the signal molecule(s) involved is still elusive. Here, a micro-culture system was established to enable the culturing of populations of barley pollen at a density too low to allow unaided embryogenesis to occur, and this was then exploited to assess the effect of using various parts of the pistil as nurse tissue. A five-fold increase in the number of embryogenic calli formed was obtained by simply cutting the pistils in half. The effectiveness of the pistil-conditioned medium was transitory, since it needed replacement at least every 4 days to measurably ensure embryogenic development. The differential effect of various size classes of compounds present in the pistil-conditioned medium showed that the relevant molecule(s) was of molecular weight below 3 kDa. This work narrows down possible feeder molecules to lower molecular weight compounds and showed that the cellular origin of the active compound(s) is not specific to any tested part of the pistil. Furthermore, the increased recovery of calli during treatment with cut pistils may provide a useful tool for plant breeders and researchers using haploid technology in barley and other plant species.

  16. Low molecular weight hyaluronic acid effects on murine macrophage nitric oxide production.

    PubMed

    Lyle, Daniel B; Breger, Joyce C; Baeva, Larissa F; Shallcross, Jonathan C; Durfor, Charles N; Wang, Nam Sun; Langone, John J

    2010-09-01

    Hyaluronic acid (HA) is increasingly used for a number of medical device applications. Since the chemical structure of HA is identical no matter its bacterial or animal origin, it should be the ideal biomaterial. However, short term transient inflammatory reactions are common, while rare long-term adverse events may correlate with subclinical chronic inflammation. Concern has been raised that low molecular weight components or degradation fragments from implanted HA may directly stimulate inflammatory reactions. This study examined a panel of HA molecular weights from the unitary disaccharide up to 1.7 x 10(6) Dalton lengths, in which endotoxin was assayed at a very low level (less than 0.03 EU/mg). The murine cell line RAW 264.7, rat splenocytes, and rat adherent differentiated primary macrophages were assayed for nitric oxide production under a variety of inflammatory conditions plus or minus HA. Under the highest inflammatory states, nitric oxide production was mildly suppressed by HMW-HA while slightly augmented by LMW-HA at mg/mL concentrations. However, at micromolar concentrations fragments below 5000 Daltons, thought to have drug-like qualities, were without effect. These data support the hypothesis that if endotoxin is reduced to an extremely low level, LMW-HA may not directly provoke normal tissue macrophage-mediated inflammatory reactions. (c) 2010 Wiley Periodicals, Inc.

  17. Prostatic origin of a zinc binding high molecular weight protein complex in human seminal plasma.

    PubMed

    Siciliano, L; De Stefano, C; Petroni, M F; Vivacqua, A; Rago, V; Carpino, A

    2000-03-01

    The profile of the zinc ligand high molecular weight proteins was investigated in the seminal plasma of 55 normozoospermic subjects by size exclusion high performance liquid chromatography (HPLC). The proteins were recovered from Sephadex G-75 gel filtration of seminal plasma in three zinc-containing fractions which were then submitted to HPLC analysis. The results were, that in all the samples, the protein profiles showed two peaks with apparent molecular weight of approximately 660 and approximately 250 kDa. Dialysis experiments revealed that both approximately 660 and approximately 250 kDa proteins were able to uptake zinc against gradient indicating their zinc binding capacity. The HPLC analysis of the whole seminal plasma evidenced only the approximately 660 kDa protein complex as a single well quantifying peak, furthermore a positive correlation between its peak area and the seminal zinc values (P < 0.001) was observed. This suggested a prostatic origin of the approximately 660 kDa protein complex which was then confirmed by the seminal plasma HPLC analysis of a subject with agenesis of the Wolffian ducts. Finally the study demonstrated the presence of two zinc binding proteins, approximately 660 and approximately 250 kDa respectively, in human seminal plasma and the prostatic origin of the approximately 660 kDa.

  18. Trypanosoma equiperdum Low Molecular Weight Proteins As Candidates for Specific Serological Diagnosis of Dourine

    PubMed Central

    Luciani, Mirella; Di Febo, Tiziana; Orsini, Massimiliano; Krasteva, Ivanka; Cattaneo, Angela; Podaliri Vulpiani, Michele; Di Pancrazio, Chiara; Bachi, Angela; Tittarelli, Manuela

    2018-01-01

    The diagnosis of dourine can be difficult because the clinical signs of this disease in horses are similar to those of surra, caused by Trypanosoma evansi. Moreover, T. equiperdum and T. evansi are closely related and, so far, they cannot be distinguished using serological tests. In a previous work, the T. equiperdum protein pattern recognized by antibodies from dourine-infected horses and the humoral immune response kinetics were investigated by immunoblotting assay; a total of 20 sera from naturally and experimentally infected horses and from healthy animals were tested. Immunoblotting analysis showed that antibodies from infected horses specifically bind T. equiperdum low molecular weight proteins (from 16 to 35 kDa), which are not recognized by antibodies from uninfected horses. In this work, we tested other 615 sera (7 from naturally infected horses and 608 sera from healthy horses and donkeys): results confirmed the data obtained previously. In addition, six SDS-PAGE bands with molecular weight ranging from 10 to 37 kDa were analyzed by mass spectrometry, in order to identify immunogenic proteins that could be used as biomarkers for the diagnosis of dourine. A total of 167 proteins were identified. Among them, 37 were found unique for T. equiperdum. Twenty-four of them could represent possible candidate diagnostic antigens for the development of serological tests specific for T. equiperdum. PMID:29556505

  19. Insights into the Toxicological Properties of a Low Molecular Weight Fraction from Zoanthus sociatus (Cnidaria)

    PubMed Central

    Domínguez-Pérez, Dany; Diaz-Garcia, Carlos Manlio; García-Delgado, Neivys; Sierra-Gómez, Yusvel; Castañeda, Olga; Antunes, Agostinho

    2013-01-01

    The phylum Cnidaria is an ancient group of venomous animals, specialized in the production and delivery of toxins. Many species belonging to the class Anthozoa have been studied and their venoms often contain a group of peptides, less than 10 kDa, that act upon ion channels. These peptides and their targets interact with high affinity producing neurotoxic and cardiotoxic effects, and even death, depending on the dose and the administration pathway. Zoanthiniaria is an order of the Subclass Hexacorallia, class Anthozoa, and unlike sea anemone (order Actiniaria), neither its diversity of toxins nor the in vivo effects of the venoms has been exhaustively explored. In this study we assessed some toxicological tests on mice with a low molecular weight fraction obtained by gel filtration in Sephadex G-50 from Zoanthus sociatus crude extract. The gel filtration chromatogram at 280 nm revealed two major peaks, the highest absorbance corresponding to the low molecular weight fraction. The toxicological effects seem to be mostly autonomic and cardiotoxic, causing death in a dose dependent manner with a LD50 of 792 μg/kg. Moreover, at a dose of 600 μg/kg the active fraction accelerated the KCl-induced lethality in mice. PMID:23945599

  20. Plasma zinc's alter ego is a low-molecular-weight humoral factor.

    PubMed

    Ou, Ou; Allen-Redpath, Keith; Urgast, Dagmar; Gordon, Margaret-Jane; Campbell, Gill; Feldmann, Jörg; Nixon, Graeme F; Mayer, Claus-Dieter; Kwun, In-Sook; Beattie, John H

    2013-09-01

    Mild dietary zinc deprivation in humans and rodents has little effect on blood plasma zinc levels, and yet cellular consequences of zinc depletion can be detected in vascular and other tissues. We proposed that a zinc-regulated humoral factor might mediate the effects of zinc deprivation. Using a novel approach, primary rat vascular smooth muscle cells (VSMCs) were treated with plasma from zinc-deficient (<1 mg Zn/kg) or zinc-adequate (35 mg Zn/kg, pair-fed) adult male rats, and zinc levels were manipulated to distinguish direct and indirect effects of plasma zinc. Gene expression changes were analyzed by microarray and qPCR, and incubation of VSMCs with blood plasma from zinc-deficient rats strongly changed the expression of >2500 genes, compared to incubation of cells with zinc-adequate rat plasma. We demonstrated that this effect was caused by a low-molecular-weight (∼2-kDa) zinc-regulated humoral factor but that changes in gene expression were mostly reversed by adding zinc back to zinc-deficient plasma. Strongly regulated genes were overrepresented in pathways associated with immune function and development. We conclude that zinc deficiency induces the production of a low-molecular-weight humoral factor whose influence on VSMC gene expression is blocked by plasma zinc. This factor is therefore under dual control by zinc.

  1. Assembly and Characterization ofWell-DefinedHigh-Molecular-Weight Poly(p-phenylene) Polymer Brushes

    SciTech Connect

    Chen, Jihua; Dadmun, Mark D; Mays, Jimmy

    2011-01-01

    The assembly and characterization of well-de ned, end-tethered poly- (p-phenylene) (PPP) brushes having high molecular weight, low polydispersity and high 1,4-stereoregularity are presented. The PPP brushes are formed using a precursor route that relies on either self-assembly or spin coating of high molecular weight (degrees of poly- merizations 54, 146, and 238) end-functionalized poly(1,3-cyclohexadiene) (PCHD) chains from benzene solutions onto silicon or quartz substrates, followed by aromatization of the end-attached PCHD chains on the surface. The approach allows the thickness (grafting density) of the brushes to be easily varied. The dry brushes before and after aromatization are characterized by ellipsometry,more » atomic force microscopy, grazing angle attenuated total re ectance Fourier transform infrared spectroscopy, and UV-Vis spectros- copy. The properties of the PPP brushes are compared with those of lms made using oligo- paraphenylenes and with ab initio density functional theory simulations of optical proper- ties. Our results suggest conversion to fully aromatized, end-tetheredPPPpolymerbrusheshaving eective conjugation lengths of 5 phenyl units.« less

  2. Assembly and Characterization of Well Defined High Molecular Weight Poly(p-phenylene) Polymer Brushes

    SciTech Connect

    Alonzo Calderon, Jose E; Kilbey, II, S Michael; Ankner, John Francis

    2011-01-01

    The assembly and characterization of well-defined, end-tethered poly(p-phenylene) (PPP) brushes having high molecular weight, low polydispersity and high 1,4-stereoregularity are presented. The PPP brushes are formed using a precursor route that relies on either self-assembly or spin coating of high molecular weight (degrees of polymerizations 54, 146, and 238) end-functionalized poly(1,3-cyclohexadiene) (PCHD) chains from benzene solutions onto silicon or quartz substrates, followed by aromatization of the end-attached PCHD chains on the surface. The approach allows the thickness (grafting density) of the brushes to be easily varied. The dry brushes before and after aromatization are characterized by ellipsometry, atomic force microscopy,more » grazing angle attenuated total reflectance Fourier transform infrared spectroscopy, and UV-Vis spectroscopy. The properties of the PPP brushes are compared with those of films made using oligo-paraphenylenes and with ab initio density functional theory simulations of optical properties. Our results suggest conversion to fully aromatized, end-tethered PPP polymer brushes having effective conjugation lengths of 5 phenyl units.« less

  3. The association of low-molecular-weight hydrophobic compounds with native casein micelles in bovine milk

    PubMed Central

    Cheema, M.; Mohan, M. S.; Campagna, S. R.; Jurat-Fuentes, J. L.; Harte, F. M.

    2015-01-01

    The agreed biological function of the casein micelles in milk is to carry minerals (calcium, magnesium, and phosphorus) from mother to young along with amino acids for growth and development. Recently, native and modified casein micelles were used as encapsulating and delivery agents for various hydrophobic low-molecular-weight probes. The ability of modified casein micelles to bind certain probes may derive from the binding affinity of native casein micelles. Hence, a study with milk from single cows was conducted to further elucidate the association of hydrophobic molecules into native casein micelles and further understand their biological function. Hydrophobic and hydrophilic extraction followed by ultraperformance liquid chromatography-high resolution mass spectrometry analysis were performed over protein fractions obtained from size exclusion fractionation of raw skim milk. Hydrophobic compounds, including phosphatidylcholine, lyso-phosphatidylcholine, phosphatidylethanolamine, and sphingomyelin, showed strong association exclusively to casein micelles as compared with whey proteins, whereas hydrophilic compounds did not display any preference for their association among milk proteins. Further analysis using liquid chromatography-tandem mass spectrometry detected 42 compounds associated solely with the casein-micelles fraction. Mass fragments in tandem mass spectrometry identified 4 of these compounds as phosphatidylcholine with fatty acid composition of 16:0/18:1, 14:0/16:0, 16:0/16:0, and 18:1/18:0. These results support that transporting low-molecular-weight hydrophobic molecules is also a biological function of the casein micelles in milk. PMID:26074238

  4. Advanced glycation end products (AGEs) and cardiovascular dysfunction: focus on high molecular weight AGEs.

    PubMed

    Deluyker, Dorien; Evens, Lize; Bito, Virginie

    2017-09-01

    Advanced glycation end products (AGEs) are a group of proteins and lipids becoming glycated and oxidized after persistent contact with reducing sugars or short-chain aldehydes with amino group and/or high degree of oxidative stress. The accumulation of AGEs in the body is a natural process that occurs with senescence, when the turnover rate of proteins is reduced. However, increased circulating AGEs have been described to arise at early lifetime and are associated with adverse outcome and survival, in particular in settings of cardiovascular diseases. AGEs contribute to the development of cardiac dysfunction by two major mechanisms: cross-linking of proteins or binding to their cell surface receptor. Recently, growing evidence shows that high-molecular weight AGEs (HMW-AGEs) might be as important as the characterized low-molecular weight AGEs (LMW-AGEs). Here, we point out the targets of AGEs in the heart and the mechanisms that lead to heart failure with focus on the difference between LMW-AGEs and the less characterized HMW-AGEs. As such, this review is a compilation of relevant papers in the form of a useful resource tool for researchers who want to further investigate the role of HMW-AGEs on cardiac disorders and need a solid base to start on this specific topic.

  5. 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.

  6. Extraction of High Molecular Weight DNA from Fungal Rust Spores for Long Read Sequencing.

    PubMed

    Schwessinger, Benjamin; Rathjen, John P

    2017-01-01

    Wheat rust fungi are complex organisms with a complete life cycle that involves two different host plants and five different spore types. During the asexual infection cycle on wheat, rusts produce massive amounts of dikaryotic urediniospores. These spores are dikaryotic (two nuclei) with each nucleus containing one haploid genome. This dikaryotic state is likely to contribute to their evolutionary success, making them some of the major wheat pathogens globally. Despite this, most published wheat rust genomes are highly fragmented and contain very little haplotype-specific sequence information. Current long-read sequencing technologies hold great promise to provide more contiguous and haplotype-phased genome assemblies. Long reads are able to span repetitive regions and phase structural differences between the haplomes. This increased genome resolution enables the identification of complex loci and the study of genome evolution beyond simple nucleotide polymorphisms. Long-read technologies require pure high molecular weight DNA as an input for sequencing. Here, we describe a DNA extraction protocol for rust spores that yields pure double-stranded DNA molecules with molecular weight of >50 kilo-base pairs (kbp). The isolated DNA is of sufficient purity for PacBio long-read sequencing, but may require additional purification for other sequencing technologies such as Nanopore and 10× Genomics.

  7. Partial Hydrothermal Oxidation of High Molecular Weight Unsaturated Carboxylic Acids for Upgrading of Biodiesel Fuel

    NASA Astrophysics Data System (ADS)

    Kawasaki, K.; Jin, F.; Kishita, A.; Tohji, K.; Enomoto, H.

    2007-03-01

    With increasing environmental awareness and crude oil price, biodiesel fuel (BDF) is gaining recognition as a renewable fuel which may be used as an alternative diesel fuel without any modification to the engine. The cold flow and viscosity of BDF, however, is a major drawback that limited its use in cold area. In this study, therefore, we investigated that partial oxidation of high molecular weight unsaturated carboxylic acids in subcritical water, which major compositions in BDF, to upgrade biodiesel fuel. Oleic acid, (HOOC(CH2)7CH=CH(CH2)7CH3), was selected as a model compound of high molecular weight unsaturated carboxylic acids. All experiments were performed with a batch reactor made of SUS 316 with an internal volume of 5.7 cm3. Oleic acid was oxidized at 300 °C with oxygen supply varying from 1-10 %. Results showed that a large amount of carboxylic acids and aldehydes having 8-9 carbon atoms were formed. These experimental results suggest that the hydrothermal oxidative cleavage may mainly occur at double bonds and the cleavage of double bonds could improve the cold flow and viscosity of BDF.

  8. Phase behaviour of oat β-glucan/sodium caseinate mixtures varying in molecular weight.

    PubMed

    Agbenorhevi, Jacob K; Kontogiorgos, Vassilis; Kasapis, Stefan

    2013-05-01

    The isothermal phase behaviour at 5 °C of mixtures of sodium caseinate and oat β-glucan isolates varying in molecular weight (MW) was investigated by means of phase diagram construction, rheometry, fluorescence microscopy and electrophoresis. Phase diagrams indicated that the compatibility of the β-glucan/sodium caseinate system increases as β-glucan MW decreases. Images of mixtures taken at various biopolymer concentrations revealed phase separated domains. Results also revealed that at the state of thermodynamic equilibrium, lower MW samples yielded considerable viscosity in the mixture. At equivalent hydrodynamic volume of β-glucan in the mixtures, samples varying in molecular weight exhibited similar flow behaviour. A deviation dependent on the protein concentration was observed for the high MW sample in the concentrated regime due to the size of β-glucan aggregates formed. Results demonstrate that by controlling the structural features of β-glucan in mixtures with sodium caseinate, informed manipulation of rheological properties in these systems can be achieved. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. High and Low Molecular Weight Hyaluronic Acid Differentially Regulate Human Fibrocyte Differentiation

    PubMed Central

    Maharjan, Anu S.; Pilling, Darrell; Gomer, Richard H.

    2011-01-01

    Background Following tissue injury, monocytes can enter the tissue and differentiate into fibroblast-like cells called fibrocytes, but little is known about what regulates this differentiation. Extracellular matrix contains high molecular weight hyaluronic acid (HMWHA; ∼2×106 Da). During injury, HMWHA breaks down to low molecular weight hyaluronic acid (LMWHA; ∼0.8–8×105 Da). Methods and Findings In this report, we show that HMWHA potentiates the differentiation of human monocytes into fibrocytes, while LMWHA inhibits fibrocyte differentiation. Digestion of HMWHA with hyaluronidase produces small hyaluronic acid fragments, and these fragments inhibit fibrocyte differentiation. Monocytes internalize HMWHA and LMWHA equally well, suggesting that the opposing effects on fibrocyte differentiation are not due to differential internalization of HMWHA or LMWHA. Adding HMWHA to PBMC does not appear to affect the levels of the hyaluronic acid receptor CD44, whereas adding LMWHA decreases CD44 levels. The addition of anti-CD44 antibodies potentiates fibrocyte differentiation, suggesting that CD44 mediates at least some of the effect of hyaluronic acid on fibrocyte differentiation. The fibrocyte differentiation-inhibiting factor serum amyloid P (SAP) inhibits HMWHA-induced fibrocyte differentiation and potentiates LMWHA-induced inhibition. Conversely, LMWHA inhibits the ability of HMWHA, interleukin-4 (IL-4), or interleukin-13 (IL-13) to promote fibrocyte differentiation. Conclusions We hypothesize that hyaluronic acid signals at least in part through CD44 to regulate fibrocyte differentiation, with a dominance hierarchy of SAP>LMWHA≥HMWHA>IL-4 or IL-13. PMID:22022512

  10. Single-handed helical carbonaceous nanotubes prepared using a pair of cationic low molecular weight gelators

    SciTech Connect

    Sun, Huayan; Wang, Qing; Guo, Yongmin

    Highlights: • 3-aminophenol-formaldeyde resins were prepared through a templating method. • A pair of cationic gelators have been used as the templates. • Single-handed helical carbonaceous nanotubes were obtained after carbonization. • The carbonaceous nanotubes showed optical activity. - Abstract: We design a facile route to obtain enantiopure carbonaceous nanostructures, which have potential application as chiral sensors, electromagnetic wave absorbers, and asymmetric catalysts. A pair of cationic low molecular weight gelators was synthesized, which were able to self-assemble into twisted nanoribbons in ethanol at a concentration of 20 g L{sup −1} at 25 °C. Single-handed helical 3-aminophenol-formaldehyde resin nanotubes withmore » optical activity were prepared using the self-assembly of the low molecular weight gelators as templates. After carbonization, single-handed helical carbonaceous nanotubes were obtained and characterized using circular dichroism, wide-angle X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The results indicate that the walls of the nanotubes are amorphous carbon. Moreover, the left- and right-handed helical nanotubes exhibit opposite optical activity.« less

  11. Isolation, purification and characterisation of low molecular weight xylanase from Bacillus pumilus SSP-34.

    PubMed

    Subramaniyan, S

    2012-04-01

    Low molecular weight endo-xylanase from Bacillus pumilus SSP-34 was purified to homogeneity using ion exchange and size exclusion chromatographies. Xylanases were isolated by novel purification protocol which includes the use of anion exchange matrix such as DEAE Sepharose CL 6B with less affinity towards enzyme protein. The purified B. pumilus SSP-34 have a molecular weight of 20 kDa, with optimum pH and temperature at 6.0 and 50 °C, respectively. The enzyme was stable at 50 °C for 30 min. It showed remarkable stability at pH values ranging from 4.5 to 9 when the reaction was carried out at 50 °C. K (m) and V (max) values, determined with oats spelts xylan were 6.5 mg ml⁻¹ and 1,233 μmol min⁻¹ mg⁻¹ protein, respectively, and the specific activity was 1,723 U mg⁻¹.

  12. Quantification of low molecular weight compounds by MALDI imaging mass spectrometry - A tutorial review.

    PubMed

    Rzagalinski, Ignacy; Volmer, Dietrich A

    2017-07-01

    Matrix-assisted laser desorption/ionization (MALDI)-mass spectrometry imaging (MSI) permits label-free in situ analysis of chemical compounds directly from the surface of two-dimensional biological tissue slices. It links qualitative molecular information of compounds to their spatial coordinates and distribution within the investigated tissue. MALDI-MSI can also provide the quantitative amounts of target compounds in the tissue, if proper calibration techniques are performed. Obviously, as the target molecules are embedded within the biological tissue environment and analysis must be performed at their precise locations, there is no possibility for extensive sample clean-up routines or chromatographic separations as usually performed with homogenized biological materials; ion suppression phenomena therefore become a critical side effect of MALDI-MSI. Absolute quantification by MALDI-MSI should provide an accurate value of the concentration/amount of the compound of interest in relatively small, well-defined region of interest of the examined tissue, ideally in a single pixel. This goal is extremely challenging and will not only depend on the technical possibilities and limitations of the MSI instrument hardware, but equally on the chosen calibration/standardization strategy. These strategies are the main focus of this article and are discussed and contrasted in detail in this tutorial review. This article is part of a Special Issue entitled: MALDI Imaging, edited by Dr. Corinna Henkel and Prof. Peter Hoffmann. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Isoleucine epimerization in the high-molecular-weight fraction of pleistocene Arctica

    NASA Astrophysics Data System (ADS)

    Kaufman, Darrell S.; Sejrup, Hans-Petter

    The extent of amino acid racemization, as traditionally determined in the entire (total acid hydrolysate) pool of amino acids comprising the organic remains of fossils, is a function of the integrated effects of a complex diagenetic reaction network. We investigated the possibility that some of the complications involved in protein diagenesis might be circumvented by isolating one component of the reaction network and studying the extent of racemization in that fraction alone. We used gel-filtration to extract the high-molecular-weight (HMW) fraction of proteinaceous matter from fossil and modem molluscan shells. This fraction contains the largest (ca. > 15,000 MW), most-pristine macromolecules and has been less affected by diagenesis than the more-degraded, lower molecular-weight fractions. Variations in the extent of racemization (isoleucine epimerization; alle/Ile) measured in the HMW fraction of subsamples taken along cross sections of Arctica shells from two interglacial sites, Bø and Fjøsanger, southwestern Norway, are within the range of analytical uncertainty [coefficient of variation (cv) = 5-8%], despite the strong gradient (cv = 20-24%) in alle/Ile of the total amino acid population. Because there is no age difference across a shell, this finding supports the idea that the HMW fraction contains more geochronologically reliable proteinaceous matter than the total amino acid pool. Weighted mean alle/Ile ratios in the HMW fraction of aliquots of powdered sample from the two shells overlap at ± 1σ, despite significantly different alle/Ile ratios in the total amino acid population of some shells from the two sites. The difference in alle/Ile ratios in the total population is attributed to a greater proportion of low-molecular-weight (ca. 300 MW), and hence, extensively epimerized molecules measured in gel-filtered samples from the Fjøsanger shell. Because the rate of epimerization in the HMW fraction is much lower than in the total population, the

  14. Purification of two high molecular weight proteases from rabbit reticulocyte lysate

    SciTech Connect

    Hough, R.; Pratt, G.; Rechsteiner, M.

