DOE Office of Scientific and Technical Information (OSTI.GOV)

J Cai; B Hsiao; R Gross

Poly({omega}-pentadecalactone) (PPDL), a model polymer in the poly({omega}-hydroxyl fatty acids) family, is a new biopolymer with monomer synthesized by yeast-catalyzed {omega}-hydroxylation of fatty acids. In this study, deformation-induced structural changes in two PPDL samples with different molecular weights were studied by in situ wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. The high molecular weight PPDL (PPDL-high) sample exhibited notable strain hardening, while the low molecular weight PPDL (PPDL-low) sample did not. The behavior can be explained by the entanglement density concept. The evolution of crystallinity (from WAXD) as a function of strain could be divided into fourmore » distinct regions, but their respective mechanisms differ slightly in each sample. During stretching, a mesomorphic phase formed in both samples, bridging between the amorphous and strain-induced crystal phases. The SAXS data verified the effect of molecular weight (or the entanglement density) on the deformation-induced structure of PPDL. The parameters of chain orientation factor (f) calculated from the orthorhombic crystal cell as well as the nonorthorhombic crystal cell proposed by Wilchinsky were used to follow the orientation process during stretching of PPDLs. It was found that the different molecular entanglement network (i.e., PPDL-low versus PPDL-high) led to different crystal orientation behavior, especially in the low strain range.« less

Insights in groundwater organic matter from Liquid Chromatography-Organic Carbon Detection

NASA Astrophysics Data System (ADS)

Rutlidge, H.; Oudone, P.; McDonough, L.; Andersen, M. S.; Baker, A.; Meredith, K.; O'Carroll, D. M.

2017-12-01

Understanding the processes that control the concentration and characteristics of organic matter in groundwater has important implications for the terrestrial global carbon budget. Liquid Chromatography - Organic Carbon Detection (LC-OCD) is a size-exclusion based chromatography technique that separates the organic carbon into molecular weight size fractions of biopolymers, humic substances, building blocks (degradation products of humic substances), low molecular weight acids and low molecular weight neutrals. Groundwater and surface water samples were collected from a range of locations in Australia representing different surface soil, land cover, recharge type and hydrological properties. At one site hyporheic zone samples were also collected from beneath a stream. The results showed a general decrease in the aromaticity and molecular weight indices going from surface water, hyporheic downwelling and groundwater samples. The aquifer substrate also affected the organic composition. For example, groundwater samples collected from a zone of fractured rock showed a relative decrease in the proportion of humic substances, suggestive of sorption or degradation of humic substances. This work demonstrates the potential for using LC-OCD in elucidating the processes that control the concentration and characteristics of organic matter in groundwater.

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.

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…

Determination of Physical and Chemical Structure of New High-Temperature Polymers

DTIC Science & Technology

toward determination of the molecular weight of both perfluorosebacate and perfluoroalkyl ether-linked polymers. In addition, solubility, thermal...thermal properties, and molecular weight. Several samples of the perfluoroalkyl bibenzoxazole polymers were examined. Considerable effort was directed...stability and subambient DTA of the perfluoroalkyl ether- linked polymers (elastomers) were investigated. Samples of the aromatic heterocyclic-ladder type

Microbial degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in soils.

PubMed Central

Mergaert, J; Webb, A; Anderson, C; Wouters, A; Swings, J

1993-01-01

The microbial degradation of tensile test pieces made of poly(3-hydroxybutyrate) [P(3HB)] or a copolymer of 90% 3-hydroxybutyric acid and 10% 3-hydroxyvaleric acid was studied in soils incubated at a constant temperature of 15, 28, or 40 degrees C for up to 200 days. In addition, hydrolytic degradation in sterile buffer at temperatures ranging from 4 to 55 degrees C was monitored for 98 days. Degradation was measured through loss of weight (surface erosion), molecular weight, and mechanical strength. While no weight loss was recorded in sterile buffer, samples incubated in soils were degraded at an erosion rate of 0.03 to 0.64% weight loss per day, depending on the polymer, the soil, and the incubation temperature. The erosion rate was enhanced by incubation at higher temperatures, and in most cases the copolymer lost weight at a higher rate than the homopolymer. The molecular weights of samples incubated at 40 degrees C in soils and those incubated at 40 degrees C in sterile buffer decreased at similar rates, while the molecular weights of samples incubated at lower temperatures remained almost unaffected, indicating that molecular weight decrease is due to simple hydrolysis and not to the action of biodegrading microorganisms. The degradation resulted in loss of mechanical properties. From the samples used in the biodegradation studies, 295 dominant microbial strains capable of degrading P (3HB) and the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer in vitro were isolated and identified.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8250550

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.

Correlation of the physicochemical properties of natural organic matter samples from different sources to their effects on gold nanoparticle aggregation in monovalent electrolyte.

PubMed

Louie, Stacey M; Spielman-Sun, Eleanor R; Small, Mitchell J; Tilton, Robert D; Lowry, Gregory V

2015-02-17

Engineered nanoparticles (NPs) released into natural environments will interact with natural organic matter (NOM) or humic substances, which will change their fate and transport behavior. Quantitative predictions of the effects of NOM are difficult because of its heterogeneity and variability. Here, the effects of six types of NOM and molecular weight fractions of each on the aggregation of citrate-stabilized gold NPs are investigated. Correlations of NP aggregation rates with electrophoretic mobility and the molecular weight distribution and chemical attributes of NOM (including UV absorptivity or aromaticity, functional group content, and fluorescence) are assessed. In general, the >100 kg/mol components provide better stability than lower molecular weight components for each type of NOM, and they contribute to the stabilizing effect of the unfractionated NOM even in small proportions. In many cases, unfractionated NOM provided better stability than its separated components, indicating a synergistic effect between the high and low molecular weight fractions for NP stabilization. Weight-averaged molecular weight was the best single explanatory variable for NP aggregation rates across all NOM types and molecular weight fractions. NP aggregation showed poorer correlation with UV absorptivity, but the exponential slope of the UV-vis absorbance spectrum was a better surrogate for molecular weight. Functional group data (including reduced sulfur and total nitrogen content) were explored as possible secondary parameters to explain the strong stabilizing effect of a low molecular weight Pony Lake fulvic acid sample to the gold NPs. These results can inform future correlations and measurement requirements to predict NP attachment in the presence of NOM.

Molecular-Size-Separated Brown Carbon Absorption for Biomass-Burning Aerosol at Multiple Field Sites.

PubMed

Di Lorenzo, Robert A; Washenfelder, Rebecca A; Attwood, Alexis R; Guo, Hongyu; Xu, Lu; Ng, Nga L; Weber, Rodney J; Baumann, Karsten; Edgerton, Eric; Young, Cora J

2017-03-21

Biomass burning is a known source of brown carbon aerosol in the atmosphere. We collected filter samples of biomass-burning emissions at three locations in Canada and the United States with transport times of 10 h to >3 days. We analyzed the samples with size-exclusion chromatography coupled to molecular absorbance spectroscopy to determine absorbance as a function of molecular size. The majority of absorption was due to molecules >500 Da, and these contributed an increasing fraction of absorption as the biomass-burning aerosol aged. This suggests that the smallest molecular weight fraction is more susceptible to processes that lead to reduced light absorption, while larger-molecular-weight species may represent recalcitrant brown carbon. We calculate that these large-molecular-weight species are composed of more than 20 carbons with as few as two oxygens and would be classified as extremely low volatility organic compounds (ELVOCs).

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.

MALDI-TOF mass spectrometry analysis of small molecular weight compounds (under 10 KDa) as biomarkers of rat hearts undergoing arecoline challenge.

PubMed

Chen, Tung-Sheng; Chang, Mu-Hsin; Kuo, Wei-Wen; Lin, Yueh-Min; Yeh, Yu-Lan; Day, Cecilia Hsuan; Lin, Chien-Chung; Tsai, Fuu-Jen; Tsai, Chang-Hai; Huang, Chih-Yang

2013-04-01

Statistical and clinical reports indicate that betel nut chewing is strongly associated with progression of oral cancer because some ingredients in betel nuts are potential cancer promoters, especially arecoline. Early diagnosis for cancer biomarkers is the best strategy for prevention of cancer progression. Several methods are suggested for investigating cancer biomarkers. Among these methods, gel-based proteomics approach is the most powerful and recommended tool for investigating biomarkers due to its high-throughput. However, this proteomics approach is not suitable for screening biomarkers with molecular weight under 10 KDa because of the characteristics of gel electrophoresis. This study investigated biomarkers with molecular weight under 10 KDa in rats with arecoline challenge. The centrifuging vials with membrane (10 KDa molecular weight cut-off) played a crucial role in this study. After centrifuging, the filtrate (containing compounds with molecular weight under 10 KDa) was collected and spotted on a sample plate for MALDI-TOF mass spectrometry analysis. Compared to control, three extra peaks (m/z values were 1553.1611, 1668.2097 and 1740.1832, respectively) were found in sera and two extra peaks were found in heart tissue samples (408.9719 and 524.9961, respectively). These small compounds should play important roles and may be potential biomarker candidates in rats with arecoline. This study successfully reports a mass-based method for investigating biomarker candidates with small molecular weight in different types of sample (including serum and tissue). In addition, this reported method is more time-efficient (1 working day) than gel-based proteomics approach (5~7 working days).

Peptidylation for the determination of low-molecular-weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

PubMed

Tang, Feng; Cen, Si-Ying; He, Huan; Liu, Yi; Yuan, Bi-Feng; Feng, Yu-Qi

2016-05-23

Determination of low-molecular-weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) has been a great challenge in the analytical research field. Here we developed a universal peptide-based derivatization (peptidylation) strategy for the sensitive analysis of low-molecular-weight compounds by MALDI-TOF-MS. Upon peptidylation, the molecular weights of target analytes increase, thus avoiding serious matrix ion interference in the low-molecular-weight region in MALDI-TOF-MS. Since peptides typically exhibit good signal response during MALDI-TOF-MS analysis, peptidylation endows high detection sensitivities of low-molecular-weight analytes. As a proof-of-concept, we analyzed low-molecular-weight compounds of aldehydes and thiols by the developed peptidylation strategy. Our results showed that aldehydes and thiols can be readily determined upon peptidylation, thus realizing the sensitive and efficient determination of low-molecular-weight compounds by MALDI-TOF-MS. Moreover, target analytes also can be unambiguously detected in biological samples using the peptidylation strategy. The established peptidylation strategy is a universal strategy and can be extended to the sensitive analysis of various low-molecular-weight compounds by MALDI-TOF-MS, which may be potentially used in areas such as metabolomics.

Morphological, spectral and chromatography analysis and forensic comparison of PET fibers.

PubMed

Farah, Shady; Tsach, Tsadok; Bentolila, Alfonso; Domb, Abraham J

2014-06-01

Poly(ethylene terephthalate) (PET) fiber analysis and comparison by spectral and polymer molecular weight determination was investigated. Plain fibers of PET, a common textile fiber and plastic material was chosen for this study. The fibers were analyzed for morphological (SEM and AFM), spectral (IR and NMR), thermal (DSC) and molecular weight (MS and GPC) differences. Molecular analysis of PET fibers by Gel Permeation Chromatography (GPC) allowed the comparison of fibers that could not be otherwise distinguished with high confidence. Plain PET fibers were dissolved in hexafluoroisopropanol (HFIP) and analyzed by GPC using hexafluoroisopropanol:chloroform 2:98 v/v as eluent. 14 PET fiber samples, collected from various commercial producers, were analyzed for polymer molecular weight by GPC. Distinct differences in the molecular weight of the different fiber samples were found which may have potential use in forensic fiber comparison. PET fibers with average molecular weights between about 20,000 and 70,000 g mol(-1) were determined using fiber concentrations in HFIP as low as 1 μg mL(-1). This GPC analytical method can be applied for exclusively distinguish between PET fibers using 1 μg of fiber. This method can be extended to forensic comparison of other synthetic fibers such as polyamides and acrylics. Copyright © 2014 Elsevier B.V. All rights reserved.

Deproteinization assessment using isotopically enriched compounds to trace the coprecipitation of low-molecular-weight selenium species with proteins.

PubMed

Godin, Simon; Bouzas-Ramos, Diego; Fontagné-Dicharry, Stéphanie; Bouyssière, Brice; Bueno, Maïté

2017-08-01

Studies have shown that information related to the presence of low-molecular-weight metabolites is frequently lost after deproteinization of complex matrices, such as blood and plasma, during sample preparation. Therefore, the effect of several deproteinization reagents on low-molecular-weight selenium species has been compared by species-specific isotope labeling. Two isotopically enriched selenium tracers were used to mimic models of small inorganic anionic ( 77 Se-selenite) and organic zwitterionic ( 76 Se-selenomethionine) species. The results presented here show that the use of a methanol-acetonitrile-acetone (1:1:1 v/v/v) mixture provided approximately two times less tracer loss from plasma samples in comparison with the classic procedure using acetonitrile, which may not be optimal as it leads to important losses of low-molecular-weight selenium species. In addition, the possible interactions between selenium tracers and proteins were investigated, revealing that both coprecipitation phenomena and association with proteins were potentially responsible for selenite tracer losses during protein precipitation in blood samples. However, coprecipitation phenomena were found to be fully responsible for losses of both tracers observed in plasma samples and of the selenomethionine tracer in blood samples. This successfully applied strategy is anticipated to be useful for more extensive future studies in selenometabolomics. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

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

A new general method for the assessment of the molecular-weight distribution of polydisperse preparations. Its application to an intestinal epithelial glycoprotein and two dextran samples, and comparison with a monodisperse glycoprotein

PubMed Central

Gibbons, Richard A.; Dixon, Stephen N.; Pocock, David H.

1973-01-01

A specimen of intestinal glycoprotein isolated from the pig and two samples of dextran, all of which are polydisperse (that is, the preparations may be regarded as consisting of a continuous distribution of molecular weights), have been examined in the ultracentrifuge under meniscus-depletion conditions at equilibrium. They are compared with each other and with a glycoprotein from Cysticercus tenuicollis cyst fluid which is almost monodisperse. The quantity c−⅓ (c=concentration) is plotted against ξ (the reduced radius); this plot is linear when the molecular-weight distribution approximates to the `most probable', i.e. when Mn:Mw:Mz: M(z+1)....... is as 1:2:3:4: etc. The use of this plot, and related procedures, to evaluate qualitatively and semi-quantitatively molecular-weight distribution functions where they can be realistically approximated to Schulz distributions is discussed. The theoretical basis is given in an Appendix. PMID:4778265

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.

Determination of the molecular weight of low-molecular-weight heparins by using high-pressure size exclusion chromatography on line with a triple detector array and conventional methods.

PubMed

Bisio, Antonella; Mantegazza, Alessandra; Vecchietti, Davide; Bensi, Donata; Coppa, Alessia; Torri, Giangiacomo; Bertini, Sabrina

2015-03-19

The evaluation of weight average molecular weight (Mw) and molecular weight distribution represents one of the most controversial aspects concerning the characterization of low molecular weight heparins (LMWHs). As the most commonly used method for the measurement of such parameters is high performance size exclusion chromatography (HP-SEC), the soundness of results mainly depends on the appropriate calibration of the chromatographic columns used. With the aim of meeting the requirement of proper Mw standards for LMWHs, in the present work the determination of molecular weight parameters (Mw and Mn) by HP-SEC combined with a triple detector array (TDA) was performed. The HP-SEC/TDA technique permits the evaluation of polymeric samples by exploiting the combined and simultaneous action of three on-line detectors: light scattering detectors (LALLS/RALLS); refractometer and viscometer. Three commercial LMWH samples, enoxaparin, tinzaparin and dalteparin, a γ-ray depolymerized heparin (γ-Hep) and its chromatographic fractions, and a synthetic pentasaccharide were analysed by HP-SEC/TDA. The same samples were analysed also with a conventional HP-SEC method employing refractive index (RI) and UV detectors and two different chromatographic column set, silica gel and polymeric gel columns. In both chromatographic systems, two different calibration curves were built up by using (i) γ-Hep chromatographic fractions and the corresponding Mw parameters obtained via HP-SEC/TDA; (ii) the whole γ-Hep preparation with broad Mw dispersion and the corresponding cumulative distribution function calculated via HP-SEC/TDA. In addition, also a chromatographic column calibration according to European Pharmacopoeia indication was built up. By comparing all the obtained results, some important differences among Mw and size distribution values of the three LMWHs were found with the five different calibration methods and with HP-SEC/TDA method. In particular, the detection of the lower molecular weight components turned out to be the most critical aspect. Whereas HP-SEC/TDA may underestimate species under 2 KDa when present in low concentration, other methods appeared to emphasize their content.

Method development for compositional analysis of low molecular weight poly(vinyl acetate) by matrix-assisted/laser desorption-mass spectrometry and its application to analysis of chewing gum.

PubMed

Tisdale, Evgenia; Wilkins, Charles

2014-04-11

The influence of the sample preparation parameters (the choice of the solvent and of the matrix:analyte ratio) was investigated and optimal conditions were established for MALDI mass spectrometry analysis of the pristine low molecular weight polyvinyl acetate (PVAc). It was demonstrated that comparison of polymer's and solvent's Hansen solubility parameters could be used as a guide when choosing the solvent for MALDI sample preparation. The highest intensity PVAc signals were obtained when ethyl acetate was used as a solvent along with the lowest matrix-analyte ratio (2,5-dihydroxybenzoic acid was used as a matrix in all experiments). The structure of the PVAc was established with high accuracy using the matrix-assisted laser desorption/ionization-Fourier transform mass spectrometry (MALDI-FTMS) analysis. It was demonstrated that PVAc undergoes unimolecular decomposition by losing acetic acid molecules from its backbone under the conditions of FTMS measurements. Number and weight average molecular weights as well as polydispersity indices were determined with both MALDI-TOF and MALDI-FTMS methods. The sample preparation protocol developed was applied to the analysis of a chewing gum and the molecular weight and structure of the polyvinyl acetate present in the sample were established. Thus, it was shown that optimized MALDI mass spectrometry could be used successfully for characterization of polyvinyl acetate in commercially available chewing gum. Copyright © 2014 Elsevier B.V. All rights reserved.

A statistical approach to the interpretation of aliphatic hydrocarbon distributions in marine sediments

USGS Publications Warehouse

Rapp, J.B.

1991-01-01

Q-mode factor analysis was used to quantitate the distribution of the major aliphatic hydrocarbon (n-alkanes, pristane, phytane) systems in sediments from a variety of marine environments. The compositions of the pure end members of the systems were obtained from factor scores and the distribution of the systems within each sample was obtained from factor loadings. All the data, from the diverse environments sampled (estuarine (San Francisco Bay), fresh-water (San Francisco Peninsula), polar-marine (Antarctica) and geothermal-marine (Gorda Ridge) sediments), were reduced to three major systems: a terrestrial system (mostly high molecular weight aliphatics with odd-numbered-carbon predominance), a mature system (mostly low molecular weight aliphatics without predominance) and a system containing mostly high molecular weight aliphatics with even-numbered-carbon predominance. With this statistical approach, it is possible to assign the percentage contribution from various sources to the observed distribution of aliphatic hydrocarbons in each sediment sample. ?? 1991.

Synthesis and Thermal Degradation Studies of Melamine Formaldehyde Resins

PubMed Central

Ullah, Sami; Bustam, M. A.; Nadeem, M.; Tan, W. L.; Shariff, A. M.

2014-01-01

Melamine formaldehyde (MF) resins have been synthesized at different reaction temperature and pH values. Different molar ratios of melamine and formaldehyde were used to synthesize the corresponding resins. The prepared resin samples were characterized by using molecular weight determination viscometry and thermogravimetric analysis (TGA). The maximum percentage of solid content (69.7%) was obtained at pH 8.5 and 75°C temperature. The molecular weight of MF resin was increased with an increase of melamine monomer concentration. The highest residual weight 14.125 wt.% was obtained with sample 10. PMID:25436237

The structure of tracheobronchial mucins from cystic fibrosis and control patients.

PubMed

Gupta, R; Jentoft, N

1992-02-15

Tracheobronchial mucin samples from control and cystic fibrosis patients were purified by gel filtration chromatography on Sephacryl S-1000 and by density gradient centrifugation. Normal secretions contained high molecular weight (approximately 10(7] mucins, whereas the cystic fibrosis secretions contained relatively small amounts of high molecular weight mucin together with larger quantities of lower molecular weight mucin fragments. These probably represent products of protease digestion. Reducing the disulfide bonds in either the control or cystic fibrosis high molecular weight mucin fractions released subunits of approximately 2000 kDa. Treating these subunits with trypsin released glycopeptides of 300 kDa. Trypsin treatment of unreduced mucin also released fragments of 2000 kDa that could be converted into 300-kDa glycopeptides upon disulfide bond reduction. Thus, protease-susceptible linkages within these mucins must be cross-linked by disulfide bonds so that the full effects of proteolytic degradation of mucins remain cryptic until disulfide bonds are reduced. Since various combinations of protease treatment and disulfide bond reduction release either 2000- or 300-kDa fragments, these fragments must represent important elements of mucin structure. The high molecular weight fractions of cystic fibrosis mucins appear to be indistinguishable from control mucins. Their amino acid compositions are the same, and various combinations of disulfide bond reduction and protease treatment release products of identical size and amino acid composition. Sulfate and carbohydrate compositions did vary considerably from sample to sample, but the limited number of samples tested did not demonstrate a cystic fibrosis-specific pattern. Thus, tracheobronchial mucins from cystic fibrosis and control patients are very similar, and both share the same generalized structure previously determined for salivary, cervical, and intestinal mucins.

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).

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).

Characterization of organic matter in cloud waters sampled at the puy de Dôme mountain using FT-ICR-MS

NASA Astrophysics Data System (ADS)

Bianco, A.; Chaumerliac, N.; Vaitilingom, M.; Deguillaume, L.; Bridoux, M. C.

2017-12-01

The chemical composition of organic matter in cloud water is highly complex. The organic species result from their dissolution from the gas phase or from the soluble fraction of the particle phase. They are also produced by aqueous phase reactivity. Several low molecular weight organic species have been quantified such as aldehydes and carboxylic acids. Recently, amino acids were also detected in cloud water and their presence is related to the presence of microorganisms. Compounds presenting similarities with high molecular weight organic substances or HULIS found in aerosols were also observed in clouds. Overall, these studies mainly focused on individual compounds or functional groups rather than the complex mixture at the molecular level. This study presents a non-targeted approach to characterize the organic matter in clouds. Samples were collected at the puy de Dôme Mountain (France). Two cloud water samples (June & July 2016) were analyzed using high resolution mass spectrometry (ESI-FT-ICR-MS 9.4T). A reversed solid phase extraction (SPE) procedure was performed to concentrate dissolved organic matter components. Composer (v.1.5.3) software was used to filter the mass spectral data, recalibrate externally the dataset and calculate all possible formulas for detected anions. The first cloud sample (June) resulted from air mass coming from the North (North Sea) while the second one (July) resulted from air mass coming from the West (Atlantic Ocean). Thus, both cloud events derived from marine air masses but were characterized by different hydrogen peroxide concentration and dissolved organic carbon content and were sampled at different periods during the day. Elemental compositions of 6487 and 3284 unique molecular species were identified in each sample. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS & CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 800 Da were detected. The main class is CHNO (53% for both samples) while sulfur-containing compounds represent for the two samples respectively 21 & 14% of the total assigned molecular formulas. CHO compounds molecular formulas are respectively 25 & 32%. Among the two samples, only 2490 molecular formulas were found common to the two samples.

Investigation of Polymer Liquid Crystals

NASA Technical Reports Server (NTRS)

Han, Kwang S.

1996-01-01

The positron annihilation lifetime spectroscopy (PALS) using a low energy flux generator may provide a reasonably accurate technique for measuring molecular weights of linear polymers and characterization of thin polyimide films in terms of their dielectric constants and hydrophobity etc. Among the tested samples are glassy poly arylene Ether Ketone films, epoxy and other polyimide films. One of the proposed techniques relates the free volume cell size (V(sub f)) with sample molecular weight (M) in a manner remarkably similar to that obtained by Mark Houwink (M-H) between the inherent viscosity (eta) and molecular wieght of polymer solution. The PALS has also demonstrated that free-volume cell size in thermoset is a versatile, useful parameter that relates directly to the polymer segmental molecular weight, the cross-link density, and the coefficient of thermal expansion. Thus, a determination of free volume cell size provides a viable basis for complete microstructural characterization of thermoset polyimides and also gives direct information about the cross-link density and coefficient of expansion of the test samples. Seven areas of the research conducted are reported here.

Variation and correlation of protein molecular weight distribution and semolina quality parameters for durum genotypes grown in North Dakota

USDA-ARS?s Scientific Manuscript database

This research assessed the associations between protein molecular weight distribution (MWD) and quality characteristics for durum semolina samples that were obtained from thirteen durum genotypes grown at seven locations for two years in North Dakota. Sodium dodecyl sulfate (SDS) extractable and un...

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.

Direct mass spectrometry approaches to characterize polyphenol composition of complex samples.

PubMed

Fulcrand, Hélène; Mané, Carine; Preys, Sébastien; Mazerolles, Gérard; Bouchut, Claire; Mazauric, Jean-Paul; Souquet, Jean-Marc; Meudec, Emmanuelle; Li, Yan; Cole, Richard B; Cheynier, Véronique

2008-12-01

Lower molecular weight polyphenols including proanthocyanidin oligomers can be analyzed after HPLC separation on either reversed-phase or normal phase columns. However, these techniques are time consuming and can have poor resolution as polymer chain length and structural diversity increase. The detection of higher molecular weight compounds, as well as the determination of molecular weight distributions, remain major challenges in polyphenol analysis. Approaches based on direct mass spectrometry (MS) analysis that are proposed to help overcome these problems are reviewed. Thus, direct flow injection electrospray ionization mass spectrometry analysis can be used to establish polyphenol fingerprints of complex extracts such as in wine. This technique enabled discrimination of samples on the basis of their phenolic (i.e. anthocyanin, phenolic acid and flavan-3-ol) compositions, but larger oligomers and polymers were poorly detectable. Detection of higher molecular weight proanthocyanidins was also restricted with matrix-assisted laser desorption ionization (MALDI) MS, suggesting that they are difficult to desorb as gas-phase ions. The mass distribution of polymeric fractions could, however, be determined by analyzing the mass distributions of bovine serum albumin/proanthocyanidin complexes using MALDI-TOF-MS.

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

DOE PAGES

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.; ...

2017-09-06

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less

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.

The effect of different extraction techniques on property and bioactivity of polysaccharides from Dioscorea hemsleyi.

PubMed

Zhao, Chengcheng; Li, Xia; Miao, Jing; Jing, Songsong; Li, Xuejiao; Huang, Luqi; Gao, Wenyuan

2017-09-01

The rhizoma of Dioscorea hemsleyi (DH) has been used as a treatment of diabetes in China for hundreds of years. Polysaccharides in DH were extracted by using ultrasonic-assisted extraction (UAE), cold water extraction (CWE), warm water extraction (WWE) and hot water extraction (HWE), separately. Then the different characterizations of four DH polysaccharide (DHP) samples were analyzed by high-performance liquid chromatography (HPLC), high-performance Gel permeation chromatography (HGPC), ultraviolet-visible spectroscopy(UV), fourier transform-infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Their activities in vitro of DHP were compared. Experimental results showed that HWE had the highest yield and large molecular weight. CWE had the highest uronic acid yield and little molecular weight, and its DPPH, AGI and AAI activity were the best. The molecular weight of UAE was small, and its RP and FRAP activity were the best. Four DHP samples had differences in the surface topography, while they all had the typical IR spectra characteristic of polysaccharides. According the correlation analysis, it showed that the more uronic acid and the lower molecular weight was, the higher the antioxidant activity was. The high content of monosaccharide composition of Xyl, Ara, GlcA and GalA, and little molecular weight have good effect on antidiabetic activity. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of low molecular weight alcohols including fusel oil in various samples by diethyl ether extraction and capillary gas chromatography.

PubMed

Woo, Kang-Lyung

2005-01-01

Low molecular weight alcohols including fusel oil were determined using diethyl ether extraction and capillary gas chromatography. Twelve kinds of alcohols were successfully resolved on the HP-FFAP (polyethylene glycol) capillary column. The diethyl ether extraction method was very useful for the analysis of alcohols in alcoholic beverages and biological samples with excellent cleanliness of the resulting chromatograms and high sensitivity compared to the direct injection method. Calibration graphs for all standard alcohols showed good linearity in the concentration range used, 0.001-2% (w/v) for all alcohols. Salting out effects were significant (p < 0.01) for the low molecular weight alcohols methanol, isopropanol, propanol, 2-butanol, n-butanol and ethanol, but not for the relatively high molecular weight alcohols amyl alcohol, isoamyl alcohol, and heptanol. The coefficients of variation of the relative molar responses were less than 5% for all of the alcohols. The limits of detection and quantitation were 1-5 and 10-60 microg/L for the diethyl ether extraction method, and 10-50 and 100-350 microg/L for the direct injection method, respectively. The retention times and relative retention times of standard alcohols were significantly shifted in the direct injection method when the injection volumes were changed, even with the same analysis conditions, but they were not influenced in the diethyl ether extraction method. The recoveries by the diethyl ether extraction method were greater than 95% for all samples and greater than 97% for biological samples.

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

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.

DETECTION OF HIGH MOLECULAR WEIGHT ORGANIC TRACERS IN VEGETATION SMOKE SAMPLES BY HIGH-TEMPERATURE GAS CHROMATOGRAPHY-MASS SPECTROMETRY. (R823990)

EPA Science Inventory

High-temperature high-resolution gas chromatography
(HTGC) is an established technique for the separation of
complex mixtures of high molecular weight (HMW) compounds
which do not elute when analyzed on conventional GC
columns. The combination of this technique wit...

Precise measurement of the self-diffusion coefficient for poly(ethylene glycol) in aqueous solution using uniform oligomers

NASA Astrophysics Data System (ADS)

Shimada, Kayori; Kato, Haruhisa; Saito, Takeshi; Matsuyama, Shigetomo; Kinugasa, Shinichi

2005-06-01

Uniform poly(ethylene glycol) (PEG) oligomers, with a degree of polymerization n =1-40, were separated by preparative supercritical fluid chromatography from commercial monodispersed samples. Diffusion coefficients, D, for separated uniform PEG oligomers were measured in dilute solutions of deuterium oxide (D2O) at 30 ° C, using pulsed-field gradient nuclear magnetic resonance. The measured D for each molecular weight was extrapolated to infinite dilution. Diffusion coefficients obtained at infinite dilution follow the scaling behavior of Zimm-type diffusion, even in the lower molecular weight range. Molecular-dynamics simulations for PEG in H2O also showed this scaling behavior, and reproduced close hydrodynamic interactions between PEG and water. These findings suggest that diffusion of PEG in water is dominated by hydrodynamic interaction over a wide molecular weight range, including at low molecular weights around 1000.

High-pressure size exclusion chromatography analysis of dissolved organic matter isolated by tangential-flow ultra filtration

USGS Publications Warehouse

Everett, C.R.; Chin, Y.-P.; Aiken, G.R.

1999-01-01

A 1,000-Dalton tangential-flow ultrafiltration (TFUF) membrane was used to isolate dissolved organic matter (DOM) from several freshwater environments. The TFUF unit used in this study was able to completely retain a polystyrene sulfonate 1,800-Dalton standard. Unaltered and TFUF-fractionated DOM molecular weights were assayed by high-pressure size exclusion chromatography (HPSEC). The weight-averaged molecular weights of the retentates were larger than those of the raw water samples, whereas the filtrates were all significantly smaller and approximately the same size or smaller than the manufacturer-specified pore size of the membrane. Moreover, at 280 nm the molar absorptivity of the DOM retained by the ultrafilter is significantly larger than the material in the filtrate. This observation suggests that most of the chromophoric components are associated with the higher molecular weight fraction of the DOM pool. Multivalent metals in the aqueous matrix also affected the molecular weights of the DOM molecules. Typically, proton-exchanged DOM retentates were smaller than untreated samples. This TFUF system appears to be an effective means of isolating aquatic DOM by size, but the ultimate size of the retentates may be affected by the presence of metals and by configurational properties unique to the DOM phase.

Direct Determination of Molecular Weight Distribution of Calf-Thymus DNAs and Study of Their Fragmentation under Ultrasonic and Low-Energy IR Irradiations. A Charge Detection Mass Spectrometry Investigation.

PubMed

Halim, Mohammad A; Bertorelle, Franck; Doussineau, Tristan; Antoine, Rodolphe

2018-06-09

Calf-thymus (CT-DNA) is widely used as binding agent. The commercial samples are known to be "highly polymerized DNA" samples. CT-DNA is known to be fragile in particular upon ultrasonic wave irradiation. Degradation products might have dramatic consequence on its bio-sensing activity, and an accurate determination of the molecular weight distribution and stability of commercial samples is highly demanded. We investigated the sensitivity of charge detection mass spectrometry (CDMS), a single-molecule MS method, both with single-pass and ion trap CDMS ("Benner" trap) modes to the determination of the composition and stability (under multiphoton IR irradiation) of calf-thymus DNAs. We also investigated the changes of molecular weight distributions in the course of sonication by irradiating ultrasonic wave to CT-DNA. We report for the first time, the direct molecular weight (MW) distribution of DNA sodium salt from calf-thymus revealing two populations at high (~10 MDa) and low (~3 MDa) molecular weights. We evidence a transition between the high-MW to the low-MW distribution, confirming that the low-MW distribution results from degradation of CT-DNA. Finally, we report also IRMPD experiments carried out on trapped single-stranded linear DNAs from calf-thymus allowing to extract their activation energy for unimolecular dissociation. We show that single-pass CDMS is a direct, efficient and accurate MS-based approach to determine the composition of calf-thymus DNAs. Furthermore, ion trap CDMS allows us to evaluate the stability (both under multiphoton IR irradiation and in the course of sonication by irradiating ultrasonic wave) of calf-thymus DNAs. This article is protected by copyright. All rights reserved.

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.

Solid phase sequencing of biopolymers

DOEpatents

Cantor, Charles; Koster, Hubert

2010-09-28

This invention relates to methods for detecting and sequencing target nucleic acid sequences, to mass modified nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probes comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Nucleic acids whose sequences can be determined include DNA or RNA in biological samples such as patient biopsies and environmental samples. Probes may be fixed to a solid support such as a hybridization chip to facilitate automated molecular weight analysis and identification of the target sequence.

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.

The colligative properties of fruit juices by photopyroelectric calorimetry

NASA Astrophysics Data System (ADS)

Frandas, A.; Surducan, V.; Nagy, G.; Bicanic, D.

1999-03-01

The photopyroelectric method was used to study the depression of freezing point in juices prepared from selected apple and orange juice concentrates. By using the models for real solutions, the effective molecular weight of the dissolved solids was obtained. The acids concentration in the fruit juice is reflected both in the equivalent molecular weight (by lowering it) and in the interaction coefficients b and C. Using the data for the molecular weight and the characteristic coefficients, prediction curves for the samples investigated can be used in practice. Freezing point depression can also be used as an indicator of the degree of spoilage of fruit juices.

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 analytical laboratory equipment.

Comparison of microdialysis sampling perfusion fluid components on the foreign body reaction in rat subcutaneous tissue.

PubMed

Keeler, Geoffrey D; Durdik, Jeannine M; Stenken, Julie A

2014-06-16

Microdialysis sampling is a commonly used technique for collecting solutes from the extracellular space of tissues in laboratory animals and humans. Large molecular weight solutes can be collected using high molecular weight cutoff (MWCO) membranes (100kDa or greater). High MWCO membranes require addition of high molecular weight dextrans or albumin to the perfusion fluid to prevent fluid loss via ultrafiltration. While these perfusion fluid additives are commonly used during microdialysis sampling, the tissue response to the loss of these compounds across the membrane is poorly understood. Tissue reactions to implanted microdialysis sampling probes containing different microdialysis perfusion fluids were compared over a 7-day time period in rats. The base perfusion fluid was Ringer's solution supplemented with either bovine serum albumin (BSA), rat serum albumin (RSA), Dextran-70, or Dextran-500. A significant inflammatory response to Dextran-70 was observed. No differences in the tissue response between BSA and RSA were observed. Among these agents, the BSA, RSA, and Dextran-500 produced a significantly reduced inflammatory response compared to the Dextran-70. This work demonstrates that use of Dextran-70 in microdialysis sampling perfusion fluids should be eliminated and replaced with Dextran-500 or other alternatives. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Effect of dark, hard, and vitreous kernel content on protein molecular weight distribution and on milling and breadmaking quality characteristics for hard spring wheat samples from diverse growing regions

USDA-ARS?s Scientific Manuscript database

Kernel vitreousness is an important grading characteristic for segregation of sub-classes of hard red spring (HRS) wheat in the U.S. This research investigated the protein molecular weight distribution (MWD), and flour and baking quality characteristics of different HRS wheat market sub-classes. T...

Compliance Testing of Eielson Air Force Base Central Heating and Power Plant, Coal Fired Boiler Number 3, Eielson Air Force Base, Alaska

DTIC Science & Technology

1988-12-01

a flue gas grab sample for orsat analysis (measures oxygen, and carbon dioxide for stack gas molecular weight determination and emissions correction... molecular weight, was obtained during particulate sampling. Testing was initially started on boiler 2 at the maximum rated steam output of 120,000 lbs/hr...I, r*~td AN[D l FL B( R\\ ViQ( lPjN L!II(,t 1 (d) Open burning of put.rcible iear- i\\ % ~i~ emisions , ec.dirig c dn jc p. c ,f1 pre- cri :rig pair

Pyrolysis responses of kevlar/epoxy composite materials on laser irradiating

NASA Astrophysics Data System (ADS)

Liu, Wei-ping; Wei, Cheng-hua; Zhou, Meng-lian; Ma, Zhi-liang; Song, Ming-ying; Wu, Li-xiong

2017-05-01

The pyrolysis responses of kevlar/epoxy composite materials are valuable to study in a case of high temperature rising rate for its widely application. Distinguishing from the Thermal Gravimetric Analysis method, an apparatus is built to research the pyrolysis responses of kevlar/epoxy composite materials irradiated by laser in order to offer a high temperature rising rate of the sample. By deploying the apparatus, a near real-time gas pressure response can be obtained. The sample mass is weighted before laser irradiating and after an experiment finished. Then, the gas products molecular weight and the sample mass loss evolution are derived. It is found that the pressure and mass of the gas products increase with the laser power if it is less than 240W, while the molecular weight varies inversely. The variation tendency is confusing while the laser power is bigger than 240W. It needs more deeper investigations to bring it to light.

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 eight amino acids or combinations of amino acids) is more uniform in the HMW of the four samples compared to lower-molecular-weight fractions. The greater "compositional stability" of the HMW indicates that it contains a residuum of macromolecules that have not been affected by the diagenetically driven changes observed in lower-molecular-weight fractions.

Improvement of liquid stored boar semen quality by removing low molecular weight proteins and supplementation with α-tocopherol.

PubMed

Zakošek Pipan, M; Mrkun, J; Nemec Svete, A; Zrimšek, P

2017-11-01

Seminal plasma contains low-molecular weight components that can exert a harmful effect on sperm function. We have evaluated the effects of removing low-molecular weight components from seminal plasma and adding α-tocopherol on boar semen quality after 72h of liquid storage. Semen was evaluated on the basis of motility, morphology, acrosome integrity, plasma membrane modifications, mitochondrial activity, DNA fragmentation and lipid peroxidation. Thiobarbituric acid reactive substances (TBARS), 8-isoprostane, and antioxidant status (total antioxidant capacity (TAC) and superoxide dismutase activity (SOD)) were measured in seminal plasma. Removal of low-molecular weight components from seminal plasma, together with the addition of α-tocopherol, kept the lipid peroxidation and mitochondrial activity and DNA fragmentation at the same level as in native semen samples. Dialysing semen and adding 200μM of α-tocopherol led to higher progressive motility, a higher proportion of morphologically normal spermatozoa and a significantly lower level of acrosomal reacted spermatozoa compared to non-dialyzed semen samples after 72h of storage. In conclusion, liquid stored boar semen was better preserved, and oxidative stress in the semen was reduced when semen was dialyzed and α-tocopherol was added prior to storage. Copyright © 2017 Elsevier B.V. All rights reserved.

Recovery of oxygenated ignitable liquids by zeolites, Part I: Novel extraction methodology in fire debris analysis.

PubMed

St Pierre, Kathryne A; Desiderio, Vincent J; Hall, Adam B

2014-07-01

The recovery of low molecular weight oxygenates in fire debris samples is severely compromised by the use of heated passive headspace concentration with an activated charcoal strip, as outlined in ASTM E-1412. The term "oxygenate" is defined herein as a small, polar, organic molecule, such as acetone, methanol, ethanol, or isopropanol, which can be employed as an ignitable liquid and referred to in the ASTM classification scheme as the "oxygenated solvents" class. Although a well accepted technique, the higher affinity of activated carbon strips for heavy molecular weight products over low molecular weight products and hydrocarbons over oxygenated products, it does not allow for efficient recovery of oxygenates such as low molecular weight alcohols and acetone. The objective of this study was to develop and evaluate a novel method for the enhanced recovery of oxygenates from fire debris samples. By optimizing conditions of the heated passive headspace technique, the utilization of zeolites allowed for the successful collection and concentration of oxygenates. The results demonstrated that zeolites increased the recovery of oxygenates by at least 1.5-fold compared to the activated carbon strip and may complement the currently used extraction technique. Copyright © 2014. Published by Elsevier Ireland Ltd.

Nanostructured solid substrates for efficient laser desorption/ionization mass spectrometry (LDI-MS) of low molecular weight compounds.

PubMed

Silina, Yuliya E; Volmer, Dietrich A

2013-12-07

Analytical applications often require rapid measurement of compounds from complex sample mixtures. High-speed mass spectrometry approaches frequently utilize techniques based on direct ionization of the sample by laser irradiation, mostly by means of matrix-assisted laser desorption/ionization (MALDI). Compounds of low molecular weight are difficult to analyze by MALDI, however, because of severe interferences in the low m/z range from the organic matrix used for desorption/ionization. In recent years, surface-assisted laser desorption/ionization (SALDI) techniques have shown promise for small molecule analysis, due to the unique properties of nanostructured surfaces, in particular, the lack of a chemical background in the low m/z range and enhanced production of analyte ions by SALDI. This short review article presents a summary of the most promising recent developments in SALDI materials for MS analysis of low molecular weight analytes, with emphasis on nanostructured materials based on metals and semiconductors.

Cellulose microfibrils grafted with PBA via surface-initiated atom transfer radical polymerization for biocomposite reinforcement.

PubMed

Li, Shuzhao; Xiao, Miaomiao; Zheng, Anna; Xiao, Huining

2011-09-12

Immobilizing poly(butyl acrylate) (PBA) on cellulose microfibrils (CMFs) by atom transfer radical polymerization (ATRP) of butyl acrylate (BA) on the surface of 2-bromoisobutyryl-functionalized CMF generated highly hydrophobic microfibrils (CMF-PBA) with a hard core and a soft-shell structure. TGA and static water contact angle results suggested that the surfaces of the modified CMF samples were not completely covered by PBA chains until the molecular weight of grafts became sufficiently long. The GPC results indicated that the grafts with low molecular weight showed controlled/"living" characteristics of the surface-initiated ATRP; however, there existed more side reactions with the increase in molecular weights. Biocomposites consisting of polypropylene (PP) and CMF-PBA samples exhibited significantly improved compatibility, interface adhesion, and mechanical properties with the increase in PBA graft length. The findings confirmed that the longer grafts facilitated the better entanglement of PBA grafts with PP macromolecules and thus further improved the mechanical properties.

Solid phase sequencing of double-stranded nucleic acids

DOEpatents

Fu, Dong-Jing; Cantor, Charles R.; Koster, Hubert; Smith, Cassandra L.

2002-01-01

This invention relates to methods for detecting and sequencing of target double-stranded nucleic acid sequences, to nucleic acid probes and arrays of probes useful in these methods, and to kits and systems which contain these probes. Useful methods involve hybridizing the nucleic acids or nucleic acids which represent complementary or homologous sequences of the target to an array of nucleic acid probes. These probe comprise a single-stranded portion, an optional double-stranded portion and a variable sequence within the single-stranded portion. The molecular weights of the hybridized nucleic acids of the set can be determined by mass spectroscopy, and the sequence of the target determined from the molecular weights of the fragments. Nucleic acids whose sequences can be determined include nucleic acids in biological samples such as patient biopsies and environmental samples. Probes may be fixed to a solid support such as a hybridization chip to facilitate automated determination of molecular weights and identification of the target sequence.

Cyclodextrin-supported organic matrix for application of MALDI-MS for forensics. Soft-ionization to obtain protonated molecules of low molecular weight compounds

NASA Astrophysics Data System (ADS)

Yonezawa, Tetsu; Asano, Takashi; Fujino, Tatsuya; Nishihara, Hiroshi

2013-06-01

A mass measurement technique for detecting low-molecular-weight drugs with a cyclodextrin-supported organic matrix was investigated. By using cyclodextrin-supported 2,4,6-trihydroxyacetophenone (THAP), the matrix-related peaks of drugs were suppressed. The peaks of protonated molecules of the sample and THAP were mainly observed, and small fragments were detected in a few cases. Despite the Na+ and K+ peaks were observed in the spectrum, Na+ or K+ adduct sample molecules were undetected, owing to the sugar units of cyclodextrin. The advantages of MALDI-MS with cyclodextrin-supported matrices as an analytical tool for forensic samples are discussed. The suppression of alkali adducted molecules and desorption process are also discussed.

The Cuban scorpion Rhopalurus junceus (Scorpiones, Buthidae): component variations in venom samples collected in different geographical areas

PubMed Central

2013-01-01

Backgound The venom of the Cuban scorpion Rhopalurus junceus is poorly study from the point of view of their components at molecular level and the functions associated. The purpose of this article was to conduct a proteomic analysis of venom components from scorpions collected in different geographical areas of the country. Results Venom from the blue scorpion, as it is called, was collected separately from specimens of five distinct Cuban towns (Moa, La Poa, Limonar, El Chote and Farallones) of the Nipe-Sagua-Baracoa mountain massif and fractionated by high performance liquid chromatography (HPLC); the molecular masses of each fraction were ascertained by mass spectrometry analysis. At least 153 different molecular mass components were identified among the five samples analyzed. Molecular masses varied from 466 to 19755 Da. Scorpion HPLC profiles differed among these different geographical locations and the predominant molecular masses of their components. The most evident differences are in the relative concentration of the venom components. The most abundant components presented molecular weights around 4 kDa, known to be K+-channel specific peptides, and 7 kDa, known to be Na+-channel specific peptides, but with small molecular weight differences. Approximately 30 peptides found in venom samples from the different geographical areas are identical, supporting the idea that they all probably belong to the same species, with some interpopulational variations. Differences were also found in the presence of phospholipase, found in venoms from the Poa area (molecular weights on the order of 14 to 19 kDa). The only ubiquitous enzyme identified in the venoms from all five localities studied (hyaluronidase) presented the same 45 kD molecular mass, identified by gel electrophoresis analysis. Conclusions The venom of these scorpions from different geographical areas seem to be similar, and are rich in peptides that have of the same molecular masses of the peptides purified from other scorpions that affect ion-channel functions. PMID:23849540

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 continuity with the current CRS batch. In phase 2, participants also determined molecular weight parameters for the seven different LMM heparin samples using both the 1st IRR (90/686) and its Broad Standard Table and the candidate World Health Organization (WHO) 2nd International Standard (05/112) (2nd IS) using a Broad Standard Table established in phase 1. Mean molecular weights calculated using 2nd IS were slightly higher than with 1st IRR, and participants in the study indicated that this systematic difference precluded establishment of 2nd IS with the table supplied. A replacement Broad Standard Table has been devised on the basis of the central recalculations of raw data supplied by participants; this table gives improved agreement between values derived using the 1st IRR and the candidate 2nd IS. On the basis of this study a recommendation was made for the establishment of 2nd IS and its proposed Broad Standard Table as a replacement for the 1st International Reference Reagent Low Molecular Weight Heparin for Molecular Weight Calibration. Unlike the 1st IRR however, the candidate material 2nd IS is not suitable for use with the method of Nielsen. The candidate materials were established as heparin low-molecular-mass for calibration batches 2 and 3 by the Ph. Eur. Commission in March 2007 and as 2nd IS low-molecular-weight heparin for molecular weight calibration (05/112) by the Expert Committee on Biological Standardization in November 2007.

Organic compounds in radiation fogs in Davis (California)

NASA Astrophysics Data System (ADS)

Herckes, Pierre; Hannigan, Michael P.; Trenary, Laurie; Lee, Taehyoung; Collett, Jeffrey L.

New stainless steel active fogwater collectors were designed and used in Davis (CA, USA) to collect fogwater for the speciation of organic matter. Organic compounds in fog samples were extracted by liquid-liquid extraction and analyzed by gas chromatography coupled to mass spectrometry. Numerous organic compounds, including various alkanes, polycyclic aromatic hydrocarbons (PAH) and alkanoic acids, have been identified in the fogwater samples. Higher molecular weight (MW) compounds are preferentially associated with an insoluble phase inside the fog drops, whereas lower molecular weight and more polar compounds are found predominantly in the dissolved phase. Concentrations in the dissolved phase were sometimes much higher than estimated by the compounds' aqueous solubilities.

Concentration and fractionation of hydrophobic organic acid constituents from natural waters by liquid chromatography

USGS Publications Warehouse

Thurman, E.M.; Malcolm, R.L.

1979-01-01

A scheme is presented which used adsorption chromatography with pH gradient elution and size-exclusion chromatography to concentrate and separate hydrophobic organic acids from water. A review of chromatographic processes involved in the flow scheme is also presented. Organic analytes which appear in each aqueous fraction are quantified by dissolved organic carbon analysis. Hydrophobic organic acids in a water sample are concentrated on a porous acrylic resin. These acids usually constitute approximately 30-50 percent of the dissolved organic carbon in an unpolluted water sample and are eluted with an aqueous eluent (dilute base). The concentrate is then passed through a column of polyacryloylmorpholine gel, which separates the acids into high- and low-molecular-weight fractions. The high- and low-molecular-weight eluates are reconcentrated by adsorption chromatography, then are eluted with a pH gradient into strong acids (predominately carboxylic acids) and weak acids (predominately phenolic compounds). For standard compounds and samples of unpolluted waters, the scheme fractionates humic substances into strong and weak acid fractions that are separated from the low molecular weight acids. A new method utilizing conductivity is also presented to estimate the acidic components in the methanol fraction.

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.

Determination of the linear coefficient of thermal expansion in polymer films at the nanoscale: influence of the composition of EVA copolymers and the molecular weight of PMMA.

PubMed

González-Benito, J; Castillo, E; Cruz-Caldito, J F

2015-07-28

Nanothermal-expansion of poly(ethylene-co-vinylacetate), EVA, and poly(methyl methacrylate), PMMA, in the form of films was measured to finally obtain linear coefficients of thermal expansion, CTEs. The simple deflection of a cantilever in an atomic force microscope, AFM, was used to monitor thermal expansions at the nanoscale. The influences of: (a) the structure of EVA in terms of its composition (vinylacetate content) and (b) the size of PMMA chains in terms of the molecular weight were studied. To carry out this, several polymer samples were used, EVA copolymers with different weight percents of the vinylacetate comonomer (12, 18, 25 and 40%) and PMMA polymers with different weight average molecular weights (33.9, 64.8, 75.600 and 360.0 kg mol(-1)). The dependencies of the vinyl acetate weight fraction of EVA and the molecular weight of PMMA on their corresponding CTEs were analyzed to finally explain them using new, intuitive and very simple models based on the rule of mixtures. In the case of EVA copolymers a simple equation considering the weighted contributions of each comonomer was enough to estimate the final CTE above the glass transition temperature. On the other hand, when the molecular weight dependence is considered the free volume concept was used as novelty. The expansion of PMMA, at least at the nanoscale, was well and easily described by the sum of the weighted contributions of the occupied and free volumes, respectively.

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.

Impact of water extractable arabinoxylan from rye bran on the frozen steamed bread dough quality.

PubMed

Wang, Pei; Tao, Han; Jin, Zhengyu; Xu, Xueming

2016-06-01

Impact of water extractable arabinoxylan from rye bran on frozen steamed bread dough quality was investigated in terms of the bread characteristics, ice crystallization, yeast activity as well as the gluten molecular weight distribution and glutenin macropolymer content in the present study. Results showed that water extractable arabinoxylan significantly improved bread characteristics during the 60-day frozen storage. Less water was crystallized in the water extractable arabinoxylan dough during storage, which could explain the alleviated yeast activity loss. For all the frozen dough samples, more soluble high molecular weight (Mw ≈ 91,000-688,000) and low molecular weight (Mw ≈ 91,000-16,000) proteins were derived from glutenin macropolymer depolymerization. Nevertheless, water extractable arabinoxylan dough developed higher glutenin macropolymer content with lowered level of soluble low molecular weight proteins throughout the storage. This study suggested water extractable arabinoxylan from rye bran had great potential to be served as an effective frozen steamed bread dough improver. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polar organic compounds in pore waters of the Chesapeake Bay impact structure, Eyreville core hole: Character of the dissolved organic carbon and comparison with drilling fluids

USGS Publications Warehouse

Rostad, C.E.; Sanford, W.E.

2009-01-01

Pore waters from the Chesapeake Bay impact structure cores recovered at Eyreville Farm, Northampton County, Virginia, were analyzed to characterize the dissolved organic carbon. After squeezing or centrifuging, a small volume of pore water, 100 ??L, was taken for analysis by electrospray ionization-mass spectrometry. Porewater samples were analyzed directly without filtration or fractionation, in positive and negative mode, for polar organic compounds. Spectra in both modes were dominated by low-molecular-weight ions. Negative mode had clusters of ions differing by -60 daltons, possibly due to increasing concentrations of inorganic salts. The numberaverage molecular weight and weight-average molecular weight values for the pore waters from the Chesapeake Bay impact structure are higher than those reported for other aquatic sources of natural dissolved organic carbon as determined by electrospray ionization-mass spectrometry. In order to address the question of whether drilling mud fluids may have contaminated the pore waters during sample collection, spectra from the pore waters were compared to spectra from drilling mud fluids. Ions indicative of drilling mud fluids were not found in spectra from the pore waters, indicating there was no detectable contamination, and highlighting the usefulness of this analytical technique for detecting potential contamination during sample collection. ?? 2009 The Geological Society of America.

Resolution of molecular weight distributions in slightly pyrolyzed cellulose using the weibull function

Treesearch

A. Broido; Hsiukang Yow

1977-01-01

Even before weight loss in the low-temperature pyrolysis of cellulose becomes significant, the average degree of polymerization of the partially pyrolyzed samples drops sharply. The gel permeation chromatograms of nitrated derivatives of the samples can be described in terms of a small number of mixed size populations—each component fitted within reasonable limits by a...

Solid sorbent air sampling and analytical procedure for methyl-, dimethyl-, ethyl-, and diethylamine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elskamp, C.J.; Schultz, G.R.

1986-01-01

A sampling and analytical procedure for methyl-, dimethyl-, ethyl-, and diethylamine was developed in order to avoid problems typically encountered in the sampling and analysis of low molecular weight aliphatic amines. Samples are collected with adsorbent tubes containing Amberlite XAD-7 resin coated with the derivatizing reagent, NBD chloride (7-chloro-4-nitrobenzo-2-oxa-1,3-diazole). Analysis is performed by high performance liquid chromatography with the use of a fluorescence and/or UV/visible detector. All four amines can be monitored simultaneously, and neither collection nor storage is affected by humidity. Samples are stable at room temperature for at least two weeks. The methodology has been tested for eachmore » of the four amines at sample loadings equivalent to air concentration ranges of 0.5 to 30 ppm for a sample volume of 10 liters. The method shows promise for determining other airborne primary and secondary low molecular weight aliphatic amines.« less

Development of SPE for recovery of polysaccharides and its application to the determination of monosaccharides composition of the polysaccharide sample of a lactobacillus KLB 58.

PubMed

Baik, Yoon Suk; Cheong, Won Jo

2007-07-01

A new SPE cartridge has been prepared in this study to purify polysaccharides of high molecular weights. A porous nonpolar styrene-divinylbenzene copolymer phase (Hamilton PRP-1) was used to make the new cartridge. The cartridge was conditioned with methanol, water, and ACN in sequence, and the sample dissolved in a small amount of water was loaded. Impurities of low molecular weights were removed first by elution of 80:20 or 90:10 v/v% ACN/water, and polysaccharides were quantitatively recovered by elution of 50:50 v/v% ACN/water or pure water. The recovery of pure dextran 10000 was 90-95%. The SPE method was applied to purification of the polysaccharide sample of KLB58, a new lactobacillus discovered in Korea. The purified KLB 58 sample (weight recovery after SPE purification; 60%) was hydrolyzed for analysis of composition of monosaccharides. The hydrolysate was found to be composed primarily of fructose, glucose, galactose, rhamnose, mannose with small amounts of fucose and ribose.

Analysis of a MIL-L-27502 lubricant from a gas-turbine engine test by size-exclusion chromatography

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Morales, W.

1983-01-01

Size exclusion chromatography was used to determine the chemical degradation of MIL-L-27502 oil samples from a gas turbine engine test run at a bulk oil temperature of 216 C. Results revealed a progressive loss of primary ester and additive depletion and the formation of higher molecular weight products with time. The high molecular weight products absorbed strongly in the ultraviolet indicating the presence of chromophoric groups.

Adiponectin isoform patterns in ethnic-specific ADIPOQ mutation carriers: The IRAS Family Study

PubMed Central

Tabb, Keri L.; Gao, Chuan; Hicks, Pamela J.; Hawkins, Gregory A.; Rotter, Jerome I.; da Chen, Yii-Der I; Guo, Xiuqing; Norris, Jill M.; Lorenzo, Carlos; Freedman, Barry I.; Bowden, Donald W.; Palmer, Nicholette D.

2017-01-01

Objective Adiponectin is found in human serum in three groups of multimers (high, medium, and low molecular weight). Previously, we reported two ethnic-specific variants in ADIPOQ, G45R (Hispanic Americans) and R55C (African Americans). Although carriers of both variants had mean adiponectin levels ≤20% of those of non-carriers, they were not clinically different from non-carriers. To compare carriers of both variants and non-carriers, relative quantification of adiponectin isoforms to total adiponectin was performed on serum samples. Methods The multimeric patterns of serum adiponectin in G45R carriers (n=23), R55C carriers (n=3), and Hispanic and African American non-carriers (n=84 and 44, respectively) from the IRAS Family Study were explored using native western blotting and densitometry. Results Serum samples from carriers showed an absence of the high molecular weight (HMW) isoform and a marked reduction in the medium molecular weight isoform but an approximate two-fold increase in the amount of the low molecular weight isoform (LMW). Thus, individuals making only LMW adiponectin are metabolically normal. Conclusions The results contrast with the proposed biological importance of the HMW multimer. This suggests that the LMW isoform may functionally compensate for some of the loss/reduction of the higher-order multimers in carriers of the G45R and R55C mutations. PMID:28643464

Variables controlling the recovery of ignitable liquid residues from simulated fire debris samples using solid-phase microextraction/gas chromatography

NASA Astrophysics Data System (ADS)

Furton, Kenneth G.; Almirall, Jose R.; Wang, Jing

1999-02-01

In this paper, we present data comparing a variety of different conditions for extracting ignitable liquid residues from simulated fire debris samples in order to optimize the conditions for using Solid Phase Microextraction. A simulated accelerant mixture containing 30 components, including those from light petroleum distillates, medium petroleum distillates and heavy petroleum distillates were used to study the important variables controlling Solid Phase Microextraction (SPME) recoveries. SPME is an inexpensive, rapid and sensitive method for the analysis of volatile residues from the headspace over solid debris samples in a container or directly from aqueous samples followed by GC. The relative effects of controllable variables, including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time, have been optimized. The addition of water and ethanol to simulated debris samples in a can was shown to increase the sensitivity when using headspace SPME extraction. The relative enhancement of sensitivity has been compared as a function of the hydrocarbon chain length, sample temperature, time, and added ethanol concentrations. The technique has also been optimized to the extraction of accelerants directly from water added to the fire debris samples. The optimum adsorption time for the low molecular weight components was found to be approximately 25 minutes. The high molecular weight components were found at a higher concentration the longer the fiber was exposed to the headspace (up to 1 hr). The higher molecular weight components were also found in higher concentrations in the headspace when water and/or ethanol was added to the debris.

Comparing molecular composition of dissolved organic matter in soil and stream water: Influence of land use and chemical characteristics.

PubMed

Seifert, Anne-Gret; Roth, Vanessa-Nina; Dittmar, Thorsten; Gleixner, Gerd; Breuer, Lutz; Houska, Tobias; Marxsen, Jürgen

2016-11-15

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) was used to examine the molecular composition of dissolved organic matter (DOM) from soils under different land use regimes and how the DOM composition in the catchment is reflected in adjacent streams. The study was carried out in a small area of the Schwingbach catchment, an anthropogenic-influenced landscape in central Germany. We investigated 30 different soil water samples from 4 sites and different depths (managed meadow (0-5cm, 40-50cm), deciduous forest (0-5cm), mixed-coniferous forest (0-5cm) and agricultural land (0-5cm, 40-50cm)) and 8 stream samples. 6194 molecular formulae and their magnitude-weighted parameters ((O/C)w, (H/C)w, (N/C)w, (AI-mod)w, (DBE/C)w, (DBE/O)w, (DBE-O)w, (C#)w, (MW)w) were used to describe the molecular composition of the samples. The samples can be roughly divided in three groups. Group 1 contains samples from managed meadow 40-50cm and stream water, which are characterized by high saturation compared to samples from group 2 including agricultural samples and samples from the surface meadow (0-5cm), which held more nitrogen containing and aromatic compounds. Samples from both forested sites (group 3) are characterized by higher molecular weight and O/C ratio. Environmental parameters vary between sites and among these parameters pH and nitrate significantly affect chemical composition of DOM. Results indicate that most DOM in streams is of terrestrial origin. However, 120 molecular formulae were detected only in streams and not in any of the soil samples. These compounds share molecular formulae with peptides, unsaturated aliphatics and saturated FA-CHO/FA-CHOX. Compounds only found in soil samples are much more aromatic, have more double bonds and a much lower H/C ratio but higher oxygen content, which indicates the availability of fresh plant material and less microbial processed material compared to stream samples. Copyright © 2016 Elsevier B.V. All rights reserved.

PALS Free Volume Measurements of Fractionated Hydrido- Silsesquioxane Resin.

NASA Astrophysics Data System (ADS)

Madani, Mahmoud M.; Granata, Richard D.; Pernisz, Udo C.

1997-03-01

Hydrido-Silsesquioxane (HSQ) is a resinous polymer with monomer unit formula (HSiO_3/2)_n. For n=8...16, it forms cages which in turn cross-link to yield a resin with a broad molecular weight distribution. It is soluble and forms thin films that may be converted to low-density silica with excellent dielectric properties. These, and the HSQ solubility, depend on molecular structure and size distribution of the cages. Samples of different molecular weight fractions were prepared from HSQ by SCF and the free volume of several cuts was measured by PALS in a conventional fast-fast system. POSITRONFIT and CONTIN programs were used to analyze the spectra. Three separate lifetime regions were identified with free volume regimes that correlate strongly with the molecular weight. The lowest is identified with the monomer cage unit, the larger values with intramolecular separation.

Molecular size and molecular size distribution affecting traditional balsamic vinegar aging.

PubMed

Falcone, Pasquale Massimiliano; Giudici, Paolo

2008-08-27

A first attempt at a semiquantitative study of molecular weight (MW) and molecular weight distribution (MWD) in cooked grape must and traditional balsamic vinegar (TBV) with increasing well-defined age was performed by high-performance liquid size exclusion chromatography (SEC) using dual detection, that is, differential refractive index (DRI) and absorbance (UV-vis) based detectors. With this aim, MW and MWD, including number- and weight-average MW and polydispersity, were determined with respect to a secondary standard and then analyzed. All investigated vinegar samples were recognized as compositionally and structurally heterogeneous blends of copolymers (melanoidins) spreading over a wide range of molecular sizes: the relative MW ranged from 2 to >2000 kDa. The extent of the polymerization reactions was in agreement with the TBV browning kinetics. MWD parameters varied asymptotically toward either upper or lower limits during aging, reflecting a nonequilibrium status of the balance between polymerization and depolymerization reactions in TBV. MWD parameters were proposed as potential aging markers of TBV.