    1987-05-01

    The authors have purified two large proteases from rabbit reticulocyte lysate. The enzymes are so similar in their chromatographic behavior that each is the only significant contaminant of the other during the final stages of purification. At pH 7.8, both hydrolyze /sup 125/I-..cap alpha..-casein and 4-methylcoumaryl-7-amide (MCA) derivatives with tyrosine, phenylalanine or arginine at the P/sub 1/ position. The larger, ATP-dependent enzyme degrades ubiquitin-lysozyme conjugates, but it does not degrade unmodified lysozyme. Hydrolysis of Suc-Leu-Leu-Val-Tyr-MCA by this enzyme is also stimulated two-fold in the presence of ATP. The protease has a molecular weight of 950,000 based on sedimentation, gel filtrationmore » and non-denaturing PAGE. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis revealed that the protease is composed of a number of subunits with molecular masses between 32 and 110 kDa. Densitometric analysis showed equivalent amounts of the two larger chains, and the presence of one copy of each in the native enzyme would be consistent with an M/sub r/ of 950,000. The smaller protease has a molecular weight of 700,000 and is composed of 8 to 10 subunits ranging from 21,000 to 32,000. It cleaves ubiquitin-lysozyme conjugates only slightly, and hydrolysis of conjugates or fluorogenic peptide substrates is not stimulated by ATP. This protease appears similar, if not identical, to the multicatalytic protease complex first purified by Wilk and Orlowski.« less

  15. Monitoring therapeutic anticoagulation with low molecular weight heparins: is it useful or misleading?

    PubMed

    Hammerstingl, C

    2008-10-01

    Weight adapted low molecular weight heparin (LMWH) treatment is recommended as initial anticoagulant therapy of deep vein thrombosis, pulmonary embolism, in patients with myocardial ischemia or when oral anticoagulation (OAC) must be interrupted peri- operatively. Traditionally unfractioned heparin (UFH) was used as standard short acting anticoagulant, with the therapy monitored by frequent laboratory testing. Currently LMWH have broadly replaced UFH as first- choice anticoagulant due to more preferable pharmacokinetics and a better safety profile. Therapeutic anticoagulation with LMWH can be achieved by subcutaneous weight adapted application and measurement of anti-factor Xa- activity (anti-Xa) has been established as gold standard for LMWH- monitoring. However, since almost all LMWH dosing regimens have been developed empirically without laboratory monitoring, there is still a debate ongoing about the usefulness and impact of anti-Xa-testing. Data are lacking that prove a clear correlation between obtained levels of anti-Xa and the patients' clinical outcome. Newer methods have been developed aiming to determine a broader spectrum of LMWH depending anticoagulant activity. Even though there are some promising preliminary results, these alternative methods are not ready for routine clinical use yet. Nevertheless, current guidelines advise determination of anti-Xa in special patient populations with markedly altered LMWH metabolism or to exclude residual LMWH- activity before surgery at very high risk of bleeding. The aim of this article is to review critically the usefulness of anti- Xa guidance of LMWH- therapy and to give new perspectives on upcoming methods of LMWH- monitoring.

  16. Molecular weight analyses and enzymatic degradation profiles of the soft-tissue fillers Belotero Balance, Restylane, and Juvéderm Ultra.

    PubMed

    Flynn, Timothy Corcoran; Thompson, David H; Hyun, Seok-Hee

    2013-10-01

    In this study, the authors sought to determine the molecular weight distribution of three hyaluronic acids-Belotero Balance, Restylane, and Juvéderm Ultra-and their rates of degradation following exposure to hyaluronidase. Lot consistency of Belotero Balance also was analyzed. Three lots of Belotero Balance were analyzed using liquid chromatography techniques. The product was found to have high-molecular-weight and low-molecular-weight species. One lot of Belotero Balance was compared to one lot each of Juvéderm Ultra and Restylane. Molecular weights of the species were analyzed. The hyaluronic acids were exposed to ovine testicular hyaluronidase at six time points-baseline and 0.5, 1, 2, 6, and 24 hours-to determine degradation rates. Belotero Balance lots were remarkably consistent. Belotero Balance had the largest high-molecular-weight species, followed by Juvéderm Ultra and Restylane (p < 0.001). Low-molecular-weight differences among all three hyaluronic acids were not statistically significant. Percentages of high-molecular-weight polymer differ among the three materials, with Belotero Balance having the highest fraction of high-molecular-weight polymer. Degradation of the high-molecular-weight species over time showed different molecular weights of the high-molecular-weight fraction. Rates of degradation of the hyaluronic acids following exposure to ovine testicular hyaluronidase were similar. All hyaluronic acids were fully degraded at 24 hours. Fractions of high-molecular-weight polymer differ across the hyaluronic acids tested. The low-molecular-weight differences are not statistically significant. The high-molecular-weight products have different molecular weights at the 0.5- and 2-hour time points when exposed to ovine testicular hyaluronidase and are not statistically different at 24 hours.

  17. Molecular weight dependent glucose lowering effect of low molecular weight Chitosan Oligosaccharide (GO2KA1) on postprandial blood glucose level in SD rats model.

    PubMed

    Jo, Sung-Hoon; Ha, Kyoung-Soo; Moon, Kyoung-Sik; Kim, Jong-Gwan; Oh, Chen-Gum; Kim, Young-Cheul; Apostolidis, Emmanouil; Kwon, Young-In

    2013-07-09

    This research investigated the effect of enzymatically digested low molecular weight (MW) chitosan oligosaccharide on type 2 diabetes prevention. Three different chitosan oligosaccharide samples with varying MW were evaluated in vitro for inhibition of rat small intestinal α-glucosidase and porcine pancreatic α-amylase (GO2KA1; <1000 Da, GO2KA2; 1000-10,000 Da, GO2KA3; MW > 10,000 Da). The in vitro results showed that all tested samples had similar rat α-glucosidase inhibitory and porcine α-amylase inhibitory activity. Based on these observations, we decided to further investigate the effect of all three samples at a dose of 0.1 g/kg, on reducing postprandial blood glucose levels in Sprague-Dawley (SD) rat model after sucrose loading test. In the animal trial, all tested samples had postprandial blood glucose reduction effect, when compared to control, however GO2KA1 supplementation had the strongest effect. The glucose peak (Cmax) for GO2KA1 and control was 152 mg/dL and 193 mg/dL, respectively. The area under the blood glucose-time curve (AUC) for GO2KA1 and control was 262 h mg/dL and 305 h mg/dL, respectively. Furthermore, the time of peak plasma concentration of blood glucose (Tmax) for GO2KA1 was significantly delayed (0.9 h) compared to control (0.5 h). These results suggest that GO2KA1 could have a beneficial effect for blood glucose management relevant to diabetes prevention in normal and pre-diabetic individuals. The suggested mechanism of action is via inhibition of the carbohydrate hydrolysis enzyme α-glucosidase and since GO2KA1 (MW < 1000 Da) had higher in vivo effect, we hypothesize that it is more readily absorbed and might exert further biological effect once it is absorbed in the blood stream, relevant to blood glucose management.

  18. High molecular weight glucan of the culinary medicinal mushroom Agaricus bisporus is an alpha-glucan that forms complexes with low molecular weight galactan.

    PubMed

    Smiderle, Fhernanda R; Sassaki, Guilherme L; van Arkel, Jeroen; Iacomini, Marcello; Wichers, Harry J; Van Griensven, Leo J L D

    2010-08-25

    An alpha-glucan was isolated from the culinary medicinal mushroom A. bisporus by hot water extraction, ethanol precipitation and DEAE-cellulose chromatography. The resulting material showed a single HMW peak excluded from a Sephadex G50 column that could completely be degraded by alpha-amylase treatment. After heating in 1% SDS a small additional peak of low MW eluted from the G50 column. The monosaccharide composition of the main peak was evaluated by HPLC, and was found to consist of a majority of glucose (97.6%), and a minor proportion of galactose (2.4%). Methylation analysis and degradation by alpha-amylase indicated the presence of an alpha-glucan with a main chain consisting of (1(R)4)-linked units, substituted at O-6 by alpha-D-glucopyranose single-units in the relation 1:8. Mono- (13C-, 1H-NMR) and bidimensional [1H (obs.),13C-HSQC] spectroscopy analysis confirmed the alpha-configuration of the Glcp residues by low frequency resonances of C-1 at delta 100.6, 100.2, and 98.8 ppm and H-1 high field ones at delta 5.06, 5.11, and 4.74 ppm. The DEPT-13C-NMR allowed assigning the non-substituted and O-substituted -CH(2) signals at delta 60.3/60.8 and 66.2 ppm, respectively. Other assignments were attributed to C-2, C-3, C-4, C-5 and C-6 of the non-reducing ends at delta 71.8; 72.8; 70.0; 71.3 and 60.3/60.8 ppm, respectively. The minor proportion of galactose that was demonstrated was probably derived from a complex between the alpha-glucan and a low molecular weight galactan.

  19. Low molecular weight heparin and cancer survival: clinical trials and experimental mechanisms.

    PubMed

    Zhang, Ning; Lou, Weihua; Ji, Fang; Qiu, Lihua; Tsang, Benjamin K; Di, Wen

    2016-08-01

    The relationship between cancer and thrombosis is complex, as the hemostatic system is inextricably linked to the mechanisms of cancer growth and metastasis. The coagulation system thus appears to be a site for oncogenic events and necessary for the survival and spread of malignant cells. Although several meta-analyses on the effectiveness of unfractionated heparin and low molecular weight heparin (LMWH) in the treatment of venous thromboembolism (VTE) have suggested a lower mortality risk in cancer patients receiving LMWH, this contention has not received general acceptance. In fact, there exist no sufficiently powered studies to date supporting the routine use of LMWH to improve cancer survival. Meanwhile, the molecular mechanism underlying the anti-neoplastic effect of LMWH which is independent of its anti-coagulant function is largely unexplored and is a topic of active investigation. In this communication, we aimed to review comprehensively evidences from clinical trials, meta-analysis as well as experimental molecular research and to identify future research areas of importance so as to stimulate future research on the potential anti-tumor action of LMWH. Although benefit of LMWH on cancer patients' survival is controversial depending on the tumor type, cancer stage as well as LMWH type, it appears to be associated with a reduction in VTE and increased bleeding is minor and controllable; thus, randomized controlled trials targeting the survival benefit of certain specific LWMH are needed and justified, and more in-depth experimental researches are imperative to elucidate the anti-tumor effect of anticoagulants.

  20. Unique fluorescence and high-molecular weight characteristics of protein isolates from manuka honey (Leptospermum scoparium).

    PubMed

    Rückriemen, Jana; Hohmann, Christoph; Hellwig, Michael; Henle, Thomas

    2017-09-01

    This study compared the fluorescence properties (λ ex/em =350/450nm) and molecular size of proteins from manuka and non-manuka honey. The fluorescence characteristics of non-manuka and manuka proteins differ markedly, whereby manuka honey protein fluorescence increases with increasing methylglyoxal (MGO) content of the honey. It was concluded that manuka honey proteins are modified due to MGO-derived glycation and crosslinking reactions, thus resulting in fluorescent structures. The molecular size of honey proteins was studied using size exclusion chromatography. Manuka honey proteins contain a significantly higher amount of high molecular weight (HMW) fraction compared to non-manuka honey proteins. Moreover, HMW fraction of manuka honey proteins was stable against reducing agents such as dithiothreitol, whereas HMW fraction of non-manuka honey proteins was significantly decreased. Thus, the chemical nature of manuka honey HMW fraction is probably covalent MGO crosslinking, whereas non-manuka HMW fraction is caused by disulfide bonds. Storage of a non-manuka honey, which was artificially spiked with MGO and DHA, did not induce above mentioned fluorescence properties of proteins during 84days of storage. Hence, MGO-derived fluorescence and crosslinking of honey proteins can be useful parameters to characterize manuka honey. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Development of solvent-free offset ink using vegetable oil esters and high molecular-weight resin.

    PubMed

    Park, Jung Min; Kim, Young Han; Kim, Sung Bin

    2013-01-01

    In the development of solvent-free offset ink, the roles of resin molecular weight and used solvent on the ink performance were evaluated by examining the relationship between the various properties of resin and solvent and print quality. To find the best performing resin, the soy-oil fatty acid methyl ester (FAME) was applied to the five modified-phenolic resins having different molecular weights. It is found from the experimental results that the ink made of higher molecular weight and better solubility resin gives better printability and print quality. It is because larger molecular weight resin with better solubility gives higher rate of ink transfer. From the ink application of different esters to high molecular weight resin, the best printing performance was yielded from the soy-oil fatty acid butyl ester (FABE). It is due to its high kinematic viscosity resulting in the smallest change of ink transfer weight upon multiple number of printing, which improves the stability of ink quality.

  2. Effect of molecular weight of starch on the properties of cassava starch microspheres prepared in aqueous two-phase system.

    PubMed

    Xia, Huiping; Li, Bing-Zheng; Gao, Qunyu

    2017-12-01

    Starch microspheres (SMs) were fabricated in an aqueous two-phase system (ATPS). A series of starch samples with different molecular weight were prepared by acid hydrolysis, and the effect of molecular weight of starch on the fabrication of SMs were investigated. Scanning electron microscopy (SEM) showed that the morphologies of SMs varied with starch molecular weight, and spherical SMs with sharp contours were obtained while using starch samples with weight-average molecular weight (M¯w)≤1.057×10 5 g/mol. X-ray diffraction (XRD) results revealed that crystalline structure of SMs were different from that of native cassava starch, and the relative crystallinity of SMs increased with the molecular weight of starch decreasing. Differential scanning calorimetry (DSC) results showed peak gelatinization temperature (T p ) and enthalpy of gelatinization (ΔH) of SMs increased with decreased M¯wof starch. Stability tests indicated that the SMs were stable under acid environment, but not stable under α-amylase hydrolysis. Copyright © 2017. Published by Elsevier Ltd.

  3. Vapor-pressure osmometric study of the molecular weight and aggregation tendency of a reference-soil fulvic acid

    USGS Publications Warehouse

    Marinsky, J.A.; Reddy, M.M.

    1990-01-01

    The molecular weight and aggregation tendency of a reference-soil fulvic acid in Armadale horizon Bh were determined by vapor-pressure osmometry using tetrahydrofuran and water as solvents. With tetrahydrofuran, number-average molecular weight values of 767 ?? 34 and 699 ?? 8 daltons were obtained from two separate sets of measurements. Two sets of measurements with water also yielded values within this range (754 ?? 70 daltons) provided that the fulvic acid concentration in water did not exceed 7 mg ml-1; at higher concentrations (9.1-13.7 mg ml-1) a number-average molecular weight of 956 ?? 25 daltons was resolved, providing evidence of molecular aggregation. Extension of these studies to 80% neutralized fulvic acid showed that a sizeable fraction of the sodium counter ion is not osmotically active.

  4. Long-term low-molecular-weight heparin and the post-thrombotic syndrome: a systematic review.

    PubMed

    Hull, Russell D; Liang, Jane; Townshend, Grace

    2011-08-01

    Post-thrombotic syndrome causes considerable morbidity. The Home-LITE study showed a lower incidence of post-thrombotic syndrome and venous ulcers after 3 months of treating deep vein thrombosis with the low-molecular-weight heparin tinzaparin versus oral anticoagulation. This systematic review examined whether long-term treatment of deep vein thrombosis using low-molecular-weight heparin, rather than oral anticoagulation, reduces development of post-thrombotic syndrome. We identified 9 articles comparing treatment of deep vein thrombosis using long-term low-molecular-weight heparin with any comparator, which reported outcomes relevant to the post-thrombotic syndrome assessed ≥ 3 months post-deep vein thrombosis. Pooled analysis of 2 studies yielded an 87% risk reduction with low-molecular-weight heparin in the incidence of venous ulcers at ≥ 3 months (P = .019). One study showed an overall odds ratio of 0.77 (P = .001) favoring low-molecular-weight heparin for the presence of 8 patient-reported post-thrombotic syndrome signs and symptoms. Pooled analysis of 5 studies showed a risk ratio for low-molecular-weight heparin versus oral anticoagulation of 0.66 (P < .0001) for complete recanalization of thrombosed veins. These results support the lower incidence of post-thrombotic syndrome and venous ulcers observed in Home-LITE. Long-term treatment with low-molecular-weight heparin rather than oral anticoagulation after a deep vein thrombosis may reduce or prevent development of signs and symptoms associated with post-thrombotic syndrome. Post-thrombotic syndrome and associated acute ulcers may develop more rapidly after deep vein thrombosis than previously recognized. Copyright © 2011 Elsevier Inc. All rights reserved.

  5. Effect of high molecular weight plasticizers on the gelatinization of starch under static and shear conditions.

    PubMed

    Taghizadeh, Ata; Favis, Basil D

    2013-02-15

    Starch gelatinization in the presence of high molecular weight polyol plasticizers and water was studied under static and dynamic conditions and was compared to a glycerol reference. For static gelatinization, glycerol, sorbitol, diglycerol and polyglycerol were examined using polarized light microscopy and differential scanning calorimetry. A wide range of starch/water/plasticizer compositions were prepared to explore the gelatinization regime for each plasticizer. The plasticizers show that the onset and conclusion temperatures for sorbitol and glycerol are in the same range and are lower than the other two plasticizers. On the other hand, polyglycerol shows a higher gelatinization temperature than diglycerol because of its higher molecular weight and viscosity. The results indicate that in the case of all plasticizers, increasing the water content tends to decrease the gelatinization temperature and, except for polyglycerol, increasing the plasticizer content increases the gelatinization temperature. In the case of polyglycerol, however, increasing the plasticizer content had the opposite effect and this was found to be related to the borderline solubility of polyglycerol in water. When the polyglycerol/water solubility was increased by increasing the temperature of the water/plasticizer/starch slurry, the gelatinization temperature dependence was found to be similar to the other polyols. A rheological technique was developed to study the dynamic gelatinization process by tracking the influence of shear on the complex viscosity in a couette flow system. Glycerol, diglycerol and sorbitol were subjected to different dynamic gelatinization treatments and the results were compared with static gelatinization. It is quantitatively shown that shear has a major effect on the gelatinization process. The conclusion temperature of gelatinization is significantly diminished (up to 21 °C) in the presence of shear whereas the onset temperature of gelatinization remains

  6. Effects of cross-linked high-molecular-weight hyaluronic acid on epidural fibrosis: experimental study.

    PubMed

    Isık, Semra; Taşkapılıoğlu, M Özgür; Atalay, Fatma Oz; Dogan, Seref

    2015-01-01

    Epidural fibrosis is nonphysiological scar formation, usually at the site of neurosurgical access into the spinal canal, in the intimate vicinity of and around the origin of the radicular sheath. The formation of dense fibrous tissue causes lumbar and radicular pain. In addition to radicular symptoms, the formation of scar tissue may cause problems during reoperation. The authors aimed to investigate the effects of cross-linked high-molecular-weight hyaluronic acid (HA), an HA derivative known as HA gel, on the prevention of epidural fibrosis by using histopathological and biochemical parameters. Fifty-six adult female Sprague-Dawley rats were evaluated. The rats were divided into 4 groups. Rats in the sham group (n = 14) underwent laminectomy and discectomy and received no treatment; rats in the control group (n = 14) underwent laminectomy and discectomy and received 0.9% NaCl treatment in the surgical area; rats in the HA group (n = 14) received HA treatment at the surgical area after laminectomy and discectomy; and rats in the HA gel group (n = 14) underwent laminectomy and discectomy in addition to receiving treatment with cross-linked high-molecular-weight HA in the surgical area. All rats were decapitated after 4 weeks, and the specimens were evaluated histopathologically and biochemically. The results were statistically compared using the Mann-Whitney U-test. Compared with the sham and control groups, the HA and HA gel groups showed significantly lower fibroblast cell density and tissue hydroxyproline concentrations (p < 0.05). There was statistically significant lower dural adhesion and foreign-body reaction between the control and HA gel groups (p < 0.05). Granulation tissue and epidural fibrosis were significantly lower in the HA and HA gel groups compared with the sham group (p < 0.05). There were no significant differences in any histopathological parameters or biochemical values between Groups 3 and 4 (p > 0.05). Cross-linked high-molecular-weight HA

  7. Synthesis and characterization of sugar based low molecular weight gelators and the preparation of chiral sulfinamides

    NASA Astrophysics Data System (ADS)

    Mangunuru, Hari Prasad Reddy

    Low molecular weight gelators (LMWGs) have received considerable attention in the field of chemistry from last few decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and forms gel, because of the self-assembly phenomenon and their demonstrated potential uses in a variety of areas, ranging from environmental to medicinal applications. Sugars are good starting materials to synthesize the new class of LMWG's, because these are different from some expensive materials, these are natural products. We have synthesized and characterized the LMGS's based on D-glucose and D-glucosamine. D-glucosamine is the versatile starting material to make different peptoids and triazoles. Several series of compounds were synthesized using compounds 1-3 as starting material and studied the gelation behavior all the compounds. We have studied the self-assembling properties of a new class of tripeptoids, synthesized by one-pot Ugi reaction from simple starting materials. Among the focused library of tripeptoids synthesized, we found that several efficient low molecular weight organogelators were obtained for aqueous DMSO and ethanol mixtures. We have also synthesized and characterized a series of monosaccharide triazole derivatives. These compounds were synthesized from N-acetyl glucosamine and D-glucose via a Cu(I) catalyzed azide/alkyne cycloaddition reaction (CuAAc). The compounds have been screened for their gelation properties and several efficient low molecular weight organo/hydro gelators were obtained, among these compounds, five per-acetyl glucosamine derivatives and one peracetyl glucose derivative were able to form gels in water. These new molecules are expected to be useful in drug delivery and tissue engineering.*. Asymmetric synthesis of chiral amines is a challenging in synthetic organic chemistry. The development of new catalysts for asymmetric organic

  8. Surface engineering on mesoporous silica chips for enriching low molecular weight phosphorylated proteins

    NASA Astrophysics Data System (ADS)

    Hu, Ye; Peng, Yang; Lin, Kevin; Shen, Haifa; Brousseau, Louis C., III; Sakamoto, Jason; Sun, Tong; Ferrari, Mauro

    2011-02-01

    Phosphorylated peptides and proteins play an important role in normal cellular activities, e.g., gene expression, mitosis, differentiation, proliferation, and apoptosis, as well as tumor initiation, progression and metastasis. However, technical hurdles hinder the use of common fractionation methods to capture phosphopeptides from complex biological fluids such as human sera. Herein, we present the development of a dual strategy material that offers enhanced capture of low molecular weight phosphoproteins: mesoporous silica thin films with precisely engineered pore sizes that sterically select for molecular size combined with chemically selective surface modifications (i.e. Ga3+, Ti4+ and Zr4+) that target phosphoroproteins. These materials provide high reproducibility (CV = 18%) and increase the stability of the captured proteins by excluding degrading enzymes, such as trypsin. The chemical and physical properties of the composite mesoporous thin films were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy and ellipsometry. Using mass spectroscopy and biostatistics analysis, the enrichment efficiency of different metal ions immobilized on mesoporous silica chips was investigated. The novel technology reported provides a platform capable of efficiently profiling the serum proteome for biomarker discovery, forensic sampling, and routine diagnostic applications.Phosphorylated peptides and proteins play an important role in normal cellular activities, e.g., gene expression, mitosis, differentiation, proliferation, and apoptosis, as well as tumor initiation, progression and metastasis. However, technical hurdles hinder the use of common fractionation methods to capture phosphopeptides from complex biological fluids such as human sera. Herein, we present the development of a dual strategy material that offers enhanced capture of low molecular weight phosphoproteins: mesoporous

  9. Significance of Interactions of Low Molecular Weight Crystallin Fragments in Lens Aging and Cataract Formation*

    PubMed Central

    Santhoshkumar, Puttur; Udupa, Padmanabha; Murugesan, Raju; Sharma, K. Krishna

    2008-01-01

    Analysis of aged and cataract lenses shows the presence of increased amounts of crystallin fragments in the high molecular weight aggregates of water-soluble and water-insoluble fractions. However, the significance of accumulation and interaction of low molecular weight crystallin fragments in aging and cataract development is not clearly understood. In this study, 23 low molecular mass (<3.5-kDa) peptides in the urea-soluble fractions of young, aged, and aged cataract human lenses were identified by mass spectroscopy. Two peptides, αB-(1–18) (MDIAIHHPWIRRPFFPFH) and βA3/A1-(59–74) (SD(N)AYHIERLMSFRPIC), present in aged and cataract lens but not young lens, and a third peptide, γS-(167–178) (SPAVQSFRRIVE) present in all three lens groups were synthesized to study the effects of interaction of these peptides with intact α-, β-, and γ-crystallins and alcohol dehydrogenase, a protein used in aggregation studies. Interaction of αB-(1–18) and βA3/A1-(59–74) peptides increased the scattering of light by β- and γ-crystallin and alcohol dehydrogenase. The ability of α-crystallin subunits to function as molecular chaperones was significantly reduced by interaction with αB-(1–18) and βA3/A1-(59–74) peptides, whereas γS peptide had no effect on chaperone-like activity of α-crystallin. The βA3/A1-(59–74 peptide caused a 5.64-fold increase in αB-crystallin oligomeric mass and partial precipitation. Replacing hydrophobic residues in αB-(1–18) and βA3/A1-(59–74) peptides abolished their ability to induce crystallin aggregation and light scattering. Our study suggests that interaction of crystallin-derived peptides with intact crystallins could be a key event in age-related protein aggregation in lens and cataractogenesis. PMID:18227073

  10. Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry.

    PubMed

    Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

    2016-09-01

    Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by "unknown" screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Isolation of New Aureobasidium Strains That Produce High-Molecular-Weight Pullulan with Reduced Pigmentation

    PubMed Central

    Pollock, Thomas J.; Thorne, Linda; Armentrout, Richard W.

    1992-01-01

    New isolates of Aureobasidium pullulans were obtained from plant leaf surfaces gathered in San Diego County. The new fungal isolates were identified as A. pullulans on the basis of the appearance of polymorphic colonies formed on agar plates, the electrophoretic profiles of repeated genomic DNA sequences, and the production of pullulan in shake flask cultures. The isolates showed different degrees of pigmentation. One of the natural isolates was nonpigmented under mock production conditions in liquid culture, but was still able to synthesize a reduced amount of pigment on agar plates at late times. A mutagenic treatment with ethidium bromide produced derivatives of normally pigmented natural isolates that exhibited an increased tendency toward yeastlike growth and reduced pigmentation. Additionally, some of the new isolates and mutant derivatives accumulated pullulan of relatively high molecular weight in the culture broths. Images PMID:16348676

  12. Mechanical properties of ultrahigh molecular weight PHEMA hydrogels synthesized using initiated chemical vapor deposition.

    PubMed

    Bose, Ranjita K; Lau, Kenneth K S

    2010-08-09

    In this work, poly(2-hydroxyethyl methacrylate) (PHEMA), a widely used hydrogel, is synthesized using initiated chemical vapor deposition (iCVD), a one-step surface polymerization that does not use any solvents. iCVD synthesis is capable of producing linear stoichiometric polymers that are free from entrained unreacted monomer or solvent and, thus, do not require additional purification steps. The resulting films, therefore, are found to be noncytotoxic and also have low nonspecific protein adsorption. The kinetics of iCVD polymerization are tuned so as to achieve rapid deposition rates ( approximately 1.5 microm/min), which in turn yield ultrahigh molecular weight polymer films that are mechanically robust with good water transport and swellability. The films have an extremely high degree of physical chain entanglement giving rise to high tensile modulus and storage modulus without the need for chemical cross-linking that compromises hydrophilicity.

  13. Low molecular weight polylactic acid as a matrix for the delayed release of pesticides.

    PubMed

    Zhao, Jing; Wilkins, Richard M

    2005-05-18

    Low molecular weight polylactic acid (LMW PLA) was used as a matrix to formulate biodegradable matrix granules and films with bromacil using a melt process. The compatibility of the PLA with bromacil was evaluated. The release characteristics of the formulations were investigated in vitro. The degradation and erosion of the formulations were monitored by pH and gravimetric analysis during the course of release. Various granules and films had similar biphasic release patterns, a delayed release followed by an explosive release. The release rates were independent of bromacil content in the matrix, but varied with the geometry of matrices. The mechanisms of diffusion and erosion were involved in the release. The delayed release of the formulations was dominantly governed by the degradation and erosion of PLA. LMW PLA underwent bulk erosion. LMW PLA-based matrix formulations could thus be useful for the application of pesticides to sensitive targets such as seed treatment.

  14. Characterization of Low-Molecular-Weight Heparins by Strong Anion-Exchange Chromatography.

    PubMed

    Sadowski, Radosław; Gadzała-Kopciuch, Renata; Kowalkowski, Tomasz; Widomski, Paweł; Jujeczka, Ludwik; Buszewski, Bogusław

    2017-11-01

    Currently, detailed structural characterization of low-molecular-weight heparin (LMWH) products is an analytical subject of great interest. In this work, we carried out a comprehensive structural analysis of LMWHs and applied a modified pharmacopeial method, as well as methods developed by other researchers, to the analysis of novel biosimilar LMWH products; and, for the first time, compared the qualitative and quantitative composition of commercially available drugs (enoxaparin, nadroparin, and dalteparin). For this purpose, we used strong anion-exchange (SAX) chromatography with spectrophotometric detection because this method is more helpful, easier, and faster than other separation techniques for the detailed disaccharide analysis of new LMWH drugs. In addition, we subjected the obtained results to statistical analysis (factor analysis, t-test, and Newman-Keuls post hoc test).

  15. Skin: Major target organ of allergic reactions to small molecular weight compounds

    SciTech Connect

    Merk, Hans F.; Baron, Jens M.; Neis, Mark M.

    2007-11-01

    Skin is a major target organ for allergic reactions to small molecular weight compounds. Drug allergic reactions may be life-threatening such as in the case of anaphylactic reactions or bullous drug reactions and occur in about 5% of all hospitalized patients. Allergic contact dermatitis has an enormous influence on the social life of the patient because it is the most frequent reason for occupational skin diseases and the treatment and prevention of this disease cost approximately Euro 3 billion per year in Germany. The different proposed pathophysiological pathways leading to a drug eruption are discussed in this paper. All majormore » enzymes which are involved in the metabolism of xenobiotica were shown to be present in skin. Evidence supporting the role of metabolism in the development of drug allergy and allergic contact dermatitis is demonstrated in the example of sulphonamides and fragrances.« less

  16. Effect of low molecular weight heparin rectal suppository on experimental ulcerative colitis in mice.

    PubMed

    Luo, Junyong; Cao, Jichao; Jiang, Xueliang; Cui, Huifei

    2010-09-01

    The objective of this study was to investigate the effect and possible mechanism of rectally administered low molecular weight heparin (LMWH) on experimental ulcerative colitis. LMWH rectal suppository was prepared and its efficacy was studied by macroscopical and histological scoring systems as well as myeloperoxidase activity. Serum levels, including tumor necrosis factor-α (TNFα), interleukin-6 (IL-6) and a link factor of blood coagulation and inflammation factor Xa (FXa) were assayed by enzyme-linked immunosorbent assay. The expression of Musashi-1 (as an intestinal stem cell marker) in the colons was assessed by immunohistochemical analysis. The results showed that LMWH rectal suppository significantly decreased serum levels of TNF-α, IL-6 as well as FXa, while increased the expression of Musashi-1 in colon compared with acetic acid induced ulcerative colitis model group. All these preliminary results indicate LMWH rectal suppository is promising for treatment of ulcerative colitis. 2010 Elsevier Masson SAS. All rights reserved.

  17. Effect of soil sieving on respiration induced by low-molecular-weight substrates

    NASA Astrophysics Data System (ADS)

    Datta, Rahul; Vranová, Valerie; Pavelka, Marian; Rejšek, Klement; Formánek, Pavel

    2014-03-01

    The mesh size of sieves has a significant impact upon soil disturbance, affecting pore structure, fungal hyphae, proportion of fungi to bacteria, and organic matter fractions. The effects are dependent upon soil type and plant coverage. Sieving through a 2 mm mesh increases mineralization of exogenously supplied carbohydrates and phenolics compared to a 5 mm mesh and the effect is significant (p<0.05), especially in organic horizons, due to increased microbial metabolism and alteration of other soil properties. Finer mesh size particularly increases arabinose, mannose, galactose, ferulic and pthalic acid metabolism, whereas maltose mineralization is less affected. Sieving through a 5 mm mesh size is suggested for all type of experiments where enhanced mineralization of low-molecular-weight organic compounds needs to be minimalized.

  18. Enhancing Accuracy in Molecular Weight Determination of Highly Heterogeneously Glycosylated Proteins by Native Tandem Mass Spectrometry.

    PubMed

    Wang, Guanbo; de Jong, Rob N; van den Bremer, Ewald T J; Parren, Paul W H I; Heck, Albert J R

    2017-05-02

    The determination of molecular weights (MWs) of heavily glycosylated proteins is seriously hampered by the physicochemical characteristics and heterogeneity of the attached carbohydrates. Glycosylation impacts protein migration during sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis (PAGE) and size-exclusion chromatography (SEC) analysis. Standard electrospray ionization (ESI)-mass spectrometry does not provide a direct solution as this approach is hindered by extensive interference of ion signals caused by closely spaced charge states of broadly distributed glycoforms. Here, we introduce a native tandem MS-based approach, enabling charge-state resolution and charge assignment of protein ions including those that escape mass analysis under standard MS conditions. Using this method, we determined the MW of two model glycoproteins, the extra-cellular domains of the highly and heterogeneously glycosylated proteins CD38 and epidermal growth factor receptor (EGFR), as well as the overall MW and binding stoichiometries of these proteins in complex with a specific antibody.

  19. Effects of inhaled high-molecular weight hyaluronan in inflammatory airway disease.

    PubMed

    Lamas, Adelaida; Marshburn, Jamie; Stober, Vandy P; Donaldson, Scott H; Garantziotis, Stavros

    2016-10-03

    Cystic fibrosis (CF) is a chronic inflammatory disease that is affecting thousands of patients worldwide. Adjuvant anti-inflammatory treatment is an important component of cystic fibrosis treatment, and has shown promise in preserving lung function and prolonging life expectancy. Inhaled high molecular weight hyaluronan (HMW-HA) is reported to improve tolerability of hypertonic saline and thus increase compliance, and has been approved in some European countries for use as an adjunct to hypertonic saline treatment in cystic fibrosis. However, there are theoretical concerns that HMW-HA breakdown products may be pro-inflammatory. In this clinical pilot study we show that sputum cytokines in CF patients receiving HMW-HA are not increased, and therefore HMW-HA does not appear to adversely affect inflammatory status in CF airways.

  20. High performance carbon fibers from very high molecular weight polyacrylonitrile precursors

    SciTech Connect

    Morris, E. Ashley; Weisenberger, Matthew C.; Abdallah, Mohamed G.

    In this study, carbon fibers are unique reinforcing agents for lightweight composite materials due to their outstanding mechanical properties and low density. Current technologies are capable of producing carbon fibers with 90-95% of the modulus of perfect graphite (~1025 GPa). However, these same carbon fibers possess less than 10% of the theoretical carbon fiber strength, estimated to be about 100 GPa.[1] Indeed, attempts to increase carbon fiber rigidity results in lower breaking strength. To develop advanced carbon fibers with both very high strength and modulus demands a new manufacturing methodology. Here, we report a method of manufacturing high strength, verymore » high modulus carbon fibers from a very high molecular weight (VHMW) polyacrylonitrile (PAN) precursor without the use of nanomaterial additives such as nucleating or structure-templating agents, as have been used by others.[2,3]« less

  1. High performance carbon fibers from very high molecular weight polyacrylonitrile precursors

    DOE PAGES

    Morris, E. Ashley; Weisenberger, Matthew C.; Abdallah, Mohamed G.; ...

    2016-02-02

    In this study, carbon fibers are unique reinforcing agents for lightweight composite materials due to their outstanding mechanical properties and low density. Current technologies are capable of producing carbon fibers with 90-95% of the modulus of perfect graphite (~1025 GPa). However, these same carbon fibers possess less than 10% of the theoretical carbon fiber strength, estimated to be about 100 GPa.[1] Indeed, attempts to increase carbon fiber rigidity results in lower breaking strength. To develop advanced carbon fibers with both very high strength and modulus demands a new manufacturing methodology. Here, we report a method of manufacturing high strength, verymore » high modulus carbon fibers from a very high molecular weight (VHMW) polyacrylonitrile (PAN) precursor without the use of nanomaterial additives such as nucleating or structure-templating agents, as have been used by others.[2,3]« less

  2. Sharp Absorption Peaks in THz Spectra Valuable for Crystal Quality Evaluation of Middle Molecular Weight Pharmaceuticals

    NASA Astrophysics Data System (ADS)

    Sasaki, Tetsuo; Sakamoto, Tomoaki; Otsuka, Makoto

    2018-05-01

    Middle molecular weight (MMW) pharmaceuticals (MW 400 4000) are attracting attention for their possible use in new medications. Sharp absorption peaks were observed in MMW pharmaceuticals at low temperatures by measuring with a high-resolution terahertz (THz) spectrometer. As examples, high-resolution THz spectra for amoxicillin trihydrate, atorvastatin calcium trihydrate, probucol, and α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin p-toluenesulfonate (TMPyP) were obtained at 10 K. Typically observed as peaks with full width at half-height (FWHM) values as low as 5.639 GHz at 0.96492 THz in amoxicillin trihydrate and 8.857 GHz at 1.07974 THz for probucol, many sharp peaks of MMW pharmaceuticals could be observed. Such narrow absorption peaks enable evaluation of the crystal quality of MMW pharmaceuticals and afford sensitive detection of impurities.

  3. High molecular weight FGF2: the biology of a nuclear growth factor

    PubMed Central

    Chlebova, K.; Bryja, V.; Dvorak, P.; Kozubik, A.; Wilcox, W. R.

    2011-01-01

    Fibroblast growth factor 2 (FGF2) is one of the most studied growth factors to date. Most attention has been dedicated to the smallest, 18kDa FGF2 variant that is released by cells and acts through activation of cell-surface FGF-receptor tyrosine kinases. There are, however, several higher molecular weight (HMW) variants of FGF2 that rarely leave their producing cells, are retained in the nucleus and act independently of FGF-receptors (FGFR). Despite significant evidence documenting the expression and intracellular trafficking of HMW FGF2, many important questions remain about the physiological roles and mechanisms of action of HMW FGF2. In this review, we summarize the current knowledge about the biology of HMW FGF2, its role in disease and areas for future investigation. PMID:18850066

  4. [Allelic variation at high-molecular-weight glutenin subunit loci in Aegilops biuncialis Vis].

    PubMed

    Kozub, N A; Sozinov, I A; Ksinias, I N; Sozinov, A A

    2011-09-01

    Alleles at the high-molecular-weight glutenin subunit loci Glu-U1 and Glu-M(b)1 were analyzed in the tetraploid species Aegilops biuncialis (UUM(b)M(b)). The material for the investigation included the collection of 39 accessions of Ae. biuncialis from Ukraine (the Crimea), one Hellenic accession, one accession of unknown origin, F2 seeds from different crosses, as well as samples from natural populations from the Crimea. Ae. umbellulata and Ae. comosa accessions were used to allocate components of the HMW glutenin subunit patterns of Ae. biuncialis to U or M(b) genomes. Eight alleles were identified at the Glu-U1 locus and ten alleles were revealed at the Glu-M(b) 1 locus. Among alleles at the Glu-M(b) 1 locus ofAe. biuncialis there were two alleles controlling the y-type subunit only and one allele encoding the x-subunit only.

  5. Low molecular weight heparin restores antithrombin III activity from hyperglycemia induced alterations.

    PubMed

    Ceriello, A; Marchi, E; Palazzni, E; Quatraro, A; Giugliano, D

    1990-01-01

    Alteration of antithrombin III (ATIII) activity, glycemia level dependent, exists in diabetes mellitus. In this study the ability of a low molecular weight heparin (LMWH) (Fluxum, Alfa-Wassermann S.p.A., Bologna, Italy), as well as unfractioned héparin, to preserve ATIII activity from glucose-induced alterations, both in vitro and in vivo, is reported. The subcutaneous and intravenous LMWH and heparin administration increases basal depressed ATIII activity in diabetic patients. Heparin shows an equivalent effect on both anti-IIa and anti-Xa activity of ATIII, while LMWH is more effective in preserving the anti-Xa activity. Similarity, heparin preserves ATIII activity from hyperglycemia-induced alterations, during hyperglycemic clamp, and LMWH infusion is able to preserve a significant amount of anti-Xa activity from glucose-induced alterations. Since diabetic patients show a high incidence of thrombotic accidents, LMWH appears to be a promising innovation for the prevention of diabetic thrombophylia.

  6. In vivo endothelial siRNA delivery using polymeric nanoparticles with low molecular weight

    NASA Astrophysics Data System (ADS)

    Dahlman, James E.; Barnes, Carmen; Khan, Omar F.; Thiriot, Aude; Jhunjunwala, Siddharth; Shaw, Taylor E.; Xing, Yiping; Sager, Hendrik B.; Sahay, Gaurav; Speciner, Lauren; Bader, Andrew; Bogorad, Roman L.; Yin, Hao; Racie, Tim; Dong, Yizhou; Jiang, Shan; Seedorf, Danielle; Dave, Apeksha; Singh Sandhu, Kamaljeet; Webber, Matthew J.; Novobrantseva, Tatiana; Ruda, Vera M.; Lytton-Jean, Abigail K. R.; Levins, Christopher G.; Kalish, Brian; Mudge, Dayna K.; Perez, Mario; Abezgauz, Ludmila; Dutta, Partha; Smith, Lynelle; Charisse, Klaus; Kieran, Mark W.; Fitzgerald, Kevin; Nahrendorf, Matthias; Danino, Dganit; Tuder, Rubin M.; von Andrian, Ulrich H.; Akinc, Akin; Panigrahy, Dipak; Schroeder, Avi; Koteliansky, Victor; Langer, Robert; Anderson, Daniel G.

    2014-08-01

    Dysfunctional endothelium contributes to more diseases than any other tissue in the body. Small interfering RNAs (siRNAs) can help in the study and treatment of endothelial cells in vivo by durably silencing multiple genes simultaneously, but efficient siRNA delivery has so far remained challenging. Here, we show that polymeric nanoparticles made of low-molecular-weight polyamines and lipids can deliver siRNA to endothelial cells with high efficiency, thereby facilitating the simultaneous silencing of multiple endothelial genes in vivo. Unlike lipid or lipid-like nanoparticles, this formulation does not significantly reduce gene expression in hepatocytes or immune cells even at the dosage necessary for endothelial gene silencing. These nanoparticles mediate the most durable non-liver silencing reported so far and facilitate the delivery of siRNAs that modify endothelial function in mouse models of vascular permeability, emphysema, primary tumour growth and metastasis.

  7. Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

    DOE PAGES

    Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin; ...

    2017-01-10

    In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

  8. Possible hypoglycemic effect of Aloe vera L. high molecular weight fractions on type 2 diabetic patients

    PubMed Central

    Yagi, Akira; Hegazy, Sahar; Kabbash, Amal; Wahab, Engy Abd-El

    2009-01-01

    Aloe vera L. high molecular weight fractions (AHM) containing less than 10 ppm of barbaloin and polysaccharide (MW: 1000 kDa) with glycoprotein, verectin (MW: 29 kDa), were prepared by patented hyper-dry system in combination of freeze–dry technique with microwave and far infrared radiation. AHM produced significant decrease in blood glucose level sustained for 6 weeks of the start of the study. Significant decrease in triglycerides was only observed 4 weeks after treatment and continued thereafter. No deterious effects on kidney and liver functions were apparent. Treatment of diabetic patients with AHM may relief vascular complications probably via activation of immunosystem. PMID:23964163

  9. Low molecular weight heparins in the prevention of deep-vein thrombosis in general surgery.

    PubMed

    Breddin, H K

    1999-01-01

    Unfractionated heparin (UFH) was the established treatment in the early 1980s for the prophylaxis of venous thromboembolic disease (VTED) in patients undergoing general surgery. This was one of the earliest indications in which low molecular weight heparins (LMWHs) were tested, and about 40 trials have revealed that these agents are at least as effective and safe as UFH with a tendency of superiority when higher dosages are used. In most trials, the fibrinogen uptake test has been used to assess the frequency of deep vein thrombosis. LMWHs exhibit a number of improved features over UFH, including ease of administration and convenient once daily dosing, facilitating outpatient management. A still open question is the ideal time and dose of the first one or two injections of a LMWH. To determine the clinical relevance of product differentiation further, clinical trials, directly comparing different LMWHs, are required.