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.

A study of the gamma radiation induced molecular weight changes in poly (phenyl methacrylate), poly (methyl methacrylate) and their copolymers

NASA Astrophysics Data System (ADS)

Hussain, R.; Mohammad, D.

The homopolymers and copolymers of phenyl methacrylate and methyl methacrylate synthesized by free radical polymerization were characterized by infra red and nuclear magnetic resonance spectroscopy. The molecular weight changes produced as a result of gamma irradiation in an argon atmosphere were monitored as a function of dose absorbed by the sample. The radiation induced effects have been discussed in terms of G(Scission), energy absorbed per break and number of bonds broken per gram in a polymer sample. The results reveal that poly (phenyl methacrylate) is more stable than poly (methyl methacrylate) while, the radiation stability of the copolymers depends upon the concentrations of the respective monomers.

The Influence of Sintering Method on Kaolin-Based Geopolymer Ceramics with Addition of Ultra High Molecular Weight Polyethylene as Binder

NASA Astrophysics Data System (ADS)

Romisuhani, A.; AlBakri, M. M.; Kamarudin, H.; Andrei, S. V.

2017-11-01

The influence of sintering method on kaolin-based geopolymer ceramics with addition of Ultra High Molecular Weight Polyethylene as binder were studied. Geopolymer were formed at room temperature from kaolin and sodium silicate in a highly alkaline medium, followed by curing and drying at 80 °C. 12 M of sodium hydroxide solution were mixed with sodium silicate at a ratio of 0.24 to form alkaline activator. Powder metallurgy technique were used in order to produce kaolin geopolymer ceramics with addition of Ultra High Molecular Weight Polyethylene. The samples were heated at temperature of 1200 °C with two different sintering method which are conventional method and two-step sintering method. The strength and density were tested.

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.

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.

Effects of molecular weight and cationization agent on the sensitivity of Bi cluster secondary ion mass spectrometry.

PubMed

Fujii, Makiko; Shishido, Rie; Satoh, Takaya; Suzuki, Shigeru; Matsuo, Jiro

2016-07-30

Bi cluster secondary ion mass spectrometry (SIMS) is one of the most promising tools for precise analysis of synthetic polymers. However, the sensitivity in the high-mass region is still insufficient compared with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Accordingly, the effects of metal assistance (cationization agents) were investigated in this study. To investigate the effects caused by varying the ionization agent, three different polyethylene glycol (PEG) samples were prepared, one with an Ag-deposited film, and two others mixed with Ag and Na, respectively. The measurements were performed by using a commercial Bi cluster SIMS and MALDI-TOFMS systems. The mass spectrum obtained with MALDI-TOFMS was used as a reference molecular weight distribution to evaluate the effects of molecular weight and primary ion species (Bi + , Bi 3 + , Bi 3 2 + ) on the sensitivity of Bi cluster SIMS. The intensity of each secondary ion was the highest in Bi 3 2 + irradiation, and the lowest in Bi + irradiation. Regarding the cationization agents, the secondary ion yield was the highest for the sample mixed with Ag, while the degree of decay of sensitivity along with the increase in molecular weight was the smallest for the sample mixed with Na. It was suggested that the cationization mechanism consists of pre-formed ionization and gas-phase ionization processes. The sensitivity of Bi cluster SIMS decreases to approximately one-fiftieth in every 1000 u. These results might help in understanding the mechanism of cationization and further enhancement of secondary ion yields of polymers. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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.

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.

Degradation of chitosan by gamma ray with presence of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Mahmud, Maznah; Naziri, Muhammad Ihsan; Yacob, Norzita; Talip, Norhashidah; Abdullah, Zahid

2014-02-01

The radiation degraded chitosan samples were prepared by swelling the chitosan powder in water and exposed for gamma irradiation. The ratio chitosan to water was 1:6 with the presence of hydrogen peroxide (H2O2), 1%-5%. These chitosan-water mixtures were irradiated at 6kGy, which is the lowest irradiation dose that facility can offered. All samples were purified and proceed with characterization. The molecular weight (MW) study was monitored by size exclusion chromatography-multi angle laser light scattering (SEC-MALLS). Results showed that MW of chitosan reduced as the dose increased. Application of H2O2 enhanced the degradation rate of chitosan even at very low irradiation dose. Homogenous degradation also occurred during treatment with H2O2based on the polydispersity index (PDI) derived from the calculation of weight average molecular weight over number average molecular weight (Mw/Mn). Mechanism of chitosan radiation degradation with and without hydrogen peroxide was also discussed in this paper. Structure of degraded products was characterized with Fourier-transform infrared spectra. The degree of deacetylation (DDA) values of the samples was determined by acid-base titration. Solubility test results showed that, chitosan powder even at low Mw was insoluble in water even at low pH water. Chitosan as well as irradiated chitosan powder are soluble in strong and weak acid solution. Further discussion on behaviours of radiation degraded chitosan will be elaborated more in this paper.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahmud, Maznah; Yacob, Norzita; Talip, Norhashidah

The radiation degraded chitosan samples were prepared by swelling the chitosan powder in water and exposed for gamma irradiation. The ratio chitosan to water was 1:6 with the presence of hydrogen peroxide (H{sub 2}O{sub 2}), 1%–5%. These chitosan-water mixtures were irradiated at 6kGy, which is the lowest irradiation dose that facility can offered. All samples were purified and proceed with characterization. The molecular weight (MW) study was monitored by size exclusion chromatography-multi angle laser light scattering (SEC-MALLS). Results showed that MW of chitosan reduced as the dose increased. Application of H{sub 2}O{sub 2} enhanced the degradation rate of chitosan evenmore » at very low irradiation dose. Homogenous degradation also occurred during treatment with H{sub 2}O{sub 2}based on the polydispersity index (PDI) derived from the calculation of weight average molecular weight over number average molecular weight (Mw/Mn). Mechanism of chitosan radiation degradation with and without hydrogen peroxide was also discussed in this paper. Structure of degraded products was characterized with Fourier-transform infrared spectra. The degree of deacetylation (DDA) values of the samples was determined by acid-base titration. Solubility test results showed that, chitosan powder even at low Mw was insoluble in water even at low pH water. Chitosan as well as irradiated chitosan powder are soluble in strong and weak acid solution. Further discussion on behaviours of radiation degraded chitosan will be elaborated more in this paper.« less

Electrospray-assisted encapsulation of caffeine in alginate microhydrogels.

PubMed

Nikoo, Alireza Mehregan; Kadkhodaee, Rassoul; Ghorani, Behrouz; Razzaq, Hussam; Tucker, Nick

2018-05-02

One of the major challenges with microencapsulation and delivery of low molecular weight bioactive compounds is their diffusional loss during storage and process conditions as well as under gastric conditions. In an attempt to slow down the release rate of core material, electrospray fabricated calcium alginate microhydrogels were coated with low molecular weight and high molecular weight chitosans. Caffeine as a hydrophilic model compound was used due to its several advantages on human behavior especially increasing consciousness. Mathematical modeling of the caffeine release by fitting the data with Korsmeyer-Peppas model showed that Fick's diffusion law could be the prevalent mechanism of the release. Electrostatic interaction between alginate and chitosan (particularly in the presence of 1% low molecular weight chitosan) provided an effective barrier against caffeine release and significantly reduced swelling of particles compared to control samples. The results of this study demonstrated that calcium alginate microhydrogels coated by chitosan could be used for encapsulation of low molecular compounds. However, more complementary research must be done in this field. In addition, electrospray, by producing monodisperse particles, would be as an alternative method for fabrication of microparticles based on natural polymers. Copyright © 2018. Published by Elsevier B.V.

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.

[Search for potential gastric cancer biomarkers using low molecular weight blood plasma proteome profiling by mass spectrometry].

PubMed

Shevchenko, V E; Arnotskaia, N E; Ogorodnikova, E V; Davydov, M M; Ibraev, M A; Turkin, I N; Davydov, M I

2014-01-01

Gastric cancer, one of the most widespread malignant tumors, still lacks reliable serum/plasma biomarkers of its early detection. In this study we have developed, unified, and tested a new methodology for search of gastric cancer biomarkers based on profiling of low molecular weight proteome (LMWP) (1-17 kDa). This approach included three main components: sample pre-fractionation, matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS), data analysis by a bioinformatics software package. Applicability and perspectives of the developed approach for detection of potential gastric cancer markers during LMWP analysis have been demonstrated using 69 plasma samples from patients with gastric cancer (stages I-IV) and 238 control samples. The study revealed peptides/polypeptides, which may be potentially used for detection of this pathology.

Effect of Ambient Temperature on Hydrophobic Recovery Behavior of Silicone Rubber Composites

NASA Astrophysics Data System (ADS)

Peng, Xiangyang; Li, Zijian; Zheng, Feng; Zhang, Ni; Huang, Zhen; Fang, Pengfei

A series of silicone rubber samples with different cyclosiloxanes contents have been successfully prepared, and their hydrophobic recovery behaviors and mechanism were investigated in detail. The gas chromatography-mass spectroscopy technique after Soxhlet extraction was utilized to examine the low molecular weight siloxanes in the sample, SEM was used to observe the surface morphology of the silicone rubber influenced by plasma treatment, and contact angle measurement was applied to probe the hydrophobic recovery of the sample surface after plasma treatment at different storage temperatures. The storage time-dependent contact angle of water can be well fitted by the diffusion model calculated from Fick’s second law. The results imply that the hydrophobic recovery of silicone rubber is related to the diffusion of low molecular weight siloxanes, while larger content or higher temperature can induce faster hydrophobic recovery.

Fractography of poly(methyl methacrylates).

PubMed

Kusy, R P; Turner, D T

1975-07-01

For convenience in clinical manipulation, it is the practice to fabricate PMMA protheses from mixtures of powder and monomer. When the monomer is subsequently polymerized an unusual 2-phase polymeric material results in which grains of PMMA are dispersed in a matrix of the same polymer. The mechanical properties of the 2-phase materials are inferior in certain respects relative to 1-phase polymers. The purpose of the present work is to evaluate the failure of 2-phase materials by microscopical examination of their fracture surfaces. A granular microstructure was clearly distinguishable and a distinction made between materials which fail exclusively by transgranular fracture and others which additionally exhibit intergranular fracture. In order to interpret markings observed on the fracture surfaces of the complex 2-phase systems a study was made of the influence of molecular weight on the fractography of 1-phase PMMA. Molecular weight was reduced by degradation of samples by exposure to gamma-rays. The spacing of periodic rib markings on fracture surfaces was found to decrease with molecular weight and this relationship used to provide an estimate of the molecular weight of polymer in the matrix of 2-phase materials.

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.

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.

Cartilage collagen damage in hip osteoarthritis similar to that seen in knee osteoarthritis; a case-control study of relationship between collagen, glycosaminoglycan and cartilage swelling.

PubMed

Hosseininia, Shahrzad; Lindberg, Lisbeth R; Dahlberg, Leif E

2013-01-09

It remains to be shown whether OA shares molecular similarities between different joints in humans. This study provides evidence for similarities in cartilage molecular damage in osteoarthritic (OA) joints. Articular cartilage from osteoarthritic hip joints were analysed and compared to non-OA controls regarding collagen, glycosaminoglycan and water content. Femoral heads from 16 osteoarthritic (OA) and 20 reference patients were obtained from hip replacement surgery due to OA and femoral neck fracture, respectively. Cartilage histological changes were assessed by Mankin grading and denatured collagen type II immunostaining and cartilage was extracted by α-chymotrypsin. Hydroxyproline and Alcian blue binding assays were used to measure collagen and glycosaminoglycan (GAG) content, respectively. Mankin and immunohistology scores were significantly higher in hip OA samples than in reference samples. Cartilage water content was 6% higher in OA samples than in references. 2.5 times more collagen was extracted from OA than from reference samples. There was a positive association between water content and percentage of extractable collagen pool (ECP) in both groups. The amounts of collagen per wet and dry weights did not differ statistically between OA and reference cartilage. % Extractable collagen was not related to collagen per dry weight in either group. However when collagen was expressed by wet weight there was a negative correlation between % extractable and collagen in OA cartilage. The amount of GAG per wet weight was similar in both groups but the amount of GAG per dry weight was higher in OA samples compared to reference samples, which suggests a capacity for GAG biosynthesis in hip OA cartilage. Neither of the studied parameters was related to age in either group. Increased collagen extractability and water content in human hip cartilage is associated with OA pathology and can be observed at early stages of the degenerative hip OA process. Our results suggest a common degradative pathway of collagen in articular cartilage of different joints. Furthermore, the study suggests that biochemical changes precede more overt OA changes and that chondrocytes may have a capability to compensate molecular loss in the early phase of OA.

Morphological and physical characterization of poly(styrene-isobutylene-styrene) block copolymers and ionomers thereof

NASA Astrophysics Data System (ADS)

Baugh, Daniel Webster, III

Poly(styrene-isobutylene-styrene) block copolymers made by living cationic polymerization using a difunctional initiator and the sequential monomer addition technique were analyzed using curve-resolution software in conjunction with high-resolution GPC. Fractional precipitation and selective solvent extraction were applied to a representative sample in order to confirm the identity of contaminating species. The latter were found to be low molecular weight polystyrene homopolymer, diblock copolymer, and higher molecular weight segmented block copolymers formed by intermolecular electrophilic aromatic substitution linking reactions occurring late in the polymerization of the styrene outer blocks. Solvent-cast films of poly(styrene-isobutylene-styrene) (PS-PIB-PS) block copolymers and block ionomers were analyzed using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Four block copolymer samples with center block molecular weights of 52,000 g/mol and PS volume fractions (o sbPS) ranging from 0.17 to 0.31 were studied. All samples exhibited hexagonally packed cylinders of PS within the PIB matrix. Cylinder spacing was in the range 32 to 36 nm for most samples, while cylinder diameters varied from 14 to 21 nm. Porod analysis of the scattering data indicated the presence of isolated phase mixing and sharp phase boundaries. PS-PIB-PS block copolymers and ionomers therefrom were analyzed using dynamic mechanical analysis (DMA) and tensile testing. The study encompassed five block copolymer samples with similar PIB center blocks with molecular weights of approx52,000 g/mol and PS weight fractions ranging from 0.127 to 0.337. Ionomers were prepared from two of these materials by lightly sulfonating the PS outer blocks. Sulfonation levels varied from 1.7 to 4.7 mol % and the sodium and potassium neutralized forms were compared to the parent block copolymers. Dynamic mechanical analysis (DMA) of the block copolymer films indicated the existence of a third phase attributed to PIB chains near the PS domain interface which experience reduced mobility due to their firm attachment to the hard PS domain. The relative amount of this phase decreased in samples with larger PS blocks, while the temperature of the associated transition increased. Tensile testing showed increased tensile strength but decreased elongation at break with larger PS blocks. DMA of the ionomers indicated improved dynamic modulus at temperatures above 100spcirc$C. Tensile testing of the ionomers indicated slight improvements in tensile strength with little loss in elongation at break. PS-PIB-PS block copolymer ionomer (BCP01, center block molecular weight = 53,000 g/mole; 25.5 wt % polystyrene, 4.7% sulfonation of phenyl units, 100% neutralized with KOH) was compounded with various organic and inorganic acid salts of 2-ethylhexyl-p-dimethyl aminobenzoate (ODAB) to explore the efficacy of these compounds as ionic plasticizers. (Abstract shortened by UMI.)

Contamination of agricultural lands by polycyclic aromatic hydrocarbons (Tver region, Russia)

NASA Astrophysics Data System (ADS)

Zhidkin, Andrey; Koshovskii, Timur; Gennadiev, Alexander

2016-04-01

It is important to study sources and concentrations of polycyclic aromatic hydrocarbons (PAHs) in the agriculture soils within areas without intensive contaminations. Our studied object was soil and snow cover in the taiga zone (Tver region, Russia). A total of 52 surface (0-30 cm) and 31 subsurface (30-50 cm) soil samples, and 13 snow samples were collected in 35 soil pits, located in forest, crop and layland soils. Studied concentrations of the following 11 individual compounds: two-ring compounds (diphenyl and naphthalene homologues); three-ring compounds (fluorene, phenanthrene, anthracene); four-ring compounds (chrysene, pyrene, tetraphene); five-ring compounds (perylene, benzo[a]pyrene); and six-ring compounds (benzo[ghi]perylene). Analyses made by specrtofluorometry method at the temperature of liquid nitrogen. The total concentrations of all PAHs in soil samples ranged from 9 to 770 ng*g-1 with a median of 96 ng*g-1. The sum of high molecular weight PAHs was significantly lower than the sum of low molecular weight PAHs in the studied soils. The phenanthrene concentration was highest and ranged from 1.2 to 720 ng*g-1 (medium 72 ng*g-1). Compared PAHs reserves in snow cover (μg*m-2) with the reserves in topsoil layer (μg*m-2 in the upper 30 cm). Low molecular weight PAHs (fluorene, phenanthrene, diphenyl, naphthalene) reserves in snow was less than 20% from the reserves in the soil surface layer. High molecular weight PAHs (benzo[a]pyrene, chrysene, perylene, pyrene and tetraphene) reserves in snow was about 50-70% from the reserves in soil surface layer. High molecular weight PAHs (benzo[ghi]perylene and anthracene) reserves in snow was more than in topsoil. PAHs vertical distribution in soil profiles was statistically examined. The total concentration of all PAHs decreased with depth in all studied forest soils. In the arable soils was no significant trend in domination of PAHs total concentrations in the plowing and subsoil layers. The ratio of topsoil to subsoil concentrations of PAHs is different for differ congeners. Contents of phenanthrene and fluorene predominantly increase with the depth. Content of high molecular weight PAHs (benzo[a]pyrene, anthracene, tetraphene, perylene and pyrene) predominantly decreased with the depth. Other PAHs congeners have indistinct profile distributions in studied pits. Based on studied results PAHs divided to associations with different concentrations, sources and vertical distribution in soils: a) phenanthrene and fluorine; b) naphthalene, diphenyl; c) pyrene, benzo(a)pyrene, tetraphene, perylene, chrysene; d) anthracene and benzo(ghi)perylene. Research is funded by Russian Science Foundation (Project 14-27-00083).

Chemical characteristics of dissolved organic matter (DOM) in relation to heavy metal concentrations in soil water from boreal peatlands after clear-cut harvesting

NASA Astrophysics Data System (ADS)

Kiikkilä, O.; Nieminen, T.; Starr, M.; Ukonmaanaho, L.

2012-04-01

Boreal peatlands form an important terrestrial carbon reserve and are a major source of dissolved organic matter (DOM) to surface waters, particularly when disturbed through forestry practices such as draining or timber harvesting. Heavy metals show a strong affinity to organic matter and so, along with DOM, heavy metals can be mobilized and transported from the soil to surface waters and sediments where they may become toxic to aquatic organisms and pass up the food chain. The complexation of heavy metals with DOM can be expected to be related and determined by the chemical characteristics of DOM and oxidation/reducing conditions in the peat. We extracted interstitial water from peat samples and determined the concentrations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and Al, Cu, Zn and Fe in various fractions of DOM isolated by adsorption properties (XAD-8 fractionation) and molecular-weight (ultrafiltration). The peat samples were taken from 0-30 and 30-50 cm depth in drained peatland catchments two years after whole-tree or stem-only clear-cut harvesting (Scots pine or Norway spruce) had been carried out. The samples from the upper layer had been subject to alternating saturation/aeration conditions while the deeper layer had been continuously under the water table. The fractionation of DOC and DON according to both adsorption properties and molecular-weight fractions clearly differed between the upper and lower peat layers. While the hydrophobic acid fraction contained proportionally more DOC and DON than the hydrophilic acid fraction in the upper peat layer the results were vice versa in the lower peat layer. High-molecular-weight compounds (> 100 kDa) were proportionally more abundant in the upper and low-molecular-weight compounds (< 1 kDa) in the lower peat layer. These differences are assumed to reflect differences in the aerobic/ anaerobic conditions and degree of decomposition between the two layers. The concentrations of Zn, Al, Fe and DON correlated positively with DOC concentrations whereas the concentration Cu did not correlate with DOC concentrations. Heavy metal concentrations in different molecular-weight fractions indicated that Al, Cu, Zn and Fe were mostly associated with high-molecular-weight compounds and only a small fraction existed as free metal ions in solution. There were no clear differences in the chemical characteristics of DOC or DON or heavy metal concentrations between the two harvesting treatments.

Investigation and reduction of sub-microgram peptide loss using molecular weight cut-off fractionation prior to mass spectrometric analysis

PubMed Central

Cunningham, Robert; Wang, Jingxin; Wellner, Daniel; Li, Lingjun

2013-01-01

This work investigates the suitability of molecular weight cut-off membrane-based centrifugal filter devices (MWCO) for sub-microgram peptide enrichment passing through the membrane by introduction of methanol and a salt modifier. Using a neuropeptide standard, bradykinin, a reduction in sample loss of over two orders of magnitude is demonstrated with and without undigested protein present. Additionally, a bovine serum albumin (BSA) tryptic digestion was investigated and 27 tryptic peptides were identified using MALDI mass spectrometry whereas only two BSA tryptic peptides were identified after MWCO separation using H2O. The protocol presented here enhances recovery from MWCO separation for sub-μg peptide samples. PMID:23019164

Evaporative purification to produce highly monodisperse polymers: Application to polystyrene for n =3 -13 and quantification of Tg from oligomer to polymer

NASA Astrophysics Data System (ADS)

Zhu, S.; Chai, Y.; Forrest, J. A.

2017-07-01

We demonstrate the use of selective thermal evaporation to separate and purify small molecular weight polymers into highly monodisperse polymers over an extended range of polymerization index. By exploiting the calculated dependence of polymer vapor pressure on polymerization index N and temperature T , we can isolate individual components (N -mers) of an initially polydisperse mixture. To demonstrate this ability, we consider polystyrene samples of Mw=600 g/mol and Mw=890 g/mol with narrow molecular weight distributions, as well as a Mw=1200 g/mol sample with a broader distribution. In each case we are able to separate the sample into milligram quantities of many different components. Using this technique, we have been able to isolate N -mers from 3 to 13. We use differential scanning calorimetry to measure the Tg values of these components, and find that the components have the same Tg values independent of the Mw or polydispersity of the sample they originate from. We find that even initially narrow molecular weight distributions have many different components whose Tg values can differ by more than 50 K. Calculations suggest the isolated components have Mw/Mn values less than 1.001 and through a second iteration of the process could become as low as 1.000 003. The measured Tg values for the N -mers as well as large N polymers are well described by a simple relation derived from the Fox equation for the Tg of mixtures.

Investigating the effects of polymer molecular weight and non-solvent content on the phase separation, surface morphology and hydrophobicity of polyvinyl chloride films

NASA Astrophysics Data System (ADS)

Khoryani, Zahra; Seyfi, Javad; Nekoei, Mehdi

2018-01-01

The main aim of this research is to study the effects of polymer molecular weight as well as non-solvent concentration on the phase separation, surface morphology and wettability of polyvinyl chloride (PVC) films. Gel permeation chromatography (GPC) results showed that the Mn of the used PVC grades is 6 × 104, 8.7 × 104 and 1.26 × 105 g/mol. It was found that a proper combination of polymer molecular weight and non-solvent content could result in superhydrophobic and self-cleaning behaviors. Scanning electron microscopy (SEM) results demonstrated that addition of ethanol causes the polymer chains to be severely aggregated at the films' surface forming strand-like structures decorated by nano-scale polymer spheres. The polymer molecular weight was found to affect the degree of porosity which is highly influential on the hydrophobicity of the films. The mechanism of phase separation process was also discussed and it was found that the instantaneous demixing is the dominant mechanism once higher contents of non-solvent were used. However, a delayed demixing mechanism was detected when the lower molecular weight PVC has been used which resulted in a pore-less and dense skin layer. Differential scanning calorimetry was also utilized to study the crystallization and glass transition behavior of samples.

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.

Characteristics of hydrocarbons in sediment core samples from the northern Okinawa Trough.

PubMed

Huang, Xin; Chen, Shuai; Zeng, Zhigang; Pu, Xiaoqiang; Hou, Qinghua

2017-02-15

Sediment core samples from the northern Okinawa Trough (OT) were analyzed to determine abundances and distributions of hydrocarbons by gas chromatography-mass spectrometer (GC-MS). The results show that the n-alkanes in this sediment core conform to a bimodal distribution, and exhibit an odd-to-even predominance of high molecular weights compared to an even-to-odd predominance in low molecular weight n-alkanes with maxima at C 16 and C 18 . The concentrations of bitumen, alkanes and polyaromatic hydrocarbons (PAHs) were higher in samples S10-07 than all others. Three maturity parameters as well as the ratios between parent phenanthrenes (Ps) and methylphenanthrenes (MPs) in samples S10-07 and S10-17 were higher. The distribution and composition of hydrocarbons in sample S10-07 suggest that one, or several, undetected hydrothermal fields may be present in the region of this sediment core. Results also suggest that volcanism may be the main reason for the observed distribution and composition of hydrocarbons in S10-17 sample. Copyright © 2016 Elsevier Ltd. All rights reserved.

Origins and fates of PAHs in the coastal marine environment off San Diego (California)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, E.Y.; Yu, C.C.; Vista, C.L.

1995-12-31

The main inputs of anthropogenic hydrocarbons to the coastal marine environment off San Diego include the Point Lama wastewater outfall (City of San Diego), Tijuana River (crossing the boarder between the US and Mexico) and several storm drains along the coastline and in San Diego Bay, inadvertent spills, and aerial deposition. Samples collected (in January and June 1994) from the Point Loma wastewater effluent, Tijuana River runoff, and microlayer, sediment trap, and surface sediment at several locations adjacent to the Point Loma outfall, entrance of Tijuana River into the ocean, and San Diego Bay (near the San Diego International Airport)more » were analyzed to determine the origins and fates of PAHs in the coastal marine environment. Alkyl homologue distributions (AHDS) for naphthalene indicated a mainly petrogenic origin for low molecular-weight PAHs in the effluent, water column particle, and sediment near the outfall. Parent compound distributions (PCDS) for PAHs with molecular weights 178, 202, 228, 252, 276, and 278 showed combustion-related inputs in the water column particle and sediment, especially for mid to high molecular-weight PAHs. PAHs with molecular weight equal to or higher than 252 were not detected in the effluent. The compositions of PAHs were substantially different in the effluent particulates and filtrates, implying a great deal about the fates of PAHs from the outfall and their bioaccumulation by organisms. PAHs detected in Tijuana River runoff had similar AHDs and PCDs to those of the Point Loma outfall effluent. AHDs in the San Diego Bay sediment exhibited marked seasonal variation; low molecular-weight PAHs were significantly combustion-related in January and more petrogenic in June. Microlayer samples generally contained dominant combustion-generated PAHs. The impact of the wastewater outfall discharge on the nearby water column and sediment appeared compromised by other non-point source inputs.« less

Carbon nanodots as a matrix for the analysis of low-molecular-weight molecules in both positive- and negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and quantification of glucose and uric acid in real samples.

PubMed

Chen, Suming; Zheng, Huzhi; Wang, Jianing; Hou, Jian; He, Qing; Liu, Huihui; Xiong, Caiqiao; Kong, Xianglei; Nie, Zongxiu

2013-07-16

Carbon nanodots were applied for the first time as a new matrix for the analysis of low-molecular-weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) in both positive- and negative-ion modes. A wide range of small molecules including amino acids, peptides, fatty acids, as well as β-agonists and neutral oligosaccharides were analyzed by MALDI MS with carbon nanodots as the matrix, and the lowest 0.2 fmol limits-of-detection were obtained for octadecanoic acid. Clear sodium and potassium adducts and deprotonated signals were produced in positive- and negative-ion modes. Furthermore, the glucose and uric acid in real samples were quantitatively determined by the internal standard method with the linear range of 0.5-9 mM and 0.1-1.8 mM (R(2) > 0.999), respectively. This work gives new insight into the application of carbon nanodots and provides a general approach for rapid analysis of low-molecular-weight compounds.

Removal of humic acid using TiO2 photocatalytic process--fractionation and molecular weight characterisation studies.

PubMed

Liu, Sanly; Lim, May; Fabris, Rolando; Chow, Christopher; Chiang, Ken; Drikas, Mary; Amal, Rose

2008-05-01

The photocatalytic removal of humic acid (HA) using TiO2 under UVA irradiation was examined by monitoring changes in the UV(254) absorbance, dissolved organic carbon (DOC) concentration, apparent molecular weight distribution, and trihalomethane formation potentials (THMFPs) over treatment time. A resin fractionation technique in which the samples were fractionated into four components: very hydrophobic acids (VHA), slightly hydrophobic acids, hydrophilic charged (CHA) and hydrophilic neutral (NEU) was also employed to elucidate the changes in the chemical nature of the HA components during treatment. The UVA/TiO2 process was found to be effective in removing more than 80% DOC and 90% UV(254) absorbance. The THMFPs of samples were decreased to below 20 microg l(-1) after treatments, which demonstrate the potential to meet increasingly stringent regulatory level of trihalomethanes in water. Resin fractionation analysis showed that the VHA fraction was decreased considerably as a result of photocatalytic treatments, forming CHA intermediates which were further degraded with increased irradiation time. The NEU fraction, which comprised of non-UV-absorbing low molecular weight compounds, was found to be the most persistent component.

Organic secondary ion mass spectrometry: sensitivity enhancement by gold deposition.

PubMed

Delcorte, A; Médard, N; Bertrand, P

2002-10-01

Hydrocarbon oligomers, high-molecular-weight polymers, and polymer additives have been covered with 2-60 nmol of gold/cm2 in order to enhance the ionization efficiency for static secondary ion mass spectrometry (s-SIMS) measurements. Au-cationized molecules (up to -3,000 Da) and fragments (up to the trimer) are observed in the positive mass spectra of metallized polystyrene (PS) oligomer films. Beyond 3,000 Da, the entanglement of polymer chains prevents the ejection of intact molecules from a "thick" organic film. This mass limit can be overcome by embedding the polymer chains in a low-molecular-weight matix. The diffusion of organic molecules over the metal surfaces is also demonstrated for short PS oligomers. In the case of high-molecular-weight polymers (polyethylene, polypropylene, PS) and polymer additives (Irganox 1010, Irgafos 168), the metallization procedure induces a dramatic increase of the fingerprint fragment ion yields as well as the formation of new Aucationized species that can be used for chemical diagnostics. In comparison with the deposition of submonolayers of organic molecules on metallic surfaces, metal evaporation onto organic samples provides a comparable sensitivity enhancement. The distinct advantage of the metal evaporation procedure is that it can be used for any kind of organic sample, irrespective of thickness, opening new perspectives for "real world" sample analysis and chemical imaging by s-SIMS.

Comparison of Methods for Determining the Mechanical Properties of Semiconducting Polymer Films for Stretchable Electronics.

PubMed

Rodriquez, Daniel; Kim, Jae-Han; Root, Samuel E; Fei, Zhuping; Boufflet, Pierre; Heeney, Martin; Kim, Taek-Soo; Lipomi, Darren J

2017-03-15

This paper describes a comparison of two characterization techniques for determining the mechanical properties of thin-film organic semiconductors for applications in soft electronics. In the first method, the film is supported by water (film-on-water, FOW), and a stress-strain curve is obtained using a direct tensile test. In the second method, the film is supported by an elastomer (film-on-elastomer, FOE), and is subjected to three tests to reconstruct the key features of the stress-strain curve: the buckling test (tensile modulus), the onset of buckling (yield point), and the crack-onset strain (strain at fracture). The specimens used for the comparison are four poly(3-hexylthiophene) (P3HT) samples of increasing molecular weight (M n = 15, 40, 63, and 80 kDa). The methods produced qualitatively similar results for mechanical properties including the tensile modulus, the yield point, and the strain at fracture. The agreement was not quantitative because of differences in mode of loading (tension vs compression), strain rate, and processing between the two methods. Experimental results are corroborated by coarse-grained molecular dynamics simulations, which lead to the conclusion that in low molecular weight samples (M n = 15 kDa), fracture occurs by chain pullout. Conversely, in high molecular weight samples (M n > 25 kDa), entanglements concentrate the stress to few chains; this concentration is consistent with chain scission as the dominant mode of fracture. Our results provide a basis for comparing mechanical properties that have been measured by these two techniques, and provide mechanistic insight into fracture modes in this class of materials.