  10. Synthesis of a high molecular weight thyroglobulin dimer by two ovine thyroid cell lines: the OVNIS.

    PubMed

    Hovsépian, S; Aouani, A; Fayet, G

    1986-05-01

    The OVNIS 6H and 5H thyroid cells, 2 permanent cell lines isolated 3 years ago from ovine tissue, synthesize a high molecular weight glycosylated protein, immunologically related to ovine thyroglobulin, which is similar to the prothyroid hormone dimer (17-19) S: thyroglobulin. Using sucrose gradient centrifugation and cell labelling with [14C]Leu or [3H]GlNH2, radioactivity was observed in proteins purified from cell layers and from cell culture media. Addition of thyrotropin to or removal from the media resulted respectively in an increase (+773%) or decrease (-1090%) of the total radioactivity detected in the (17-19)S thyroglobulin fraction. Estimation of thyroglobulin by RIA gave similar though less pronounced effects. These experiments prove (1) that thyroglobulin is still expressed in these OVNIS thyroid cell lines even after 3 years of permanent culture, (2) that TSH modulates the level of this protein through a TSH-receptor functional system.

  11. High-Flow, High-Molecular-Weight, Addition-Curing Polyimides

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Vannucci, Raymond D.

    1993-01-01

    In developed series of high-flow PMR-type polyimide resins, 2, 2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl (BTDB) substituted for 1, 4-pheylenediamine in PMR-II formulation. Polyimides designated either as PMR-12F when nadic ester (NE) end caps used, or as V-CAP-12F when p-aminostyrene end caps used. High-molecular-weight, addition-curing polyimides based on BTBD and HFDE highly processable high-temperature matrix resins used to make composite materials with excellent retention of properties during long-term exposure to air at 650 degrees F or higher temperature. Furthermore, 12F addition-curing polyimides useful for electronic applications; fluorinated rigid-rod polyimides known to exhibit low thermal expansion coefficients as well as low absorption of moisture.

  12. Detergent-dispersant additives based on high-molecular-weight alkylphenols

    SciTech Connect

    Kulieva, K.N.; Namazova, I.I.; Ismailova, N.D.

    1988-09-01

    This article describes the synthesis and investigation of Mannich bases produced for alkylphenols, obtained in turn from ethylene oligomers. These oligomers are the still bottoms from distillation products of high-temperature oligomerization of ethylene in the presence of triethylaluminum. Two narrow cuts obtained from the distillation of oligomer fraction were used to study the influence of ethylene oligomer molecular weight on the properties of the additives. The additives were blended in DS-11 oil to evaluate their detergency-dispersancy and other properties. Comparison blends were made with succinimide additives based on the same ethylene oligomers. The Mannich bases give improvements in the oxidationmore » resistance, anticorrosion properties, and detergency-dispersancy of the DS-11 diesel oil.« less

  13. Structural Characterization of the Low-Molecular-Weight Heparin Dalteparin by Combining Different Analytical Strategies.

    PubMed

    Bisio, Antonella; Urso, Elena; Guerrini, Marco; de Wit, Pauline; Torri, Giangiacomo; Naggi, Annamaria

    2017-06-24

    A number of low molecular weight heparin (LMWH) products are available for clinical use and although all share a similar mechanism of action, they are classified as distinct drugs because of the different depolymerisation processes of the native heparin resulting in substantial pharmacokinetic and pharmacodynamics differences. While enoxaparin has been extensively investigated, little information is available regarding the LMWH dalteparin. The present study is focused on the detailed structural characterization of Fragmin ® by LC-MS and NMR applied both to the whole drug and to its enzymatic products. For a more in-depth approach, size homogeneous octasaccharide and decasaccharide components together with their fractions endowed with high or no affinity toward antithrombin were also isolated and their structural profiles characterized. The combination of different analytical strategies here described represents a useful tool for the assessment of batch-to-batch structural variability and for comparative evaluation of structural features of biosimilar products.

  14. The design and synthesis of new synthetic low molecular weight heparins

    PubMed Central

    Chandarajoti, K.; Liu, J.; Pawlinski, R.

    2016-01-01

    Low molecular weight heparins (LMWH) have remained the most favorable form of heparin in clinics since 1990s’ owing to its predictable pharmacokinetic properties. However, LMWH is mainly eliminated through kidney, thus limits its use in renal-impaired patients. In addition, the anticoagulant activity of LMWH is only partially neutralized by protamine. LMWH is obtained from a full-length, highly sulfated polysaccharide harvested from porcine mucosal tissue. The depolymerization involved in LMWH production generates a broad size distribution of LMWH fragments (6-22 sugar residues). This, combined with the various methods used to produce commercial LMWHs, result in variable pharmacological and pharmacokinetic properties. An alternative, chemoenzymatic approach offers a method for the synthesis of LMWH that has the potential to overcome the limitations of current LMWHs. This review summarizes the application of a chemoenzymatic approach to generate LMWH and the rationale for development of a synthetic LMWH. PMID:26990516

  15. The design and synthesis of new synthetic low-molecular-weight heparins.

    PubMed

    Chandarajoti, K; Liu, J; Pawlinski, R

    2016-06-01

    Low-molecular-weight heparin (LMWH) has remained the most favorable form of heparin in clinics since the 1990s owing to its predictable pharmacokinetic properties. However, LMWH is mainly eliminated through the kidney, which limits its use in renal-impaired patients. In addition, the anticoagulant activity of LMWH is only partially neutralized by protamine. LMWH is obtained from a full-length, highly sulfated polysaccharide harvested from porcine mucosal tissue. The depolymerization involved in LMWH production generates a broad distribution of LMWH fragments (6-22 sugar residues). This, combined with the various methods used to produce commercial LMWHs, results in variable pharmacological and pharmacokinetic properties. An alternative chemoenzymatic approach offers a method for the synthesis of LMWH that has the potential to overcome the limitations of current LMWHs. This review summarizes the application of a chemoenzymatic approach to generate LMWH and the rationale for development of a synthetic LMWH. © 2016 International Society on Thrombosis and Haemostasis.

  16. Low-molecular-weight heparins and cancer: focus on antitumoral effect.

    PubMed

    Franchini, Massimo; Mannucci, Pier Mannuccio

    2015-03-01

    A close relationship between cancer and thrombosis does exist, documented by the fact that an overall 7-fold increased risk of venous thromboembolism (VTE) has been reported in patients with malignancy compared to non-malignancy. The potential impact of antithrombotic agents in cancer-associated VTE has long been recognized, and, in particular, several clinical trials in the last 20 years have reported the safety and efficacy of low-molecular-weight heparins (LMWHs) for treatment and prophylaxis of VTE in patients with various types of cancer. More recently, a number of preclinical and clinical studies have suggested that LMWHs may improve survival in cancer patients with mechanisms that are different from its antithrombotic effect but are linked to the ability of influencing directly the tumor biology. This paper reviews the evidence around the potential survival benefits of LMWHs by analyzing the suggested mechanisms and the available clinical data.

  17. Comparison of Low-Molecular-Weight Heparins Prepared From Bovine Heparins With Enoxaparin.

    PubMed

    Liu, Xinyue; St Ange, Kalib; Fareed, Jawed; Hoppensteadt, Debra; Jeske, Walter; Kouta, Ahmed; Chi, Lianli; Jin, Caijuan; Jin, Yongsheng; Yao, Yiming; Linhardt, Robert J

    2017-09-01

    Heparin and its low-molecular-weight heparin (LMWH) derivatives are widely used clinical anticoagulants. These drugs are critical for the practice of medicine in applications including kidney dialysis, cardiopulmonary bypass, and in the management of venous thromboembolism. Currently, these drugs are derived from livestock, primarily porcine intestine. The worldwide dependence on a single animal species has made the supply chain for this critical drug quite fragile, leading to the search for other sources of these drugs, including bovine tissues such as bovine intestine or lung. A number of laboratories are currently examining the similarities and differences between heparins prepared from porcine and bovine tissues. The current study is designed to compare LMWH prepared from bovine heparins through chemical β-elimination, a process currently used to prepare the LMWH, enoxaparin, from porcine heparin. Using top-down, bottom-up, compositional analysis and bioassays, LMWHs, derived from bovine lung and intestine, are shown to closely resemble enoxaparin.

  18. Non-anticoagulant effects of low molecular weight heparins in inflammatory disorders: A review.

    PubMed

    Yan, Yishu; Ji, Yang; Su, Nan; Mei, Xiang; Wang, Yi; Du, Shanshan; Zhu, Wenming; Zhang, Chong; Lu, Yuan; Xing, Xin-Hui

    2017-03-15

    Low molecular weight heparins (LMWHs) are produced by chemical or enzymatic depolymerization of unfractionated heparin (UFH). Besides their well-known anticoagulant effects, LMWHs have also been reported to exhibit numerous anti-inflammatory properties. Previous studies have, however, shown that different production processes result in unique structural characteristics of LMWHs. The structural variations may help explain the different therapeutic spectrums in disease treatment for non-anticoagulant effects. In the present review, we summarize major advances in understanding and exploiting the anti-inflammatory disorder activities of LMWHs, based on mechanistic studies, preclinical experiments and clinical trials. We highlight differences in these activities of commercially available LMWHs produced using different manufacturing processes. We stress the importance of structure-activity relationship (SAR) studies on the non-anticoagulant effects of LMWHs and discuss strategies for exploring new clinical indications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Electrophoretic variation in low molecular weight lens crystallins from inbred strains of rats.

    PubMed

    Donner, M E; Skow, L C; Kunz, H W; Gill, T J

    1985-10-01

    Analysis of rat lens soluble proteins by analytical isoelectric focusing detected two inherited electrophoretic differences in low molecular weight (LM) crystallins from inbred strains of rats (Rattus norvegicus). The polymorphic lens crystallins were shown to be similar to a genetically variant LM crystallin, LEN-1, previously described in mice (Mus musculus) and encoded on chromosome 1, at a locus linked to Pep-3 (dipeptidase). Linkage analysis demonstrated that the rat crystallin locus was loosely linked to Pep-3 at a recombination distance of 38 +/- 4.5 U. These data suggest the conservation of a large chromosomal region during the evolution of Rodentia and support the hypothesis that the gamma-crystallins are evolving more rapidly than alpha- or beta-crystallins.

  20. Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

    SciTech Connect

    Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin

    In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

  1. Mobile-bearing knee systems: ultra-high molecular weight polyethylene wear and design issues.

    PubMed

    Greenwald, A Seth; Heim, Christine S

    2005-01-01

    In June 2004, the U.S. Food and Drug Administration Orthopaedic Advisory Panel recommended the reclassification of mobile-bearing knee systems for general use. This reflects the increasing use of mobile-bearing knee systems internationally, which is currently limited in the United States by regulatory requirement. Mobile-bearing knee systems are distinguished from conventional, fixed-plateau systems in that they allow dual-surface articulation between an ultra-high molecular weight polyethylene insert and metallic femoral and tibial tray components. Their in vivo success is dependent on patient selection, design, and material choice, as well as surgical precision during implantation. Laboratory and clinical experience extending over 25 years with individual systems suggests that mobile-bearing knee systems represent a viable treatment option for patients with knee arthrosis.

  2. Determination of nanoparticle size distribution together with density or molecular weight by 2D analytical ultracentrifugation

    PubMed Central

    Carney, Randy P.; Kim, Jin Young; Qian, Huifeng; Jin, Rongchao; Mehenni, Hakim; Stellacci, Francesco; Bakr, Osman M.

    2011-01-01

    Nanoparticles are finding many research and industrial applications, yet their characterization remains a challenge. Their cores are often polydisperse and coated by a stabilizing shell that varies in size and composition. No single technique can characterize both the size distribution and the nature of the shell. Advances in analytical ultracentrifugation allow for the extraction of the sedimentation (s) and diffusion coefficients (D). Here we report an approach to transform the s and D distributions of nanoparticles in solution into precise molecular weight (M), density (ρP) and particle diameter (dp) distributions. M for mixtures of discrete nanocrystals is found within 4% of the known quantities. The accuracy and the density information we achieve on nanoparticles are unparalleled. A single experimental run is sufficient for full nanoparticle characterization, without the need for standards or other auxiliary measurements. We believe that our method is of general applicability and we discuss its limitations. PMID:21654635

  3. A versatile electrophoresis system for the analysis of high- and low-molecular-weight proteins

    PubMed Central

    Tastet, Christophe; Lescuyer, Pierre; Diemer, Hélène; Luche, Sylvie; van Dorsselaer, Alain; Rabilloud, Thierry

    2003-01-01

    A new, versatile, multiphasic buffer system for high resolution sodium dodecyl sulfatepolyacrylamide gel electrophoresis of proteins in the relative molecular weight Mw range of 300,000-3000 Da is described. The system, based on the theory of multiphasic zone electrophoresis, allows complete stacking and destacking of proteins in the above Mw range. The buffer system uses taurine and chloride as trailing and leading ion, respectively, and Tris, at a pH close to its pKa, as the buffering counter ion. Coupled with limited variation in the acrylamide concentration, this electrophoresis system allows to tailor the resolution in the 6–200 kDa Mw range, with minimal difficulties in the post electrophoretic identification processes. PMID:12783456

  4. Antioxidation activities of low-molecular-weight gelatin hydrolysate isolated from the sea cucumber Stichopus japonicus

    NASA Astrophysics Data System (ADS)

    Wang, Jingfeng; Wang, Yuming; Tang, Qingjuan; Wang, Yi; Chang, Yaoguang; Zhao, Qin; Xue, Changhu

    2010-03-01

    Gelatin extracted from the body wall of the sea cucumber ( Stichopus japonicus) was hydrolyzed with flavourzyme. Low-molecular-weight gelatin hydrolysate (LMW-GH) of 700-1700 Da was produced using an ultrafiltration membrane bioreactor system. Chemiluminescence analysis revealed that LMW-GH scavenges high free radicals in a concentration-dependent manner; IC50 value for superoxide and hydroxyl radicals was 442 and 285 μg mL-1, respectively. LMW-GH exhibited excellent inhibitory characteristics against melanin synthesis and tyrosinase activity in B16 cells. Furthermore, LMW-GH notably increased intracellular glutathione (GSH), which in turn suppressed melanogenesis. LMW-GH performs antioxidation activity, holding the potential of being used as a valuable ingredient in function foods, cosmetics and pharmaceuticals or nutriceuticals.

  5. Can thiolation render a low molecular weight polymer of just 20-kDa mucoadhesive?

    PubMed

    Mahmood, Arshad; Bonengel, Sonja; Laffleur, Flavia; Ijaz, Muhammad; Idrees, Muneeb Ahmad; Hussain, Shah; Huck, Christian W; Matuszczak, Barbara; Bernkop-Schnürch, Andreas

    2016-01-01

    The objective was to investigate whether even low-molecular weight polymers (LMWPs) can be rendered mucoadhesive due to thiolation. Interceded by the double catalytic system carbodiimide/N-hydroxysuccinimide, cysteamine was covalently attached to a copolymer, poly(4-styrenesulfonic acid-co-maleic acid) (PSSA-MA) exhibiting a molecular weight of just 20 kDa. Depending on the amount of added N-hydroxysuccinimide and cysteamine, the resulting PSSA-MA-cysteamine (PC) conjugates exhibited increasing degree of thiolation, highest being "PC 2300" exhibiting 2300.16 ± 149.86 μmol thiol groups per gram of polymer (mean ± SD; n = 3). This newly developed thiolated polymer was evaluated regarding mucoadhesive, rheological and drug release properties as well from the toxicological point of view. Swelling behavior in 100 mM phosphate buffer pH 6.8 was improved up to 180-fold. Furthermore, due to thiolation, the mucoadhesive properties of the polymer were 240-fold improved. Rheological measurements of polymer/mucus mixtures confirmed results obtained by mucoadhesion studies. In comparison to unmodified polymer, PC 2300 showed 2.3-, 2.3- and 2.4-fold increase in dynamic viscosity, elastic modulus and viscous modulus, respectively. Sustained release of the model drug codeine HCl out of the thiomer was provided for 2.5 h (p < 0.05), whereas the drug was immediately released from the unmodified polymer. Moreover, the thiomer was found non-toxic over Caco-2 cells for a period of 6- and 24-h exposure. Findings of the present study provide evidence that due to thiolation LMWPs can be rendered highly mucoadhesive as well as cohesive and that a controlled drug release out of such polymers can be provided.

  6. Effects of low molecular weight organic acids on (137)Cs release from contaminated soils.

    PubMed

    Chiang, Po Neng; Wang, Ming Kuang; Huang, Pan Ming; Wang, Jeng Jong

    2011-06-01

    Radio pollutant removal is one of several priority restoration strategies for the environment. This study assessed the effect of low molecular weight organic acid on the lability and mechanisms for release of (137)Cs from contaminated soils. The amount of (137)Cs radioactivity released from contaminated soils reacting with 0.02 M low molecular weight organic acids (LMWOAs) specifically acetic, succinic, oxalic, tartaric, and citric acid over 48 h were 265, 370, 760, 850, and 1002 Bq kg(-1), respectively. The kinetic results indicate that (137)Cs exhibits a two-step parabolic diffusion equation and a good linear relationship, indicating that the parabolic diffusion equation describes the data quite well, as shown by low p and high r(2) values. The fast stage, which was found to occur within a short period of time (0.083-3 h), corresponds to the interaction of LMWOAs with the surface of clay minerals; meanwhile, during the slow stage, which occurs over a much longer time period (3-24 h), desorption primarily is attributed to inter-particle or intra-particle diffusion. After a fifth renewal of the LMWOAs, the total levels of (137)Cs radioactivity released by acetic, succinic, oxalic, tartaric, and citric acid were equivalent to 390, 520, 3949, 2061, and 4422 Bq kg(-1) soil, respectively. H(+) can protonate the hydroxyl groups and oxygen atoms at the broken edges or surfaces of the minerals, thereby weakening Fe-O and Al-O bonds. After protonation of H(+), organic ligands can attack the OH and OH(2) groups in the minerals easily, to form complexes with surface structure cations, such as Al and Fe. The amounts of (137)Cs released from contaminated soil treated with LMWOAs were substantially increased, indicating that the LMWOAs excreted by the roots of plants play a critical role in (137)Cs release. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. Physicochemical and immunologic characterization of low-molecular-weight allergoids of Dactylis glomerata pollen proteins.

    PubMed

    Cirković, T D; Bukilica, M N; Gavrović, M D; Vujcić, Z M; Petrović, S; Jankov, R M

    1999-02-01

    Orchard grass (Dactylis glomerata) pollen proteins were chemically modified by means of acid anhydrides (maleic and succinic anhydride) to obtain low-molecular-weight allergoids. Chemical modification in both cases led to the replacement of one positive charge (epsilon amino group of Lys) by one negative charge, yielding proteins with changed physicochemical properties in comparison to the native orchard grass-pollen proteins. Physicochemical characterization of derivatives was done by gel chromatography, SDS-PAGE, and isoelectric focusing. To examine the IgE-binding properties of these derivatives, we carried out immunoblotting. To examine the ability of derivatives to induce IgG production, we immunized rabbits. Skin prick testing with the allergoids was performed on 15 individuals allergic to orchard grass pollens and on two healthy subjects. It was shown that the modified proteins retain their original molecular weights, but change pI to more acidic values. In the case of allergoids, a strong reduction in IgE binding was found. Immunization of rabbits with allergoids showed that the derivatives retain the ability to induce IgG production, and that the antisera obtained in such a way react to native (unmodified) extract. The ability of derivatives to induce allergic reaction was significantly reduced. The patients (86.6%) included in our study exhibited less than 50% of native extract response. Among them, 53.3% had no response to one or both allergoids. These modification procedures yield allergoids with a reduced allergenic activity and preserved immunogenic potential suitable for use in immunotherapy.

  8. Mechanical properties and biocompatibility of melt processed, self-reinforced ultrahigh molecular weight polyethylene.

    PubMed

    Huang, Yan-Fei; Xu, Jia-Zhuang; Li, Jian-Shu; He, Ben-Xiang; Xu, Ling; Li, Zhong-Ming

    2014-08-01

    The low efficiency of fabrication of ultrahigh molecular weight polyethylene (UHMWPE)-based artificial knee joint implants is a bottleneck problem because of its extremely high melt viscosity. We prepared melt processable UHMWPE (MP-UHMWPE) by addition of 9.8 wt% ultralow molecular weight polyethylene (ULMWPE) as a flow accelerator. More importantly, an intense shear flow was applied during injection molding of MP-UHMWPE, which on one hand, promoted the self-diffusion of UHMWPE chains, thus effectively reducing the structural defects; on the other hand, increased the overall crystallinity and induced the formation of self-reinforcing superstructure, i.e., interlocked shish-kebabs and oriented lamellae. Aside from the good biocompatibility, and the superior fatigue and wear resistance to the compression-molded UHMWPE, the injection-molded MP-UHMWPE exhibits a noteworthy enhancement in tensile properties and impact strength, where the yield strength increases to 46.3 ± 4.4 MPa with an increment of 128.0%, the ultimate tensile strength and Young's modulus rise remarkably up to 65.5 ± 5.0 MPa and 1248.7 ± 45.3 MPa, respectively, and the impact strength reaches 90.6 kJ/m(2). These results suggested such melt processed and self-reinforced UHMWPE parts hold a great application promise for use of knee joint implants, particularly for younger and more active patients. Our work sets up a new method to fabricate high-performance UHMWPE implants by tailoring the superstructure during thermoplastic processing. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. High molecular weight of polysaccharides from Hericium erinaceus against amyloid beta-induced neurotoxicity.

    PubMed

    Cheng, Jai-Hong; Tsai, Chia-Ling; Lien, Yi-Yang; Lee, Meng-Shiou; Sheu, Shyang-Chwen

    2016-06-07

    Hericium erinaceus (HE) is a well-known mushroom in traditional Chinese food and medicine. HE extracts from the fruiting body and mycelia not only exhibit immunomodulatory, antimutagenic and antitumor activity but also have neuroprotective properties. Here, we purified HE polysaccharides (HEPS), composed of two high molecular weight polysaccharides (1.7 × 10(5) Da and 1.1 × 10(5) Da), and evaluated their protective effects on amyloid beta (Aβ)-induced neurotoxicity in rat pheochromocytoma PC12 cells. HEPS were prepared and purified using a 95 % ethanol extraction method. The components of HEPS were analyzed and the molecular weights of the polysaccharides were determined using high-pressure liquid chromatography (HPLC). The neuroprotective effects of the polysaccharides were evaluated through a 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay and an MTT assay and by quantifying reactive oxygen species (ROS) and mitochondrial membrane potentials (MMP) of Aβ-induced neurotoxicity in cells. Our results showed that 250 μg/ml HEPS was harmless and promoted cell viability with 1.2 μM Aβ treatment. We observed that the free radical scavenging rate exceeded 90 % when the concentration of HEPS was higher than 1 mg/mL in cells. The HEPS decreased the production of ROS from 80 to 58 % in a dose-dependent manner. Cell pretreatment with 250 μg/mL HEPS significantly reduced Aβ-induced high MMPs from 74 to 51 % and 94 to 62 % at 24 and 48 h, respectively. Finally, 250 μg/mL of HEPS prevented Aβ-induced cell shrinkage and nuclear degradation of PC12 cells. Our results demonstrate that HEPS exhibit antioxidant and neuroprotective effects on Aβ-induced neurotoxicity in neurons.

  10. High-molecular-weight polyethylene glycol inhibits myocardial ischemia-reperfusion injury in vivo.

    PubMed

    Xu, Xianyao; Philip, Jennifer L; Razzaque, Md Abdur; Lloyd, James W; Muller, Charlie M; Akhter, Shahab A

    2015-02-01

    Cardiac ischemia-reperfusion (I-R) injury remains a significant problem as there are no therapies available to minimize the cell death that can lead to impaired function and heart failure. We have shown that high-molecular-weight polyethylene glycol (PEG) (15-20 kD) can protect cardiac myocytes in vitro from hypoxia-reoxygenation injury. In this study, we investigated the potential protective effects of PEG in vivo. Adult rats underwent left anterior descending artery occlusion for 60 minutes followed by 48 hours or 4 weeks of reperfusion. One milliliter of 10% PEG solution or phosphate-buffered saline (PBS) control (n = 10 per group) was administered intravenously (IV) immediately before reperfusion. Fluorescein-labeled PEG was robustly visualized in the myocardium 1 hour after IV delivery. The PEG group had significant recovery of left ventricular ejection fraction at 4 weeks versus a 25% decline in the PBS group (P < .01). There was 50% less LV fibrosis in the PEG group versus PBS with smaller peri-infarct and remote territory fibrosis (P < .01). Cell survival signaling was upregulated in the PEG group with increased Akt (3-fold, P < .01) and ERK (4-fold, P < .05) phosphorylation compared to PBS controls at 48 hours. PEG also inhibited apoptosis as measured by TUNEL-positive nuclei (56% decrease, P < .02) and caspase 3 activity (55% decrease, P < .05). High-molecular-weight PEG appears to have a significant protective effect from I-R injury in the heart when administered IV immediately before reperfusion. This may have important clinical translation in the setting of acute coronary revascularization and myocardial protection in cardiac surgery. Copyright © 2015 The American Association for Thoracic Surgery. Published by Elsevier Inc. All rights reserved.

  11. The association of low-molecular-weight hydrophobic compounds with native casein micelles in bovine milk.

    PubMed

    Cheema, M; Mohan, M S; Campagna, S R; Jurat-Fuentes, J L; Harte, F M

    2015-08-01

    The agreed biological function of the casein micelles in milk is to carry minerals (calcium, magnesium, and phosphorus) from mother to young along with amino acids for growth and development. Recently, native and modified casein micelles were used as encapsulating and delivery agents for various hydrophobic low-molecular-weight probes. The ability of modified casein micelles to bind certain probes may derive from the binding affinity of native casein micelles. Hence, a study with milk from single cows was conducted to further elucidate the association of hydrophobic molecules into native casein micelles and further understand their biological function. Hydrophobic and hydrophilic extraction followed by ultraperformance liquid chromatography-high resolution mass spectrometry analysis were performed over protein fractions obtained from size exclusion fractionation of raw skim milk. Hydrophobic compounds, including phosphatidylcholine, lyso-phosphatidylcholine, phosphatidylethanolamine, and sphingomyelin, showed strong association exclusively to casein micelles as compared with whey proteins, whereas hydrophilic compounds did not display any preference for their association among milk proteins. Further analysis using liquid chromatography-tandem mass spectrometry detected 42 compounds associated solely with the casein-micelles fraction. Mass fragments in tandem mass spectrometry identified 4 of these compounds as phosphatidylcholine with fatty acid composition of 16:0/18:1, 14:0/16:0, 16:0/16:0, and 18:1/18:0. These results support that transporting low-molecular-weight hydrophobic molecules is also a biological function of the casein micelles in milk. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  12. A low molecular weight proteome comparison of fertile and male sterile 8 anthers of Zea mays

    PubMed Central

    Wang, Dongxue; Adams, Christopher M.; Fernandes, John F.; Egger, Rachel L.; Walbot, Virginia

    2014-01-01

    Summary During maize anther development, somatic locular cells differentiate to support meiosis in the pollen mother cells. Meiosis is an important event during anther growth and is essential for plant fertility as pollen contains the haploid sperm. A subset of maize male sterile mutants exhibit meiotic failure, including ms8 (male sterile 8) in which meiocytes arrest as dyads and the locular somatic cells exhibit multiple defects. Systematic proteomic profiles were analysed in biological triplicates plus technical triplicates comparing ms8 anthers with fertile sibling samples at both the premeiotic and meiotic stages; proteins from 3.5 to 20 kDa were fractionated by 1-D PAGE, cleaved with Lys-C and then sequenced using a LTQ Orbitrap Velos MS paradigm. Three hundred and 59proteins were identified with two or more assigned peptides in which each of those peptides were counted at least two or more times (0.4% peptide false discovery rate (FDR) and 0.2% protein FDR); 2761 proteins were identified with one or more assigned peptides (0.4% peptide FDR and 7.6% protein FDR). Stage-specific protein expression provides candidate stage markers for early anther development, and proteins specifically expressed in fertile compared to sterile anthers provide important clues about the regulation of meiosis. 49% of the proteins detected by this study are new to an independent whole anther proteome, and many small proteins missed by automated maize genome annotation were validated; these outcomes indicate the value of focusing on low molecular weight proteins. The roles of distinctive expressed proteins and methods for mass spectrometry of low molecular weight proteins are discussed. PMID:22748129

  13. Impact of Low Molecular Weight Poly(3-hexylthiophene)s as Additives in Organic Photovoltaic Devices.

    PubMed

    Seibers, Zach D; Le, Thinh P; Lee, Youngmin; Gomez, Enrique D; Kilbey, S Michael

    2018-01-24

    Despite tremendous progress in using additives to enhance the power conversion efficiency of organic photovoltaic devices, significant challenges remain in controlling the microstructure of the active layer, such as at internal donor-acceptor interfaces. Here, we demonstrate that the addition of low molecular weight poly(3-hexylthiophene)s (low-MW P3HT) to the P3HT/fullerene active layer increases device performance up to 36% over an unmodified control device. Low MW P3HT chains ranging in size from 1.6 to 8.0 kg/mol are blended with 77.5 kg/mol P3HT chains and [6,6]-phenyl C 61 butyric acid methyl ester (PCBM) fullerenes while keeping P3HT/PCBM ratio constant. Optimal photovoltaic device performance increases are obtained for each additive when incorporated into the bulk heterojunction blend at loading levels that are dependent upon additive MW. Small-angle X-ray scattering and energy-filtered transmission electron microscopy imaging reveal that domain sizes are approximately invariant at low loading levels of the low-MW P3HT additive, and wide-angle X-ray scattering suggests that P3HT crystallinity is unaffected by these additives. These results suggest that oligomeric P3HTs compatibilize donor-acceptor interfaces at low loading levels but coarsen domain structures at higher loading levels and they are consistent with recent simulations results. Although results are specific to the P3HT/PCBM system, the notion that low molecular weight additives can enhance photovoltaic device performance generally provides a new opportunity for improving device performance and operating lifetimes.

  14. Developmental expression of high molecular weight tropomyosin isoforms in Mesocestoides corti.

    PubMed

    Koziol, Uriel; Costábile, Alicia; Domínguez, María Fernanda; Iriarte, Andrés; Alvite, Gabriela; Kun, Alejandra; Castillo, Estela

    2011-02-01

    Tropomyosins are a family of actin-binding proteins with diverse roles in actin filament function. One of the best characterized roles is the regulation of muscle contraction. Tropomyosin isoforms can be generated from different genes, and from alternative promoters and alternative splicing from the same gene. In this work, we have isolated sequences for tropomyosin isoforms from the cestode Mesocestoides corti, and searched for tropomyosin genes and isoforms in other flatworms. Two genes are conserved in the cestodes M. corti and Echinococcus multilocularis, and in the trematode Schistosoma mansoni. Both genes have the same structure, and each gene gives rise to at least two different isoforms, a high molecular weight (HMW) and a low molecular weight (LMW) one. Because most exons are duplicated and spliced in a mutually exclusive fashion, isoforms from one gene only share one exon and are highly divergent. The gene duplication preceded the divergence of neodermatans and the planarian Schmidtea mediterranea. Further duplications occurred in Schmidtea, coupled to the selective loss of duplicated exons, resulting in genes that only code for HMW or LMW isoforms. A polyclonal antibody raised against a HMW tropomyosin from Echinococcus granulosus was demonstrated to specifically recognize HMW tropomyosin isoforms of M. corti, and used to study their expression during segmentation. HMW tropomyosins are expressed in muscle layers, with very low or absent levels in other tissues. No expression of HMW tropomyosins is present in early or late genital primordia, and expression only begins once muscle fibers develop in the genital ducts. Therefore, HMW tropomyosins are markers for the development of muscles during the final differentiation of genital primordia. Copyright © 2010 Elsevier B.V. All rights reserved.

  15. Local and systemic vasodilatory effects of low molecular weight S-nitrosothiols.

    PubMed

    Liu, Taiming; Schroeder, Hobe J; Wilson, Sean M; Terry, Michael H; Romero, Monica; Longo, Lawrence D; Power, Gordon G; Blood, Arlin B

    2016-02-01

    S-nitrosothiols (SNOs) such as S-nitroso-L-cysteine (L-cysNO) are endogenous compounds with potent vasodilatory activity. During circulation in the blood, the NO moiety can be exchanged among various thiol-containing compounds by S-transnitrosylation, resulting in SNOs with differing capacities to enter the cell (membrane permeability). To determine whether the vasodilating potency of SNOs is dependent upon membrane permeability, membrane-permeable L-cysNO and impermeable S-nitroso-D-cysteine (D-cysNO) and S-nitroso-glutathione (GSNO) were infused into one femoral artery of anesthetized adult sheep while measuring bilateral femoral and systemic vascular conductances. L-cysNO induced vasodilation in the infused hind limb, whereas D-cysNO and GSNO did not. L-cysNO also increased intracellular NO in isolated arterial smooth muscle cells, whereas GSNO did not. The infused SNOs remained predominantly in a low molecular weight form during first-passage through the hind limb vasculature, but were converted into high molecular weight SNOs upon systemic recirculation. At systemic concentrations of ~0.6 μmol/L, all three SNOs reduced mean arterial blood pressure by ~50%, with pronounced vasodilation in the mesenteric bed. Pharmacokinetics of L-cysNO and GSNO were measured in vitro and in vivo and correlated with their hemodynamic effects, membrane permeability, and S-transnitrosylation. These results suggest local vasodilation by SNOs in the hind limb requires membrane permeation, whereas systemic vasodilation does not. The systemic hemodynamic effects of SNOs occur after equilibration of the NO moiety amongst the plasma thiols via S-transnitrosylation. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. Colonic Absorption of Low-Molecular-Weight Metabolites Influenced by the Intestinal Microbiome: A Pilot Study.

    PubMed

    Matsumoto, Mitsuharu; Ooga, Takushi; Kibe, Ryoko; Aiba, Yuji; Koga, Yasuhiro; Benno, Yoshimi

    2017-01-01

    Low-molecular-weight metabolites produced by the intestinal microbiome play a direct role in health and disease. However, little is known about the ability of the colon to absorb these metabolites. It is also unclear whether these metabolites are bioavailable. Here, metabolomics techniques (capillary electrophoresis with time-of-flight mass spectrometry, CE-TOFMS), germ-free (GF) mice, and colonized (Ex-GF) mice were used to identify the colonic luminal metabolites transported to colonic tissue and/or blood. We focused on the differences in each metabolite between GF and Ex-GF mice to determine the identities of metabolites that are transported to the colon and/or blood. CE-TOFMS identified 170, 246, 166, and 193 metabolites in the colonic feces, colonic tissue, portal plasma, and cardiac plasma, respectively. We classified the metabolites according to the following influencing factors: (i) the membrane transport system of the colonocytes, (ii) metabolism during transcellular transport, and (iii) hepatic metabolism based on the similarity in the ratio of each metabolite between GF and Ex-GF mice and found 62 and 22 metabolites that appeared to be absorbed from the colonic lumen to colonocytes and blood, respectively. For example, 11 basic amino acids were transported to the systemic circulation from the colonic lumen. Furthermore, many low-molecular-weight metabolites influenced by the intestinal microbiome are bioavailable. The present study is the first to report the transportation of metabolites from the colonic lumen to colonocytes and somatic blood in vivo, and the present findings are critical for clarifying host-intestinal bacterial interactions.

  17. Low-Molecular-Weight Protein Tyrosine Phosphatase Predicts Prostate Cancer Outcome by Increasing the Metastatic Potential.

    PubMed

    Ruela-de-Sousa, Roberta R; Hoekstra, Elmer; Hoogland, A Marije; Queiroz, Karla C Souza; Peppelenbosch, Maikel P; Stubbs, Andrew P; Pelizzaro-Rocha, Karin; van Leenders, Geert J L H; Jenster, Guido; Aoyama, Hiroshi; Ferreira, Carmen V; Fuhler, Gwenny M

    2016-04-01

    Low-risk patients suffering from prostate cancer (PCa) are currently placed under active surveillance rather than undergoing radical prostatectomy. However, clear parameters for selecting the right patient for each strategy are not available, and new biomarkers and treatment modalities are needed. Low-molecular-weight protein tyrosine phosphatase (LMWPTP) could present such a target. To correlate expression levels of LMWPTP in primary PCa to clinical outcome, and determine the role of LMWPTP in prostate tumor cell biology. Acid phosphatase 1, soluble (ACP1) expression was analyzed on microarray data sets, which were subsequently used in Ingenuity Pathway Analysis. Immunohistochemistry was performed on a tissue microarray containing material of 481 PCa patients whose clinicopathologic data were recorded. PCa cell line models were used to investigate the role of LMWPTP in cell proliferation, migration, adhesion, and anoikis resistance. The association between LMWPTP expression and clinical and pathologic outcomes was calculated using chi-square correlations and multivariable Cox regression analysis. Functional consequences of LMWPTP overexpression or downregulation were determined using migration and adhesion assays, confocal microscopy, Western blotting, and proliferation assays. LMWPTP expression was significantly increased in human PCa and correlated with earlier recurrence of disease (hazard ratio [HR]:1.99; p<0.001) and reduced patient survival (HR: 1.53; p=0.04). Unbiased Ingenuity analysis comparing cancer and normal prostate suggests migratory propensities in PCa. Indeed, overexpression of LMWPTP increases PCa cell migration, anoikis resistance, and reduces activation of focal adhesion kinase/paxillin, corresponding to decreased adherence. Overexpression of LMWPTP in PCa confers a malignant phenotype with worse clinical outcome. Prospective follow-up should determine the clinical potential of LMWPTP overexpression. These findings implicate low-molecular-weight

  18. Placental mitochondrial DNA and CYP1A1 gene methylation as molecular signatures for tobacco smoke exposure in pregnant women and the relevance for birth weight.

    PubMed

    Janssen, Bram G; Gyselaers, Wilfried; Byun, Hyang-Min; Roels, Harry A; Cuypers, Ann; Baccarelli, Andrea A; Nawrot, Tim S

    2017-01-04

    Maternal smoking during pregnancy results in an increased risk of low birth weight through perturbations in the utero-placental exchange. Epigenetics and mitochondrial function in fetal tissues might be molecular signatures responsive to in utero tobacco smoke exposure. In the framework of the ENVIRONAGE birth cohort, we investigated the effect of self-reported tobacco smoke exposure during pregnancy on birth weight and the relation with placental tissue markers such as, (1) relative mitochondrial DNA (mtDNA) content as determined by real-time quantitative PCR, (2) DNA methylation of specific loci of mtDNA (D-loop and MT-RNR1), and (3) DNA methylation of the biotransformation gene CYP1A1 (the last two determined by bisulfite-pyrosequencing). The total pregnant mother sample included 255 non-smokers, 65 former-smokers who had quit smoking before pregnancy, and 62 smokers who continued smoking during pregnancy. Smokers delivered newborns with a birth weight on average 208 g lower [95% confidence interval (CI) -318 to -99, p = 0.0002] than mothers who did not smoke during pregnancy. In the smoker group, the relative mtDNA content was lower (-21.6%, 95% CI -35.4 to -4.9%, p = 0.01) than in the non-smoker group; whereas, absolute mtDNA methylation levels of MT-RNR1 were higher (+0.62%, 95% CI 0.21 to 1.02%, p = 0.003). Lower CpG-specific methylation of CYP1A1 in placental tissue (-4.57%, 95% CI -7.15 to -1.98%, p < 0.0001) were observed in smokers compared with non-smokers. Nevertheless, no mediation of CYP1A1 methylation nor any other investigated molecular signature was observed for the association between tobacco smoke exposure and birth weight. mtDNA content, methylation of specific loci of mtDNA, and CYP1A1 methylation in placental tissue may serve as molecular signatures for the association between gestational tobacco smoke exposure and low birth weight.

  19. Factors that affect molecular weight distribution of Suwannee river fulvic acid as determined by electrospray ionization/mass spectrometry

    USGS Publications Warehouse

    Rostad, C.E.; Leenheer, J.A.

    2004-01-01

    Effects of methylation, molar response, multiple charging, solvents, and positive and negative ionization on molecular weight distributions of aquatic fulvic acid were investigated by electrospray ionization/mass spectrometry. After preliminary analysis by positive and negative modes, samples and mixtures of standards were derivatized by methylation to minimize ionization sites and reanalyzed.Positive ionization was less effective and produced more complex spectra than negative ionization. Ionization in methanol/water produced greater response than in acetonitrile/water. Molar response varied widely for the selected free acid standards when analyzed individually and in a mixture, but after methylation this range decreased. After methylation, the number average molecular weight of the Suwannee River fulvic acid remained the same while the weight average molecular weight decreased. These differences are probably indicative of disaggregation of large aggregated ions during methylation. Since the weight average molecular weight decreased, it is likely that aggregate formation in the fulvic acid was present prior to derivatization, rather than multiple charging in the mass spectra. ?? 2004 Elsevier B.V. All rights reserved.

  20. Factors that affect molecular weight distribution of Suwannee river fulvic acid as determined by electrospray ionization/mass spectrometry

    USGS Publications Warehouse

    Rostad, Colleen E.; Leenheer, Jerry A.

    2004-01-01

    Effects of methylation, molar response, multiple charging, solvents, and positive and negative ionization on molecular weight distributions of aquatic fulvic acid were investigated by electrospray ionization/mass spectrometry. After preliminary analysis by positive and negative modes, samples and mixtures of standards were derivatized by methylation to minimize ionization sites and reanalyzed.Positive ionization was less effective and produced more complex spectra than negative ionization. Ionization in methanol/water produced greater response than in acetonitrile/water. Molar response varied widely for the selected free acid standards when analyzed individually and in a mixture, but after methylation this range decreased. After methylation, the number average molecular weight of the Suwannee River fulvic acid remained the same while the weight average molecular weight decreased. These differences are probably indicative of disaggregation of large aggregated ions during methylation. Since the weight average molecular weight decreased, it is likely that aggregate formation in the fulvic acid was present prior to derivatization, rather than multiple charging in the mass spectra.

  1. Establishment of replacement batches for heparin low-molecular-mass for calibration CRS, and the International Standard Low Molecular Weight Heparin for Calibration.

    PubMed

    Mulloy, B; Heath, A; Behr-Gross, M-E

    2007-12-01

    An international collaborative study involving fourteen laboratories has taken place, organised by the European Directorate for the Quality of Medicines & HealthCare (EDQM) with National Institute for Biological Standards & Control (NIBSC) (in its capacity as a World Health Organisation (WHO) Laboratory for Biological Standardisation) to provide supporting data for the establishment of replacement batches of Heparin Low-Molecular-Mass (LMM) for Calibration Chemical Reference Substance (CRS), and of the International Reference Reagent (IRR) Low Molecular Weight Heparin for Molecular Weight Calibration. A batch of low-molecular-mass heparin was donated to the organisers and candidate preparations of freeze-dried heparin were produced at NIBSC and EDQM. The establishment study was organised in two phases: a prequalification (phase 1, performed in 3 laboratories in 2005) followed by an international collaborative study (phase 2). In phase 2, started in March 2006, molecular mass parameters were determined for seven different LMM heparin samples using the current CRS batch and two batches of candidate replacement material with a defined number average relative molecular mass (Mn) of 3,700, determined in phase 1. The values calculated using the candidates as standard were systematically different from values calculated using the current batch with its assigned number-average molecular mass (Mna) of 3,700. Using raw data supplied by participants, molecular mass parameters were recalculated using the candidates as standard with values for Mna of 3,800 and 3,900. Values for these parameters agreed more closely with those calculated using the current batch supporting the fact that the candidates, though similar to batch 1 in view of the production processes used, differ slightly in terms of molecular mass distribution. Therefore establishment of the candidates was recommended with an assigned Mna value of 3,800 that is both consistent with phase 1 results and guarantees

  2. Selective Suppression of Endothelial Cell Apoptosis by the High Molecular Weight Form of Adiponectin

    PubMed Central

    Kobayashi, Hideki; Ouchi, Noriyuki; Kihara, Shinji; Walsh, Kenneth; Kumada, Masahiro; Abe, Yuki; Funahashi, Tohru; Matsuzawa, Yuji

    2015-01-01

    Adiponectin is an adipocyte-derived, antiatherogenic protein that is present in serum as three isoforms. Total adiponectin levels are decreased in obese or diabetic humans or animal models. This study was designed to elucidate the relative isoform distribution of adiponectin in human disease states and identify the active form of adiponectin toward vascular endothelial cells. The percentage of high molecular weight form (HMW) per total adiponectin was significantly lower in patients with coronary artery disease than control subjects, whereas the hexamer form was similar and the trimer form was significantly higher. During weight reduction in obese subjects, the HMW form increased and the trimer and hexamer forms decreased. Recombinant adiponectin dose-dependently suppressed apoptosis and caspase-3 activity in human umbilical vein endothelial cells (HUVECs). Transduction with dominant-negative AMP-activated protein kinase (AMPK) abolished the suppressive effect of adiponectin on HUVECs. Gel filtration chromatography was used to separate the adiponectin isoforms, and the antiapoptotic effect toward HUVECs was only observed with the HMW form. These data suggest that HMW adiponectin specifically confers the vascular-protective activities of this adipocytokine. PMID:14752031

  3. Epoxy resin synthesis using low molecular weight lignin separated from various lignocellulosic materials.

    PubMed

    Asada, Chikako; Basnet, Sunita; Otsuka, Masaya; Sasaki, Chizuru; Nakamura, Yoshitoshi

    2015-03-01

    A low molecular weight lignin from various lignocellulosic materials was used for the synthesis of bio-based epoxy resins. The lignin extracted with methanol from steam-exploded samples (steaming time of 5 min at steam pressure of 3.5 MPa) from different biomasses (i.e., cedar, eucalyptus, and bamboo) were functionalized by the reaction with epichlorohydrin, catalyzed by a water-soluble phase transfer catalyst tetramethylammonium chloride, which was further reacted with 30 wt% aqueous NaOH for ring closure using methyl ethyl ketone as a solvent. The glycidylated products of the lignin with good yields were cured to epoxy polymer networks with bio-based curing agents i.e., lignin itself and a commercial curing agent TD2131. Relatively good thermal properties of the bio-based epoxy network was obtained and thermal decomposition temperature at 5% weight loss (Td5) of cedar-derived epoxy resin was higher than that derived from eucalyptus and bamboo. The bio-based resin satisfies the stability requirement of epoxy resin applicable for electric circuit boards. The methanol-insoluble residues were enzymatically hydrolyzed to produce glucose. This study indicated that the biomass-derived methanol-soluble lignin may be a promising candidate to be used as a substitute for petroleum-based epoxy resin derived from bisphenol A, while insoluble residues may be processed to give a bioethanol precursor i.e., glucose. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Diabetes reversal by inhibition of the low-molecular-weight tyrosine phosphatase.