Near-monodisperse sodium polymethacrylates: characterization by linear salt gradient anion-exchange chromatography

PubMed

Freydank; Krasia; Tiddy; Patrickios

2000-05-01

A family of six near-monodisperse homopolymers of sodium methacrylate (Mn = 1100, 3200, 5500, 7200, 14100, and 21000) is characterized by linear salt gradient anion-exchange chromatography. Although the retention times depend on the initial and final salt concentrations of the gradient, they are almost independent of the molecular weight of poly(sodium methacrylate). This suggests that anion-exchange chromatography is incapable of resolving mixtures of a given polyelectrolyte to their components of various molecular weights, and it is therefore impossible to identify the polydispersity of such a sample using this method. The independence of the retention times from molecular weight is also predicted by a theory based on stoichiometric mass-action ion-exchange. Using this theory and our experimental retention times, the equilibrium anion-exchange constant and the corresponding Gibbs free energy of anion-exchange of the monomer repeat unit are calculated to be around 2.1 and -1.8 kJ/mol, respectively.

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.

Characterization and antioxidant activities of polysaccharides from thirteen boletus mushrooms.

PubMed

Zhang, Lan; Hu, Yu; Duan, Xiaoyu; Tang, Tingting; Shen, Yingbin; Hu, Bin; Liu, Aiping; Chen, Hong; Li, Cheng; Liu, Yuntao

2018-07-01

Water-soluble polysaccharides were extracted from the caps and stipes of thirteen boletus mushrooms representing five different species collected in Southwest China. Investigations of their structures and antioxidant activities allowed an evaluation of structure-function relationships. The polysaccharides were composed mainly of the monosaccharides arabinose, xylose, mannose, glucose and galactose. Most samples displayed a broad molecular weight range, with significant differences observed between the molecular weight ranges of the polysaccharides from the caps and the stipes. FT-IR spectral analysis of the polysaccharides revealed that most of polysaccharides from boletus mushrooms (except Boletus edulis) contained a pyranose ring. The antioxidant activities of the polysaccharides in stipes showed a significant correlation with their monosaccharide composition, and were also related to their molecular weight and anomeric configuration. Suillellus luridus collected in Pingwu, Mianyang, Sichuan, China had remarkably superior antioxidant activity and might be developed as a natural antioxidant. Copyright © 2018 Elsevier B.V. All rights reserved.

Characterization of Natural Organic Matter in Conventional Water Treatment Processes and Evaluation of THM Formation with Chlorine

PubMed Central

Özdemır, Kadir

2014-01-01

This study investigates the fractions of natural organic matter (NOM) and trihalomethane (THM) formation after chlorination in samples of raw water and the outputs from ozonation, coagulation-flocculation, and conventional filtration treatment units. All the water samples are passed through various ultrafiltration (UF) membranes. UF membranes with different molecular size ranges based on apparent molecular weight (AMW), such as 1000, 3000, 10,000, and 30,000 Daltons (Da), are commonly used. The NOM fraction with AMW < 1000 Da (1 K) is the dominant fraction within all the fractionated water samples. Its maximum percentage is 85.86% after the filtration process and the minimum percentage is 65.01% in raw water samples. The total THM (TTHM) yield coefficients range from 22.5 to 42 μg-TTHM/mg-DOC in all fractionated samples, which is related to their specific ultraviolet Absorbance (SUVA) levels. As the molecular weight of the fractions decreased, the TTHM yield coefficients increased. The NOM fractions with AMW values less than 1 K had lower SUVA values (<3 L/mg·m) for all treatment stages and also they had higher yield of TTHM per unit of DOC. The NOM fraction with AMW < 1 K for chlorinated raw water samples has the highest yield coefficient (42 μg-TTHM/mg-DOC). PMID:24558323

GlycCompSoft: Software for Automated Comparison of Low Molecular Weight Heparins Using Top-Down LC/MS Data

PubMed Central

Li, Lingyun; Zhang, Fuming; Hu, Min; Ren, Fuji; Chi, Lianli; Linhardt, Robert J.

2016-01-01

Low molecular weight heparins are complex polycomponent drugs that have recently become amenable to top-down analysis using liquid chromatography-mass spectrometry. Even using open source deconvolution software, DeconTools, and automatic structural assignment software, GlycReSoft, the comparison of two or more low molecular weight heparins is extremely time-consuming, taking about a week for an expert analyst and provides no guarantee of accuracy. Efficient data processing tools are required to improve analysis. This study uses the programming language of Microsoft Excel™ Visual Basic for Applications to extend its standard functionality for macro functions and specific mathematical modules for mass spectrometric data processing. The program developed enables the comparison of top-down analytical glycomics data on two or more low molecular weight heparins. The current study describes a new program, GlycCompSoft, which has a low error rate with good time efficiency in the automatic processing of large data sets. The experimental results based on three lots of Lovenox®, Clexane® and three generic enoxaparin samples show that the run time of GlycCompSoft decreases from 11 to 2 seconds when the data processed decreases from 18000 to 1500 rows. PMID:27942011

Unbiased Rare Event Sampling in Spatial Stochastic Systems Biology Models Using a Weighted Ensemble of Trajectories

PubMed Central

Donovan, Rory M.; Tapia, Jose-Juan; Sullivan, Devin P.; Faeder, James R.; Murphy, Robert F.; Dittrich, Markus; Zuckerman, Daniel M.

2016-01-01

The long-term goal of connecting scales in biological simulation can be facilitated by scale-agnostic methods. We demonstrate that the weighted ensemble (WE) strategy, initially developed for molecular simulations, applies effectively to spatially resolved cell-scale simulations. The WE approach runs an ensemble of parallel trajectories with assigned weights and uses a statistical resampling strategy of replicating and pruning trajectories to focus computational effort on difficult-to-sample regions. The method can also generate unbiased estimates of non-equilibrium and equilibrium observables, sometimes with significantly less aggregate computing time than would be possible using standard parallelization. Here, we use WE to orchestrate particle-based kinetic Monte Carlo simulations, which include spatial geometry (e.g., of organelles, plasma membrane) and biochemical interactions among mobile molecular species. We study a series of models exhibiting spatial, temporal and biochemical complexity and show that although WE has important limitations, it can achieve performance significantly exceeding standard parallel simulation—by orders of magnitude for some observables. PMID:26845334

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

NASA Astrophysics Data System (ADS)

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu; Boone, Eric; Chu, Rosalie K.; Dukett, James E.; Gunsch, Matthew J.; Zhang, Wuliang; Tolic, Nikola; Laskin, Alexander; Pratt, Kerri A.

2017-12-01

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds. Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.

Selectivity and limitations of carbon sorption tubes for capturing siloxanes in biogas during field sampling.

PubMed

Tansel, Berrin; Surita, Sharon C

2016-06-01

Siloxane levels in biogas can jeopardize the warranties of the engines used at the biogas to energy facilities. The chemical structure of siloxanes consists of silicon and oxygen atoms, alternating in position, with hydrocarbon groups attached to the silicon side chain. Siloxanes can be either in cyclic (D) or linear (L) configuration and referred with a letter corresponding to their structure followed by a number corresponding to the number of silicon atoms present. When siloxanes are burned, the hydrocarbon fraction is lost and silicon is converted to silicates. The purpose of this study was to evaluate the adequacy of activated carbon gas samplers for quantitative analysis of siloxanes in biogas samples. Biogas samples were collected from a landfill and an anaerobic digester using multiple carbon sorbent tubes assembled in series. One set of samples was collected for 30min (sampling 6-L gas), and the second set was collected for 60min (sampling 12-L gas). Carbon particles were thermally desorbed and analyzed by Gas Chromatography Mass Spectrometry (GC/MS). The results showed that biogas sampling using a single tube would not adequately capture octamethyltrisiloxane (L3), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). Even with 4 tubes were used in series, D5 was not captured effectively. The single sorbent tube sampling method was adequate only for capturing trimethylsilanol (TMS) and hexamethyldisiloxane (L2). Affinity of siloxanes for activated carbon decreased with increasing molecular weight. Using multiple carbon sorbent tubes in series can be an appropriate method for developing a standard procedure for determining siloxane levels for low molecular weight siloxanes (up to D3). Appropriate quality assurance and quality control procedures should be developed for adequately quantifying the levels of the higher molecular weight siloxanes in biogas with sorbent tubes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Impact of casein gel microstructure on self-diffusion coefficient of molecular probes measured by 1H PFG-NMR.

PubMed

Le Feunteun, Steven; Mariette, François

2007-12-26

The translational dynamics of poly(ethylene glycol) (PEG) polymers with molecular weights (Mw) varying from 6x10(2) to 5x10(5) were investigated by pulsed field gradient NMR in casein suspensions and in gels induced by acidification, enzyme action, and a combination of both. For molecules with Mwor=8000, there was strong dependence of diffusion on PEG size and on the casein network structure as revealed by scanning electron microscopy images. The diffusion coefficients of the two largest PEGs were increased after coagulation by amounts that depended on the internal structure of the gel. In addition, the 527,000 g/mol PEG was found to deviate from Gaussian diffusion behavior to greater or lesser extents according to the casein concentration and the sample microstructure. The results are discussed in terms of network rearrangements.

Poly(styrene-co-butadiene) random copolymer thin films and nanostructures on a mica surface: morphology and contact angles of nanodroplets.

PubMed

McClements, Jake; Buffone, Cosimo; Shaver, Michael P; Sefiane, Khellil; Koutsos, Vasileios

2017-09-20

The self-assembly of poly(styrene-co-butadiene) random copolymers on mica surfaces was studied by varying solution concentrations and polymer molecular weights. Toluene solutions of the poly(styrene-co-butadiene) samples were spin coated onto a mica surface and the resulting polymer morphology was investigated by atomic force microscopy. At higher concentrations, thin films formed with varying thicknesses; some dewetting was observed which depended on the molecular weight. Total dewetting did not occur despite the polymer's low glass transition temperature. Instead, partial dewetting was observed suggesting that the polymer was in a metastable equilibrium state. At lower concentrations, spherical cap shaped nanodroplets formed with varying sizes from single polymer chains to aggregates containing millions of chains. As the molecular weight was increased, fewer aggregates were observed on the surface, albeit with larger sizes resulting from increased solution viscosities and more chain entanglements at higher molecular weights. The contact angles of the nanodroplets were shown to be size dependent. A minimum contact angle occurs for droplets with radii of 100-250 nm at each molecular weight. Droplets smaller than 100 nm showed a sharp increase in contact angle; attributed to an increase in the elastic modulus of the droplets, in addition, to a positive line tension value. Droplets larger than 250 nm also showed an increased contact angle due to surface heterogeneities which cannot be avoided for larger droplets. This increase in contact angle plateaus as the droplet size reaches the macroscopic scale.

Improved radiocarbon dating for contaminated archaeological bone collagen, silk, wool and hair samples via cross-flow nanofiltrated amino acids.

PubMed

Boudin, Mathieu; Boeckx, Pascal; Vandenabeele, Peter; Van Strydonck, Mark

2013-09-30

Radiocarbon dating and stable isotope analyses of bone collagen, wool, hair and silk contaminated with extraneous carbon (e.g. humic substances) does not yield reliable results if these materials are pre-treated using conventional methods. A cross-flow nanofiltration method was developed that can be applied to various protein materials like collagen, hair, silk, wool and leather, and should be able to remove low-molecular and high-molecular weight contaminants. To avoid extraneous carbon contamination via the filter a ceramic filter (molecular weight cut-off of 200 Da) was used. The amino acids, released by hot acid hydrolysis of the protein material, were collected in the permeate and contaminants in the retentate (>200 Da). (14)C-dating results for various contaminated archaeological samples were compared for bulk material (pre-treated with the conventional methods) and for cross-flow nanofiltrated amino acids (permeate) originating from the same samples. Contamination and quality control of (14)C dates of bulk and permeate samples were obtained by measuring C:N ratios, fluorescence spectra, and δ(13)C and δ(15)N values of the samples. Cross-flow nanofiltration decreases the C:N ratio which means that contaminants have been removed. Cross-flow nanofiltration clearly improved sample quality and (14)C results. It is a quick and non-labor-intensive technique and can easily be implemented in any (14)C and stable isotope laboratory for routine sample pre-treatment analyses. Copyright © 2013 John Wiley & Sons, Ltd.

Solvent-based and solvent-free characterization of low solubility and low molecular weight polyamides by mass spectrometry: a complementary approach.

PubMed

Barrère, Caroline; Hubert-Roux, Marie; Lange, Catherine M; Rejaibi, Majed; Kebir, Nasreddine; Désilles, Nicolas; Lecamp, Laurence; Burel, Fabrice; Loutelier-Bourhis, Corinne

2012-06-15

Polyamides (PA) belong to the most used classes of polymers because of their attractive chemical and mechanical properties. In order to monitor original PA design, it is essential to develop analytical methods for the characterization of these compounds that are mostly insoluble in usual solvents. A low molecular weight polyamide (PA11), synthesized with a chain limiter, has been used as a model compound and characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the solvent-based approach, specific solvents for PA, i.e. trifluoroacetic acid (TFA) and hexafluoroisopropanol (HFIP), were tested. Solvent-based sample preparation methods, dried-droplet and thin layer, were optimized through the choice of matrix and salt. Solvent-based (thin layer) and solvent-free methods were then compared for this low solubility polymer. Ultra-high-performance liquid chromatography/electrospray ionization (UHPLC/ESI)-TOF-MS analyses were then used to confirm elemental compositions through accurate mass measurement. Sodium iodide (NaI) and 2,5-dihydroxybenzoic acid (2,5-DHB) are, respectively, the best cationizing agent and matrix. The dried-droplet sample preparation method led to inhomogeneous deposits, but the thin-layer method could overcome this problem. Moreover, the solvent-free approach was the easiest and safest sample preparation method giving equivalent results to solvent-based methods. Linear as well as cyclic oligomers were observed. Although the PA molecular weights obtained by MALDI-TOF-MS were lower than those obtained by (1)H NMR and acido-basic titration, this technique allowed us to determine the presence of cyclic and linear species, not differentiated by the other techniques. TFA was shown to induce modification of linear oligomers that permitted cyclic and linear oligomers to be clearly highlighted in spectra. Optimal sample preparation conditions were determined for the MALDI-TOF-MS analysis of PA11, a model of polyamide analogues. The advantages of the solvent-free and solvent-based approaches were shown. Molecular weight determination using MALDI was discussed. Copyright © 2012 John Wiley & Sons, Ltd.

Monitoring of occupational and environmental aeroallergens-- EAACI Position Paper. Concerted action of the EAACI IG Occupational Allergy and Aerobiology & Air Pollution.

PubMed

Raulf, M; Buters, J; Chapman, M; Cecchi, L; de Blay, F; Doekes, G; Eduard, W; Heederik, D; Jeebhay, M F; Kespohl, S; Krop, E; Moscato, G; Pala, G; Quirce, S; Sander, I; Schlünssen, V; Sigsgaard, T; Walusiak-Skorupa, J; Wiszniewska, M; Wouters, I M; Annesi-Maesano, I

2014-10-01

Exposure to high molecular weight sensitizers of biological origin is an important risk factor for the development of asthma and rhinitis. Most of the causal allergens have been defined based on their reactivity with IgE antibodies, and in many cases, the molecular structure and function of the allergens have been established. Significant information on allergen levels that cause sensitization and allergic symptoms for several major environmental and occupational allergens has been reported. Monitoring of high molecular weight allergens and allergen carrier particles is an important part of the management of allergic respiratory diseases and requires standardized allergen assessment methods for occupational and environmental (indoor and outdoor) allergen exposure. The aim of this EAACI task force was to review the essential points for monitoring environmental and occupational allergen exposure including sampling strategies and methods, processing of dust samples, allergen analysis, and quantification. The paper includes a summary of different methods for sampling and allergen quantification, as well as their pros and cons for various exposure settings. Recommendations are being made for different exposure scenarios. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Determination of molecular mass values of chondroitin sulfates by fluorophore-assisted carbohydrate electrophoresis (FACE).

PubMed

Buzzega, Dania; Maccari, Francesca; Volpi, Nicola

2010-03-11

Fluorophore-assisted carbohydrate electrophoresis (FACE) was applied to determine the molecular mass (M) values of various chondroitin sulfate (CS) samples. After labeling with 8-aminonaphthalene-1,3,6-trisulfonic acid (ANTS), FACE was able to resolve each CS sample as a discrete band depending on the M value. After densitometric acquisition, the migration distance of each CS standard was acquired and the third grade polynomial calibration standard curve was determined by plotting the logarithms of the M values as a function of migration ratio. Purified CS samples of different origin and the European Pharmacopeia CS standard 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 (M(p)), the number-average M(n), weight-average M(w), and polydispersity (M(w)/M(n)) were examined by both techniques and found to be quite similar. This study demonstrates that FACE analysis is a suitable, sensitive and simple method for the determination of the M values of CS macromolecules with possible utilization in virtually any kind of research and development such as quality control laboratories. Copyright 2009 Elsevier B.V. All rights reserved.

Optimizing of MALDI-ToF-based low-molecular-weight serum proteome pattern analysis in detection of breast cancer patients; the effect of albumin removal on classification performance.

PubMed

Pietrowska, M; Marczak, L; Polanska, J; Nowicka, E; Behrent, K; Tarnawski, R; Stobiecki, M; Polanski, A; Widlak, P

2010-01-01

Mass spectrometry-based analysis of the serum proteome allows identifying multi-peptide patterns/signatures specific for blood of cancer patients, thus having high potential value for cancer diagnostics. However, because of problems with optimization and standardization of experimental and computational design, none of identified proteome patterns/signatures was approved for diagnostics in clinical practice as yet. Here we compared two methods of serum sample preparation for mass spectrometry-based proteome pattern analysis aimed to identify biomarkers that could be used in early detection of breast cancer patients. Blood samples were collected in a group of 92 patients diagnosed at early (I and II) stages of the disease before the start of therapy, and in a group of age-matched healthy controls (104 women). Serum specimens were purified and analyzed using MALDI-ToF spectrometry, either directly or after membrane filtration (50 kDa cut-off) to remove albumin and other large serum proteins. Mass spectra of the low-molecular-weight fraction (2-10 kDa) of the serum proteome were resolved using the Gaussian mixture decomposition, and identified spectral components were used to build classifiers that differentiated samples from breast cancer patients and healthy persons. Mass spectra of complete serum and membrane-filtered albumin-depleted samples have apparently different structure and peaks specific for both types of samples could be identified. The optimal classifier built for the complete serum specimens consisted of 8 spectral components, and had 81% specificity and 72% sensitivity, while that built for the membrane-filtered samples consisted of 4 components, and had 80% specificity and 81% sensitivity. We concluded that pre-processing of samples to remove albumin might be recommended before MALDI-ToF mass spectrometric analysis of the low-molecular-weight components of human serum Keywords: albumin removal; breast cancer; clinical proteomics; mass spectrometry; pattern analysis; serum proteome.

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.

Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

NASA Astrophysics Data System (ADS)

He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

2014-03-01

With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

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.

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.

Detection of Ketones by a Novel Technology: Dipolar Proton Transfer Reaction Mass Spectrometry (DP-PTR-MS)

NASA Astrophysics Data System (ADS)

Pan, Yue; Zhang, Qiangling; Zhou, Wenzhao; Zou, Xue; Wang, Hongmei; Huang, Chaoqun; Shen, Chengyin; Chu, Yannan

2017-05-01

Proton transfer reaction mass spectrometry (PTR-MS) has played an important role in the field of real-time monitoring of trace volatile organic compounds (VOCs) due to its advantages such as low limit of detection (LOD) and fast time response. Recently, a new technology of proton extraction reaction mass spectrometry (PER-MS) with negative ions OH- as the reagent ions has also been presented, which can be applied to the detection of VOCs and even inorganic compounds. In this work, we combined the functions of PTR-MS and PER-MS in one instrument, thereby developing a novel technology called dipolar proton transfer reaction mass spectrometry (DP-PTR-MS). The selection of PTR-MS mode and PER-MS mode was achieved in DP-PTR-MS using only water vapor in the ion source and switching the polarity. In this experiment, ketones (denoted by M) were selected as analytes. The ketone (molecular weight denoted by m) was ionized as protonated ketone [M + H]+ [mass-to-charge ratio ( m/z) m + 1] in PTR-MS mode and deprotonated ketone [M - H]- ( m/z m - 1) in PER-MS mode. By comparing the m/z value of the product ions in the two modes, the molecular weight of the ketone can be positively identified as m. Results showed that whether it is a single ketone sample or a mixed sample of eight kinds of ketones, the molecular weights can be detected with DP-PTR-MS. The newly developed DP-PTR-MS not only maintains the original advantages of PTR-MS and PER-MS in sensitive and rapid detection of ketones, but also can estimate molecular weight of ketones.

Proteomics in Diagnostic Pathology

PubMed Central

Chaurand, Pierre; Sanders, Melinda E.; Jensen, Roy A.; Caprioli, Richard M.

2004-01-01

Direct tissue profiling and imaging mass spectrometry (MS) provide a molecular assessment of numerous expressed proteins within a tissue sample. MALDI MS (matrix-assisted laser desorption ionization) analysis of thin tissue sections results in the visualization of 500 to 1000 individual protein signals in the molecular weight range from 2000 to over 200,000. These signals directly correlate with protein distribution within a specific region of the tissue sample. The systematic investigation of the section allows the construction of ion density maps, or specific molecular images, for virtually every signal detected in the analysis. Ultimately, hundreds of images, each at a specific molecular weight, may be obtained. To date, profiling and imaging MS has been applied to multiple diseased tissues, including human non-small cell lung tumors, gliomas, and breast tumors. Interrogation of the resulting complex MS data sets using modern biocomputational tools has resulted in identification of both disease-state and patient-prognosis specific protein patterns. These studies suggest that such proteomic information will become more and more important in assessing disease progression, prognosis, and drug efficacy. Molecular histology has been known for some time and its value clear in the field of pathology. Imaging mass spectrometry brings a new dimension of molecular data, one focusing on the disease phenotype. The present article reviews the state of the art of the technology and its complementarity with traditional histopathological analyses. PMID:15466373

Puget Sound Dredged Disposal Analysis: Management Plan Assessment Report. Dredged Material Management Year 1990.

DTIC Science & Technology

1991-03-01

Sulfides BT Bioaccumulation Trigger L LP Ccn tract Laboratory Methods COC Chemical of Concern Corps U.S. Army Corps of Engineers cm centimeter cy cubic... Hydrocarbon (Compound) LOD Limit of Detection LPAH Low Molecular Weight Polynuclear Aromatic Hydrocarbon (Compound) MCLP Modified Contract Laboratory Method...Aromatic Hydrocarbons (HPAHs) (8 samples); * Benzofluoranthenes (7 samples); * Anthracene (6 samples); * Benzo(a)anthracene (6 samples); * Dibenzo(a,h

Leaching of polycyclic aromatic hydrocarbons from oil shale processing waste deposit: a long-term field study.

PubMed

Jefimova, Jekaterina; Irha, Natalya; Reinik, Janek; Kirso, Uuve; Steinnes, Eiliv

2014-05-15

The leaching behavior of selected polycyclic aromatic hydrocarbons (PAHs) from an oil shale processing waste deposit was monitored during 2005-2009. Samples were collected from the deposit using a special device for leachate sampling at field conditions without disturbance of the upper layers. Contents of 16 priority PAHs in leachate samples collected from aged and fresh parts of the deposit were determined by GC-MS. The sum of the detected PAHs in leachates varied significantly throughout the study period: 19-315 μg/l from aged spent shale, and 36-151 μg/l from fresh spent shale. Among the studied PAHs the low-molecular weight compounds phenanthrene, naphthalene, acenaphthylene, and anthracene predominated. Among the high-molecular weight PAHs benzo[a]anthracene and pyrene leached in the highest concentrations. A spent shale deposit is a source of PAHs that could infiltrate into the surrounding environment for a long period of time. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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

Identification of Weak Acids and Bases by Titration with Primary Standards. A Modern Version of an Old Analytical Chemistry Experiment.

ERIC Educational Resources Information Center

Thompson, Robert Q.

1988-01-01

Describes a laboratory exercise in which acid dissociation constants and molecular weights are extracted from sample data and the sample is identified. Emphasizes accurate volumetric work while bringing to practice the concepts of acid-base equilibria, activity coefficients, and thermodynamic constants. (CW)

Enabling environmental metagenomics and extremophile discovery through SCODA DNA purification

NASA Astrophysics Data System (ADS)

Lum, T.; Maydan, J.

2016-12-01

A major challenge in nucleic acid preparation from environmental samples is in the ability to separate DNA and RNA from contaminants that often co-purify with methods commonly used. This becomes even more challenging when nucleic acids are in low abundance or when enriching for high molecular weight fragments. Many column- and bead-based methods rely upon selective chemical affinity which is insufficient in dealing with similarly charged contaminants, and also often result in over fragmentation nucleic acids and substantial sample loss. Here we present a unique and alternative parameter for the separation nucleic acids based on the nonlinear response of long, charged polymers to electrophoretic fields. The synchronous coefficient of drag alteration (SCODA) technology is capable of purifying nucleic acids from highly contaminated sample matrices, with molecular weight ranges from 300 bp to over 1 Mbp, and from very low biomass origins. Using a combination of rotating dipole and quadrupole electric fields, SCODA technology concentrates ultrapure nucleic acids that enable PCR, NGS, and optical mapping applications on sample types that are otherwise difficult or impossible to analyze.

Nanomorphology of P3HT:PCBM-based absorber layers of organic solar cells after different processing conditions analyzed by low-energy scanning transmission electron microscopy.

PubMed

Pfaff, Marina; Klein, Michael F G; Müller, Erich; Müller, Philipp; Colsmann, Alexander; Lemmer, Uli; Gerthsen, Dagmar

2012-12-01

In this study the nanomorphology of P3HT:PC61BM absorber layers of organic solar cells was studied as a function of the processing parameters and for P3HT with different molecular weight. For this purpose we apply scanning transmission electron microscopy (STEM) at low electron energies in a scanning electron microscope. This method exhibits sensitive material contrast in the high-angle annular dark-field (HAADF) mode, which is well suited to distinguish materials with similar densities and mean atomic numbers. The images taken with low-energy HAADF STEM are compared with conventional transmission electron microscopy and atomic force microscopy images to illustrate the capabilities of the different techniques. For the interpretation of the low-energy HAADF STEM images, a semiempirical equation is used to calculate the image intensities. The experiments show that the nanomorphology of the P3HT:PC61BM blends depends strongly on the molecular weight of the P3HT. Low-molecular-weight P3HT forms rod-like domains during annealing. In contrast, only small globular features are visible in samples containing high-molecular-weight P3HT, which do not change significantly after annealing at 150°C up to 30 min.

Proteomic analysis of carbon concentrating chemolithotrophic bacteria Serratia sp. for sequestration of carbon dioxide.

PubMed

Bharti, Randhir K; Srivastava, Shaili; Thakur, Indu Shekhar

2014-01-01

A chemolithotrophic bacterium enriched in the chemostat in presence of sodium bicarbonate as sole carbon source was identified as Serratia sp. by 16S rRNA sequencing. Carbon dioxide sequestering capacity of bacterium was detected by carbonic anhydrase enzyme and ribulose-1, 5- bisphosphate carboxylase/oxygenase (RuBisCO). The purified carbonic anhydrase showed molecular weight of 29 kDa. Molecular weight of RuBisCO was 550 kDa as determined by fast protein liquid chromatography (FPLC), however, sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) showed presence of two subunits whose molecular weights were 56 and 14 kDa. The Western blot analysis of the crude protein and purified sample cross reacted with RuBisCO large-subunit polypeptides antibodies showed strong band pattern at molecular weight around 56 kDa regions. Whole cell soluble proteins of Serratia sp. grown under autotrophic and heterotrophic conditions were resolved by two-dimensional gel electrophoresis and MALDI-TOF/MS for differential expression of proteins. In proteomic analysis of 63 protein spots, 48 spots were significantly up-regulated in the autotrophically grown cells; seven enzymes showed its utilization in autotrophic carbon fixation pathways and other metabolic activities of bacterium including lipid metabolisms indicated sequestration potency of carbon dioxide and production of biomaterials.

Proteomic Analysis of Carbon Concentrating Chemolithotrophic Bacteria Serratia sp. for Sequestration of Carbon Dioxide

PubMed Central

Bharti, Randhir K.; Srivastava, Shaili; Thakur, Indu Shekhar

2014-01-01

A chemolithotrophic bacterium enriched in the chemostat in presence of sodium bicarbonate as sole carbon source was identified as Serratia sp. by 16S rRNA sequencing. Carbon dioxide sequestering capacity of bacterium was detected by carbonic anhydrase enzyme and ribulose-1, 5- bisphosphate carboxylase/oxygenase (RuBisCO). The purified carbonic anhydrase showed molecular weight of 29 kDa. Molecular weight of RuBisCO was 550 kDa as determined by fast protein liquid chromatography (FPLC), however, sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) showed presence of two subunits whose molecular weights were 56 and 14 kDa. The Western blot analysis of the crude protein and purified sample cross reacted with RuBisCO large-subunit polypeptides antibodies showed strong band pattern at molecular weight around 56 kDa regions. Whole cell soluble proteins of Serratia sp. grown under autotrophic and heterotrophic conditions were resolved by two-dimensional gel electrophoresis and MALDI-TOF/MS for differential expression of proteins. In proteomic analysis of 63 protein spots, 48 spots were significantly up-regulated in the autotrophically grown cells; seven enzymes showed its utilization in autotrophic carbon fixation pathways and other metabolic activities of bacterium including lipid metabolisms indicated sequestration potency of carbon dioxide and production of biomaterials. PMID:24619032

Enhanced the performance of graphene oxide/polyimide hybrid membrane for CO2 separation by surface modification of graphene oxide using polyethylene glycol

NASA Astrophysics Data System (ADS)

Wu, Li-guang; Yang, Cai-hong; Wang, Ting; Zhang, Xue-yang

2018-05-01

Polyethylene glycol (PEG) with different molecular weights was first used to modify graphene oxide (GO) samples. Subsequently, polyimide (PI) hybrid membranes containing modified-GO were fabricated via in situ polymerization. The separation performance of these hybrid membranes was evaluated using permeation experiments for CO2 and N2 gases. The morphology characterization showed that PEG with suitable molecular weight could be successfully grafted on the GO surface. PEG modification altered the surface properties of GO and introduced defective structures onto GO surface. This caused strong surface polarity and high free volume of membranes containing PEG-modified GO, thereby improving the separation performance of membranes. The addition of PEG-GO with low molecular weight effectively increased gas diffusion through hybrid membranes. The hybrid membranes containing PEG-GO with large molecular weight had high solubility performance for CO2 gas due to the introduction of numerous polar groups into polymeric membranes. With the loading content of modified GO, the CO2 gas permeability of hybrid membranes initially increased but eventually decreased. The optimal content of modified GO in membranes reached 3.0 wt%. When too much PEG added (exceeding 30 g), some impurities formed on GO surface and some aggregates appeared in the resulting hybrid membrane, which depressed the membrane performance.

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds.

PubMed

Bijan, Leila; Mohseni, Madjid

2005-10-01

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD5, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O3/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD5 enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.

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

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.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds.more » Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.« less

Seasonal distribution of aliphatic hydrocarbons in the Vaza Barris Estuarine System, Sergipe, Brazil.