    PubMed

    Stanford, Stephanie M; Aleshin, Alexander E; Zhang, Vida; Ardecky, Robert J; Hedrick, Michael P; Zou, Jiwen; Ganji, Santhi R; Bliss, Matthew R; Yamamoto, Fusayo; Bobkov, Andrey A; Kiselar, Janna; Liu, Yingge; Cadwell, Gregory W; Khare, Shilpi; Yu, Jinghua; Barquilla, Antonio; Chung, Thomas D Y; Mustelin, Tomas; Schenk, Simon; Bankston, Laurie A; Liddington, Robert C; Pinkerton, Anthony B; Bottini, Nunzio

    2017-06-01

    Obesity-associated insulin resistance plays a central role in type 2 diabetes. As such, tyrosine phosphatases that dephosphorylate the insulin receptor (IR) are potential therapeutic targets. The low-molecular-weight protein tyrosine phosphatase (LMPTP) is a proposed IR phosphatase, yet its role in insulin signaling in vivo has not been defined. Here we show that global and liver-specific LMPTP deletion protects mice from high-fat diet-induced diabetes without affecting body weight. To examine the role of the catalytic activity of LMPTP, we developed a small-molecule inhibitor with a novel uncompetitive mechanism, a unique binding site at the opening of the catalytic pocket, and an exquisite selectivity over other phosphatases. This inhibitor is orally bioavailable, and it increases liver IR phosphorylation in vivo and reverses high-fat diet-induced diabetes. Our findings suggest that LMPTP is a key promoter of insulin resistance and that LMPTP inhibitors would be beneficial for treating type 2 diabetes.

  5. A Low-Molecular-Weight Antagonist for the Human Thyrotropin Receptor with Therapeutic Potential for Hyperthyroidism

    PubMed Central

    Neumann, Susanne; Kleinau, Gunnar; Costanzi, Stefano; Moore, Susanna; Jiang, Jian-kang; Raaka, Bruce M.; Thomas, Craig J.; Krause, Gerd; Gershengorn, Marvin C.

    2008-01-01

    Low-molecular-weight (LMW) antagonists for TSH receptor (TSHR) may have therapeutic potential as orally active drugs to block stimulating antibodies (TsAbs) in Graves’ hyperthyroidism. We describe an approach to identify LMW ligands for TSHR based on Org41841, a LMW partial agonist for the LH/choriogonadotropin receptor and TSHR. We used molecular modeling and functional experiments to guide the chemical modification of Org41841. We identified an antagonist (NIDDK/CEB-52) that selectively inhibits activation of TSHR by both TSH and TsAbs. Whereas initially characterized in cultured cells overexpressing TSHRs, the antagonist was also active under more physiologically relevant conditions in primary cultures of human thyrocytes expressing endogenous TSHRs in which it inhibited TSH- and TsAb-induced up-regulation of mRNA transcripts for thyroperoxidase. Our results establish this LMW compound as a lead for the development of higher potency antagonists and serve as proof of principle that LMW ligands that target TSHR could serve as drugs in patients with Graves’ disease. PMID:18669595

  6. Lens protein composition, glycation and high molecular weight aggregation in aging rats.

    PubMed

    Swamy, M S; Abraham, E C

    1987-10-01

    Because of minimal or no turnover, lens proteins are subjected to substantial post-translational modifications which in turn disrupt lens architecture and change the optical properties leading to senile cataract formation. Progressive glycation is believed to have the potential to initiate the changes that are conducive to lens opacification. Fisher 344 rats were systematically followed from juvenile to older and aged phases of their life to study the relationship between lens glycation and high molecular weight (HMW) aggregate formation as well as quantitative and qualitative changes in lens crystallins. Levels of glycated proteins were quantified by affinity chromatography. Changes in lens crystallin composition and HMW aggregate formation were monitored by molecular sieve HPLC, further confirmed by SDS-PAGE and IEF techniques. As the age advances HMW and insoluble proteins increase with a concomitant disappearance of gamma-crystallins from soluble fraction. This disappearance of gamma-crystallins coincided with increased glycation (approximately 2-fold higher in insoluble fraction) and decreased sulfhydryl groups from soluble fraction. It appears that lens protein glycation, disappearance of gamma-crystallins and sulfhydryls from soluble fraction and increase of insoluble fraction and HMW aggregate are interrelated.

  7. Purification of High Molecular Weight Genomic DNA from Powdery Mildew for Long-Read Sequencing.

    PubMed

    Feehan, Joanna M; Scheibel, Katherine E; Bourras, Salim; Underwood, William; Keller, Beat; Somerville, Shauna C

    2017-03-31

    The powdery mildew fungi are a group of economically important fungal plant pathogens. Relatively little is known about the molecular biology and genetics of these pathogens, in part due to a lack of well-developed genetic and genomic resources. These organisms have large, repetitive genomes, which have made genome sequencing and assembly prohibitively difficult. Here, we describe methods for the collection, extraction, purification and quality control assessment of high molecular weight genomic DNA from one powdery mildew species, Golovinomyces cichoracearum. The protocol described includes mechanical disruption of spores followed by an optimized phenol/chloroform genomic DNA extraction. A typical yield was 7 µg DNA per 150 mg conidia. The genomic DNA that is isolated using this procedure is suitable for long-read sequencing (i.e., > 48.5 kbp). Quality control measures to ensure the size, yield, and purity of the genomic DNA are also described in this method. Sequencing of the genomic DNA of the quality described here will allow for the assembly and comparison of multiple powdery mildew genomes, which in turn will lead to a better understanding and improved control of this agricultural pathogen.

  8. Quantification of a Non-conventional Protein Secretion: The Low-Molecular-Weight FGF-2 Example.

    PubMed

    Arcondéguy, Tania; Touriol, Christian; Lacazette, Eric

    2016-01-01

    Quantification of secreted factors is most often measured with enzyme-linked immunosorbent assay (ELISA), Western Blot, or more recently with antibody arrays. However, some of these, like low-molecular-weight fibroblast growth factor-2 (LMW FGF-2; the 18 kDa form), exemplify a set of secreted but almost non-diffusible molecular actors. It has been proposed that phosphorylated FGF-2 is secreted via a non-vesicular mechanism and that heparan sulfate proteoglycans function as extracellular reservoir but also as actors for its secretion. Heparan sulfate is a linear sulfated polysaccharide present on proteoglycans found in the extracellular matrix or anchored in the plasma membrane (syndecan). Moreover the LMW FGF-2 secretion appears to be activated upon FGF-1 treatment. In order to estimate quantification of such factor export across the plasma membrane, technical approaches are presented (evaluation of LMW FGF-2: (1) secretion, (2) extracellular matrix reservoir, and (3) secretion modulation by surrounding factors) and the importance of such procedures in the comprehension of the biology of these growth factors is underlined.

  9. A low molecular weight artificial RNA of unique size with multiple probe target regions

    NASA Technical Reports Server (NTRS)

    Pitulle, C.; Dsouza, L.; Fox, G. E.

    1997-01-01

    Artificial RNAs (aRNAs) containing novel sequence segments embedded in a deletion mutant of Vibrio proteolyticus 5S rRNA have previously been shown to be expressed from a plasmid borne growth rate regulated promoter in E. coli. These aRNAs accumulate to high levels and their detection is a promising tool for studies in molecular microbial ecology and in environmental monitoring. Herein a new construct is described which illustrates the versatility of detection that is possible with aRNAs. This 3xPen aRNA construct carries a 72 nucleotide insert with three copies of a unique 17 base probe target sequence. This aRNA is 160 nucleotides in length and again accumulates to high levels in the E. coli cytoplasm without incorporating into ribosomes. The 3xPen aRNA illustrates two improvements in detection. First, by appropriate selection of insert size, we obtained an aRNA which provides a unique and hence, easily quantifiable peak, on a high resolution gel profile of low molecular weight RNAs. Second, the existence of multiple probe targets results in a nearly commensurate increase in signal when detection is by hybridization. These aRNAs are naturally amplified and carry sequence segments that are not found in known rRNA sequences. It thus may be possible to detect them directly. An experimental step involving RT-PCR or PCR amplification of the gene could therefore be avoided.

  10. Scoring of Side-Chain Packings: An Analysis of Weight Factors and Molecular Dynamics Structures.

    PubMed

    Colbes, Jose; Aguila, Sergio A; Brizuela, Carlos A

    2018-02-26

    The protein side-chain packing problem (PSCPP) is a central task in computational protein design. The problem is usually modeled as a combinatorial optimization problem, which consists of searching for a set of rotamers, from a given rotamer library, that minimizes a scoring function (SF). The SF is a weighted sum of terms, that can be decomposed in physics-based and knowledge-based terms. Although there are many methods to obtain approximate solutions for this problem, all of them have similar performances and there has not been a significant improvement in recent years. Studies on protein structure prediction and protein design revealed the limitations of current SFs to achieve further improvements for these two problems. In the same line, a recent work reported a similar result for the PSCPP. In this work, we ask whether or not this negative result regarding further improvements in performance is due to (i) an incorrect weighting of the SFs terms or (ii) the constrained conformation resulting from the protein crystallization process. To analyze these questions, we (i) model the PSCPP as a bi-objective combinatorial optimization problem, optimizing, at the same time, the two most important terms of two SFs of state-of-the-art algorithms and (ii) performed a preprocessing relaxation of the crystal structure through molecular dynamics to simulate the protein in the solvent and evaluated the performance of these two state-of-the-art SFs under these conditions. Our results indicate that (i) no matter what combination of weight factors we use the current SFs will not lead to better performances and (ii) the evaluated SFs will not be able to improve performance on relaxed structures. Furthermore, the experiments revealed that the SFs and the methods are biased toward crystallized structures.

  11. Equilibrating high-molecular-weight symmetric and miscible polymer blends with hierarchical back-mapping

    NASA Astrophysics Data System (ADS)

    Ohkuma, Takahiro; Kremer, Kurt; Daoulas, Kostas

    2018-05-01

    Understanding properties of polymer alloys with computer simulations frequently requires equilibration of samples comprised of microscopically described long molecules. We present the extension of an efficient hierarchical backmapping strategy, initially developed for homopolymer melts, to equilibrate high-molecular-weight binary blends. These mixtures present significant interest for practical applications and fundamental polymer physics. In our approach, the blend is coarse-grained into models representing polymers as chains of soft blobs. Each blob stands for a subchain with N b microscopic monomers. A hierarchy of blob-based models with different resolution is obtained by varying N b. First the model with the largest N b is used to obtain an equilibrated blend. This configuration is sequentially fine-grained, reinserting at each step the degrees of freedom of the next in the hierarchy blob-based model. Once the blob-based description is sufficiently detailed, the microscopic monomers are reinserted. The hard excluded volume is recovered through a push-off procedure and the sample is re-equilibrated with molecular dynamics (MD), requiring relaxation on the order of the entanglement time. For the initial method development we focus on miscible blends described on microscopic level through a generic bead-spring model, which reproduces hard excluded volume, strong covalent bonds, and realistic liquid density. The blended homopolymers are symmetric with respect to molecular architecture and liquid structure. To parameterize the blob-based models and validate equilibration of backmapped samples, we obtain reference data from independent hybrid simulations combining MD and identity exchange Monte Carlo moves, taking advantage of the symmetry of the blends. The potential of the backmapping strategy is demonstrated by equilibrating blend samples with different degree of miscibility, containing 500 chains with 1000 monomers each. Equilibration is verified by comparing

  12. The role of metals in mammalian olfaction of low molecular weight organosulfur compounds

    PubMed Central

    Block, Eric; Batista, Victor S.; Matsunami, Hiroaki; Zhuang, Hanyi; Ahmed, Lucky

    2017-01-01

    While suggestions concerning the possible role of metals in olfaction and taste date back 50 years, only recently has it been possible to confirm these proposals with experiments involving individual olfactory receptors (ORs). A detailed discussion of recent experimental results demonstrating the key role of metals in enhancing the response of human and other vertebrate ORs to specific odorants is presented against the backdrop of our knowledge of how the sense of smell functions both at the molecular and whole animal levels. This review emphasizes the role of metals in the detection of low molecular weight thiols, sulfides, and other organosulfur compounds, including those found in strong-smelling animal excretions and plant volatiles, and those used in gas odorization. Alternative theories of olfaction are described, with evidence favoring the modified “shape” theory. The use of quantum mechanical/molecular modeling (QM/MM), site-directed mutagenesis and saturation-transfer-difference (STD) NMR is discussed, providing support for biological studies of mouse and human receptors, MOR244-3 and OR OR2T11, respectively. Copper is bound at the active site of MOR244-3 by cysteine and histidine, while cysteine, histidine and methionine are involved with OR2T11. The binding pockets of these two receptors are found in different locations in the three-dimensional seven transmembrane models. Another recently deorphaned human olfactory receptor, OR2M3, highly selective for a thiol from onions, and a broadly-tuned thiol receptor, OR1A1, are also discussed. Other topics covered include the effects of nanoparticles and heavy metal toxicants on vertebrate and fish ORs, intranasal zinc products and the loss of smell (anosmia). PMID:28471462

  13. Equilibrating high-molecular-weight symmetric and miscible polymer blends with hierarchical back-mapping.

    PubMed

    Ohkuma, Takahiro; Kremer, Kurt; Daoulas, Kostas

    2018-05-02

    Understanding properties of polymer alloys with computer simulations frequently requires equilibration of samples comprised of microscopically described long molecules. We present the extension of an efficient hierarchical backmapping strategy, initially developed for homopolymer melts, to equilibrate high-molecular-weight binary blends. These mixtures present significant interest for practical applications and fundamental polymer physics. In our approach, the blend is coarse-grained into models representing polymers as chains of soft blobs. Each blob stands for a subchain with N b microscopic monomers. A hierarchy of blob-based models with different resolution is obtained by varying N b . First the model with the largest N b is used to obtain an equilibrated blend. This configuration is sequentially fine-grained, reinserting at each step the degrees of freedom of the next in the hierarchy blob-based model. Once the blob-based description is sufficiently detailed, the microscopic monomers are reinserted. The hard excluded volume is recovered through a push-off procedure and the sample is re-equilibrated with molecular dynamics (MD), requiring relaxation on the order of the entanglement time. For the initial method development we focus on miscible blends described on microscopic level through a generic bead-spring model, which reproduces hard excluded volume, strong covalent bonds, and realistic liquid density. The blended homopolymers are symmetric with respect to molecular architecture and liquid structure. To parameterize the blob-based models and validate equilibration of backmapped samples, we obtain reference data from independent hybrid simulations combining MD and identity exchange Monte Carlo moves, taking advantage of the symmetry of the blends. The potential of the backmapping strategy is demonstrated by equilibrating blend samples with different degree of miscibility, containing 500 chains with 1000 monomers each. Equilibration is verified by comparing

  14. Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

    NASA Astrophysics Data System (ADS)

    Eitel, Eryn M.; Taillefert, Martial

    2017-10-01

    Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

  15. Effect of molecular weight of polystyrensulfonic acid sodium salt polymers on the precipitation kinetics of sodium bicarbonate

    NASA Astrophysics Data System (ADS)

    Martínez-Cruz, Nancy; Carrillo-Romo, Felipe; Jaramillo-Vigueras, David

    2004-10-01

    This paper analyzes the effect of polystyrensulfonic acid sodium salt (NaPSS), obtained by kinetic precipitation from solutions of polymers of molecular weight 245 000 and 38 000 g mol-1 in sodium bicarbonate (NaHCO3) itself precipitated from synthetic brine. Crystal size, shape and the additive adsorbed are reported. X shaped and hexagonal prisms crystals with different aspect ratios were obtained. The results show that with increasing polymer concentration the crystal size decreases, from 0.27 to 0.48 mm. Additionally, the higher molecular weight polymer shows both higher adsorption capacity and higher crystal habit modification. Crystal shape patterns were similar for both polymers; however, the higher molecular weight material induced changes at lower concentration. It was observed that the precipitation rate reached a minimum with increasing additive concentration.

  16. Selenium/Tellurium-Containing Hyperbranched Polymers: Effect of Molecular Weight and Degree of Branching on Glutathione Peroxidase-Like Activity.

    PubMed

    Thomas, Joice; Dong, Zeyuan; Dehaen, Wim; Smet, Mario

    2012-12-21

    A series of novel hyperbranched polyselenides and polytellurides with multiple catalytic sites at the branching units has been synthesized via the polycondensation of A2 + B3 monomers. The GPx-like activities of these polymer mimics were assessed and it was found that the polytellurides showed higher GPx-like activities than the corresponding polyselenides. Interestingly, the polymers with higher molecular weights and degree of branching (DB) showed higher GPx-like activities than the analogous lower molecular weight polymer. The enhancement in the catalytical activity of the hyperbranched polymers with increasing molecular weight affirmed the importance of the incorporation of multiple catalytic groups in the macromolecule which increases the local concentration of catalytic sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Effect of alkali lignins with different molecular weights from alkali pretreated rice straw hydrolyzate on enzymatic hydrolysis.

    PubMed

    Li, Yun; Qi, Benkun; Luo, Jianquan; Wan, Yinhua

    2016-01-01

    This study investigated the effect of alkali lignins with different molecular weights on enzymatic hydrolysis of lignocellulose. Different alkali lignins fractions, which were obtained from cascade ultrafiltration, were added into the dilute acid pretreated (DAP) and alkali pretreated (AP) rice straws respectively during enzymatic hydrolysis. The results showed that the addition of alkali lignins enhanced the hydrolysis and the enhancement for hydrolysis increased with increasing molecular weights of alkali lignins, with maximum enhancement being 28.69% for DAP and 20.05% for AP, respectively. The enhancement was partly attributed to the improved cellulase activity, and filter paper activity increased by 18.03% when adding lignin with highest molecular weight. It was found that the enhancement of enzymatic hydrolysis was correlated with the adsorption affinity of cellulase on alkali lignins, and the difference in surface charge and hydrophobicity of alkali lignins were responsible for the difference in affinity between cellulase and lignins. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Removal of Anabaena spiroides by potassium permanganate pre-oxidation: effect on photosynthetic capacity and molecular weight distribution.

    PubMed

    Qiao, Junlian; Zhang, Xiaodong; Lv, Liping

    2017-11-01

    Bench scale tests were conducted to investigate the effect of potassium permanganate pre-oxidation on the photosynthetic activity and molecular weight distribution of Anabaena spiroides. Different concentrations of potassium permanganate were added into the suspension of Anabaena spiroides, one of the dominant algae in water bloom, and after pre-oxidation of permanganate for 1 h, the results show that the removal rate significantly increases by 33.99~36.35% compared to direct coagulation. Then, the algal characteristics, including photosynthetic ability, the changes in extracellular organic matter three-dimensional fluorescence, and the distribution of molecular weight were conducted and the results show that along with increasing concentration of potassium permanganate, the photosynthetic ability of algae decreases, more extracellular organic matter is secreted, and large molecular weight matter (humic-like and fulvic-like substances) are generated. Therefore, this study demonstrates that potassium permanganate could be used in addressing the algae-rich water.

  19. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K [Pleasanton, CA; Snyderman, Neal J [Berkeley, CA; Rowland, Mark S [Alamo, CA

    2012-05-15

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  20. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K [Pleasanton, CA; Snyderman, Neal J [Berkeley, CA; Rowland, Mark S [Alamo, CA

    2010-07-13

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  1. Conversion of calibration curves for accurate estimation of molecular weight averages and distributions of polyether polyols by conventional size exclusion chromatography.

    PubMed

    Xu, Xiuqing; Yang, Xiuhan; Martin, Steven J; Mes, Edwin; Chen, Junlan; Meunier, David M

    2018-08-17

    Accurate measurement of molecular weight averages (M¯ n, M¯ w, M¯ z ) and molecular weight distributions (MWD) of polyether polyols by conventional SEC (size exclusion chromatography) is not as straightforward as it would appear. Conventional calibration with polystyrene (PS) standards can only provide PS apparent molecular weights which do not provide accurate estimates of polyol molecular weights. Using polyethylene oxide/polyethylene glycol (PEO/PEG) for molecular weight calibration could improve the accuracy, but the retention behavior of PEO/PEG is not stable in THF-based (tetrahydrofuran) SEC systems. In this work, two approaches for calibration curve conversion with narrow PS and polyol molecular weight standards were developed. Equations to convert PS-apparent molecular weight to polyol-apparent molecular weight were developed using both a rigorous mathematical analysis and graphical plot regression method. The conversion equations obtained by the two approaches were in good agreement. Factors influencing the conversion equation were investigated. It was concluded that the separation conditions such as column batch and operating temperature did not have significant impact on the conversion coefficients and a universal conversion equation could be obtained. With this conversion equation, more accurate estimates of molecular weight averages and MWDs for polyether polyols can be achieved from conventional PS-THF SEC calibration. Moreover, no additional experimentation is required to convert historical PS equivalent data to reasonably accurate molecular weight results. Copyright © 2018. Published by Elsevier B.V.

  2. Anticancer, antioxidant, and antibacterial activities of low molecular weight bioactive subfractions isolated from cultures of wood degrading fungus Cerrena unicolor

    PubMed Central

    Jaszek, Magdalena; Stefaniuk, Dawid; Ciszewski, Tomasz; Matuszewski, Łukasz

    2018-01-01

    The aim of this study is to investigate in vitro the anticancer, antioxidant, and antibacterial activities of three low molecular weight subfractions I, II and III isolated from secondary metabolites produced by the wood degrading fungus Cerrena unicolor. The present study demonstrated that the low molecular weight subfractions III exhibited the strongest inhibitory activity towards breast carcinoma cells MDA-MB-231, prostatic carcinoma cells PC3, and breast cancer cells MCF7 with the half-maximal inhibitory concentration (IC50) value of 52,25 μg/mL, 60,66 μg/mL, and 54,92 μg/mL, respectively. The highest percentage of inhibition was noted at a concentration of 300 μg/mL in all the examined tumor lines. A significant percentage (59.08%) of ex-LMSIII inhibition of the MDA-MB-231 tumor line was reached at a concentration of 15 μg/ml, while the concentration applied did not affect normal human fibroblast cells. The low molecular weight subfraction III was the most effective and additionally showed the highest free radical 1,1-diphenyl-2-picryl-hydrazyl scavenging activity (IC50 20.39 μg/mL) followed by the low molecular weight subfraction I (IC50 64.14 μg/mL) and II (IC50 49.22 μg/mL). The antibacterial activity of the tested preparations was evaluated against three microorganisms: Bacillus subtilis, Staphylococcus aureus, and Escherichia coli. The MIC minimal inhibitory concentration (MIC) values for the low molecular weight subfraction I, II, and III showed a stronger inhibition effect on S. aureus than on B. subtilis and E. coli cells. The MIC values for the low molecular weight subfraction II against S. aureus, B. subtilis, and E. coli were 6.25, 12.5, and 100 mg/mL, respectively. PMID:29874240

  3. Effects of molecular weight of hyaluronic acid on its viscosity and enzymatic activities of lysozyme and peroxidase.

    PubMed

    Kim, Jihoon; Chang, Ji-Youn; Kim, Yoon-Young; Kim, Moon-Jong; Kho, Hong-Seop

    2018-05-01

    To investigate the effects of the molecular weight of hyaluronic acid on its viscosity and enzymatic activities of lysozyme and peroxidase in solution and on the hydroxyapatite surface. Hyaluronic acids of four different molecular weights (10 kDa, 100 kDa, 1 MDa, and 2 MDa), hen egg-white lysozyme, bovine lactoperoxidase, and human whole saliva were used. Viscosity values of hyaluronic acids were measured using a cone-and-plate viscometer at six different concentrations (0.1-5.0 mg/mL). Enzymatic activities of lysozyme and peroxidase were examined by hydrolysis of fluorescein-labeled Micrococcus lysodeikticus and oxidation of fluorogenic 2',7'-dichlorofluorescein to fluorescing 2',7'-dichlorofluorescein, respectively. In solution assays, only 2 MDa-hyaluronic acid significantly inhibited lysozyme activities in saliva. In surface assays, hyaluronic acids inhibited lysozyme and peroxidase activities; the inhibitory activities were more apparent with high-molecular-weight ones in saliva than in purified enzymes. The 100 kDa-hyaluronic acid at 5.0 mg/mL, 1 MDa-one at 0.5 mg/mL, and 2 MDa-one at 0.2 mg/mL showed viscosity values similar to those of human whole saliva at a shear rate range required for normal oral functions. The differences among the influences of the three conditions on the enzymatic activities were not statistically significant. High-molecular-weight hyaluronic acids at low concentration and low-molecular-weight ones at high concentration showed viscosity values similar to those of human whole saliva. Inhibitory effects of hyaluronic acids on lysozyme and peroxidase activities were more significant with high-molecular-weight ones on the surface and in saliva compared with in solution and on purified enzymes. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Composition, variation, expression and evolution of low-molecular-weight glutenin subunit genes in Triticum urartu.

    PubMed

    Luo, Guangbin; Zhang, Xiaofei; Zhang, Yanlin; Yang, Wenlong; Li, Yiwen; Sun, Jiazhu; Zhan, Kehui; Zhang, Aimin; Liu, Dongcheng

    2015-02-28

    Wheat (AABBDD, 2n = 6x = 42) is a major dietary component for many populations across the world. Bread-making quality of wheat is mainly determined by glutenin subunits, but it remains challenging to elucidate the composition and variation of low-molecular-weight glutenin subunits (LMW-GS) genes, the major components for glutenin subunits in hexaploid wheat. This problem, however, can be greatly simplified by characterizing the LMW-GS genes in Triticum urartu, the A-genome donor of hexaploid wheat. In the present study, we exploited the high-throughput molecular marker system, gene cloning, proteomic methods and molecular evolutionary genetic analysis to reveal the composition, variation, expression and evolution of LMW-GS genes in a T. urartu population from the Fertile Crescent region. Eight LMW-GS genes, including four m-type, one s-type and three i-type, were characterized in the T. urartu population. Six or seven genes, the highest number at the Glu-A3 locus, were detected in each accession. Three i-type genes, each containing more than six allelic variants, were tightly linked because of their co-segregation in every accession. Only 2-3 allelic variants were detected for each m- and s-type gene. The m-type gene, TuA3-385, for which homologs were previously characterized only at Glu-D3 locus in common wheat and Aegilops tauschii, was detected at Glu-A3 locus in T. urartu. TuA3-460 was the first s-type gene identified at Glu-A3 locus. Proteomic analysis showed 1-4 genes, mainly i-type, expressed in individual accessions. About 62% accessions had three active i-type genes, rather than one or two in common wheat. Southeastern Turkey might be the center of origin and diversity for T. urartu due to its abundance of LMW-GS genes/genotypes. Phylogenetic reconstruction demonstrated that the characterized T. urartu might be the direct donor of the Glu-A3 locus in common wheat varieties. Compared with the Glu-A3 locus in common wheat, a large number of highly

  5. Separation of both fibrous and globular proteins on the basis of molecular weight using high-performance size exclusion chromatography.

    PubMed

    Barden, J A

    1983-11-01

    A high-performance size exclusion liquid chromatographic system has been used to separate proteins with different shapes solely on the basis of their molecular weights. After the effects of ionic and hydrophobic interactions with the stationary phase have been overcome, protein elution is normally governed by their effective size in solution. Conditions are described under which proteins, with isoelectric points within the normal operating pH range of the columns, are eluted independent of their Stokes' radii. Even fibrous proteins with axial ratios of 50 elute according to their known molecular weights over the range 2000-2,000,000.

  6. Use of Low Molecular Weight Heparin and Aminocaproic Acid in Chronic DIC Associated with Prostate Cancer- A Case Report

    PubMed Central

    Shirai, Keisuke; Chaudhary, Uzair B.

    2007-01-01

    Disseminated Intravascular Coagulopathy (DIC) is the most common coagulopathy in patients with prostate cancer. Though rare, it could be fatal without treatment. Literature suggests that there is significant activation of fibrinolytic pathway. Pathophysiology of DIC in patients with prostate cancer is not completely understood. We present here a case of chronic DIC in a patient with metastatic androgen independent prostate cancer. His DIC was managed successfully with a combination of aminocaproic acid and low weight molecular heparin. The use of low molecular weight heparin may make management of chronic DIC in prostate cancer more feasible in an out patient setting. PMID:17619757

  7. Preparation of Low Molecular Weight Gelatin Using Microwave Discharge Electrodeless Lamp/TiO2 Photocatalyst Hybrid System.

    PubMed

    Lee, Do-Jin; Kim, Hangun; Park, Young-Kwon; Kim, Byung Hoon; Lee, Heon; Jungf, Sana-Chul

    2016-02-01

    In this study, an MDEL/TiO2 photocatalyst hybrid system was applied to the production of low molecular weight gelatin. The molecular weight of produed gelatin decreased with increasing microwave intensity and increasing treatment time. The abscission of the chemical bonds between the con- stituents of gelatin by photocatalytic reaction did not alter the characteristics of gelatin. Formation of any by-products due to side reaction was not observed. It is suggested that gelatin was depolymerized by hydroxyl radicals produced during the MDEL/TiO2 photochemical reaction.

  8. Preparation of Low Molecular Weight Heparin by Microwave Discharge Electrodeless Lamp/TiO2 Photo-Catalytic Reaction.

    PubMed

    Lee, Do-Jin; Kim, Byung Hoon; Kim, Sun-Jae; Kim, Jung-Sik; Lee, Heon; Jung, Sang-Chul

    2015-01-01

    An MDEL/TiO2 photo-catalyst hybrid system was applied, for the first time, for the production of low molecular weight heparin. The molecular weight of produed heparin decreased with increasing microwave intensity and treatment time. The abscission of the chemical bonds between the constituents of heparin by photo-catalytic reaction did not alter the characteristics of heparin. Formation of by-products due to side reaction was not observed. It is suggested that heparin was depolymerized by active oxygen radicals produced during the MDEL/TiO2 photo-chemical reaction.

  9. Antiedematogenic and antioxidant properties of high molecular weight protein sub-fraction of Calotropis procera latex in rat.

    PubMed

    Chaudhary, Priyanka; de Araújo Viana, Carolina; Ramos, Marcio V; Kumar, Vijay L

    2015-03-01

    The aim was to evaluate the effect of high molecular weight protein fraction of Calotropis procera latex on edema formation and oxidative stress in carrageenan-induced paw inflammation. A sub-plantar injection of carrageenan was given to induce edema in the hind paw of the rat. The inhibitory effect of high molecular weight protein fraction of C. procera latex was evaluated following intravenous administration (5 and 25 mg/kg body weight) and was compared with that of diclofenac given orally (5 mg/kg). The levels of reduced glutathione (GSH), thiobarbituric acid reactive substances (TBARS) and myeloperoxidase (MPO) were measured in the inflamed paw tissue at the end of the study. The high molecular weight protein fraction obtained from the latex of C. procera produced a dose-dependent inhibition of edema formation that was accompanied by normalization of levels of oxidative stress markers (GSH and TBARS) and MPO, a marker for neutrophils in the paw tissue. The high molecular weight protein fraction of C. procera latex ameliorates acute inflammation in the paw through its antioxidant effect.

  10. Low molecular weight components in an aquatic humic substance as characterized by membrane dialysis and orbitrap mass spectrometry.

    PubMed

    Remucal, Christina K; Cory, Rose M; Sander, Michael; McNeill, Kristopher

    2012-09-04

    Suwannee River fulvic acid (SRFA) was dialyzed through a 100-500 molecular weight cutoff dialysis membrane, and the dialysate and retentate were analyzed by UV-visible absorption and high-resolution Orbitrap mass spectrometry (MS). A significant fraction (36% based on dissolved organic carbon) of SRFA passed through the dialysis membrane. The fraction of SRFA in the dialysate had a different UV-visible absorption spectrum and was enriched in low molecular weight molecules with a more aliphatic composition relative to the initial SRFA solution. Comparison of the SRFA spectra collected by Orbitrap MS and Fourier transform ion cyclotron resonance MS (FT-ICR MS) demonstrated that the mass accuracy of the Orbitrap MS is sufficient for determination of unique molecular formulas of compounds with masses <600 Da in a complex mixture, such as SRFA. The most intense masses detected by Orbitrap MS were found in the 100-200 Da mass range. Many of these low molecular masses corresponded to molecular formulas of previously identified compounds in organic matter, lignin, and plants, and the use of the standard addition method provided an upper concentration estimate of selected target compounds in SRFA. Collectively, these results provide evidence that SRFA contains low molecular weight components that are present individually or in loosely bound assemblies.

  11. Extended Fujita Approach to the Molecular Weight Distribution of Polysaccharides and other Polymeric Systems

    PubMed Central

    Harding, Stephen E.; Schuck, Peter; Abdelhameed, Ali Saber; Adams, Gary; Kök, M. Samil; Morris, Gordon A.

    2011-01-01

    In 1962 H. Fujita (Mathematical Theory of Sedimentation Analysis, Academic Press, New York, pp. 182–192) examined the possibility of transforming a quasi-continuous distribution g(s) of sedimentation coefficient s into a distribution f(M) of molecular weight M for linear polymers using the relation f(M) = g(s).(ds/dM) and showed that this could be done if information about the relation between s and M is available from other sources. Fujita provided the transformation based on the scaling relation s = κM0.5, where κ is taken as a constant for that particular polymer and the exponent 0.5 essentially corresponds to a randomly coiled polymer under ideal conditions. This method was successfully applied to mucus glycoproteins (S.E. Harding, Adv. Carbohyd. Chem. Biochem. 47 (1989), 345–381). We now describe an extension of the method to general conformation types via the scaling relation s = κMb, where b = 0.4–0.5 for a coil, ~0.15–0.2 for a rod and ~0.67 for a sphere. We give examples of distributions f(M) vs M obtained for polysaccharides from SEDFIT derived least squares g(s) vs s profiles (P. Schuck, Biophys. J. 78 (2000) 1606–1619) and the analytical derivative for ds/dM performed with Microcal ORIGIN. We also describe a more direct route from a direct numerical solution of the integral equation describing the molecular weight distribution problem. Both routes give identical distributions although the latter offers the advantage of being incorporated completely within SEDFIT. The method currently assumes that solutions behave ideally: sedimentation velocity has the major advantage over sedimentation equilibrium in that concentrations less than 0.2 mg/ml can be employed, and for many systems non-ideality effects can be reasonably ignored. For large, non-globular polymer systems, diffusive contributions are also likely to be small. PMID:21276851

  12. Ingestion of High Molecular Weight Carbohydrate Enhances Subsequent Repeated Maximal Power: A Randomized Controlled Trial

    PubMed Central

    Oliver, Jonathan M.; Almada, Anthony L.; Van Eck, Leighsa E.; Shah, Meena; Mitchell, Joel B.; Jones, Margaret T.; Jagim, Andrew R.; Rowlands, David S.

    2016-01-01

    Athletes in sports demanding repeat maximal work outputs frequently train concurrently utilizing sequential bouts of intense endurance and resistance training sessions. On a daily basis, maximal work within subsequent bouts may be limited by muscle glycogen availability. Recently, the ingestion of a unique high molecular weight (HMW) carbohydrate was found to increase glycogen re-synthesis rate and enhance work output during subsequent endurance exercise, relative to low molecular weight (LMW) carbohydrate ingestion. The effect of the HMW carbohydrate, however, on the performance of intense resistance exercise following prolonged-intense endurance training is unknown. Sixteen resistance trained men (23±3 years; 176.7±9.8 cm; 88.2±8.6 kg) participated in a double-blind, placebo-controlled, randomized 3-way crossover design comprising a muscle-glycogen depleting cycling exercise followed by ingestion of placebo (PLA), or 1.2 g•kg•bw-1 of LMW or HMW carbohydrate solution (10%) with blood sampling for 2-h post-ingestion. Thereafter, participants performed 5 sets of 10 maximal explosive repetitions of back squat (75% of 1RM). Compared to PLA, ingestion of HMW (4.9%, 90%CI 3.8%, 5.9%) and LMW (1.9%, 90%CI 0.8%, 3.0%) carbohydrate solutions substantially increased power output during resistance exercise, with the 3.1% (90% CI 4.3, 2.0%) almost certain additional gain in power after HMW-LMW ingestion attributed to higher movement velocity after force kinematic analysis (HMW-LMW 2.5%, 90%CI 1.4, 3.7%). Both carbohydrate solutions increased post-exercise plasma glucose, glucoregulatory and gut hormones compared to PLA, but differences between carbohydrates were unclear; thus, the underlying mechanism remains to be elucidated. Ingestion of a HMW carbohydrate following prolonged intense endurance exercise provides superior benefits to movement velocity and power output during subsequent repeated maximal explosive resistance exercise. This study was registered with

  13. High Molecular Weight Barley β-Glucan Alters Gut Microbiota Toward Reduced Cardiovascular Disease Risk

    PubMed Central

    Wang, Yanan; Ames, Nancy P.; Tun, Hein M.; Tosh, Susan M.; Jones, Peter J.; Khafipour, Ehsan

    2016-01-01

    The physiological cholesterol-lowering benefits of β-glucan have been well documented, however, whether modulation of gut microbiota by β-glucan is associated with these physiological effects remains unknown. The objectives of this study were therefore to determine the impact of β-glucan on the composition of gut microbiota in mildly hypercholesterolemic individuals and to identify if the altered microbiota are associated with bioactivity of β-glucan in improving risk factors of cardiovascular disease (CVD). Using a randomized, controlled crossover study design, individuals received for 5-week either a treatment breakfast containing 3 g high molecular weight (HMW), 3 g low molecular weight (LMW), 5 g LMW barley β-glucan, or wheat and rice. The American Heart Association (AHA) diet served as the background diet for all treatment groups. Phases were separated by 4-week washout periods. Fecal samples were collected at the end of each intervention phase and subjected to Illumina sequencing of 16S rRNA genes. Results revealed that at the phylum level, supplementation of 3 g/d HMW β-glucan increased Bacteroidetes and decreased Firmicutes abundances compared to control (P < 0.001). At the genus level, consumption of 3 g/d HMW β-glucan increased Bacteroides (P < 0.003), tended to increase Prevotella (P < 0.1) but decreased Dorea (P < 0.1), whereas diets containing 5 g LMW β-glucan and 3 g LMW β-glucan failed to alter the gut microbiota composition. Bacteroides, Prevotella, and Dorea composition correlated (P < 0.05) with shifts of CVD risk factors, including body mass index, waist circumference, blood pressure, as well as triglyceride levels. Our data suggest that consumption of HMW β-glucan favorably alters the composition of gut microbiota and this altered microbiota profile associates with a reduction of CVD risk markers. Together, our study suggests that β-glucan induced shifts in gut microbiota in a MW-dependent manner and that might be one of the

  14. Ingestion of High Molecular Weight Carbohydrate Enhances Subsequent Repeated Maximal Power: A Randomized Controlled Trial.

    PubMed

    Oliver, Jonathan M; Almada, Anthony L; Van Eck, Leighsa E; Shah, Meena; Mitchell, Joel B; Jones, Margaret T; Jagim, Andrew R; Rowlands, David S

    2016-01-01

    Athletes in sports demanding repeat maximal work outputs frequently train concurrently utilizing sequential bouts of intense endurance and resistance training sessions. On a daily basis, maximal work within subsequent bouts may be limited by muscle glycogen availability. Recently, the ingestion of a unique high molecular weight (HMW) carbohydrate was found to increase glycogen re-synthesis rate and enhance work output during subsequent endurance exercise, relative to low molecular weight (LMW) carbohydrate ingestion. The effect of the HMW carbohydrate, however, on the performance of intense resistance exercise following prolonged-intense endurance training is unknown. Sixteen resistance trained men (23±3 years; 176.7±9.8 cm; 88.2±8.6 kg) participated in a double-blind, placebo-controlled, randomized 3-way crossover design comprising a muscle-glycogen depleting cycling exercise followed by ingestion of placebo (PLA), or 1.2 g•kg•bw-1 of LMW or HMW carbohydrate solution (10%) with blood sampling for 2-h post-ingestion. Thereafter, participants performed 5 sets of 10 maximal explosive repetitions of back squat (75% of 1RM). Compared to PLA, ingestion of HMW (4.9%, 90%CI 3.8%, 5.9%) and LMW (1.9%, 90%CI 0.8%, 3.0%) carbohydrate solutions substantially increased power output during resistance exercise, with the 3.1% (90% CI 4.3, 2.0%) almost certain additional gain in power after HMW-LMW ingestion attributed to higher movement velocity after force kinematic analysis (HMW-LMW 2.5%, 90%CI 1.4, 3.7%). Both carbohydrate solutions increased post-exercise plasma glucose, glucoregulatory and gut hormones compared to PLA, but differences between carbohydrates were unclear; thus, the underlying mechanism remains to be elucidated. Ingestion of a HMW carbohydrate following prolonged intense endurance exercise provides superior benefits to movement velocity and power output during subsequent repeated maximal explosive resistance exercise. This study was registered with

  15. Isolation and identification of a high molecular weight protein in sow milk.

    PubMed

    Qin, Y; Qi, N; Tang, Y; He, J; Li, X; Gu, F; Zou, S

    2015-05-01

    A high molecular weight protein (HMWP) was isolated and purified from sow milk, and some of its biochemical characteristics and biological functions were identified. The origin of HMWP was also investigated. The molecular weight of HMWP was determined to be about 115 000 and 114 800 by SDS-PAGE and gel filtration, respectively. The sequence of 10 amino acids in N-terminal of HMWP was Ala-Leu-Val-Gln-Ser-Cys-Leu-Asn-Leu-Val. The sequence was blasted against GenBank. No protein showed significant similarity with this sequence suggesting the HMWP may be novel. The result of liquid chromatography mass spectrometry (LC-MS) also proved HMWP could be a novel protein. By amino acid assay, HMWP was rich in glutamate (including glutamine), cysteine, glycine, aspartic acid (including asparagines) and proline. The content of hydrophobic amino acids (Ala, Val, Leu, Ile, Met, Phe and Pro) was lower at 18.59% of the total amino acids suggesting HMWP has high solubility in water. Western blots of lectins were used to identify the kinds of carbohydrate residues attached to HMWP qualitatively. The result showed that HMWP was a kind of glycoprotein containing N-acetylneuraminic acid (NeuNAc), mannose (Man) and/or N-acetylglucosamine (GlcNAc). By isoelectric focusing, HMWP pI was found to be 5.1. Compared with milk fat globule membrane protein (MFGMP) isolated from the sow milk in SDS-PAGE, MFGMP did not contain HMWP. HMWP was assumed to be a secretory milk protein. HMWP was not found in bovine, goat, rabbit or human milk in SDS-PAGE gel suggesting HMWP may be unique to sow milk. By Western blot, HMWP could be detected in sow milk, not in sow serum, which suggests it is synthesized and secreted by the mammary gland. HMWP concentrations in sows milk were the lowest in the first day of lactation, rose significantly during lactation 1 to 7 days. The HMWP content of sows milk remained relatively constant ((1.95±0.13) g/l) during lactation 7 to 20 days. HMWP significantly inhibited

  16. Extended Fujita approach to the molecular weight distribution of polysaccharides and other polymeric systems.

    PubMed

    Harding, Stephen E; Schuck, Peter; Abdelhameed, Ali Saber; Adams, Gary; Kök, M Samil; Morris, Gordon A

    2011-05-01

    In 1962 H. Fujita (H. Fujita, Mathematical Theory of Sedimentation Analysis, Academic Press, New York, 1962) examined the possibility of transforming a quasi-continuous distribution g(s) of sedimentation coefficient s into a distribution f(M) of molecular weight M for linear polymers using the relation f(M)=g(s)·(ds/dM) and showed that this could be done if information about the relation between s and M is available from other sources. Fujita provided the transformation based on the scaling relation s=κ(s)M(0.5), where κ(s) is taken as a constant for that particular polymer and the exponent 0.5 essentially corresponds to a randomly coiled polymer under ideal conditions. This method has been successfully applied to mucus glycoproteins (S.E. Harding, Adv. Carbohyd. Chem. Biochem. 47 (1989) 345-381). We now describe an extension of the method to general conformation types via the scaling relation s=κM(b), where b=0.4-0.5 for a coil, ∼0.15-0.2 for a rod and ∼0.67 for a sphere. We give examples of distributions f(M) versus M obtained for polysaccharides from SEDFIT derived least squares g(s) versus s profiles (P. Schuck, Biophys. J. 78 (2000) 1606-1619) and the analytical derivative for ds/dM performed with Microcal ORIGIN. We also describe a more direct route from a direct numerical solution of the integral equation describing the molecular weight distribution problem. Both routes give identical distributions although the latter offers the advantage of being incorporated completely within SEDFIT. The method currently assumes that solutions behave ideally: sedimentation velocity has the major advantage over sedimentation equilibrium in that concentrations less than 0.2mg/ml can be employed, and for many systems non-ideality effects can be reasonably ignored. For large, non-globular polymer systems, diffusive contributions are also likely to be small. Copyright © 2011 Elsevier Inc. All rights reserved.

  17. Plasticization of poly(lactic acid) using different molecular weight of Poly(ethylene glycol)

    NASA Astrophysics Data System (ADS)

    Septevani, Athanasia Amanda; Bhakri, Samsul

    2017-11-01

    Poly (lactic acid) (PLA) has been known as an excellent candidate for developing the future bioplastic due to its biodegradability and competitive price. However, inherent brittleness and low thermal stability of PLA have limited its applications. Considerable studies have been developed to improve the flexibility of PLA, in which blending PLA with various plasticizers has been identified as a cost-effective way to lower glass-transition temperature (Tg) and thus improve its elongation property. In this study, PLA was modified by incorporating poly(ethylene glycol) as a plasticizer with different molecular weights (M¯w 400, 1000, and 6000, called respectively as PEG 400, PEG 1000, and PEG 6000) via a solvent-casting blend method. FTIR was used for analyzing the chemical interaction while TGA and DSC measured the thermal behavior of PLA/PEG. The results indicated that the addition of lower M¯w (PEG 400 and PEG 1000) could reduce the Tg due to the enhancement of chain mobility of PLA with PEG and so driving into a more amorphous states resulted reduction of melting temperature (Tm) compared to the neat PLA. Further, at a higher M¯w of PEG 6000, the longer chain of ethylene glycol, in contrast, resulted a gradual increase in the Tg as well as Tm where the value went back to the point of neat PLA compared to the other lower molecular weight of PLA. This was due to the decrease in polymer miscibility with the increasing of M¯w. In terms of thermal stability, the addition of PEG exhibited two step degradation behavior while the neat PLA only possessed single step degradation. The presence of PEG could act as a protective barrier layer that could hinder the permeability of the volatile compound and product during decomposition reaction and thus could eventually delay and slower the degradation process. It was observed that the addition of PEG at higher M¯w (PEG1000 and PEG 6000) exhibited a higher second degradation temperature up to 380 °C.