PubMed

Barbosa, José Carlos S; Santos, Lukas G G V; Sant'Anna, Mércia V S; Souza, Michel R R; Damasceno, Flaviana C; Alexandre, Marcelo R

2016-03-15

The seasonal assessment of anthropogenic activities in the Vaza Barris estuarine river system, located in the Sergipe state, northeastern Brazil, was performed using the aliphatic hydrocarbon distribution. The aliphatic hydrocarbon and isoprenoid (Pristane and Phytane) concentrations ranged between 0.19 μg g(-1) and 8.5 μg g(-1) of dry weight. Data were analyzed using Kruskal-Wallis test, with significance level set at p<0.05, and no seasonality distribution change was observed. The Carbon Preference Index (CPI), associated with n-alkanes/n-C16, Low Molecular Weight/High Molecular Weight ratio (LMW/HMW) and Terrigenous to Aquatic Ratio (TAR) suggested biogenic input of aliphatic hydrocarbons for most samples, with significant contribution of higher plants. Copyright © 2016 Elsevier Ltd. All rights reserved.

Plasma Desorption Mass Spectrometry: Coming of Age.

ERIC Educational Resources Information Center

Cotter, Robert J.

1988-01-01

Discusses the history and development of Plasma Desorption Mass Spectrometry to determine molecular weights and structures of proteins and polymers. Outlines theory, instrumentation, and sample preparation commonly used. Gives several examples of resulting spectra. (ML)

Enzyme and Microbial Development | Bioenergy | NREL

Science.gov Websites

samples of powdered biomass into a reactor plate, part of the high-throughput biomass recalcitrance the molecular weight of cellA on blue and white containers of SDS PAGE gel in a laboratory

[Preliminary Investigation of the Amount, the Molecular Weight and the Activity of Polysaccharides from Chaenomeles Speciosa Fruits in Ethanol Fractional Precipitation].

PubMed

Tian, Bing-mei; Xie, Xiao-mei; Shen, Pan-pan; Yang, Mo; Zhang, Sheng-long; Tang, Qing-jiu

2015-05-01

Chaenomeles speciosa fruits were extracted using water. The extracts were precipitated with 20%~95% (φ) ethanol, respectively. The amount of total polysaccharide was measured with phenol-sulfuric acid method. A method using high-performance size-exclusion chromatography (HPSEC) equipped with multiangle laser-light-scattering photometry (MALLS) and differential refractometry (RI) was presented for determining the molecular weight and molecular weigh distribution. RAW264.7 macrophage were cultured and stimulated with the polysaccharides in vitro and the production of nitric oxide in the cells was determined by the Griess assay. The aim of the study is to determine the amount and the molecular weight of the polysaccharides from Chaenomeles speciosa fruits, and preliminary investigate the immunomodulatory activity, The study provided the basis datas for the further research of Chaenomeles speciosa fruits. , and provided a simple and system method for the research of natural polysaccharide. The ethanol fractional precipitation showed that the order of total polysaccharide content was 95%>80%>40% ≥60%>20%. The results indicated that most polysaccharide from Chaenomeles speciosa fruits might be precipitated when ethanol concentration was up to 95% (T) and the crude polysaccharide purity had risen from 35. 1% to 45. 0% when the concentration of ethanol increased from 20% to 95%. HPSEC-MALLS-RI system showed that all the polysaccharide samples had the similar compositions. They appeared three chromatographic peaks and the retention time were not apparently different. The Mw were 6. 570 X 10(4) g . mol-1 and 1. 393 X 10(4) g . mol-1 respectively, and one less than 10 000 which was failure to obtain accurate values. The molecular weight of the first two polysaccharide distribution index(Mw/Mn)were 1. 336 and 1. 639 respectively. The polysaccharide samples had not exhibited immunomodulatory activity assessed on the basis of nitric oxide production by RAW264. 7 macrophage cells in the experiment.

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.

Synthesis of Well-defined Amphiphilic Block Copolymers by Organotellurium-Mediated Living Radical Polymerization (TERP).

PubMed

Kumar, Santosh; Changez, Mohammad; Murthy, C N; Yamago, Shigeru; Lee, Jae-Suk

2011-10-04

Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Aero-Thermo-Dynamic Mass Analysis

NASA Astrophysics Data System (ADS)

Shiba, Kota; Yoshikawa, Genki

2016-07-01

Each gas molecule has its own molecular weight, while such a microscopic characteristic is generally inaccessible, and thus, it is measured indirectly through e.g. ionization in conventional mass analysis. Here, we present a novel approach to the direct measurement of molecular weight through a nanoarchitectonic combination of aerodynamics, thermodynamics, and mechanics, transducing microscopic events into macroscopic phenomena. It is confirmed that this approach can provide molecular weight of virtually any gas or vaporizable liquid sample in real-time without ionization. Demonstrations through analytical calculations, numerical simulations, and experiments verify the validity and versatility of the novel mass analysis realized by a simple setup with a flexible object (e.g. with a bare cantilever and even with a business card) placed in a laminar jet. Owing to its unique and simple working principle, this aero-thermo-dynamic mass analysis (AMA) can be integrated into various analytical devices, production lines, and consumer mobile platforms, opening new chapters in aerodynamics, thermodynamics, mechanics, and mass analysis.

Transformation of molecular weight distributions of dissolved organic carbon and UV-absorbing compounds at full-scale wastewater-treatment plants.

PubMed

Esparza-Soto, Mario; Fox, Peter; Westerhoff, Paul

2006-03-01

The molecular-weight distribution (MWD) of wastewater dissolved-organic carbon (DOC) was determined in samples from seven full-scale wastewater-treatment plants (WWTPs) that use different biological treatments (air activated sludge [air-AS], pure-oxygen AS [O2-AS], and trickling filters). The research objective was to determine how different biological treatments influenced the MWD of wastewater DOC. Primary sedimentation effluent DOC from most of the WWTPs exhibited a skewed distribution toward the low-molecular-weight fraction (MWF) (40 to 50%, < 0.5 K Daltons [KDa]). The Air-AS effluent DOC exhibited a centrally clustered distribution, with the majority of DOC in the intermediate MWF (0.5 to 3 KDa). The O2-AS effluent DOC exhibited a skewed distribution toward the high MWF (> 3 KDa). The removal of DOC by air- and O2-AS bacteria followed trends predicted by a macromolecule degradation model. Trickling-filter effluent DOC exhibited a skewed distribution toward the high MWF (50% DOC, > 3 KDa).

Spectroscopic investigations of humic-like acids formed via polycondensation reactions between glycine, catechol and glucose in the presence of natural zeolites

NASA Astrophysics Data System (ADS)

Fukuchi, Shigeki; Miura, Akitaka; Okabe, Ryo; Fukushima, Masami; Sasaki, Masahide; Sato, Tsutomu

2010-10-01

Polycondensation reactions between low-molecular-weight compounds, such as amino acids, sugars and phenols, are crucially important processes in the formation of humic substances, and clay minerals have the ability to catalyze these reactions. In the present study, catechol (CT), glycine (Gly) and glucose (Gl) were used as representative phenols, amino acids and sugars, respectively, and the effects of the catalytic activities of natural zeolites on polycondensation reactions between these compounds were investigated. The extent of polycondensation was evaluated by measuring the specific absorbance at 600 nm ( E600) as an index of the degree of darkening. After a 3-week incubation period, the E600 values for solutions that contained zeolite samples were 4-10 times greater than those measured in the absence of zeolite, suggesting that the zeolite had, in fact, catalyzed the polycondensation reaction. The humic-like acids (HLAs) produced in the reactions were isolated, and their elemental composition and molecular weights determined. When formed in the presence of a zeolite, the nitrogen contents and molecular weights for the HLAs were significantly higher, compared to the HLA sample formed in the absence of zeolite. In addition, solid-state CP-MAS 13C NMR spectra and carboxylic group analyses of the HLA samples indicated that the concentration of carbonyl carbon species for quinones and ketones produced in the presence of zeolite were higher than the corresponding values for samples produced in the absence of a zeolite. Carbonyl carbons in quinones and ketones indicate the nucleophilic characteristics of the samples. Therefore, a nitrogen atom in Gly, which serves as nucleophile, is incorporated into quinones and ketones in CT and Gl. The differences in the catalytic activities of the zeolite samples can be attributed to differences in their transition metal content (Fe, Mn and Ti), which function as Lewis acids.

Surface modification of an Mg-1Ca alloy to slow down its biocorrosion by chitosan.

PubMed

Gu, X N; Zheng, Y F; Lan, Q X; Cheng, Y; Zhang, Z X; Xi, T F; Zhang, D Y

2009-08-01

The surface morphologies before and after immersion corrosion test of various chitosan-coated Mg-1Ca alloy samples were studied to investigate the effect of chitosan dip coating on the slowdown of biocorrosion. It showed that the corrosion resistance of the Mg-Ca alloy increased after coating with chitosan, and depended on both the chitosan molecular weight and layer numbers of coating. The Mg-Ca alloy coated by chitosan with a molecular weight of 2.7 x 10(5) for six layers has smooth and intact surface morphology, and exhibits the highest corrosion resistance in a simulated body fluid.

A Method for Characterizing Thermoset Polyimides

NASA Technical Reports Server (NTRS)

Ranganathaiah, C.; Sprinkle, D. R.; Pater, R. H.; Eftekhari, A.

1996-01-01

Thermoset polyimides have great potential for successfully meeting tough stress and temperature challenges in the advanced aircraft development program. However, studies of structure-property relationships in these materials have not been very successful so far. Positron lifetime spectroscopy (PLS) has been used to investigate free volumes and associated parameters in a series of variable, segmental molecular weight samples. The free volume correlates well with the molecular weight M(sub c), the cross-link density v, and the coefficient of thermal expansion (CTE) of these materials. Currently, no other techniques are available for direct measurement of these parameters, particularly for polymers in solid phase. Experimental results and their interpretations are presented.

Search for organic compounds in the lunar dust from the Sea of Tranquillity

USGS Publications Warehouse

Ponnamperuma, C.; Kvenvolden, K.; Chang, S.; Johnson, Richard; Pollock, G.; Philpott, D.; Kaplan, I.; Smith, J.; Schopf, J.W.; Gehrke, C.; Hodgson, G.; Breger, I.A.; Halpern, B.; Duffield, A.; Krauskopf, K.; Barghoorn, E.; Holland, H.; Keil, Klaus

1970-01-01

A sample of lunar dust was examined for organic compounds. Carbon detected in concentrations of 157 micrograms per gram had a δ13C per mil (PDB) value of + 20. Treatment with hydrochloric acid yielded hydrocarbons of low molecular weight, suggesting the presence of carbides. The gas chromatogram of the acylated and esterified derivatives of the hydrolyzate was similar to that obtained for the Pueblito de Allende meteorite. There were no detectable amounts of extractable high-molecular-weight alkanes, aromatic hydrocarbons, isoprenoid hydrocarbons, normal alkanes, fatty acids, amino acids, sugars, or nucleic acid bases. Traces of porphyrins were found, perhaps arising from rocket exhaust materials.

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-insoluble pharmaceutical compounds and functional foods.

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 enhance the bioavailability of water-insoluble pharmaceutical compounds and functional foods. PMID:22745556

A new method for differentiating adducts of common drinking water DBPs from higher molecular weight DBPs in electrospray ionization-mass spectrometry analysis.

PubMed

Zhai, Hongyan; Zhang, Xiangru

2009-05-01

With the presence of bromide in source waters, numerous brominated disinfection byproducts (DBPs) are formed during chlorination. Many of them are polar/highly polar DBPs and thus hard to be detected by gas chromatography mass spectrometry. Electrospray ionization triple quadrupole mass spectrometry (ESI-MS/MS) is reported to be an effective method in finding polar brominated DBPs by setting precursor ion scans of m/z 79 and 81. But as a soft ionization technique, ESI could form adducts of common DBPs, which may complicate ESI-MS/MS spectra and hinder the efforts in finding new brominated DBPs. In this paper, a new method was developed for differentiating adducts of common DBPs from higher molecular weight DBPs. This method was based on the ESI-MS/MS precursor ion scans of the fragments that correspond to the molecular ions of common DBPs. Adducts of common DBPs were selectively detected in the ESI-MS/MS spectra of a simulated drinking water sample. Moreover, the structures of several new brominated DBPs in the sample were tentatively proposed.

Small-scale hydrous pyrolysis of macromolecular material in meteorites

NASA Astrophysics Data System (ADS)

Sephton, M. A.; Pillinger, C. T.; Gilmour, I.

1998-12-01

The hydrous pyrolysis method, usually performed on several hundred grams of terrestrial rock sample, has been scaled down to accommodate less than two grams of meteorite sample. This technique makes full use of the high yields associated with hydrous pyrolysis experiments and permits the investigation of the meteorite macromolecular material, the major organic component in carbonaceous meteorites. The hydrous pyrolysis procedure transforms the high molecular weight macromolecular material into low molecular weight fragments. The released entities can then be extracted with supercritical fluid extraction. In contrast to the parent structure, the pyrolysis products are amenable for analysis by gas chromatography-based techniques. When subjected to hydrous pyrolysis, two carbonaceous chondrites (Orgueil and Cold Bokkeveld) released generally similar products, which consisted of abundant volatile aromatic and alkyl-substituted aromatic compounds. These results revealed the ability of small-scale hydrous pyrolysis to dissect extraterrestrial macromolecular material and thereby reveal its organic constitution.

Liquid chromatographic analysis of a formulated ester from a gas-turbine engine test

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Morales, W.

1983-01-01

Size exclusion chromatography (SEC) utilizing mu-Bondagel and mu-Styragel columns with a tetrahydrofuran mobile phase was used to determine the chemical degradation of lubricant samples from a gas-turbine engine test. A MIL-L-27502 candidate, ester-based lubricant was run in a J57-29 engine at a bulk oil temperature of 216 C. In general, the analyses indicated a progressive loss of primary ester, additive depletion, and formation of higher molecular weight material. An oil sample taken at the conclusion of the test showed a reversal of this trend because of large additions of new oil. The high-molecular-weight product from the degraded ester absorbed strongly in the ultraviolet region at 254 nanometers. This would indicate the presence of chromophoric groups. An analysis of a similar ester lubricant from a separate high-temperature bearing test yielded qualitatively similar results.

Contrasting effects of photochemical and microbial degradation on Cu(II) binding with fluorescent DOM from different origins.

PubMed

Xu, Huacheng; Guan, Dong-Xing; Zou, Li; Lin, Hui; Guo, Laodong

2018-08-01

Effects of photochemical and microbial degradation on variations in composition and molecular-size of dissolved organic matter (DOM) from different sources (algal and soil) and the subsequent influence on Cu(II) binding were investigated using UV-Vis, fluorescence excitation-emission matrices coupled with parallel factor analysis, flow field-flow fractionation (FlFFF), and metal titration. The degradation processes resulted in an initial rapid decline in the bulk dissolved organic carbon and chromophoric and fluorescent DOM components, followed by a small or little decrease. Specifically, photochemical reaction decreased the aromaticity, humification and apparent molecular weights of all DOM samples, whereas a reverse trend was observed during microbial degradation. The FlFFF fractograms revealed that coagulation of both protein- and humic-like DOM induced an increase in molecular weights for algal-DOM, while the molecular weight enhancement for allochthonous soil samples was mainly attributed to the self-assembly of humic-like components. The Cu(II) binding capacity of algal-derived humic-like and fulvic-like DOM consistently increased during photo- and bio-degradation, while the soil-derived DOM exhibited a slight decline in Cu(II) binding capacity during photo-degradation but a substantial increase during microbial degradation, indicating source- and degradation-dependent metal binding heterogeneities. Pearson correlation analysis demonstrated that the Cu(II) binding potential was mostly related with aromaticity and molecular size for allochthonous soil-derived DOM, but was regulated by both DOM properties and specific degradation processes for autochthonous algal-derived DOM. This study highlighted the coupling role of inherent DOM properties and external environmental processes in regulating metal binding, and provided new insights into metal-DOM interactions and the behavior and fate of DOM-bound metals in aquatic environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

A simple and compact mechanical velocity selector of use to analyze/select molecular alignment in supersonic seeded beams

NASA Astrophysics Data System (ADS)

Pirani, F.; Cappelletti, D.; Vecchiocattivi, F.; Vattuone, L.; Gerbi, A.; Rocca, M.; Valbusa, U.

2004-02-01

A light and compact mechanical velocity selector, of novel design, for applications in supersonic molecular-beam studies has been developed. It represents a simplified version of the traditional, 50 year old, slotted disks velocity selector. Taking advantage of new materials and improved machining techniques, the new version has been realized with only two rotating slotted disks, driven by an electrical motor with adjustable frequency of rotation, and thus has a much smaller weight and size with respect to the original design, which may allow easier implementation in most of the available molecular-beam apparatuses. This new type of selector, which maintains a sufficiently high velocity resolution, has been developed for sampling molecules with different degrees of rotational alignment, like those emerging from a seeded supersonic expansion. This sampling is the crucial step to realize new molecular-beam experiments to study the effect of molecular alignment in collisional processes.

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

DOE PAGES

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu; ...

2017-12-21

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds.more » Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.« less

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds.more » Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.« less

Characterization of alkanes, hopanes, and polycyclic aromatic hydrocarbons (PAHs) in tar-balls collected from the East Coast of Peninsular Malaysia.

PubMed

Chandru, Kuhan; Zakaria, Mohamad Pauzi; Anita, Sofia; Shahbazi, Azadeh; Sakari, Mahyar; Bahry, Pourya Shahpoury; Mohamed, Che Abd Rahim

2008-05-01

The East Coast of Peninsular Malaysia faces the South China Sea and is vulnerable to oil pollution because of intense petroleum production activities in the area. The South China Sea is also a favored route for supertankers carrying crude oil to the Far East. Consequently, oil spills can occur, causing pollution and contamination in the surrounding areas. Residual oil spills stranded on coastal beaches usually end up as tar-balls. Elucidating the sources of tar-balls using a molecular marker approach is essential in assessing environmental impacts and perhaps settling legal liabilities for affected parties. This study utilizes a multimodal molecular marker approach through the use of diagnostic ratios of alkanes, hopanes, and polycyclic aromatic hydrocarbons (PAHs) to determine the source, distribution and weathering of tar-balls. Hopane ratios (e.g., C29/C30, and summation C31-C35/C30 ratios) were used to identify the sources of tar-balls. The weathering effects were distinguished by using alkanes, namely the unresolved complex mixture (UCM) and low molecular weight/high molecular weight (L/H) ratios. Similarly, PAHs were also used for the determination of weathering processes undergone by the tar-balls. This multimodal molecular marker gave a very strong indication of the sources of tar-balls in this study. For example, 16 out of 17 samples originated from South East Asian Crude Oil (SEACO) with one sample from Merang, Terengganu originating from North Sea Oil (Troll). The TRME-2 sample may have come from a supertanker's ballast water discharge. The second possibility is that the tar-ball may have been transported via oceanographic currents. All 'weathered' sample characterizations were based on the presence of UCM and other ratios. The multimodal molecular marker approach applied in this study has enabled us to partially understand the transport behavior of tar-balls in the marine environment and has revealed insights into the weathering process of tar-balls.

The correlation between gelatin macroscale differences and nanoparticle properties: providing insight into biopolymer variability.

PubMed

Stevenson, André T; Jankus, Danny J; Tarshis, Max A; Whittington, Abby R

2018-05-21

From therapeutic delivery to sustainable packaging, manipulation of biopolymers into nanostructures imparts biocompatibility to numerous materials with minimal environmental pollution during processing. While biopolymers are appealing natural based materials, the lack of nanoparticle (NP) physicochemical consistency has decreased their nanoscale translation into actual products. Insights regarding the macroscale and nanoscale property variation of gelatin, one of the most common biopolymers already utilized in its bulk form, are presented. Novel correlations between macroscale and nanoscale properties were made by characterizing similar gelatin rigidities obtained from different manufacturers. Samples with significant differences in clarity, indicating sample purity, obtained the largest deviations in NP diameter. Furthermore, a statistically significant positive correlation between macroscale molecular weight dispersity and NP diameter was determined. New theoretical calculations proposing the limited number of gelatin chains that can aggregate and subsequently get crosslinked for NP formation were presented as one possible reason to substantiate the correlation analysis. NP charge and crosslinking extent were also related to diameter. Lower gelatin sample molecular weight dispersities produced statistically smaller average diameters (<75 nm), and higher average electrostatic charges (∼30 mV) and crosslinking extents (∼95%), which were independent of gelatin rigidity, conclusions not shown in the literature. This study demonstrates that the molecular weight composition of the starting material is one significant factor affecting gelatin nanoscale properties and must be characterized prior to NP preparation. Identifying gelatin macroscale and nanoscale correlations offers a route toward greater physicochemical property control and reproducibility of new NP formulations for translation to industry.

Classification and identification of molecules through factor analysis method based on terahertz spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Jianglou; Liu, Jinsong; Wang, Kejia; Yang, Zhengang; Liu, Xiaming

2018-06-01

By means of factor analysis approach, a method of molecule classification is built based on the measured terahertz absorption spectra of the molecules. A data matrix can be obtained by sampling the absorption spectra at different frequency points. The data matrix is then decomposed into the product of two matrices: a weight matrix and a characteristic matrix. By using the K-means clustering to deal with the weight matrix, these molecules can be classified. A group of samples (spirobenzopyran, indole, styrene derivatives and inorganic salts) has been prepared, and measured via a terahertz time-domain spectrometer. These samples are classified with 75% accuracy compared to that directly classified via their molecular formulas.

A new analytical approach to understanding nanoscale lead-iron interactions in drinking water distribution systems.

PubMed

Trueman, Benjamin F; Gagnon, Graham A

2016-07-05

High levels of iron in distributed drinking water often accompany elevated lead release from lead service lines and other plumbing. Lead-iron interactions in drinking water distribution systems are hypothesized to be the result of adsorption and transport of lead by iron oxide particles. This mechanism was explored using point-of-use drinking water samples characterized by size exclusion chromatography with UV and multi-element (ICP-MS) detection. In separations on two different stationary phases, high apparent molecular weight (>669 kDa) elution profiles for (56)Fe and (208)Pb were strongly correlated (average R(2)=0.96, N=73 samples representing 23 single-unit residences). Moreover, (56)Fe and (208)Pb peak areas exhibited an apparent linear dependence (R(2)=0.82), consistent with mobilization of lead via adsorption to colloidal particles rich in iron. A UV254 absorbance peak, coincident with high molecular weight (56)Fe and (208)Pb, implied that natural organic matter was interacting with the hypothesized colloidal species. High molecular weight UV254 peak areas were correlated with both (56)Fe and (208)Pb peak areas (R(2)=0.87 and 0.58, respectively). On average, 45% (std. dev. 10%) of total lead occurred in the size range 0.05-0.45 μm. Copyright © 2016 Elsevier B.V. All rights reserved.

In-vitro anticoagulant activity of fucoidan derivatives from brown seaweed Laminaria japonica

NASA Astrophysics Data System (ADS)

Wang, Jing; Zhang, Quanbin; Zhang, Zhongshan; Hou, Yun; Zhang, Hong

2011-05-01

Fucoidan, a group of sulfated heteropolysaccharides, was extracted from Laminaria japonica, an important economic alga species in China. The anticoagulant activity of fucoidan and its derivatives (including sulfated, phosphorylated, and aminated fucoidan) was examined using in-vitro anticoagulant systems. The correlation between chemical variations within the fucoidan group and anticoagulant activity was determined. The in-vitro anticoagulant properties of fucoidan and its derivatives were determined by measuring activated partial thromboplastin time (APTT), prothrombin time (PT), and thrombin time (TT). The results indicate anticoagulant activity in all samples using APTT and TT assays; however, only the fucoidan derivatives affected the PT assay. Thus, the fucoidan derivatives were able to inhibit both intrinsic and extrinsic blood coagulants. Fucoidan (FPS) and its derivatives presented better anticoagulant activity than low molecular weight fucoidan (DFPS) and its derivatives, suggesting that molecular weight and proper conformation are contributing factors for anticoagulant activity of polysaccharides. Amino groups have a positive charge and can thus change the charge density of fucoidan. Accordingly, among the tested samples, aminated fucoidan (NF) was the most active reflecting the importance of charge density for anticoagulant activity. Available data obtained using in-vitro models suggest that the sulfate content, sulfate/total-sugar ratio, molecular weight, and the substituted group of fucoidan are important factors for anticoagulant activity but that the influence of sulfate, phosphate and amino groups on anticoagulant activity was different.

Relaxation spectra of binary blends: Extension of the Doi-Edwards theory

NASA Astrophysics Data System (ADS)

Tchesnokov, M. A.; Molenaar, J.; Slot, J. J. M.; Stepanyan, R.

2007-10-01

A molecular model is presented which allows the calculation of the stress relaxation function G for binary blends consisting of two monodisperse samples with arbitrary molecular weights. It extends the Doi-Edwards reptation theory (Doi M. and Edwards S. F., The Theory of Polymer Dynamics (Oxford Press, New York) 1986) to highly polydisperse melts by including constraint release (CR) and thermal fluctuations (CLF), yet making use of the same input parameters. The model reveals an explicit nonlinear dependence of CR frequency in the blend on the blend's molecular weight distribution (MWD). It provides an alternative way to quantify polydisperse systems compared to the widely used "double-reptation" theories. The results of the present model are in a good agreement with the experimental data given in Rubinstein M. and Colby R. H., J. Chem. Phys., 89 (1988) 5291.

Cytotoxicity associated with electrospun polyvinyl alcohol.

PubMed

Pathan, Saif G; Fitzgerald, Lisa M; Ali, Syed M; Damrauer, Scott M; Bide, Martin J; Nelson, David W; Ferran, Christiane; Phaneuf, Tina M; Phaneuf, Matthew D

2015-11-01

Polyvinyl alcohol (PVA) is a synthetic, water-soluble polymer, with applications in industries ranging from textiles to biomedical devices. Research on electrospinning of PVA has been targeted toward optimizing or finding novel applications in the biomedical field. However, the effects of electrospinning on PVA biocompatibility have not been thoroughly evaluated. In this study, the cytotoxicity of electrospun PVA (nPVA) which was not crosslinked after electrospinning was assessed. PVA polymers of several molecular weights were dissolved in distilled water and electrospun using the same parameters. Electrospun PVA materials with varying molecular weights were then dissolved in tissue culture medium and directly compared against solutions of nonelectrospun PVA polymer in human coronary artery smooth muscle cells and human coronary artery endothelial cells cultures. All nPVA solutions were cytotoxic at a threshold molar concentration that correlated with the molecular weight of the starting PVA polymer. In contrast, none of the nonelectrospun PVA solutions caused any cytotoxicity, regardless of their concentration in the cell culture. Evaluation of the nPVA material by differential scanning calorimetry confirmed that polymer degradation had occurred after electrospinning. To elucidate the identity of the nPVA component that caused cytotoxicity, nPVA materials were dissolved, fractionated using size exclusion columns, and the different fractions were added to HCASMC and human coronary artery endothelial cells cultures. These studies indicated that the cytotoxic component of the different nPVA solutions were present in the low-molecular-weight fraction. Additionally, the amount of PVA present in the 3-10 kg/mol fraction was approximately sixfold greater than that in the nonelectrospun samples. In conclusion, electrospinning of PVA resulted in small-molecular-weight fractions that were cytotoxic to cells. This result demonstrates that biocompatibility of electrospun biodegradable polymers should not be assumed on the basis of success of their nonelectrospun predecessors. © 2015 Wiley Periodicals, Inc.

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.

A Survey of 42 Semi-Volatile Organic Contaminants in Groundwater along the Grand Canal from Hangzhou to Beijing, East China.

PubMed

Li, Xiaojie; Rao, Zhu; Yang, Zhipeng; Guo, Xiaochen; Huang, Yi; Zhang, Jing; Guo, Feng; Liu, Chen

2015-12-18

The status of organic pollution in groundwater in eastern China along the Grand Canal from Hangzhou to Beijing was evaluated. Forty-two semi-volatile organic contaminants were analyzed, including 16 polycyclic aromatic hydrocarbons (PAHs), seven polychlorinated biphenyls (PCBs), 12 organochlorine pesticides (OCPs) and seven organophosphorus pesticides (OPPs). Among the detected contaminants, PAHs were the most widespread compounds. One PCB and six OCPs were detected in the groundwater samples, but none of the target OPPs was detected. The total concentration of the 16 PAHs ranged from 0.21 to 1006 ng/L, among which phenanthrene (271 ng/L) and fluoranthene (233 ng/L) were present at very high concentrations and naphthalene (32 positive detections in 50 samples) and fluorene (28 detections in 50 samples) were the most frequently detected. Benzo[a]pyrene equivalents indicated a high environmental risk related to PAHs in a few groundwater samples. To identify the possible sources of PAHs, three concentration ratios, low molecular weight PAHs/high molecular weight PAHs, anthracene/(anthracene + phenanthrene) and fluoranthene/(fluoranthene + pyrene), were determined, that indicated that the PAHs mainly originated from mixed sources: pyrolytic and petrogenic sources with different ratios at different sites.

A Survey of 42 Semi-Volatile Organic Contaminants in Groundwater along the Grand Canal from Hangzhou to Beijing, East China

PubMed Central

Li, Xiaojie; Rao, Zhu; Yang, Zhipeng; Guo, Xiaochen; Huang, Yi; Zhang, Jing; Guo, Feng; Liu, Chen

2015-01-01

The status of organic pollution in groundwater in eastern China along the Grand Canal from Hangzhou to Beijing was evaluated. Forty-two semi-volatile organic contaminants were analyzed, including 16 polycyclic aromatic hydrocarbons (PAHs), seven polychlorinated biphenyls (PCBs), 12 organochlorine pesticides (OCPs) and seven organophosphorus pesticides (OPPs). Among the detected contaminants, PAHs were the most widespread compounds. One PCB and six OCPs were detected in the groundwater samples, but none of the target OPPs was detected. The total concentration of the 16 PAHs ranged from 0.21 to 1006 ng/L, among which phenanthrene (271 ng/L) and fluoranthene (233 ng/L) were present at very high concentrations and naphthalene (32 positive detections in 50 samples) and fluorene (28 detections in 50 samples) were the most frequently detected. Benzo[a]pyrene equivalents indicated a high environmental risk related to PAHs in a few groundwater samples. To identify the possible sources of PAHs, three concentration ratios, low molecular weight PAHs/high molecular weight PAHs, anthracene/(anthracene + phenanthrene) and fluoranthene/(fluoranthene + pyrene), were determined, that indicated that the PAHs mainly originated from mixed sources: pyrolytic and petrogenic sources with different ratios at different sites. PMID:26694442

Characterization of a humic acid-like brown substance in airborne particulate matter and tentative identification of its origin

NASA Astrophysics Data System (ADS)

Mukai, Hitoshi; Ambe, Yoshinari

A brown substance having the solubility characteristics of humic acid was extracted from airborne particulate matter sampled in a rural area of Japan. This brown substance contributed 0.6-3% of the total carbon in airborne particulate matter. This fraction also contained pollen protein in samples collected during the pollen season. Patterns of elution from gel permeation chromatography suggested a molecular weight range from 500 to 10,000, with a still higher upper limit for one sample. The infrared spectra were compared with those of humic acid from the local soil, extracts from dead leaves, smoke from burning plant matter, and soot from automotive exhaust, all possible sources of the brown substance. The closest similarity was with the extract smoke. This identification is strengthened by lack of correlation of the brown substance with aluminum, a tracer for soil content, and a value of K/Fe ratio in the associated particulate matter higher than any plausible source other than combustion. It is probable that the primary source of this brown, high molecular weight acidic materials is agricultural burning.

Rapid and highly sensitive determination of low-molecular-weight carbonyl compounds in drinking water and natural water by preconcentration HPLC with 2,4-dinitrophenylhydrazine.