  18. Hypervelocity Impact Experiments on Epoxy/Ultra-High Molecular Weight Polyethylene Composite Panels Reinforced with Nanotubes

    NASA Technical Reports Server (NTRS)

    Khatiwada, Suman; Laughman, Jay W.; Armada, Carlos A.; Christiansen, Eric L.; Barrera, Enrique V.

    2012-01-01

    Advanced composites with multi-functional capabilities are of great interest to the designers of aerospace structures. Polymer matrix composites (PMCs) reinforced with high strength fibers provide a lightweight and high strength alternative to metals and metal alloys conventionally used in aerospace architectures. Novel reinforcements such as nanofillers offer potential to improve the mechanical properties and add multi-functionality such as radiation resistance and sensing capabilities to the PMCs. This paper reports the hypervelocity impact (HVI) test results on ultra-high molecular weight polyethylene (UHMWPE) fiber composites reinforced with single-walled carbon nanotubes (SWCNT) and boron nitride nanotubes (BNNT). Woven UHMWPE fabrics, in addition to providing excellent impact properties and high strength, also offer radiation resistance due to inherent high hydrogen content. SWCNT have exceptional mechanical and electrical properties. BNNT (figure 1) have high neutron cross section and good mechanical properties that add multi-functionality to this system. In this project, epoxy based UHMWPE composites containing SWCNT and BNNT are assessed for their use as bumper shields and as intermediate plates in a Whipple Shield for HVI resistance. Three composite systems are prepared to compare against one another: (I) Epoxy/UHMWPE, (II) Epoxy/UHMWPE/SWCNT and (III) Epoxy/UHMWPE/SWCNT/BNNT. Each composite is a 10.0 by 10.0 by 0.11 cm3 panel, consisting of 4 layers of fabrics arranged in cross-ply orientation. Both SWCNT and BNNT are 0.5 weight % of the fabric preform. Hypervelocity impact tests are performed using a two-stage light gas gun at Rice University

  19. The determination of density and molecular weight distributions of lipoproteins by sedimentation equilibrium.

    PubMed

    Jeffrey, P D; Nichol, L W; Smith, G D

    1975-01-25

    A method is presented by which an experimental record of total concentration as a function of radial distance, obtained in a sedimentation equilibrium experiment conducted with a noninteracting mixture in the absence of a density gradient, may be analyzed to obtain the unimodal distributions of molecular weight and of partial molar volume when these vary concomitantly and continuously. Particular attention is given to the caracterization of classes of lipoproteins exhibiting Gaussian distributions of these quantities, although the analysis is applicable to other types of unimodal distribution. Equations are also formulated permitting the definition of the corresponding distributions of partial specific volume and of density. The analysis procedure is based on a method (employing Laplace transforms) developed previously, but differs from it in that it avoids the necessity of differentiating experimental results, which introduces error. The method offers certain advantages over other procedures used to characterize and compare lipoprotein samples (exhibiting unimodal distributions) with regard to the duration of the experiment, economy of the sample, and, particularly, the ability to define in principle all of the relevant distributions from one sedimentation equilibrium experiment and an external measurement of the weight average partial specific volume. These points and the steps in the analysis procedure are illustrated with experimental results obtained in the sedimentation equilibrium of a sample of human serum low density lipoprotein. The experimental parameters (such as solution density, column height, and angular velocity) used in the conduction of these experiments were selected on the basis of computer-simulated examples, which are also presented. These provide a guide for other workers interested in characterizing lipoproteins of this class.

  20. Relationship between chemical structure and the occupational asthma hazard of low molecular weight organic compounds

    PubMed Central

    Jarvis, J; Seed, M; Elton, R; Sawyer, L; Agius, R

    2005-01-01

    Aims: To investigate quantitatively, relationships between chemical structure and reported occupational asthma hazard for low molecular weight (LMW) organic compounds; to develop and validate a model linking asthma hazard with chemical substructure; and to generate mechanistic hypotheses that might explain the relationships. Methods: A learning dataset used 78 LMW chemical asthmagens reported in the literature before 1995, and 301 control compounds with recognised occupational exposures and hazards other than respiratory sensitisation. The chemical structures of the asthmagens and control compounds were characterised by the presence of chemical substructure fragments. Odds ratios were calculated for these fragments to determine which were associated with a likelihood of being reported as an occupational asthmagen. Logistic regression modelling was used to identify the independent contribution of these substructures. A post-1995 set of 21 asthmagens and 77 controls were selected to externally validate the model. Results: Nitrogen or oxygen containing functional groups such as isocyanate, amine, acid anhydride, and carbonyl were associated with an occupational asthma hazard, particularly when the functional group was present twice or more in the same molecule. A logistic regression model using only statistically significant independent variables for occupational asthma hazard correctly assigned 90% of the model development set. The external validation showed a sensitivity of 86% and specificity of 99%. Conclusions: Although a wide variety of chemical structures are associated with occupational asthma, bifunctional reactivity is strongly associated with occupational asthma hazard across a range of chemical substructures. This suggests that chemical cross-linking is an important molecular mechanism leading to the development of occupational asthma. The logistic regression model is freely available on the internet and may offer a useful but inexpensive adjunct to the

  1. Total and high molecular weight adiponectin are elevated in patients with Laron syndrome despite marked obesity.

    PubMed

    Kanety, Hannah; Hemi, Rina; Ginsberg, Shira; Pariente, Clara; Yissachar, Eleanor; Barhod, Ehud; Funahashi, Tohru; Laron, Zvi

    2009-12-01

    Patients with Laron syndrome (LS; primary GH insensitivity) caused by molecular defects of the GH receptor gene, are characterized by dwarfism, profound obesity, and hyperlipidemia. The aim of the current study was to evaluate adiponectin levels in LS, as obesity is known to be associated with low adiponectin. We studied nine untreated LS adult patients (5 males, 4 females) and six girls with LS receiving once-daily treatment by IGF1. Total and high molecular weight (HMW) adiponectin levels, adiponectin multimers distribution, and metabolic indices were analyzed in serum samples obtained during several years of follow-up. Adiponectin levels in the severely obese adult LS patients (percent body fat; females 61.0+/-2.5%, males 40.6+/-8.1%) were two- to three-fold higher than those reported for subjects of corresponding age, gender and degree of adiposity. Total adiponectin was significantly higher in females compared with males (21.4+/-3.5 vs 10.2+/-4.6 microg/ml, P<0.001). The elevated adiponectin in LS subjects was associated with an increased abundance of the HMW isoform, and positively correlated with body fat percentage (r=0.65, P=0.017) and leptin (r=0.65, P=0.012). There was no correlation between adiponectin levels (total and HMW) and the degree of insulin resistance in LS subjects or their blood lipids levels. Adiponectin was also high in young girls with LS (22.9+/-7.4 microg/ml) and did not change during long-term IGF1 replacement therapy. Adiponectin hypersecretion in LS, despite profound obesity, suggests that GH activity may negatively impact adiponectin secretion from adipocytes.

  2. One pot synthesis of gold nanoparticles using chitosan with varying degree of deacetylation and molecular weight.

    PubMed

    Sun, Lijun; Li, Jin; Cai, Jun; Zhong, Lian; Ren, Guohui; Ma, Qimin

    2017-12-15

    Gold nanoparticles (AuNPs) were synthesized in one-step by reducing gold salt using nontoxic and biodegradable chitosan as dual roles of reducing agent and stabilizer. The obtained AuNPs were characterized with UV-vis spectroscopy and transmission electron microscopy. The results indicated that control over the size and shape of AuNPs is achieved through the careful selection of experimental conditions, such as reaction temperature, reaction time, concentration of gold salt and chitosan, and chitosan molecular parameters, i.e., degree of deacetylation (DD) and molecular weight (MW). At low chitosan concentration (0.005% and 0.01% (w/v)), individual spherical AuNPs with average particle size around 10nm were obtained regardless of chitosan DD and MW, while anisotropic AuNPs were obtained at concentration above 0.05% (w/v) for all investigated chitosan at the optimum condition (1mL of 1mmol/L HAuCl 4 added to 3mL of chitosan solution reacted for 120min at 70°C). The growth of larger polygonal AuNPs was promoted as the higher concentration and lower DD chitosan was used as reducing agent and stabilizer. Au nanoplate was synthesized by water-soluble chitosan (M v 566kDa, DD 53%) at concentration above 0.15% (w/v). Chitooligomers (M v 2.4kDa, DD 94%) showed the highest reduction ability for Au 3+ and the synthesized AuNPs exhibited aggregation on morphology. It was considered that chitosan DD and concentration played a more important role than MW in the size and shape of AuNPs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Progress in the development of immunoanalytical methods incorporating recombinant antibodies to small molecular weight biotoxins.

    PubMed

    Kavanagh, Owen; Elliott, Christopher T; Campbell, Katrina

    2015-04-01

    Rapid immunoanalytical screening of food and environmental samples for small molecular weight (hapten) biotoxin contaminations requires the production of antibody reagents that possess the requisite sensitivity and specificity. To date animal-derived polyclonal (pAb) and monoclonal (mAb) antibodies have provided the binding element of the majority of these assays but recombinant antibodies (rAb) isolated from in vitro combinatorial phage display libraries are an exciting alternative due to (1) circumventing the need for experimental animals, (2) speed of production in commonly used in vitro expression systems and (3) subsequent molecular enhancement of binder performance. Short chain variable fragments (scFv) have been the most commonly employed rAb reagents for hapten biotoxin detection over the last two decades but antibody binding fragments (Fab) and single domain antibodies (sdAb) are increasing in popularity due to increased expression efficiency of functional binders and superior resistance to solvents. rAb-based immunochromatographic assays and surface plasmon resonance (SPR) biosensors have been reported to detect sub-regulatory levels of fungal (mycotoxins), marine (phycotoxins) and aquatic biotoxins in a wide range of food and environmental matrices, however this technology has yet to surpass the performances of the equivalent mAb- and pAb-based formats. As such the full potential of rAb technology in hapten biotoxin detection has yet to be achieved, but in time the inherent advantages of engineered rAb are set to provide the next generation of ultra-high performing binder reagents for the rapid and specific detection of hapten biotoxins.

  4. Scanning number and brightness yields absolute protein concentrations in live cells: a crucial parameter controlling functional bio-molecular interaction networks.

    PubMed

    Papini, Christina; Royer, Catherine A

    2018-02-01

    Biological function results from properly timed bio-molecular interactions that transduce external or internal signals, resulting in any number of cellular fates, including triggering of cell-state transitions (division, differentiation, transformation, apoptosis), metabolic homeostasis and adjustment to changing physical or nutritional environments, amongst many more. These bio-molecular interactions can be modulated by chemical modifications of proteins, nucleic acids, lipids and other small molecules. They can result in bio-molecular transport from one cellular compartment to the other and often trigger specific enzyme activities involved in bio-molecular synthesis, modification or degradation. Clearly, a mechanistic understanding of any given high level biological function requires a quantitative characterization of the principal bio-molecular interactions involved and how these may change dynamically. Such information can be obtained using fluctation analysis, in particular scanning number and brightness, and used to build and test mechanistic models of the functional network to define which characteristics are the most important for its regulation.

  5. High molecular weight kininogen regulates platelet-leukocyte interactions by bridging Mac-1 and glycoprotein Ib.

    PubMed

    Chavakis, Triantafyllos; Santoso, Sentot; Clemetson, Kenneth J; Sachs, Ulrich J H; Isordia-Salas, Irma; Pixley, Robin A; Nawroth, Peter P; Colman, Robert W; Preissner, Klaus T

    2003-11-14

    Leukocyte-platelet interaction is important in mediating leukocyte adhesion to a thrombus and leukocyte recruitment to a site of vascular injury. This interaction is mediated at least in part by the beta2-integrin Mac-1 (CD11b/CD18) and its counter-receptor on platelets, glycoprotein Ibalpha (GPIbalpha). High molecular weight kininogen (HK) was previously shown to interact with both GPIbalpha and Mac-1 through its domains 3 and 5, respectively. In this study we investigated the ability of HK to interfere with the leukocyte-platelet interaction. In a purified system, HK binding to GPIbalpha was inhibited by HK domain 3 and the monoclonal antibody (mAb) SZ2, directed against the epitope 269-282 of GPIbalpha, whereas mAb AP1, directed to the region 201-268 of GPIbalpha had no effect. In contrast, mAb AP1 inhibited the Mac-1-GPIbalpha interaction. Binding of GPIbalpha to Mac-1 was enhanced 2-fold by HK. This effect of HK was abrogated in the presence of HK domains 3 or 5 or peptides from the 475-497 region of the carboxyl terminus of domain 5 as well as in the presence of mAb SZ2 but not mAb AP1. Whereas no difference in the affinity of the Mac-1-GPIbalpha interaction was observed in the absence or presence of HK, maximal binding of GPIbalpha to Mac-1 doubled in the presence of HK. Moreover, HK/HKa increased the Mac-1-dependent adhesion of myelomonocytic U937 cells and K562 cells transfected with Mac-1 to immobilized GPIbalpha or to GPIbalpha-transfected Chinese hamster ovary cells. Finally, Mac-1-dependent adhesion of neutrophils to surface-adherent platelets was enhanced by HK. Thus, HK can bridge leukocytes with platelets by interacting via its domain 3 with GPIbalpha and via its domain 5 with Mac-1 thereby augmenting the Mac-1-GPIbalpha interaction. These distinct molecular interactions of HK with leukocytes and platelets contribute to the regulation of the adhesive behavior of vascular cells and provide novel molecular targets for reducing atherothrombotic

  6. Major bleeding risks of different low-molecular-weight heparin agents: a cohort study in 12 934 patients treated for acute venous thrombosis.

    PubMed

    van Rein, N; Biedermann, J S; van der Meer, F J M; Cannegieter, S C; Wiersma, N; Vermaas, H W; Reitsma, P H; Kruip, M J H A; Lijfering, W M

    2017-07-01

    Essentials Low-molecular-weight-heparins (LMWH) kinetics differ which may result in different bleeding risks. A cohort of 12 934 venous thrombosis patients on LMWH was followed until major bleeding. The absolute major bleeding risk was low among patients registered at the anticoagulation clinic. Once-daily dosing was associated with a lower bleeding risk as compared with twice-daily. Background Low-molecular-weight heparins (LMWHs) are considered members of a class of drugs with similar anticoagulant properties. However, pharmacodynamics and pharmacokinetics between LMWHs differ, which may result in different bleeding risks. As these agents are used by many patients, small differences may lead to a large effect on numbers of major bleeding events. Objectives To determine major bleeding risks for different LMWH agents and dosing schedules. Methods A cohort of acute venous thrombosis patients from four anticoagulation clinics who used an LMWH and a vitamin K antagonist were followed until they ceased LMWH treatment or until major bleeding. Exposures were classified according to different types of LMWHs and for b.i.d. and o.d. use. Cumulative incidences for major bleeding per 1000 patients and risk ratios were calculated and adjusted for study center. Results The study comprised 12 934 patients with a mean age of 59 years; 6218 (48%) were men. The cumulative incidence of major bleeding was 2.5 per 1000 patients (95% confidence interval [CI], 1.7-3.5). Enoxaparin b.i.d. or o.d. was associated with a relative bleeding risk of 1.7 (95% CI, 0.2-17.5) compared with nadroparin o.d. In addition, a nadroparin b.i.d. dosing schedule was associated with a 2.0-fold increased major bleeding risk (95% CI, 0.8-5.1) as compared with a nadroparin o.d. dosing schedule. Conclusions Absolute major bleeding rates were low for all LMWH agents and dosing schedules in a large unselected cohort. Nevertheless, twice-daily dosing with nadroparin appeared to be associated with an increased

  7. Surface functionalization of solid state ultra-high molecular weight polyethylene through chemical grafting

    NASA Astrophysics Data System (ADS)

    Sherazi, Tauqir A.; Rehman, Tayyiba; Naqvi, Syed Ali Raza; Shaikh, Ahson Jabbar; Shahzad, Sohail Anjum; Abbas, Ghazanfar; Raza, Rizwan; Waseem, Amir

    2015-12-01

    The surface of ultra-high molecular weight polyethylene (UHMWPE) powder was functionalized with styrene using chemical grafting technique. The grafting process was initiated through radical generation on base polymer matrix in the solid state by sodium thiosulfate, while peroxides formed at radical sites during this process were dissociated by ceric ammonium nitrate. Various factors were optimized and reasonably high level of monomer grafting was achieved, i.e., 15.6%. The effect of different acids as additive and divinyl benzene (DVB) as a cross-linking agent was also studied. Post-grafting sulfonation was conducted to introduce the ionic moieties to the grafted polymer. Ion-exchange capacity (IEC) was measured experimentally and is found to be 1.04 meq g-1, which is in close agreement with the theoretical IEC values. The chemical structure of grafted and functionalized polymer was characterized by attenuated total reflection infrared spectroscopy (ATR-FTIR) and thermal properties were investigated by thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Thermal analysis depicts that the presence of radicals on the polymer chain accelerates the thermal decomposition process. The results signify that the chemical grafting is an effective tool for substantial surface modification and subsequent functionalization of polyethylene.

  8. Characterization and quantitation of low and high molecular weight phenolic compounds in apple seeds.

    PubMed

    Fromm, Matthias; Bayha, Sandra; Carle, Reinhold; Kammerer, Dietmar R

    2012-02-08

    The phenolic constituents of seeds of 12 different apple cultivars were fractionated by sequential extraction with aqueous acetone (30:70, v/v) and ethyl acetate after hexane extraction of the lipids. Low molecular weight phenolic compounds were individually quantitated by RP-HPLC-DAD. The contents of extractable and nonextractable procyanidins were determined by applying RP-HPLC following thiolysis and n-butanol/HCl hydrolysis, respectively. As expected, the results revealed marked differences of the ethyl acetate extracts, aqueous acetone extracts, and insoluble residues with regard to contents and mean degrees of polymerization of procyanidins. Total phenolic contents in the defatted apple seed residues ranged between 18.4 and 99.8 mg/g. Phloridzin was the most abundant phenolic compound, representing 79-92% of monomeric polyphenols. Yields of phenolic compounds significantly differed among the cultivars under study, with seeds of cider apples generally being richer in phloridzin and catechins than seeds of dessert apple cultivars. This is the first study presenting comprehensive data on the contents of phenolic compounds in apple seeds comprising extractable and nonextractable procyanidins. Furthermore, the present work points out a strategy for the sustainable and complete exploitation of apple seeds as valuable agro-industrial byproducts, in particular as a rich source of phloridzin and antioxidant flavanols.

  9. Study on antithrombotic and antiplatelet activities of low molecular weight fucoidan from Laminaria japonica

    NASA Astrophysics Data System (ADS)

    Chen, Anjin; Zhang, Fang; Shi, Jie; Zhao, Xue

    2012-06-01

    The antithrombotic and antiplatelet effects of two fucoidan fractions with low molecular weight and different sulfate content from Laminaria japonica were compared in order to examine the influence of chemical character on their antithrombotic activity and the possible mechanism. Both LMW fucoidan fractions exhibited favorable antithrombotic activity in an Fecl3-induced arterial thrombosis. The antithrombotic activity of LMW fucoidan was related with decrease of TXB2 and whole blood viscosity and hematocrit. LMW fucoidan showed a correlation between anticoagulant, antiaggregant and antithrombotic effects in vivo. For LMW fucoidan, antithrombotic activity required high dose of 5-10 nmol kg-1, concomitantly with increase in anticoagulant activity and inhibition of platelet aggregation. Administration of LMW fucoidan significantly promoted the 6-keto-PGF1α content and decreased the TXB2 content, indicating its inhibition of tissue factor pathway and regulation of metabolism of arachidonic acid. By comparison, highly sulfated fucoidan LF2 with Mw 3900 seemed to be a more suitable choice for antithrombotic drug for its antithrombotic activity accompanied with specific inhibitory activity on platelet aggregation, low anticoagulant activity and low hemorrhagic risk in vivo.

  10. Preparation of low molecular weight Sargassum fusiforme polysaccharide and its anticoagulant activity

    NASA Astrophysics Data System (ADS)

    Sun, Yuhao; Chen, Xiaolin; Liu, Song; Yu, Huahua; Li, Rongfeng; Wang, Xueqin; Qin, Yukun; Li, Pengcheng

    2017-10-01

    Heparin has been used as an anticoagulant drug for many years, but it has significant side effects. In the search for good substitutes, low molecular weight (MW) polysaccharides from Sargassum fusiforme have been examined and confirmed to possess biological activities. Here, S. fusiforme polysaccharides (SFP) were extracted and subjected to a hydrogen peroxide (H2O2) oxidation method for the preparation of low-MW SFP (LSFP). The effects of temperature, pH, and H2O2 concentration on the degradation process were also examined. Several LSFP of 36, 9, 5.7, and 2.7 kDa were obtained under different conditions, and their anticoagulant activities studied in vitro. The results showed that SFP and LSFP prolonged activated partial thromboplastin (APTT), prothrombin (PT) and thrombin times (TT) significantly, indicating that these low MW polysaccharides possessed anticoagulant activity in the intrinsic, extrinsic, and common coagulation pathways. As these effects were related to the MW of the polysaccharides in APTT and TT but not in PT, the contents of the monosaccharide fucose and sulfate and the polysaccharide MW could have exerted combined effects. The details of this mechanism require further verification.

  11. Outpatient treatment of venous thromboembolism using low molecular weight heparins. An overview.

    PubMed

    Matsagas, M I

    2004-12-01

    The development of low-molecular-weight heparins (LMWHs) was a significant advance in the treatment of venous thromboembolism (VTE). Their better bioavailability and more predictable anticoagulant activity than unfractionated heparin (UFH) allow subcutaneous administration without close laboratory monitoring, and thus make outpatient treatment of deep vein thrombosis (DVT) feasible. The safety and efficacy of outpatient treatment in selected patients were established in randomized clinical trials comparing subcutaneous LMWH administered primarily at home with inpatient intravenous UFH. Furthermore, during the last few years a large number of studies have supported these findings in various clinical settings of every-day practice. It is also important that home treatment has lead to substantial cost reductions along with improvement in patients' satisfaction and quality of life. Thus, outpatient treatment of DVT provides an opportunity, rarely seen in medicine, to improve patient care while reducing the overall VTE health-care cost, and it is likely that will be the preferred regime for the majority of patients in the future. However, the implementation of a home treatment program is not simple, as the risks of insufficient or excessive anticoagulation would be considerable. A structured protocol is necessary to ensure that patient care is optimal, and the keys to a successful outpatient treatment program are patient selection, patient education, patient access to health care team, appropriate follow-up and health care team communication.

  12. Peptide and low molecular weight proteins based kidney targeted drug delivery systems.

    PubMed

    Xu, Pengfei; Zhang, Hailiang; Dang, Ruili; Jiang, Pei

    2018-05-30

    Renal disease is a worldwide public health problem, and unfortunately, the therapeutic index of regular drugs is limited. Thus, it is a great need to develop effective treatment strategies. Among the repo