PubMed

Takeda, Kazuhiko; Katoh, Shinya; Nakatani, Nobutake; Sakugawa, Hiroshi

2006-12-01

The aim of this research was to develop a simple procedure for a highly sensitive determination of low-molecular-weight (LMW) carbonyl compounds in drinking water and natural water. We employed a preconcentration HPLC system with 2,4-dinitrophenylhydrazine (DNPH) for the determination of LMW carbonyl compounds. A C-18 reverse-phase preconcentration column was used instead of a sample loop at the sample injection valve. A 0.1 - 5.0 mL portion of the derivatized sample solution was injected with a gas-tight syringe, and a 15% acetonitrile aqueous solution was pushed through the preconcentration column to remove the unreacted excess DNPH, which caused serious interference in the determination of formaldehyde. The detection limits were 1 - 3 nM with a relative standard deviation of 2 - 5% for 20 nM standard solutions (n = 5). The calibration curves were essentially unaffected by coexisting sea salts. Applications to commercial mineral water, tap water, river water, pond water and seawater are presented.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Effect of molecular weight on polymer processability

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

Natural attenuation and biosurfactant-stimulated bioremediation of estuarine sediments contaminated with diesel oil.

PubMed

Bayer, Débora M; Chagas-Spinelli, Alessandra C O; Gavazza, Sávia; Florencio, Lourdinha; Kato, Mario T

2013-09-01

We evaluated the bioremediation, by natural attenuation (NA) and by natural attenuation stimulated (SNA) using a rhamnolipid biosurfactant, of estuarine sediments contaminated with diesel oil. Sediment samples (30 cm) were put into 35 cm glass columns, and the concentrations of the 16 polycyclic aromatic hydrocarbons (PAHs) prioritized by the US Environmental Protection Agency were monitored for 111 days. Naphthalene percolated through the columns more than the other PAHs, and, in general, the concentrations of the lower molecular weight PAHs, consisting of two and three aromatic rings, changed during the first 45 days of treatment, whereas the concentrations of the higher molecular weight PAHs, consisting of four, five, and six rings, were more stable. The higher molecular weight PAHs became more available after 45 days, in the deeper parts of the columns (20-30 cm). Evidence of degradation was observed only for some compounds, such as pyrene, with a total removal efficiency of 82 and 78 % in the NA and SNA treatments, respectively, but without significant difference. In the case of total PAH removal, the efficiencies were significantly different of 82 and 67 %, respectively.

Transformations of dissolved organic matter in a landfill leachate--a size exclusion chromatography/mass spectrometric approach.

PubMed

Persson, Linn; Alsberg, Tomas; Ledin, Anna; Odham, Göran

2006-08-01

The aim of the present study was to search for qualitative changes in the landfill leachate DOM along a groundwater gradient. The study was focused on DOM characteristics of importance for its interaction with pollutants, such as molecular weight distribution and aromaticity. It was concluded that the leachate DOM underwent substantial qualitative changes along the investigated gradient at the Vejen landfill, Denmark. The molecular weight decreased, the polydispersity increased, and the aromaticity varied with the lowest values found in the middle of the gradient. The high aromaticity in the end of the gradient may explain the higher DOM binding capacity towards hydrophobic compounds seen earlier in these samples. The relative abundance of ions with mass to charge ratio (m/z) of 600-1200 seemed to be very stable along the gradient, indicating that the observed qualitative changes of the DOM is mostly attributed to changes in the m/z 100-600 range. The DOM seemed to become more similar to fulvic acids present in uncontaminated groundwater with respect to molecular weight and polydispersity along the gradient.

Study of PEG Tether Length of Pegylated-Lipid Sensing Films in QCM Odor Sensors

NASA Astrophysics Data System (ADS)

Wyszynski, Bartosz; Somboon, Pakpum; Nakamoto, Takamichi

Odor sensing system using quartz crystal microbalance (QCM) sensor array and pattern recognition technique has been for a long time an important research topic. Research of novel sensing materials for QCM odor sensors is vital for realization of artificial olfaction and related devices such as odor recorder. Herein we study quartz crystal microbalance (QCM, 20 MHz, AT-cut) sensors coated with lipopolymers with polyethylene glycol (PEG) as a tether. The tether's molecular weights were 1000, 2000 and 5000. In addition, we fabricated QCM sensors coated with PEGs of molecular weights 1000, 2000 and 4000. The fabricated sensors' properties were evaluated during experiments of exposures to vapors of alcohols, esters and acids. From the obtained results it is clear that the tether's length (molecular weight) is an important factor influencing the resulting material's sensing properties. Sensititivity patterns of the lipopolymeric sensors were clealrly different from the ones for respective polymers. The obtained sensors seem to have a good capability to discriminate among odor samples according to the functional group of an odorant.

Impact of molecular weight on the formation of electrosprayed chitosan microcapsules as delivery vehicles for bioactive compounds.

PubMed

Gómez-Mascaraque, Laura G; Sanchez, Gloria; López-Rubio, Amparo

2016-10-05

The molecular weight of chitosan is one of its most determinant characteristics, which affects its processability and its performance as a biomaterial. However, information about the effect of this parameter on the formation of electrosprayed chitosan microcapsules is scarce. In this work, the impact of chitosan molecular weight on its electrosprayability was studied and correlated with its effect on the viscosity, surface tension and electrical conductivity of solutions. A Discriminant Function Analysis revealed that the morphology of the electrosprayed chitosan materials could be correctly predicted using these three parameters for almost 85% of the samples. The suitability of using electrosprayed chitosan capsules as carriers for bioactive agents was also assessed by loading them with a model active compound, (-)-epigallocatechin gallate (EGCG). This encapsulation, with an estimated efficiency of around 80% in terms of preserved antioxidant activity, showed the potential to prolong the antiviral activity of EGCG against murine norovirus via gradual bioactive release combined with its protection against degradation in simulated physiological conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

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

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.

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.

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.

Thermochemolysis: A New Sample Preparation Approach for the Detection of Organic Components of Complex Macromolecules in Mars Rocks via Gas Chromatography Mass Spectrometry in SAM on MSL

NASA Technical Reports Server (NTRS)

Eugenbrode, J.; Glavin, D.; Dworkin, J.; Conrad, P.; Mahaffy, P.

2011-01-01

Organic chemicals, when present in extraterrestrial samples, afford precious insight into past and modern conditions elsewhere in the Solar System . No single technology identifies all molecular components because naturally occurring molecules have different chemistries (e.g., polar vs. non-polar, low to high molecular weight) and interface with the ambient sample chemistry in a variety of modes (i.e., organics may be bonded, absorbed or trapped by minerals, liquids, gases, or other organics). More than 90% of organic matter in most natural samples on Earth and in meteorites is composed of complex macromolecules (e.g. biopolymers, complex biomolecules, humic substances, kerogen) because the processes that tend to break down organic molecules also tend towards complexation of the more recalcitrant components. Thus, methodologies that tap the molecular information contained within macromolecules may be critical to detecting extraterrestrial organic matter and assessing the sources and processes influencing its nature.

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.

Characterization and distribution of polycyclic aromatic hydrocarbon contaminations in surface sediment and water from Gao-ping River, Taiwan.

PubMed

Doong, Ruey-An; Lin, Yu-Tin

2004-04-01

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in water and sediment samples collected from 12 locations in Gao-ping River, Taiwan were analyzed. Molecular ratios and principal component analysis (PCA) were used to characterize the possible pollution sources. Concentrations of total 16 PAHs (SigmaPAHs) in water samples ranged from below method detection limits (

The influence of solvent processing on polyester bioabsorbable polymers.

PubMed

Manson, Joanne; Dixon, Dorian

2012-01-01

Solvent-based methods are commonly employed for the production of polyester-based samples and coatings in both medical device production and research. The influence of solvent casting and subsequent drying time was studied using thermal analysis, spectroscopy and weight measurement for four grades of 50 : 50 poly(lactic-co-glycolic acid) (PLGA) produced by using chloroform, dichloromethane, and acetone. The results demonstrate that solvent choice and PLGA molecular weight are critical factors in terms of solvent removal rate and maintaining sample integrity, respectively. The protocols widely employed result in high levels of residual solvent and a new protocol is presented together with solutions to commonly encountered problems.

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…

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…

40 CFR 63.11551 - What are my initial compliance requirements?

Code of Federal Regulations, 2010 CFR

2010-07-01

...: (i) Method 1 or 1A (40 CFR part 60, appendix A-1) to select sampling port locations and the number of... part 60, appendix A-2) to determine the dry molecular weight of the stack gas. You may use ANSI/ASME...

REMOVAL BY COAGULATION OF TRACE ORGANICS FROM MISSISSIPPI RIVER WATER

EPA Science Inventory

In the study alum and ferric sulfate were evaluated for their effectiveness in removing four low-molecular-weight organic compounds - C14-labeled octanoic acid, salicylic acid, phenol, and benzoic acid - from Mississippi River water and from water samples free of natural organic ...

Authentication of animal origin of heparin and low molecular weight heparin including ovine, porcine and bovine species using 1D NMR spectroscopy and chemometric tools.

PubMed

Monakhova, Yulia B; Diehl, Bernd W K; Fareed, Jawed

2018-02-05

High resolution (600MHz) nuclear magnetic resonance (NMR) spectroscopy is used to distinguish heparin and low-molecular weight heparins (LMWHs) produced from porcine, bovine and ovine mucosal tissues as well as their blends. For multivariate analysis several statistical methods such as principal component analysis (PCA), factor discriminant analysis (FDA), partial least squares - discriminant analysis (PLS-DA), linear discriminant analysis (LDA) were utilized for the modeling of NMR data of more than 100 authentic samples. Heparin and LMWH samples from the independent test set (n=15) were 100% correctly classified according to its animal origin. Moreover, by using 1 H NMR coupled with chemometrics and several batches of bovine heparins from two producers were differentiated. Thus, NMR spectroscopy combined with chemometrics is an efficient tool for simultaneous identification of animal origin and process based manufacturing difference in heparin products. Copyright © 2017 Elsevier B.V. All rights reserved.

Signal Peptide and Denaturing Temperature are Critical Factors for Efficient Mammalian Expression and Immunoblotting of Cannabinoid Receptors*

PubMed Central

WANG, Chenyun; WANG, Yingying; WANG, Miao; CHEN, Jiankui; YU, Nong; SONG, Shiping; KAMINSKI, Norbert E.; ZHANG, Wei

2013-01-01

Summary Many researchers employed mammalian expression system to artificially express cannabinoid receptors, but immunoblot data that directly prove efficient protein expression can hardly be seen in related research reports. In present study, we demonstrated cannabinoid receptor protein was not able to be properly expressed with routine mammalian expression system. This inefficient expression was rescued by endowing an exogenous signal peptide ahead of cannabinoid receptor peptide. In addition, the artificially synthesized cannabinoid receptor was found to aggregate under routine sample denaturing temperatures (i.e., ≥95°C), forming a large molecular weight band when analyzed by immunoblotting. Only denaturing temperatures ≤75°C yielded a clear band at the predicted molecular weight. Collectively, we showed that efficient mammalian expression of cannabinoid receptors need a signal peptide sequence, and described the requirement for a low sample denaturing temperature in immunoblot analysis. These findings provide very useful information for efficient mammalian expression and immunoblotting of membrane receptors. PMID:22528237

Comparative evaluation of western blotting in hepatic and pulmonary cystic echinococcosis.

PubMed

Akisu, C; Delibas, S B; Bicmen, C; Ozkoc, S; Aksoy, U; Turgay, N

2006-12-01

Many serological tests are widely used in the diagnosis of cystic echinococcosis (CE), caused by the larval stages of Echinococcus granulosus. The present study was carried for differentiation between hepatic and pulmonary cystic echinococcosis by Western Blotting (WB). A total of 121 sera from patients with hepatic CE (37), pulmonary CE (31) and controls (53; consisting of six healthy, seven Hymenolepis nana infection, 20 hepatic and 20 pulmonary diseases other than CE) were examined. In all of the CE patients, E. gronulosus infection was confirmed by surgical intervention. Sera were previously tested using IHA and ELISA to detect the E. gronulosus specific antibodies. Sera from hepatic cases of CE reacted with 16 polypeptides of 6-116 kDa and sera from pulmonary cases of CE reacted with 14 polypeptides of 4-130 kDa by Western Blotting. The WB test enabled the detection of antibodies in the hepatic CE samples for proteins of 24, 32 34, 44-46 and 52-54 kDa in molecular weight in 78.4%, 75.7%, 78.4% and 89.2% of the patients, respectively. In the pulmonary CE samples sera WB test enabled the detection of antibodies 24, 44-46, 100, 110, 116 and 120 124 kDa in molecular weight in 81.3%, 75.0%, 87.5%, 71.9%, 84.4% and 65.6% of the patients, respectively. We indicated that the antigenic components of high molecular weight can be good candidates for differentiation of hepatic CE from pulmonary CE.

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.

Characterization of the nitrogen compounds released during yeast autolysis in a model wine system.

PubMed

Martínez-Rodríguez, A J; Polo, M C

2000-04-01

The nitrogen composition of wines aged with yeast for a long period of time, as in the case of sparkling wines, depends on the composition of the base wine and on the compounds released by the yeast. In this paper, the release of the different classes of nitrogen compounds during autolysis of one of the strains of yeast used in the manufacture of sparkling wines has been studied. The yeast, Saccharomyces bayanus, was suspended in a model wine buffer, pH 3.0 and 10% ethanol, and incubated at 30 degrees C. Samples of the autolysate were taken after 4, 24, 48, 72, 168, and 360 h of autolysis. An electrophoretic and chromatographic study was conducted of the proteins, peptides with molecular weights higher and lower than 700 Da, and amino acids released during the autolysis. Using SDS-PAGE, it was observed that it was predominantly polypeptides with molecular weights lower than 10 000 that were released. Through HPLC of the fraction lower than 10 000 Da, it was observed that it is polypeptides with molecular weights of between 10 000 and 700 Da that are released first and that these later break up to give rise to peptides with molecular weights lower than 700 Da, which in turn break down into amino acids. This indicates that the nature of the nitrogen compounds present in wines aged with yeast depends on the aging time, being less polymerized as the aging time increases.

Broadening of polymer chromatographic signals: Analysis, quantification and correction through effective diffusion coefficients.

PubMed

Suárez, Inmaculada; Coto, Baudilio

2015-08-14

Average molecular weights and polydispersity indexes are some of the most important parameters considered in the polymer characterization. Usually, gel permeation chromatography (GPC) and multi angle light scattering (MALS) are used for this determination, but GPC values are overestimated due to the dispersion introduced by the column separation. Several procedures were proposed to correct such effect usually involving more complex calibration processes. In this work, a new method of calculation has been considered including diffusion effects. An equation for the concentration profile due to diffusion effects along the GPC column was considered to be a Fickian function and polystyrene narrow standards were used to determine effective diffusion coefficients. The molecular weight distribution function of mono and poly disperse polymers was interpreted as a sum of several Fickian functions representing a sample formed by only few kind of polymer chains with specific molecular weight and diffusion coefficient. Proposed model accurately fit the concentration profile along the whole elution time range as checked by the computed standard deviation. Molecular weights obtained by this new method are similar to those obtained by MALS or traditional GPC while polydispersity index values are intermediate between those obtained by the traditional GPC combined to Universal Calibration method and the MALS method. Values for Pearson and Lin coefficients shows improvement in the correlation of polydispersity index values determined by GPC and MALS methods when diffusion coefficients and new methods are used. Copyright © 2015 Elsevier B.V. All rights reserved.

Microwave-assisted on-spot derivatization for gas chromatography-mass spectrometry based determination of polar low molecular weight compounds in dried blood spots.

PubMed

Sadones, Nele; Van Bever, Elien; Archer, John R H; Wood, David M; Dargan, Paul I; Van Bortel, Luc; Lambert, Willy E; Stove, Christophe P

2016-09-23

Dried blood spot (DBS) sampling and analysis is increasingly being applied in bioanalysis. Although the use of DBS has many advantages, it is also associated with some challenges. E.g. given the limited amount of available material, highly sensitive detection techniques are often required to attain sufficient sensitivity. In gas chromatography coupled to mass spectrometry (GC-MS), derivatization can be helpful to achieve adequate sensitivity. Because this additional sample preparation step is considered as time-consuming, we introduce a new derivatization procedure, i.e. "microwave-assisted on-spot derivatization", to minimize sample preparation of DBS. In this approach the derivatization reagents are directly applied onto the DBS and derivatization takes place in a microwave instead of via conventional heating. In this manuscript we evaluated the applicability of this new concept of derivatization for the determination of two polar low molecular weight molecules, gamma-hydroxybutyric acid (GHB) and gabapentin, in DBS using a standard GC-MS configuration. The method was successfully validated for both compounds, with imprecision and bias values within acceptance criteria (<20% at LLOQ, <15% at 3 other QC levels). Calibration lines were linear over the 10-100μg/mL and 1-30μg/mL range for GHB and gabapentin, respectively. Stability studies revealed no significant decrease of gabapentin and GHB in DBS upon storage at room temperature for at least 84 days. Furthermore, DBS-specific parameters, including hematocrit and volume spotted, were evaluated. As demonstrated by the analysis of GHB and gabapentin positive samples, "microwave-assisted on-spot derivatization" proved to be reliable, fast and applicable in routine toxicology. Moreover, other polar low molecular weight compounds of interest in clinical and/or forensic toxicology, including vigabatrin, beta-hydroxybutyric acid, propylene glycol, diethylene glycol, 1,4-butanediol and 1,2-butanediol, can also be detected using this method. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

Flow-induced crystallization in isotactic polypropylene

NASA Astrophysics Data System (ADS)

Hamad, Fawzi Ghassan

Brief intervals of strong flow stretch chains in a semicrystalline polymer melt, which results in an increase in the nuclei number density and a transformation of the crystal structure. This flow-induced crystallization (FIC) phenomenon is explored in this study using highly isotactic polypropylene (iPP) samples. Using one synthesized and five commercial linear isotactic polypropylene samples, we investigate the FIC behavior by imposing shear onto these samples in a rotational rheometer. Equipped with a good temperature control and flexible shear protocol, we apply different temperature and flow conditions. The magnitude of the FIC effect varies with basic processing parameters (shear rate, specific work, crystallization temperature, and shearing temperature) and material properties (totalistic, molecular weight distribution, and particle concentration in the polymer). The scope of this study is to systematically investigate the influences of these parameters on FIC. The FIC effects that are investigated in this dissertation are: crystallization kinetics, persistence time of flow-induced nuclei, and crystal morphology. The crystallization time was measured in the rheometer by monitoring the onset of crystallization after quenching samples sheared above Tm. These samples were subsequently used to study their flow-induced nuclei persistence time and crystal morphology. The lifetime of flow-induced nuclei was determined by measuring the time required to return from FIC back to quiescent crystallization using a differential scanning calorimeter. The crystal morphology was imaged using polarized optical microscopy and atomic force microscopy. We investigated the influence of specific work on the three FIC characteristics, and found three regimes that are separated by the critical work ( Wc) and the saturation work (Wsat) thresholds. Below the critical work threshold, the morphology is composed of mostly spherulite crystals, which keep a constant volume, and a small fraction of rice grain (anisotropic) crystals. The number of rice grain crystals increases with specific work, speeding up the crystallization time of the semicrystalline polymer. At critical work, spherulite formation stops, and the morphology consists only of rice grain structures. This morphology allows the sample to crystallize at higher temperatures when cooling at 5 C/min, with the sheared sample crystallizing at 129C compared to the unsheared sample at 113C. . Shearing isotactic polypropylene at higher temperatures reduced the FIC effect after subsequent quenching. Generally speaking, shearing at higher temperatures results in slower crystallization, but surprisingly, the influence of temperature is rather weak. Flow-induced crystallization persists even when shear is applied well above the equilibrium melting temperature (187C), finally weakening above the Hoffman-Weeks temperature (210C). This is likely due to the long lifetime of flow- induced precursors (crystallize to form rice grains), which remain stable at temperatures below 210C and only start to disappear slowly in prolonged annealing at temperatures above 210C (diminishing the FIC effect). Tacticity was found to govern the maximum nuclei number density in sheared samples; samples with lower isotactic content show a stronger FIC effect. Similarly, it was found that the concentration of particulates (mainly catalyst residue) are crucially important to FIC, samples with lower amounts of particles lowering the FIC nuclei number density. Data shows that the rate at which the crystallization time changes correlates with the prominence of the high molecular weight tail. A sample with a higher molecular weight tail in its distribution exhibits a faster change in crystallization time as a function of specific work. Similarly, increasing the molecular weight of the added component in a blend induces a larger change in the FIC behavior. (Abstract shortened by ProQuest.).

Agarose and Polyacrylamide Gel Electrophoresis Methods for Molecular Mass Analysis of 5–500 kDa Hyaluronan

PubMed Central

Bhilocha, Shardul; Amin, Ripal; Pandya, Monika; Yuan, Han; Tank, Mihir; LoBello, Jaclyn; Shytuhina, Anastasia; Wang, Wenlan; Wisniewski, Hans-Georg; de la Motte, Carol; Cowman, Mary K.

2011-01-01

Agarose and polyacrylamide gel electrophoresis systems for the molecular mass-dependent separation of hyaluronan (HA) in the size range of approximately 5–500 kDa have been investigated. For agarose-based systems, the suitability of different agarose types, agarose concentrations, and buffers systems were determined. Using chemoenzymatically synthesized HA standards of low polydispersity, the molecular mass range was determined for each gel composition, over which the relationship between HA mobility and logarithm of the molecular mass was linear. Excellent linear calibration was obtained for HA molecular mass as low as approximately 9 kDa in agarose gels. For higher resolution separation, and for extension to molecular masses as low as approximately 5 kDa, gradient polyacrylamide gels were superior. Densitometric scanning of stained gels allowed analysis of the range of molecular masses present in a sample, and calculation of weight-average and number-average values. The methods were validated for polydisperse HA samples with viscosity-average molecular masses of 112, 59, 37, and 22 kDa, at sample loads of 0.5 µg (for polyacrylamide) to 2.5 µg (for agarose). Use of the methods for electrophoretic mobility shift assays was demonstrated for binding of the HA-binding region of aggrecan (recombinant human aggrecan G1-IGD-G2 domains) to a 150 kDa HA standard. PMID:21684248

Microbial Degradation of Octamethylcyclotetrasiloxane

PubMed Central

Grümping, R.; Michalke, K.; Hirner, A. V.; Hensel, R.

1999-01-01

The microbial degradation of low-molecular-weight polydimethylsiloxanes was investigated through laboratory experiments. Octamethylcyclotetrasiloxane was found to be biodegraded under anaerobic conditions in composted sewage sludge, as monitored by the occurrence of the main polydimethylsiloxane degradation product, dimethylsilanediol, compared to that found in experiments with sterilized control samples. PMID:10224038

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.

Effect of natural flocculants on purity and properties of β-glucan extracted from barley and oat.

PubMed

Kurek, Marcin Andrzej; Karp, Sabina; Stelmasiak, Adrian; Pieczykolan, Ewelina; Juszczyk, Karolina; Rieder, Anne

2018-05-15

In this study, β-glucan was extracted from wholegrain oat and barley flours by a novel extraction and purification method employing natural flocculants (chitosan, guar gum and gelatin). The use of flocculants decreased the total amount of extracted gum, which was highest in control samples (9.07 and 7.9% for oat and barley, respectively). The β-glucan specific yield, however, increased with the use of chitosan and guar gum, which were able to remove protein and ash impurities resulting in gums with a higher purity.The highest concentration of chitosan (0.6 %) resulted in gums with the highest β-glucan content (82.0 ± 0.23 and 79.0 ± 0.19 for barley and oat, respectively) and highest β-glucan specific yield (96.9 and 93.3 % for oat and barley, respectively). Explanation is in R&D section. The use of gelatin was not successful. All gum samples had a high content of total dietary fiber (>74%) and a high water holding capacity (4.6-7.4 g/g), but differed in apparent viscosity, which was highest for the oat sample extracted with 0.6% chitosan. This sample also showed the highest β-glucan molecular weight among the oat samples, which were in general 10-fold higher than for the barley samples. Among the barley samples, β-glucan molecular weight was highest for the control. Copyright © 2018 Elsevier Ltd. All rights reserved.

Qualitative and Quantitative Analysis of Proteome and Peptidome of Human Follicular Fluid Using Multiple Samples from Single Donor with LC-MS and SWATH Methodology.

PubMed

Lewandowska, Aleksandra E; Macur, Katarzyna; Czaplewska, Paulina; Liss, Joanna; Łukaszuk, Krzysztof; Ołdziej, Stanisław

2017-08-04

Human follicular fluid (hFF) is a natural environment of oocyte maturation, and some components of hFF could be used to judge oocyte capability for fertilization and further development. In our pilot small-scale study three samples from four donors (12 samples in total) were analyzed to determine which hFF proteins/peptides could be used to differentiate individual oocytes and which are patient-specific. Ultrafiltration was used to fractionate hFF to high-molecular-weight (HMW) proteome (>10 kDa) and low-molecular-weight (LMW) peptidome (<10 kDa) fractions. HMW and LMW compositions were analyzed using LC-MS in SWATH data acquisition and processing methodology. In total we were able to identify 158 proteins, from which 59 were never reported before as hFF components. 55 (45 not reported before) proteins were found by analyzing LMW fraction, 67 (14 not reported before) were found by analyzing HMW fraction, and 36 were identified in both fractions of hFF. We were able to perform quantitative analysis for 72 proteins from HMW fraction of hFF. We found that concentrations of 11 proteins varied substantially among hFF samples from single donors, and those proteins are promising targets to identify biomarkers useful in oocyte quality assessment.

Characterization of low molecular weight dissolved natural organic matter along the treatment trait of a waterworks using Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Zhang, Haifeng; Zhang, Yahe; Shi, Quan; Ren, Shuoyi; Yu, Jianwei; Ji, Feng; Luo, Wenbin; Yang, Min

2012-10-15

Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH(4) against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water. Copyright © 2012 Elsevier Ltd. All rights reserved.

Characterization of dissolved organic matter in drinking water sources impacted by multiple tributaries.

PubMed

Rosario-Ortiz, Fernando L; Snyder, Shane A; Suffet, I H

2007-10-01

The characterization of dissolved organic matter (DOM) in drinking water sources is important as this material contributes to the formation of disinfection by-products (DBPs) and affects how water treatment unit operations are optimized. Drinking water utilities often draw water from sources impacted by multiple tributaries, with possible shifts in DOM concentrations and reactivity over time, depending on specific environmental conditions. In this study, results are presented on the characterization of DOM under varying ambient conditions from the four main tributaries of Lake Mead, a large reservoir in the southwest United States. The tributaries include the Las Vegas Wash (LVW), Muddy River (MR), Virgin River (VR) and the upper Colorado River (UCR). One additional sample was collected at the outflow of the reservoir (lower Colorado River (LCR)). The DOM was characterized by both bulk parameters (specific ultraviolet absorbance (SUVA)) and specific physicochemical properties, i.e. size, polarity and fluorescence. The analyses were performed emphasizing limited changes in its natural configuration by eliminating analytical preparation steps, excluding sample filtration (0.45 microm filter). Results indicate that each tributary had a different molecular weight distribution, as well as fluorescence properties, which helped in the identification of the relative source of DOM (allochthonous versus autochthonous). The largest apparent molecular weight distribution was observed for DOM samples collected at the MR site, which is fed mostly by groundwater seepage. The smallest apparent molecular weight was observed for DOM collected at the LCR site, suggesting that retention in the reservoir resulted in a decrease in molecular weight as a probable result of photo oxidation and microbial processes. Fluorescence analysis aided the differentiation of DOM by clearly identifying waters that were affected by microbial activity (LVW, UCR, and LCR), either by wastewater influence or by autochthonous processes, versus limited microbial influence (MR and VR). Polarity analysis revealed clear differences in the hydrophobic/hydrophilic nature between waters, including temporal differences within individual waters at a particular site. The DOM from the LVW and VR sites had higher hydrophobic character, as measured by retention onto non-polar sorbents. Additionally, the DOM collected at the LCR had the least hydrophobic character. This type of analysis would be beneficial to utilities who want to better understand and manage their source waters, especially in the evaluation of temporal variation within a watershed.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Size exclusion chromatography with online ICP-MS enables molecular weight fractionation of dissolved phosphorus species in water samples.

PubMed

Venkatesan, Arjun K; Gan, Wenhui; Ashani, Harsh; Herckes, Pierre; Westerhoff, Paul

2018-04-15

Phosphorus (P) is an important and often limiting element in terrestrial and aquatic ecosystem. A lack of understanding of its distribution and structures in the environment limits the design of effective P mitigation and recovery approaches. Here we developed a robust method employing size exclusion chromatography (SEC) coupled to an ICP-MS to determine the molecular weight (MW) distribution of P in environmental samples. The most abundant fraction of P varied widely in different environmental samples: (i) orthophosphate was the dominant fraction (93-100%) in one lake, two aerosols and DOC isolate samples, (ii) species of 400-600 Da range were abundant (74-100%) in two surface waters, and (iii) species of 150-350 Da range were abundant in wastewater effluents. SEC-DOC of the aqueous samples using a similar SEC column showed overlapping peaks for the 400-600 Da species in two surface waters, and for >20 kDa species in the effluents, suggesting that these fractions are likely associated with organic matter. The MW resolution and performance of SEC-ICP-MS agreed well with the time integrated results obtained using conventional ultrafiltration method. Results show that SEC in combination with ICP-MS and DOC has the potential to be a powerful and easy-to-use method in identifying unknown fractions of P in the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Gel filtration applied to the study of lipases and other esterases

PubMed Central

Downey, W. K.; Andrews, P.

1965-01-01

1. Sephadex G-100 and G-200 gel-filtration columns were calibrated for molecular-weight estimation with proteins of known molecular weights, and used to study the composition of several lipase or esterase preparations. 2. Enzymes from cow's milk, rat adipose tissue and pig pancreas were detected in the column effluents by their ability to liberate free acid from emulsified tributyrin at pH 8·5. 3. Four tributyrinases were detected in preparations from individual cow's milks. Molecular weights 62000, 75000 and 112000 were estimated for three of them, but although the fourth may be of unusually low molecular weight an estimate was not possible. 4. Extracts of rat adipose tissue apparently contained six tributyrinases (molecular weights 39000, 47000, 55000, 68000, 75000 and 200000) but the relative amounts of these enzymes varied widely from rat to rat. 5. Tributyrinase activity in juice expressed from pig pancreatic tissue was due mainly to one enzyme (molecular weight 42000). On the other hand, activity in extracts of acetone-dried pancreas was confined to material of molecular weight > 106, which may be an aggregated form of the lower-molecular-weight enzyme. 6. Activity in fractionated wheat-germ extracts was assayed with emulsified triacetin substrate, and was evidently due to one enzyme (molecular weight 51000). 7. Some problems arising in the application of gel filtration to the study of lipase–esterase systems were indicated. PMID:14340054

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

High Pressure Size Exclusion Chromatography (HPSEC) Determination of Dissolved Organic Matter Molecular Weight Revisited: Accounting for Changes in Stationary Phases, Analytical Standards, and Isolation Methods.

PubMed

McAdams, Brandon C; Aiken, George R; McKnight, Diane M; Arnold, William A; Chin, Yu-Ping

2018-01-16

We reassessed the molecular weight of dissolved organic matter (DOM) determined by high pressure size exclusion chromatography (HPSEC) using measurements made with different columns and various generations of polystyrenesulfonate (PSS) molecular weight standards. Molecular weight measurements made with a newer generation HPSEC column and PSS standards from more recent lots are roughly 200 to 400 Da lower than initial measurements made in the early 1990s. These updated numbers match DOM molecular weights measured by colligative methods and fall within a range of values calculated from hydroxyl radical kinetics. These changes suggest improved accuracy of HPSEC molecular weight measurements that we attribute to improved accuracy of PSS standards and changes in the column packing. We also isolated DOM from wetlands in the Prairie Pothole Region (PPR) using XAD-8, a cation exchange resin, and PPL, a styrene-divinylbenzene media, and observed little difference in molecular weight and specific UV absorbance at 280 nm (SUVA 280 ) between the two solid phase extraction resins, suggesting they capture similar DOM moieties. PPR DOM also showed lower SUVA 280 at similar weights compared to DOM isolates from a global range of environments, which we attribute to oxidized sulfur in PPR DOM that would increase molecular weight without affecting SUVA 280 .

EFFICIENT RECOVERY OF ENTEROCOCCI FROM MARINE AND FRESH WATER BEACHES BY A 30,000 MOLECULAR WEIGHT CUTOFF HOLLOW FIBER ULTRAFILTER

EPA Science Inventory

Ultrafiltration systems have been used to concentrate pathogens from various types of fresh water samples. However, less work has been done with marine waters for the concentration of pathogens or indicator bacteria. An ultrafiltration approach to concentrate indicator bacteria...

40 CFR 63.11466 - What are the performance test requirements for new and existing sources?

Code of Federal Regulations, 2010 CFR

2010-07-01

... (Appendix A-1) to select sampling port locations and the number of traverse points in each stack or duct... of the stack gas. (iii) Method 3, 3A, or 3B (Appendix A-2) to determine the dry molecular weight of...

Size exclusion HPLC of proteins for evaluation of durum wheat quality

USDA-ARS?s Scientific Manuscript database

The present research aimed to assess size exclusion HPLC (SE-HPLC) in protein molecular weight distribution determination for quality evaluation of durum semolina. Semolina samples were milled from 13 durum genotypes grown at 7 locations in 2009 and 2010 in ND. Sodium dodecyl sulfate (SDS) buffer ...

Determination of phytate in high molecular weight, charged organic matrices by two-dimensional size exclusion-ion chromatography

USDA-ARS?s Scientific Manuscript database

A two-dimensional chromatography method for analyzing anionic targets (specifically phytate) in complex matrices is described. Prior to quantification by anion exchange chromatography, the sample matrix was prepared by size exclusion chromatography, which removed the majority of matrix complexities....

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.

High Molecular Weight Proteins of Trypanosoma cruzi Reduce Cross-Reaction with Leishmania spp. in Serological Diagnosis Tests

PubMed Central

Cervantes-Landín, Alejandra Yunuen; Martínez, Ignacio; Schabib, Muslim; Espinoza, Bertha

2014-01-01

Chagas disease is caused by the parasite Trypanosoma cruzi. Because of its distribution throughout Latin America, sometimes it can overlap with other parasitic diseases, such as leishmaniasis, caused by Leishmania spp. This might represent a problem when performing serological diagnosis, because both parasites share antigens, resulting in cross-reactions. In the present work we evaluated Mexican sera samples: 83.8% of chagasic patients recognized at least one antigen of high molecular weight (>95 kDa) when evaluated by Western blot. Proteins of 130 kDa and 160 kDa are predominantly being recognized by asymptomatic chagasic patients. When the proteins were extracted using Triton X-100 detergent, a larger number of specific T. cruzi proteins were obtained. This protein fraction can be used to increase specificity to 100% in Western blot assays without losing sensitivity of the test. High molecular weight proteins of T. cruzi include glycoproteins with a great amount of αMan (α-mannose), αGlc (α-glucose), GlcNAc (N-acetylglucosamine), and αGal (α-galactose) content and these structures play an essential role in antigens recognition by antibodies present in patients' sera. PMID:25136581

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.

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.

A Method for Whole Protein Isolation from Human Cranial Bone

PubMed Central

Lyon, Sarah M.; Mayampurath, Anoop; Rogers, M. Rose; Wolfgeher, Donald J.; Fisher, Sean M.; Volchenboum, Samuel L.; He, Tong-Chuan; Reid, Russell R.

2016-01-01

The presence of the dense hydroxyapatite matrix within human bone limits the applicability of conventional protocols for protein extraction. This has hindered the complete and accurate characterization of the human bone proteome thus far, leaving many bone-related disorders poorly understood. We sought to refine an existing method of protein extraction from mouse bone to extract whole proteins of varying molecular weights from human cranial bone. Whole protein was extracted from human cranial suture by mechanically processing samples using a method that limits protein degradation by minimizing heat introduction to proteins. The presence of whole protein was confirmed by western blotting. Mass spectrometry was used to sequence peptides and identify isolated proteins. The data have been deposited to the ProteomeXchange with identifier PXD003215. Extracted proteins were characterized as both intra- and extracellular and had molecular weights ranging from 9.4-629 kDa. High correlation scores among suture protein spectral counts support the reproducibility of the method. Ontology analytics revealed proteins of myriad functions including mediators of metabolic processes and cell organelles. These results demonstrate a reproducible method for isolation of whole protein from human cranial bone, representing a large range of molecular weights, origins and functions. PMID:27677936

Characterization of dissolved organic matter in Dongjianghu Lake by UV-visible absorption spectroscopy with multivariate analysis.

PubMed

Zhu, Yanzhong; Song, Yonghui; Yu, Huibin; Liu, Ruixia; Liu, Lusan; Lv, Chunjian

2017-08-08

UV-visible absorption spectroscopy coupled with principal component analysis (PCA) and hierarchical cluster analysis (HCA) was applied to characterize spectroscopic components, detect latent factors, and investigate spatial variations of dissolved organic matter (DOM) in a large-scale lake. Twelve surface water samples were collected from Dongjianghu Lake in China. DOM contained lignin and quinine moieties, carboxylic acid, microbial products, and aromatic and alkyl groups, which in the northern part of the lake was largely different from the southern part. Fifteen spectroscopic indices were deduced from the absorption spectra to indicate molecular weight or humification degree of DOM. The northern part of the lake presented the smaller molecular weight or the lower humification degree of DOM than the southern part. E 2/4 , E 3/4 , E 2/3 , and S 2 were latent factors of characterizing the molecular weight of DOM, while E 2/5 , E 3/5 , E 2/6 , E 4/5 , E 3/6 , and A 2/1 were latent factors of evaluating the humification degree of DOM. The UV-visible absorption spectroscopy combined with PCA and HCA may not only characterize DOM fractions of lakes, but may be transferred to other types of waterscape.

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.

High resolution mass spectrometry method and system for analysis of whole proteins and other large molecules

DOEpatents

Reilly, Peter T. A. [Knoxville, TN; Harris, William A [Naperville, IL

2010-03-02

A matrix assisted laser desorption/ionization (MALDI) method and related system for analyzing high molecular weight analytes includes the steps of providing at least one matrix-containing particle inside an ion trap, wherein at least one high molecular weight analyte molecule is provided within the matrix-containing particle, and MALDI on the high molecular weight particle while within the ion trap. A laser power used for ionization is sufficient to completely vaporize the particle and form at least one high molecular weight analyte ion, but is low enough to avoid fragmenting the high molecular weight analyte ion. The high molecular weight analyte ion is extracted out from the ion trap, and is then analyzed using a detector. The detector is preferably a pyrolyzing and ionizing detector.

Process for crosslinking and extending conjugated diene-containing polymers

NASA Technical Reports Server (NTRS)

Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

1977-01-01

A process using a Diels-Alder reaction which increases the molecular weight and/or crosslinks polymers by reacting the polymers with bisunsaturated dienophiles is developed. The polymer comprises at least 75% by weight based on the reaction product, has a molecular weight of at least 5000 and a plurality of conjugated 1,3-diene systems incorporated into the molecular structure. A dienophile reaction with the conjugated 1,3-diene of the polymer is at least 1% by weight based on the reaction product. Examples of the polymer include polyesters, polyamides, polyethers, polysulfones and copolymers. The bisunsaturated dienophiles may include bis-maleimides, bis maleic and bis tumaric esters and amides. This method for expanding the molecular weight chains of the polymers, preferable thermoplastics, is advantageous for processing or fabricating thermoplastics. A low molecular weight thermoplastic is converted to a high molecular weight plastic having improved strength and toughness for use in the completed end use article.

Polycyclic aromatic hydrocarbons in oysters and sediments from the Yatsushiro Sea, Japan: comparison of potential risks among PAHs, dioxins and dioxin-like compounds in benthic organisms.

PubMed

Nakata, Haruhiko; Uehara, Kiriko; Goto, Yuta; Fukumura, Miki; Shimasaki, Hideyuki; Takikawa, Kiyoshi; Miyawaki, Takashi

2014-01-01

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in oysters collected from 18 stations in the Yatsushiro Sea, western Japan. PAHs were detected in all samples analyzed, and the highest concentration (mean 230 ng/g wet weight) was found in oysters from Tanoura Bay. The high molecular weight PAHs to low molecular weight PAHs ratios in oysters from Tanoura Bay were higher than at other stations. Sediment samples collected from 42 stations in Tanoura Bay were analyzed for PAHs to understand their concentrations and distribution. Higher concentrations were found in sediment samples at two stations in the southern inner bay (mean 30,200 ng/g dry weight), which were approximately two orders of magnitude higher than at a reference site. These observations strongly suggest severe contamination and significant sources of PAHs in Tanoura Bay. Dioxins and dioxin-like compounds (PCDFs, and non- and mono-ortho coplanar PCBs) were analyzed in sediments from eight stations in Tanoura Bay. The concentrations were comparable to, or lower than, at the reference sites, suggesting that there are no specific sources of these compounds in this bay. PAH, dioxins and dioxin-like compounds DR-CALUX relative potencies (REP) were applied to the sediment concentrations to evaluate the potential for toxicological effects on benthic organisms. PAHs made the highest contribution to the total REP concentration, supplying 99% of the total REP, followed by PCDDs (0.18%), PCDFs (0.04%), and PCBs (<0.001%). In this area, PAHs appear to be the most important Ah receptor binding chemicals for potential toxicity to benthic species. © 2013 Published by Elsevier Inc.

Integrated Hamiltonian sampling: a simple and versatile method for free energy simulations and conformational sampling.

PubMed

Mori, Toshifumi; Hamers, Robert J; Pedersen, Joel A; Cui, Qiang

2014-07-17

Motivated by specific applications and the recent work of Gao and co-workers on integrated tempering sampling (ITS), we have developed a novel sampling approach referred to as integrated Hamiltonian sampling (IHS). IHS is straightforward to implement and complementary to existing methods for free energy simulation and enhanced configurational sampling. The method carries out sampling using an effective Hamiltonian constructed by integrating the Boltzmann distributions of a series of Hamiltonians. By judiciously selecting the weights of the different Hamiltonians, one achieves rapid transitions among the energy landscapes that underlie different Hamiltonians and therefore an efficient sampling of important regions of the conformational space. Along this line, IHS shares similar motivations as the enveloping distribution sampling (EDS) approach of van Gunsteren and co-workers, although the ways that distributions of different Hamiltonians are integrated are rather different in IHS and EDS. Specifically, we report efficient ways for determining the weights using a combination of histogram flattening and weighted histogram analysis approaches, which make it straightforward to include many end-state and intermediate Hamiltonians in IHS so as to enhance its flexibility. Using several relatively simple condensed phase examples, we illustrate the implementation and application of IHS as well as potential developments for the near future. The relation of IHS to several related sampling methods such as Hamiltonian replica exchange molecular dynamics and λ-dynamics is also briefly discussed.

Application of ion-induced nucleation mass spectrometry in the analysis of trace gases evolved from a polyimide film during the thermal curing stages

NASA Technical Reports Server (NTRS)

Smith, A. C.

1982-01-01

Trace gases evolved from a polyimide film during its thermal curing stages have been studied using ion-induced nucleation mass spectrometry. The technique involved exposing the test gas sample to a low energy beta source and recording the masses of the ion-induced molecular clusters formed in the reaction chamber. On the basis of the experimentally observed molecular cluster spectra, it has been concluded that the dominant trace component had a molecular weight of 87 atomic mass units. This component has been identified as a molecule of dimethylacetamide (DMAC) which had been used as a solvent in the preparation of the test polyimide specimen. This identification has been further confirmed by comparing the spectra of the test gas sample and the DMAC calibration sample obtained with a conventional mass spectrometer. The advantages of the ion-induced nucleation mass spectrometer versus the conventional mass spectrometer are discussed.

Accelerated weight histogram method for exploring free energy landscapes

NASA Astrophysics Data System (ADS)

Lindahl, V.; Lidmar, J.; Hess, B.

2014-07-01

Calculating free energies is an important and notoriously difficult task for molecular simulations. The rapid increase in computational power has made it possible to probe increasingly complex systems, yet extracting accurate free energies from these simulations remains a major challenge. Fully exploring the free energy landscape of, say, a biological macromolecule typically requires sampling large conformational changes and slow transitions. Often, the only feasible way to study such a system is to simulate it using an enhanced sampling method. The accelerated weight histogram (AWH) method is a new, efficient extended ensemble sampling technique which adaptively biases the simulation to promote exploration of the free energy landscape. The AWH method uses a probability weight histogram which allows for efficient free energy updates and results in an easy discretization procedure. A major advantage of the method is its general formulation, making it a powerful platform for developing further extensions and analyzing its relation to already existing methods. Here, we demonstrate its efficiency and general applicability by calculating the potential of mean force along a reaction coordinate for both a single dimension and multiple dimensions. We make use of a non-uniform, free energy dependent target distribution in reaction coordinate space so that computational efforts are not wasted on physically irrelevant regions. We present numerical results for molecular dynamics simulations of lithium acetate in solution and chignolin, a 10-residue long peptide that folds into a β-hairpin. We further present practical guidelines for setting up and running an AWH simulation.

Accelerated weight histogram method for exploring free energy landscapes.

PubMed

Lindahl, V; Lidmar, J; Hess, B

2014-07-28

Calculating free energies is an important and notoriously difficult task for molecular simulations. The rapid increase in computational power has made it possible to probe increasingly complex systems, yet extracting accurate free energies from these simulations remains a major challenge. Fully exploring the free energy landscape of, say, a biological macromolecule typically requires sampling large conformational changes and slow transitions. Often, the only feasible way to study such a system is to simulate it using an enhanced sampling method. The accelerated weight histogram (AWH) method is a new, efficient extended ensemble sampling technique which adaptively biases the simulation to promote exploration of the free energy landscape. The AWH method uses a probability weight histogram which allows for efficient free energy updates and results in an easy discretization procedure. A major advantage of the method is its general formulation, making it a powerful platform for developing further extensions and analyzing its relation to already existing methods. Here, we demonstrate its efficiency and general applicability by calculating the potential of mean force along a reaction coordinate for both a single dimension and multiple dimensions. We make use of a non-uniform, free energy dependent target distribution in reaction coordinate space so that computational efforts are not wasted on physically irrelevant regions. We present numerical results for molecular dynamics simulations of lithium acetate in solution and chignolin, a 10-residue long peptide that folds into a β-hairpin. We further present practical guidelines for setting up and running an AWH simulation.

A rapid identification system for metallothionein proteins using expert system

PubMed Central

Praveen, Bhoopathi; Vincent, Savariar; Murty, Upadhyayula Suryanarayana; Krishna, Amirapu Radha; Jamil, Kaiser

2005-01-01

Metallothioneins (MT) are low molecular weight proteins mostly rich in cysteine residues with high metal content. Generally, MT proteins are responsible for regulating the intracellular supply of biologically essential metal ions and they protect cells from the deleterious effects of non-essential polarizable transition and post-transition metal ions. Due to their biological importance, proper characterization of MT is necessary. Here we describe a computer program (ID3 algorithm, a part of Artificial Intelligence) developed using available data for the rapid identification of MT. Tissue samples contains several low molecular weight proteins with different physical, chemical and biological characteristics. The described software solution proposes to categorize MT proteins without aromatic amino acids and high metal content. The proposed solution can be expanded to other types of proteins with specific known characteristics. PMID:17597844

Determination of high-molecular weight polycyclic aromatic hydrocarbons in high performance liquid chromatography fractions of coal tar standard reference material 1597a via solid-phase nanoextraction and laser-excited time-resolved Shpol'skii spectroscopy

PubMed Central

Wilson, Walter B.; Alfarhani, Bassam; Moore, Anthony F. T.; Bisson, Cristina; Wise, Stephen A.; Campiglia, Andres D.

2016-01-01

This article presents an alternative approach for the analysis of high molecular weight – polycyclic aromatic hydrocarbons (HMW-PAHs) with molecular mass 302 Da in complex environmental samples. This is not a trivial task due to the large number of molecular mass 302 Da isomers with very similar chromatographic elution times and similar, possibly even virtually identical, mass fragmentation patterns. The method presented here is based on 4.2 K laser-excited time-resolved Shpol'skii spectroscopy, a high resolution spectroscopic technique with the appropriate selectivity for the unambiguous determination of PAHs with the same molecular mass. The potential of this approach is demonstrated here with the analysis of a coal tar standard reference material (SRM) 1597a. Liquid chromatography fractions were submitted to the spectroscopic analysis of five targeted isomers, namely dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, naphtho[2,3-a]pyrene and dibenzo[a,h]pyrene. Prior to analyte determination, the liquid chromatographic fractions were pre-concentrated with gold nanoparticles. Complete analysis was possible with microliters of chromatographic fractions and organic solvents. The limits of detection varied from 0.05 (dibenzo[a,l]pyrene) to 0.24 μg L−1 (dibenzo[a,e]pyrene). The excellent analytical figures of merit associated to its non-destructive nature, which provides ample opportunity for further analysis with other instrumental methods, makes this approach an attractive alternative for the determination of PAH isomers in complex environmental samples. PMID:26653471

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.

Thermal Processing of PVP- and HPMC-Based Amorphous Solid Dispersions.

PubMed

LaFountaine, Justin S; Prasad, Leena Kumari; Brough, Chris; Miller, Dave A; McGinity, James W; Williams, Robert O

2016-02-01

Thermal processing technologies continue to gain interest in pharmaceutical manufacturing. However, the types and grades of polymers that can be utilized in common thermal processing technologies, such as hot-melt extrusion (HME), are often limited by thermal or rheological factors. The objectives of the present study were to compare and contrast two thermal processing methods, HME and KinetiSol® Dispersing (KSD), and investigate the influence of polymer type, polymer molecular weight, and drug loading on the ability to produce amorphous solid dispersions (ASDs) containing the model compound griseofulvin (GRIS). Dispersions were analyzed by a variety of imaging, solid-state, thermal, and solution-state techniques. Dispersions were prepared by both HME and KSD using polyvinylpyrrolidone (PVP) K17 or hydroxypropyl methylcellulose (HPMC) E5. Dispersions were only prepared by KSD using higher molecular weight grades of HPMC and PVP, as these could not be extruded under the conditions selected. Powder X-ray diffraction (PXRD) analysis showed that dispersions prepared by HME were amorphous at 10% and 20% drug load; however, it showed significant crystallinity at 40% drug load. PXRD analysis of KSD samples showed all formulations and drug loads to be amorphous with the exception of trace crystallinity seen in PVP K17 and PVP K30 samples at 40% drug load. These results were further supported by other analytical techniques. KSD produced amorphous dispersions at higher drug loads than could be prepared by HME, as well as with higher molecular weight polymers that were not processable by HME, due to its higher rate of shear and torque output.

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

Investigation into the Effect of Ethylcellulose Viscosity Variation on the Drug Release of Metoprolol Tartrate and Acetaminophen Extended Release Multiparticulates-Part I.

PubMed

Mehta, R; Teckoe, J; Schoener, C; Workentine, S; Ferrizzi, D; Rajabi-Siahboomi, A

2016-12-01

Ethylcellulose is one of the most commonly used polymers to develop reservoir type extended release multiparticulate dosage forms. For multiparticulate extended release dosage forms, the drug release is typically governed by the properties of the barrier membrane coating. The ICH Pharmaceutical Development Guideline (ICH Q8) requires an understanding of the influence of critical material attributes and critical process parameters on the drug release of a pharmaceutical product. Using this understanding, it is possible to develop robust formulations with consistent drug release characteristics. Critical material attributes for ethylcellulose were evaluated, and polymer molecular weight variation (viscosity) was considered to be the most critical attribute that can impact drug release. To investigate the effect of viscosity variation within the manufacturer's specifications of ethylcellulose, extended release multiparticulate formulations of two model drugs, metoprolol tartrate and acetaminophen, were developed using ETHOCEL™ as the rate controlling polymer. Quality by Design (QbD) samples of ETHOCEL Std. 10, 20, and 100 Premium grades representing the low, medium, and high molecular weight (viscosity) material were organically coated onto drug layered multiparticulates to a 15% weight gain (WG). The drug release was found to be similar (f 2  > 50) for both metoprolol tartrate and acetaminophen multiparticulates at different coating weight gains of ethylcellulose, highlighting consistent and robust drug release performance. The use of ETHOCEL QbD samples also serves as a means to develop multiparticulate dosage formulations according to regulatory guidelines.

High pressure size exclusion chromatography (HPSEC) determination of dissolved organic matter molecular weight revisited: Accounting for changes in stationary phases, analytical standards, and isolation methods

USGS Publications Warehouse

McAdams, Brandon C.; Aiken, George R.; McKnight, Diane M.; Arnold, William A.; Chin, Yu-Ping

2018-01-01

We reassessed the molecular weight of dissolved organic matter (DOM) determined by high pressure size exclusion chromatography (HPSEC) using measurements made with different columns and various generations of polystyrenesulfonate (PSS) molecular weight standards. Molecular weight measurements made with a newer generation HPSEC column and PSS standards from more recent lots are roughly 200 to 400 Da lower than initial measurements made in the early 1990s. These updated numbers match DOM molecular weights measured by colligative methods and fall within a range of values calculated from hydroxyl radical kinetics. These changes suggest improved accuracy of HPSEC molecular weight measurements that we attribute to improved accuracy of PSS standards and changes in the column packing. We also isolated DOM from wetlands in the Prairie Pothole Region (PPR) using XAD-8, a cation exchange resin, and PPL, a styrene-divinylbenzene media, and observed little difference in molecular weight and specific UV absorbance at 280 nm (SUVA280) between the two solid phase extraction resins, suggesting they capture similar DOM moieties. PPR DOM also showed lower SUVA280 at similar weights compared to DOM isolates from a global range of environments, which we attribute to oxidized sulfur in PPR DOM that would increase molecular weight without affecting SUVA280.

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.

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.

The impact of supervised weight loss and intentional weight regain on sex hormone binding globulin and testosterone in premenopausal women.

PubMed

Aubuchon, Mira; Liu, Ying; Petroski, Gregory F; Thomas, Tom R; Polotsky, Alex J

2016-08-01

What is the impact of intentional weight loss and regain on serum androgens in women? We conducted an ancillary analysis of prospectively collected samples from a randomized controlled trial. The trial involved supervised 10% weight loss (8.5 kg on average) with diet and exercise over 4-6 months followed by supervised intentional regain of 50% of the lost weight (4.6 kg on average) over 4-6 months. Participants were randomized prior to the partial weight regain component to either continuation or cessation of endurance exercise. Analytic sample included 30 obese premenopausal women (mean age of 40 ± 5.9 years, mean baseline body mass index (BMI) of 32.9 ± 4.2 kg/m(2)) with metabolic syndrome. We evaluated sex hormone binding globulin (SHBG), total testosterone (T), free androgen index (FAI), and high molecular weight adiponectin (HMWAdp). Insulin, homeostasis model assessment (HOMA), and quantitative insulin sensitivity check index (QUICKI), and visceral adipose tissue (VAT) measured in the original trial were reanalyzed for the current analytic sample. Insulin, HOMA, and QUICKI improved with weight loss and were maintained despite weight regain. Log-transformed SHBG significantly increased from baseline to weight loss, and then significantly decreased with weight regain. LogFAI and logVAT decreased similarly and increased with weight loss followed by weight regain. No changes were found in logT and LogHMWAdp. There was no significant difference in any tested parameters by exercise between the groups. SHBG showed prominent sensitivity to body mass fluctuations, as reduction with controlled intentional weight regain showed an inverse relationship to VAT and occurred despite stable HMWAdp and sustained improvements with insulin resistance. FAI showed opposite changes to SHBG, while T did not change significantly with weight. Continued exercise during weight regain did not appear to impact these findings.

Quantitative analysis of genomic DNA degradation in whole blood under various storage conditions for molecular diagnostic testing.

PubMed

Permenter, Jessalyn; Ishwar, Arjun; Rounsavall, Angie; Smith, Maddie; Faske, Jennifer; Sailey, Charles J; Alfaro, Maria P

2015-12-01

Proper storage of whole blood is crucial for isolating nucleic acids from leukocytes and to ensure adequate performance of downstream assays in the molecular diagnostic laboratory. Short-term and long-term storage recommendations are lacking for successful isolation of genomic DNA (gDNA). Container type (EDTA or heparin), temperature (4 °C and room temperature) and time (1-130 days) were assessed as criterion for sample acceptance policies. The percentage of integrated area (%Ti) between 150 and 10,000 bp from the 2200 TapeStation electropherogram was calculated to measure gDNA degradation. Refrigerated EDTA samples yielded gDNA with low %Ti (high quality). Heparinized samples stored at room temperature yielded gDNA of worst quality. Downstream analysis demonstrated that the quality of the gDNA correlated with the quality of the data; samples with high %Ti generated significantly lower levels of high molecular weight amplicons. Recommendations from these analyses include storing blood samples intended for nucleic acid isolation in EDTA tubes at 4 °C for long term storage (>10 days). gDNA should be extracted within 3 days when blood is stored at room temperature regardless of the container. Finally, refrigerated heparinized samples should not be stored longer than 9 days if expecting high quality gDNA isolates. Laboratories should consider many factors, in addition to the results obtained herein, to update their policies for sample acceptance for gDNA extraction intended for molecular genetic testing. Copyright © 2015 Elsevier Ltd. All rights reserved.

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 temporal resolution of the HMW technique is limited, particularly at these high-latitude sites. Therefore, we cannot use the aIle/Ile HMW data to exclude the possibility that the two sites are significantly different ages. Analyses of shells ranging in age from late Pliocene to Holocene indicate that reaction rate in the HMW fraction is about one-fifth the rate in the total amino acid population, although the difference is expected to decrease with increasing aIle/Ile.

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.

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.

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 chain conformations and liquid structure in backmapped blends with the reference data. Possible directions for further methodological developments are discussed.

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 chain conformations and liquid structure in backmapped blends with the reference data. Possible directions for further methodological developments are discussed.

Functional Comparison for Lipid Metabolism and Intestinal and Fecal Microflora Enzyme Activities between Low Molecular Weight Chitosan and Chitosan Oligosaccharide in High-Fat-Diet-Fed Rats.

PubMed

Chiu, Chen-Yuan; Feng, Shih-An; Liu, Shing-Hwa; Chiang, Meng-Tsan

2017-07-24

The present study investigated and compared the regulatory effects on the lipid-related metabolism and intestinal disaccharidase/fecal bacterial enzyme activities between low molecular weight chitosan and chitosan oligosaccharide in high-fat-diet-fed rats. Diet supplementation of low molecular weight chitosan showed greater efficiency than chitosan oligosaccharide in suppressing the increased weights in body and in liver and adipose tissues of high-fat-diet-fed rats. Supplementation of low molecular weight chitosan also showed a greater improvement than chitosan oligosaccharide in imbalance of plasma, hepatic, and fecal lipid profiles, and intestinal disaccharidase activities in high-fat-diet-fed rats. Moreover, both low molecular weight chitosan and chitosan oligosaccharide significantly decreased the fecal microflora mucinase and β-glucuronidase activities in high-fat-diet-fed rats. These results suggest that low molecular weight chitosan exerts a greater positive improvement than chitosan oligosaccharide in lipid metabolism and intestinal disaccharidase activity in high-fat-diet-induced obese rats.

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.

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...

A Size Exclusion Chromatography Laboratory with Unknowns for Introductory Students

ERIC Educational Resources Information Center

McIntee, Edward J.; Graham, Kate J.; Colosky, Edward C.; Jakubowski, Henry V.

2015-01-01

Size exclusion chromatography is an important technique in the separation of biological and polymeric samples by molecular weight. While a number of laboratory experiments have been published that use this technique for the purification of large molecules, this is the first report of an experiment that focuses on purifying an unknown small…

In vivo anti-radiation activities of the Ulva pertusa polysaccharides and polysaccharide-iron(III) complex.

PubMed

Shi, Jinming; Cheng, Cuilin; Zhao, Haitian; Jing, Jing; Gong, Ning; Lu, Weihong

2013-09-01

Polysaccharides with different molecular weights were extracted from Ulva pertusa and fractionated by ultrafiltration. Iron(III) complex of the low molecular-weight U. pertusa polysaccharides were synthesized. Atomic absorption spectrum showed that the iron content of iron(III)-polysaccharide complex was 27.4%. The comparison between U. pertusa polysaccharides and their iron(III) complex showed that iron chelating altered the structural characteristics of the polysaccharides. The bioactivity analysis showed that polysaccharide with low molecular weight was more effective than polysaccharide with high molecular weight in protecting mice from radiation induced damages on bone marrow cells and immune system. Results also proved that the anti-radiation and anti-oxidative activity of iron(III) complex of low molecular-weight polysaccharides were not less than that of low molecular-weight polysaccharides. Copyright © 2013 Elsevier B.V. All rights reserved.

Supplementing formula-fed piglets with a low molecular weight fraction of bovine colostrum whey results in an improved intestinal barrier.

PubMed

De Vos, M; Huygelen, V; Van Raemdonck, G; Willemen, S; Fransen, E; Van Ostade, X; Casteleyn, C; Van Cruchten, S; Van Ginneken, C

2014-08-01

To test the hypothesis that a low molecular weight fraction of colostral whey could affect the morphology and barrier function of the small intestine, 30 3-d-old piglets (normal or low birth weight) were suckled (n = 5), artificially fed with milk formula (n = 5), or artificially fed with milk formula with a low molecular weight fraction of colostral whey (n = 5) until 10 d of age. The small intestine was sampled for histology (haematoxylin and eosin stain; anti-KI67 immunohistochemistry) and enzyme activities (aminopeptidase A, aminopeptidase N, dipeptidylpeptidase IV, lactase, maltase, and sucrase). In addition, intestinal permeability was evaluated via a dual sugar absorption test and via the measurement of occludin abundance. Artificially feeding of piglets reduced final BW (P < 0.001), villus height (P < 0.001), lactase (P < 0.001), and dipeptidylpeptidase IV activities (P < 0.07), whereas crypt depth (P < 0.001) was increased. No difference was observed with regard to the permeability measurements when comparing artificially fed with naturally suckling piglets. Supplementing piglets with the colostral whey fraction did not affect BW, enzyme activities, or the outcome of the dual sugar absorption test. On the contrary, the small intestines of supplemented piglets had even shorter villi (P = 0.001) than unsupplemented piglets and contained more occludin (P = 0.002). In conclusion, at 10 d of age, no differences regarding intestinal morphology and permeability measurements were observed between the 2 BW categories. In both weight categories, the colostral whey fraction affected the morphology of the small intestine but did not improve the growth performances or the in vivo permeability. These findings should be acknowledged when developing formulated milk for neonatal animals with the aim of improving the performance of low birth weight piglets.

Effect of Processing on Silk-Based Biomaterials: Reproducibility and Biocompatibility

PubMed Central

Wray, Lindsay S.; Hu, Xiao; Gallego, Jabier; Georgakoudi, Irene; Omenetto, Fiorenzo G.; Schmidt, Daniel; Kaplan, David L.

2012-01-01

Silk fibroin has been successfully used as a biomaterial for tissue regeneration. In order to prepare silk fibroin biomaterials for human implantation a series of processing steps are required to purify the protein. Degumming to remove inflammatory sericin is a crucial step related to biocompatibility and variability in the material. Detailed characterization of silk fibroin degumming is reported. The degumming conditions significantly affected cell viability on the silk fibroin material and the ability to form three-dimensional porous scaffolds from the silk fibroin, but did not affect macrophage activation or β-sheet content in the materials formed. Methods are also provided to determine the content of residual sericin in silk fibroin solutions and to assess changes in silk fibroin molecular weight. Amino acid composition analysis was used to detect sericin residuals in silk solutions with a detection limit between 1.0% and 10% wt/wt, while fluorescence spectroscopy was used to reproducibly distinguish between silk samples with different molecular weights. Both methods are simple and require minimal sample volume, providing useful quality control tools for silk fibroin preparation processes. PMID:21695778

Dual x-ray fluorescence spectrometer and method for fluid analysis

DOEpatents

Wilson, Bary W.; Shepard, Chester L.

2005-02-22

Disclosed are an X-ray fluorescence (SRF) spectrometer and method for on-site and in-line determination of contaminant elements in lubricating oils and in fuel oils on board a marine vessel. An XRF source block 13 contains two radionuclide sources 16, 17 (e.g. Cd 109 and Fe 55), each oriented 180 degrees from the other to excite separate targets. The Cd 109 source 16 excites sample lube oil flowing through a low molecular weight sample line 18. The Fe 55 source 17 excites fuel oil manually presented to the source beam inside a low molecular weight vial 26 or other container. Two separate detectors A and B are arranged to detect the fluorescent x-rays from the targets, photons from the analyte atoms in the lube oil for example, and sulfur identifying x-rays from bunker fuel oil for example. The system allows both automated in-line and manual on-site analysis using one set of signal processing and multi-channel analyzer electronics 34, 37 as well as one computer 39 and user interface 43.

Generation of a large volume of clinically relevant nanometre-sized ultra-high-molecular-weight polyethylene wear particles for cell culture studies

PubMed Central

Ingham, Eileen; Fisher, John; Tipper, Joanne L

2014-01-01

It has recently been shown that the wear of ultra-high-molecular-weight polyethylene in hip and knee prostheses leads to the generation of nanometre-sized particles, in addition to micron-sized particles. The biological activity of nanometre-sized ultra-high-molecular-weight polyethylene wear particles has not, however, previously been studied due to difficulties in generating sufficient volumes of nanometre-sized ultra-high-molecular-weight polyethylene wear particles suitable for cell culture studies. In this study, wear simulation methods were investigated to generate a large volume of endotoxin-free clinically relevant nanometre-sized ultra-high-molecular-weight polyethylene wear particles. Both single-station and six-station multidirectional pin-on-plate wear simulators were used to generate ultra-high-molecular-weight polyethylene wear particles under sterile and non-sterile conditions. Microbial contamination and endotoxin levels in the lubricants were determined. The results indicated that microbial contamination was absent and endotoxin levels were low and within acceptable limits for the pharmaceutical industry, when a six-station pin-on-plate wear simulator was used to generate ultra-high-molecular-weight polyethylene wear particles in a non-sterile environment. Different pore-sized polycarbonate filters were investigated to isolate nanometre-sized ultra-high-molecular-weight polyethylene wear particles from the wear test lubricants. The use of the filter sequence of 10, 1, 0.1, 0.1 and 0.015 µm pore sizes allowed successful isolation of ultra-high-molecular-weight polyethylene wear particles with a size range of < 100 nm, which was suitable for cell culture studies. PMID:24658586

Generation of a large volume of clinically relevant nanometre-sized ultra-high-molecular-weight polyethylene wear particles for cell culture studies.

PubMed

Liu, Aiqin; Ingham, Eileen; Fisher, John; Tipper, Joanne L

2014-04-01

It has recently been shown that the wear of ultra-high-molecular-weight polyethylene in hip and knee prostheses leads to the generation of nanometre-sized particles, in addition to micron-sized particles. The biological activity of nanometre-sized ultra-high-molecular-weight polyethylene wear particles has not, however, previously been studied due to difficulties in generating sufficient volumes of nanometre-sized ultra-high-molecular-weight polyethylene wear particles suitable for cell culture studies. In this study, wear simulation methods were investigated to generate a large volume of endotoxin-free clinically relevant nanometre-sized ultra-high-molecular-weight polyethylene wear particles. Both single-station and six-station multidirectional pin-on-plate wear simulators were used to generate ultra-high-molecular-weight polyethylene wear particles under sterile and non-sterile conditions. Microbial contamination and endotoxin levels in the lubricants were determined. The results indicated that microbial contamination was absent and endotoxin levels were low and within acceptable limits for the pharmaceutical industry, when a six-station pin-on-plate wear simulator was used to generate ultra-high-molecular-weight polyethylene wear particles in a non-sterile environment. Different pore-sized polycarbonate filters were investigated to isolate nanometre-sized ultra-high-molecular-weight polyethylene wear particles from the wear test lubricants. The use of the filter sequence of 10, 1, 0.1, 0.1 and 0.015 µm pore sizes allowed successful isolation of ultra-high-molecular-weight polyethylene wear particles with a size range of < 100 nm, which was suitable for cell culture studies.

Adsorption of Poly(methyl methacrylate) on Concave Al2O3 Surfaces in Nanoporous Membranes

PubMed Central

Nunnery, Grady; Hershkovits, Eli; Tannenbaum, Allen; Tannenbaum, Rina

2009-01-01

The objective of this study was to determine the influence of polymer molecular weight and surface curvature on the adsorption of polymers onto concave surfaces. Poly(methyl methacrylate) (PMMA) of various molecular weights was adsorbed onto porous aluminum oxide membranes having various pore sizes, ranging from 32 to 220 nm. The surface coverage, expressed as repeat units per unit surface area, was observed to vary linearly with molecular weight for molecular weights below ~120 000 g/mol. The coverage was independent of molecular weight above this critical molar mass, as was previously reported for the adsorption of PMMA on convex surfaces. Furthermore, the coverage varied linearly with pore size. A theoretical model was developed to describe curvature-dependent adsorption by considering the density gradient that exists between the surface and the edge of the adsorption layer. According to this model, the density gradient of the adsorbed polymer segments scales inversely with particle size, while the total coverage scales linearly with particle size, in good agreement with experiment. These results show that the details of the adsorption of polymers onto concave surfaces with cylindrical geometries can be used to calculate molecular weight (below a critical molecular weight) if pore size is known. Conversely, pore size can also be determined with similar adsorption experiments. Most significantly, for polymers above a critical molecular weight, the precise molecular weight need not be known in order to determine pore size. Moreover, the adsorption developed and validated in this work can be used to predict coverage also onto surfaces with different geometries. PMID:19415910

Fluorescence fingerprints and Cu2+-complexing ability of individual molecular size fractions in soil- and waste-borne DOM.

PubMed

Knoth de Zarruk, K; Scholer, G; Dudal, Y

2007-09-01

Land spreading of organic materials introduces large amounts of dissolved organic matter (DOM) into the soil. DOM has the ability to form stable complexes with heavy metals and can facilitate their transport towards the groundwater. The effects on soil processes are difficult to assess, because different DOM components might react differently towards metal ions. The objective of this study was to investigate the fluorescence signature and the Cu2+-binding capacity of individual molecular size fractions of DOM from various sources. DOM extracted from leaf compost, chicken manure, sugar cane vinasse and a fulvic hypercalcaric cambisol was fractionated by the means of dialysis into four molecular size classes: MW<500, 50012000-14000 Da. Vinasse and leaf compost contained around 80% and 70%, respectively, of the total organic carbon in the fractions with low molecular weight (MW<3500 Da); in chicken manure and soil these fractions accounted for 40% and 50% only. Fluorescence was highest in the fraction MW>12000 Da for leaf compost, chicken manure and soil. The opposite result was obtained for vinasse, where the fractions with low molecular weight showed highest fluorescence intensities, distinguishing it from all other samples. Vinasse showed the greatest ability to bind Cu2+ with a resulting complex concentration of 6.31mgl(-1) while in contact with an excess of Cu2+. Leaf compost, soil and chicken manure followed with 2.69, 1.12, and 0.85mgl(-1), respectively. Within vinasse, the fraction MW<500 Da was able to form the most DOM-Cu complexes, indicating the importance of low molecular weight fractions in metal binding.

Linear Ion Trap for the Mars Organic Molecule Analyzer

NASA Astrophysics Data System (ADS)

Brinckerhoff, William; Arevalo, Ricardo; Danell, Ryan; van Amerom, Friso; Pinnick, Veronica; Li, Xiang; Hovmand, Lars; Getty, Stephanie; Mahaffy, Paul; Goesmann, Fred; Steininger, Harald

2014-05-01

The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. MOMA includes a linear, or 2D, ion trap mass spectrometer (ITMS) that is designed to analyze molecular composition of (i) gas evolved from pyrolyzed powder samples and separated on a gas chromatograph and (ii) ions directly desorbed from solid samples at Mars ambient pressure using a pulsed laser and a fast-valve capillary ion inlet system. This "dual source" approach gives MOMA unprecedented breadth of detection over a wide range of molecular weights and volatilities. Analysis of nonvolatile, higher-molecular weight organics such as carboxylic acids and peptides even in the presence of significant perchlorate concentrations is enabled by the extremely short (~1 ns) pulses of the desorption laser. Use of the ion trap's tandem mass spectrometry mode permits selective focus on key species for isolation and controlled fragmentation, providing structural analysis capabilities. The flight-like engineering test unit (ETU) of the ITMS, now under construction, will be used to verify breadboard performance with high fidelity, while simultaneously supporting the development of analytical scripts and spectral libraries using synthetic and natural Mars analog samples guided by current results from MSL. ETU campaign data will strongly advise the specifics of the calibration applied to the MOMA flight model as well as the science operational procedures during the mission.

Online reverse phase-high-performance liquid chromatography-fluorescence detection-electrospray ionization-mass spectrometry separation and characterization of heparan sulfate, heparin, and low-molecular weight-heparin disaccharides derivatized with 2-aminoacridone.

PubMed

Galeotti, Fabio; Volpi, Nicola

2011-09-01

A high-resolution online reverse-phase-high-performance liquid chromatography (RP-HPLC)-fluorescence detector (Fd)-electrospray ionization-mass spectrometry (ESI-MS) separation and structural characterization of disaccharides prepared from heparin (Hep), heparan sulfate (HS), and various low-molecular-weight (LMW)-Hep using heparin lyases and derivatization with 2-aminoacridone (AMAC) are described. A total of 12 commercially available Hep/HS-derived unsaturated disaccharides were separated and unambiguously identified on the basis of their retention times and mass spectra. The constituent disaccharides of various samples, including unfractionated Hep/HS, fast-moving and slow-moving Hep components, and several marketed products, were characterized. Furthermore, for the first time, the saturated trisulfated disaccharide belonging to the nonreducing end of Heps was detected as being approximately 2% in unfractionated samples and ~15-21% in LMW-Heps prepared by nitrous acid depolymerization. No desalting of the commercial products prior to enzymatic digestion or prepurification steps to eliminate any excess of AMAC reagent or interference from proteins, peptides, and other sample impurities before RP-HPLC-Fd-ESI-MS injection were necessary. This method has applicability for the rapid differentiation of pharmaceutical Heps and LMW-Heps prepared by means of different depolymerization processes and for compositional analysis of small amounts of samples derived from biological sources by using the highly sensitive fluorescence detector.

Structural characterization and evaluation of antioxidant, anticancer and hypoglycemic activity of radiation degraded oat (Avena sativa) β- glucan

NASA Astrophysics Data System (ADS)

Hussain, Peerzada R.; Rather, Sarver A.; Suradkar, Prashant P.

2018-03-01

Oat β-D-glucan after extraction was degraded at doses of 3, 6, 9, 12 and 15 kGy. The average molecular weight decreased to 45 kDa at dose of 15 kGy from an initial value of 200 kDa in native sample. XRD analysis revealed no significant change in diffraction pattern of irradiated samples when compared with control, except a decrease in intensity of x-ray diffraction. The results of the antioxidant activity revealed decrease in EC50 values and corresponding increase in antioxidant activity of radiation degraded oat β-D-glucan. Results of the anticancer studies indicated that cytotoxicity of gamma irradiated oat β-D-glucan in cancer cell lines was highest against colo-205 and MCF7 cancer cells compared to T47D cell and no cytotoxicity was observed in normal cell lines at all concentrations used. Evaluation of hypoglycemic activity showed highest inhibition in α-glucosidase activity compared to α-amylase activity due to gamma irradiation of oat β-D-glucan. Comparison of the EC50 values of known standards and gamma irradiated oat beta-glucan samples indicates that radiation treatment significantly modified the biological activity of the beta-glucan samples. Therefore, it is suggested that gamma irradiation can be used for producing low molecular weight oat β-D-glucan; which can help in modifying the biological activities.

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.

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

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.

Structure and properties of polyethylene films used in heavy lift balloons

NASA Technical Reports Server (NTRS)

Khoury, F.; Crissman, J. M.; Fanconi, B. M.; Wagner, H. L.; Botz, L. H.

1985-01-01

The following features of five polyethylene films used by NASA in the construction of heavy lift balloons have been examined: molecular weight, molecular weight distribution, branching, melting behavior, density, surface texture, birefringence, orientation of crystalline regions, unlaxial deformation in the machine and transverse directions, and the effect of sample geometry and strain rate on deformation behavior. The goal of this exploratory study was to determine whether there are significant differences in any of the above mentioned features, or combination of features between the films. The acquisition of such information is a first step towards determining whether there are any specific correlations between film characteristics and the incidence of catastrophic failure of balloons during ascent through the troposphere. This exploratory study has resulted in the identification of similarities and differences between various features of the films.

Metabolism of AGEs – Bacterial AGEs Are Degraded by Metallo-Proteases

PubMed Central

Cohen-Or, Ifat; Katz, Chen; Ron, Eliora Z.

2013-01-01

Advanced Glycation End Products (AGEs) are the final products of non-enzymatic protein glycation that results in loss of protein structure and function. We have previously shown that in E. coli AGEs are continually formed as high-molecular weight protein complexes. Moreover, we showed that AGEs are removed from the cells by an active, ATP-dependent secretion and that these secreted molecules have low molecular weight. Taken together, these results indicate that E. coli contains a fraction of low molecular weight AGEs, in addition to the high-molecular weight AGEs. Here we show that the low-molecular weight AGEs originate from high-molecular weight AGEs by proteolytic degradation. Results of in-vitro and in vivo experiments indicated that this degradation is carried out not by the major ATP-dependent proteases that are responsible for the main part of bacterial protein quality control but by an alternative metal-dependent proteolysis. This proteolytic reaction is essential for the further secretion of AGEs from the cells. As the biochemical reactions involving AGEs are not yet understood, the implication of a metalloprotease in breakdown of high molecular weight AGEs and their secretion constitutes an important step in the understanding of AGEs metabolism. PMID:24130678

Metabolism of AGEs--bacterial AGEs are degraded by metallo-proteases.

PubMed

Cohen-Or, Ifat; Katz, Chen; Ron, Eliora Z

2013-01-01

Advanced Glycation End Products (AGEs) are the final products of non-enzymatic protein glycation that results in loss of protein structure and function. We have previously shown that in E. coli AGEs are continually formed as high-molecular weight protein complexes. Moreover, we showed that AGEs are removed from the cells by an active, ATP-dependent secretion and that these secreted molecules have low molecular weight. Taken together, these results indicate that E. coli contains a fraction of low molecular weight AGEs, in addition to the high-molecular weight AGEs. Here we show that the low-molecular weight AGEs originate from high-molecular weight AGEs by proteolytic degradation. Results of in-vitro and in vivo experiments indicated that this degradation is carried out not by the major ATP-dependent proteases that are responsible for the main part of bacterial protein quality control but by an alternative metal-dependent proteolysis. This proteolytic reaction is essential for the further secretion of AGEs from the cells. As the biochemical reactions involving AGEs are not yet understood, the implication of a metalloprotease in breakdown of high molecular weight AGEs and their secretion constitutes an important step in the understanding of AGEs metabolism.

How Molecular Structure Affects Mechanical Properties of an Advanced Polymer

NASA Technical Reports Server (NTRS)

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

2000-01-01

density was performed over a range of temperatures below the glass transition temperature. The physical characterization, elastic properties and notched tensile strength all as a function of molecular weight and test temperature were determined. For the uncrosslinked SI material, 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. For the crosslinked PETI-SI material, it was shown that the effect of crosslinking significantly enhances the mechanical performance of the low molecular weight material; comparable to that exhibited by the high molecular weight material.

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.

Effect of Gamma Irradiation on Structural and Biological Properties of a PLGA-PEG-Hydroxyapatite Composite

PubMed Central

Shahabi, Sima; Najafi, Farhood; Majdabadi, Abbas; Hooshmand, Tabassom; Haghbin Nazarpak, Masoumeh; Karimi, Batool

2014-01-01

Gamma irradiation is able to affect various structural and biological properties of biomaterials In this study, a composite of Hap/PLGA-PEG and their ingredients were submitted to gamma irradiation doses of 25 and 50 KGy. Various properties such as molecular weight (GPC), thermal behavior (DSC), wettability (contact angle), cell viability (MTT assay), and alkaline phosphatase activity were studied for the composites and each of their ingredients. The results showed a decrease in molecular weight of copolymer with no change in the glass transition and melting temperatures after gamma irradiation. In general gamma irradiation can increase the activation energy ΔH of the composites and their ingredients. While gamma irradiation had no effect on the wettability of copolymer samples, there was a significant decrease in contact angle of hydroxyapatite and composites with increase in gamma irradiation dose. This study showed an increase in biocompatibility of hydroxyapatite with gamma irradiation with no significant effect on cell viability in copolymer and composite samples. In spite of the fact that no change occurred in alkaline phosphatase activity of composite samples, results indicated a decrease in alkaline phosphatase activity in irradiated hydroxyapatites. These effects on the properties of PLGA-PEG-hydroxyapatite can enhance the composite application as a biomaterial. PMID:25574485

Aerobic microbial taxa dominate deep subsurface cores from the Alberta oil sands.

PubMed

Ridley, Christina M; Voordouw, Gerrit

2018-06-01

Little is known about the microbial ecology of the subsurface oil sands in Northern Alberta, Canada. Biodegradation of low molecular weight hydrocarbons by indigenous microbes has enriched high molecular weight hydrocarbons, resulting in highly viscous bitumen. This extreme subsurface environment is further characterized by low nutrient availability and limited access to water, thus resulting in low microbial biomass. Improved DNA isolation protocols and increasingly sensitive sequencing methods have allowed an in-depth investigation of the microbial ecology of this unique subsurface environmental niche. Community analysis was performed on core samples (n = 62) that were retrieved from two adjacent sites located in the Athabasca Oil Sands at depths from 220 to 320 m below the surface. Microbial communities were dominated by aerobic taxa, including Pseudomonas and Acinetobacter. Only one core sample microbial community was dominated by anaerobic taxa, including the methanogen Methanoculleus, as well as Desulfomicrobium and Thauera. Although the temperature of the bitumen-containing subsurface is low (8°C), two core samples had high fractions of the potentially thermophilic taxon, Thermus. Predominance of aerobic taxa in the subsurface suggests the potential for in situ aerobic hydrocarbon degradation; however, more studies are required to determine the functional role of these taxa within this unique environment.

Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

DOE PAGES

Sun, Jing; Jiang, Xi; Siegmund, Aaron; ...

2016-04-04

Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this study, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (Φ Npm) values ranging from 0.13 to 0.44 and dispersity (¯D) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Drymore » samples with Φ Npm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. Finally, we demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers.« less

Optimizing separations in online comprehensive two-dimensional liquid chromatography.

PubMed

Pirok, Bob W J; Gargano, Andrea F G; Schoenmakers, Peter J

2018-01-01

Online comprehensive two-dimensional liquid chromatography has become an attractive option for the analysis of complex nonvolatile samples found in various fields (e.g. environmental studies, food, life, and polymer sciences). Two-dimensional liquid chromatography complements the highly popular hyphenated systems that combine liquid chromatography with mass spectrometry. Two-dimensional liquid chromatography is also applied to the analysis of samples that are not compatible with mass spectrometry (e.g. high-molecular-weight polymers), providing important information on the distribution of the sample components along chemical dimensions (molecular weight, charge, lipophilicity, stereochemistry, etc.). Also, in comparison with conventional one-dimensional liquid chromatography, two-dimensional liquid chromatography provides a greater separation power (peak capacity). Because of the additional selectivity and higher peak capacity, the combination of two-dimensional liquid chromatography with mass spectrometry allows for simpler mixtures of compounds to be introduced in the ion source at any given time, improving quantitative analysis by reducing matrix effects. In this review, we summarize the rationale and principles of two-dimensional liquid chromatography experiments, describe advantages and disadvantages of combining different selectivities and discuss strategies to improve the quality of two-dimensional liquid chromatography separations. © 2017 The Authors. Journal of Separation Science published by WILEY-VCH Verlag GmbH & Co. KGaA.

Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

PubMed Central

2016-01-01

Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this paper, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (ϕNpm) values ranging from 0.13 to 0.44 and dispersity (Đ) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Dry samples with ϕNpm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. We demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers. PMID:27134312

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.

High molecular weight non-polar hydrocarbons as pure model substances and in motor oil samples can be ionized without fragmentation by atmospheric pressure chemical ionization mass spectrometry.

PubMed

Hourani, Nadim; Kuhnert, Nikolai

2012-10-15

High molecular weight non-polar hydrocarbons are still difficult to detect by mass spectrometry. Although several studies have targeted this problem, lack of good self-ionization has limited the ability of mass spectrometry to examine these hydrocarbons. Failure to control ion generation in the atmospheric pressure chemical ionization (APCI) source hampers the detection of intact stable gas-phase ions of non-polar hydrocarbon in mass spectrometry. Seventeen non-volatile non-polar hydrocarbons, reported to be difficult to ionize, were examined by an optimized APCI methodology using nitrogen as the reagent gas. All these analytes were successfully ionized as abundant and intact stable [M-H](+) ions without the use of any derivatization or adduct chemistry and without significant fragmentation. Application of the method to real-life hydrocarbon mixtures like light shredder waste and car motor oil was demonstrated. Despite numerous reports to the contrary, it is possible to ionize high molecular weight non-polar hydrocarbons by APCI, omitting the use of additives. This finding represents a significant step towards extending the applicability of mass spectrometry to non-polar hydrocarbon analyses in crude oil, petrochemical products, waste or food. Copyright © 2012 John Wiley & Sons, Ltd.

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.

The effect of polymer architecture on the interdiffusion in thin polymer films

NASA Astrophysics Data System (ADS)

Caglayan, Ayse; Yuan, Guangcui; Satija, Sushil K.; Uhrig, David; Hong, Kunlun; Akgun, Bulent

Branched polymer chains have been traditionally used in industrial applications as additives. Recently they have found applications in electrochromic displays, lithography, biomedical coatings and targeting multidrug resistant bacteria. In some of these applications where they are confined in thin layers, it is important to understand the relation between the mobility and polymer chain architecture to optimize the processing conditions. Earlier interdiffusion measurements on linear and cyclic polymer chains demonstrated the key role of chain architecture on mobility. We have determined the vertical diffusion coefficients of the star polystyrene chains in thin films as a function of number of polymer arms, molecular weight per arm, and film thickness using neutron reflectivity (NR) and compare our results with linear chains of identical total molecular weight. Bilayer samples of 4-arm and 8-arm protonated polystyrenes (hPS) and deuterated polystyrenes (dPS) were used to elucidate the effect of polymer chain architecture on polymer diffusion. NR measurements indicate that the mobility of polymer chains in thin films get faster as the number of polymer arms increases and the arm molecular weight decreases. Both star polymers showed faster interdiffusion compared to their linear analog. Diffusion coefficient of branched PS chains has a weak dependence on the film thickness.

Block Copolymer-Based Supramolecular Elastomers with High Extensibility and Large Stress Generation Capability

NASA Astrophysics Data System (ADS)

Noro, Atsushi; Hayashi, Mikihiro

We prepared block copolymer-based supramolecular elastomers with high extensibility and large stress generation capability. Reversible addition fragmentation chain transfer polymerizations were conducted under normal pressure and high pressure to synthesize several large molecular weight polystyrene-b-[poly(butyl acrylate)-co-polyacrylamide]-b-polystyrene (S-Ba-S) block copolymers. Tensile tests revealed that the largest S-Ba-S with middle block molecular weight of 3140k achieved a breaking elongation of over 2000% with a maximum tensile stress of 3.6 MPa and a toughness of 28 MJ/m3 while the reference sample without any middle block hydrogen bonds, polystyrene-b-poly(butyl acrylate)-b-polystyrene with almost the same molecular weight, was merely viscous and not self-standing. Hence, incorporation of hydrogen bonds into a long soft middle block was found to be beneficial to attain high extensibility and large stress generation capability probably due to concerted combination of entropic changes and internal potential energy changes originaing from the dissociation of multiple hydrogen bonds by elongation. This work was supported by JSPS KAKENHI Grant Numbers 13J02357, 24685035, 15K13785, and 23655213 for M.H. and A.N. A.N. also expresses his gratitude for Tanaka Rubber Science & Technology Award by Enokagaku-Shinko Foundation, Japan.

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.

Rare expression of high-molecular-weight cytokeratin in adenocarcinoma of the prostate gland: a study of 100 cases of metastatic and locally advanced prostate cancer.

PubMed

Yang, X J; Lecksell, K; Gaudin, P; Epstein, J I

1999-02-01

Immunohistochemistry with antibodies for high-molecular-weight cytokeratin labels basal cells and is used as an ancillary study in diagnosing prostate carcinoma, which reportedly lacks expression of high-molecular-weight cytokeratin. A recent report questioned the specificity of this marker, describing immunopositivity for high-molecular-weight cytokeratin in a small series of metastatic prostate cancer. We have also noted rare cases of prostate lesions on biopsy with typical histological features of adenocarcinoma showing immunopositivity for high-molecular-weight cytokeratin, either in tumor cells or in patchy cells with the morphology of basal cells. In some of these cases, it was difficult to distinguish cancer from out-pouching of high-grade prostatic intraepithelial neoplasia. To investigate whether prostate cancer cells express high-molecular-weight cytokeratin, we studied 100 cases of metastatic prostate carcinoma and 10 cases of prostate cancer invading the seminal vesicles from surgical specimens. Metastatic sites included regional lymph nodes (n = 67), bone (n = 19), and miscellaneous (n = 14). Cases with any positivity for high-molecular-weight cytokeratin antibody (34betaE12) were verified as being of prostatic origin with immunohistochemistry for prostate-specific antigen and prostate-specific acid phosphatase. Only four cases were detected positive for high-molecular-weight cytokeratin. In two cases (one metastasis, one seminal vesicle invasion) there was weakly diffuse positivity above background level. Two metastases in lymph nodes showed scattered strong staining of clusters of tumor cells, which represented <0.2% of tumor cells in the metastatic deposits. These positive cells did not have the morphology of basal cells. We conclude that prostate cancer, even high grade, only rarely expresses high-molecular-weight cytokeratin. This marker remains a very useful adjunct in the diagnosis of prostate cancer.

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

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...

A comparison study between different molecular weight polysaccharides derived from Lentinus edodes and their antioxidant activities in vivo.

PubMed

You, Ruxu; Wang, Kaiping; Liu, Jinyu; Liu, Maochang; Luo, Li; Zhang, Yu

2011-12-01

Polysaccharide purified Lentinus edodes (Berk.) Sing (Tricholomataceae) has been reported to attenuate oxidative stress in vitro. This study investigated whether polysaccharides from L. edodes with different molecular weight have protective effects against oxidative stress induced by D-galactose (D-gal) in vivo, and determined the specific relationship between molecular weight and antioxidant activity. In the present study, we successfully obtained three purified polysaccharides, coded as LT1, LT2, and LT3, and their molecular weights were 25.5, 306.2, and 605.4 kDa, respectively. The D-gal-treated mice received three polysaccharides once daily for 60 days. The activities of superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px), the content of malondialdehyde (MDA), and erythrocyte membrane fluidity were measured to evaluate the changes of the antioxidant ability. It was demonstrated that the administration of LT1, LT2, and LT3 could improve the antioxidant status to different levels. Furthermore, LT2 exhibited the highest antioxidant ability among these samples in vivo. Indeed, LT2 significantly decreased the content of MDA in liver (15.91 ± 0.31 versus 23.79 ± 1.18 nmol/mg protein for the model group, p < 0.05), enhanced the fluidity of erythrocyte membrane (2.458 ± 0.023 versus 2.167 ± 0.024 for the model group, p < 0.05), and increased the activities of SOD (147.19 ± 4.90 versus 82.26 ± 5.55 units/mg protein for the model group, p < 0.05) and GSH-Px (310.91 ± 6.24 versus 243.64 ± 6.77 units/mg protein for the model group, p < 0.05) in liver. The LT2 had a potential to be used as a novel natural antioxidant.

Revealing Sources and Distribution Changes of Dissolved Organic Matter (DOM) in Pore Water of Sediment from the Yangtze Estuary

PubMed Central

Wang, Ying; Zhang, Di; Shen, Zhenyao; Feng, Chenghong; Chen, Jing

2013-01-01

Dissolved organic matter (DOM) in sediment pore waters from Yangtze estuary of China based on abundance, UV absorbance, molecular weight distribution and fluorescence were investigated using a combination of various parameters of DOM as well as 3D fluorescence excitation emission matrix spectra (F-EEMS) with the parallel factor and principal component analysis (PARAFAC-PCA). The results indicated that DOM in pore water of Yangtze estuary was very variable which mainly composed of low aromaticity and molecular weight materials. Three humic-like substances (C1, C2, C4) and one protein-like substance (C3) were identified by PARAFAC model. C1, C2 and C4 exhibited same trends and were very similar. The separation of samples on both axes of the PCA showed the difference in DOM properties. C1, C2 and C4 concurrently showed higher positive factor 1 loadings, while C3 showed highly positive factor 2 loadings. The PCA analysis showed a combination contribution of microbial DOM signal and terrestrial DOM signal in the Yangtze estuary. Higher and more variable DOM abundance, aromaticity and molecular weight of surface sediment pore water DOM can be found in the southern nearshore than the other regions primarily due to the influence of frequent and intensive human activities and tributaries inflow in this area. The DOM abundance, aromaticity, molecular weight and fluorescence intensity in core of different depth were relative constant and increased gradually with depth. DOM in core was mainly composed of humic-like material, which was due to higher release of the sedimentary organic material into the porewater during early diagenesis. PMID:24155904

A study on the quality control of slow burning polyester

NASA Astrophysics Data System (ADS)

Chen, Bin; Wang, Yinglei; Yan, Zhengfeng; Yu, Tao

2018-04-01

In this paper, the influence of the alcohol/acid mole ratio, reaction temperature, warm-up mode, end-capping, vacuity to the quality of slow burning polyester was studied. The hydroxyl value will increase when the alcohol/acid mole ratio increase, but the acid value and molecular weight will decrease. The molecular weight and molecular weight distribution of the polyester consistent with the designed one can be obtained by stepped heating up. Monobasic alcohol end-capping can be used to control the molecular weight effectively and reduce acid value. Stripping process narrow the molecular weight distribution and reduce the hydroxyl value. Decompression is in favor of the decrease of acid value and increase of the reaction speed to get qualified production.

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

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.

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...

Effects of soil water saturation on sampling equilibrium and kinetics of selected polycyclic aromatic hydrocarbons.

PubMed

Kim, Pil-Gon; Roh, Ji-Yeon; Hong, Yongseok; Kwon, Jung-Hwan

2017-10-01

Passive sampling can be applied for measuring the freely dissolved concentration of hydrophobic organic chemicals (HOCs) in soil pore water. When using passive samplers under field conditions, however, there are factors that might affect passive sampling equilibrium and kinetics, such as soil water saturation. To determine the effects of soil water saturation on passive sampling, the equilibrium and kinetics of passive sampling were evaluated by observing changes in the distribution coefficient between sampler and soil (K sampler/soil ) and the uptake rate constant (k u ) at various soil water saturations. Polydimethylsiloxane (PDMS) passive samplers were deployed into artificial soils spiked with seven selected polycyclic aromatic hydrocarbons (PAHs). In dry soil (0% water saturation), both K sampler/soil and k u values were much lower than those in wet soils likely due to the contribution of adsorption of PAHs onto soil mineral surfaces and the conformational changes in soil organic matter. For high molecular weight PAHs (chrysene, benzo[a]pyrene, and dibenzo[a,h]anthracene), both K sampler/soil and k u values increased with increasing soil water saturation, whereas they decreased with increasing soil water saturation for low molecular weight PAHs (phenanthrene, anthracene, fluoranthene, and pyrene). Changes in the sorption capacity of soil organic matter with soil water content would be the main cause of the changes in passive sampling equilibrium. Henry's law constant could explain the different behaviors in uptake kinetics of the selected PAHs. The results of this study would be helpful when passive samplers are deployed under various soil water saturations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Size distribution and clothing-air partitioning of polycyclic aromatic hydrocarbons generated by barbecue.

PubMed

Lao, Jia-Yong; Wu, Chen-Chou; Bao, Lian-Jun; Liu, Liang-Ying; Shi, Lei; Zeng, Eddy Y

2018-10-15

Barbecue (BBQ) is one of the most popular cooking activities with charcoal worldwide and produces abundant polycyclic aromatic hydrocarbons (PAHs) and particulate matter. Size distribution and clothing-air partitioning of particle-bound PAHs are significant for assessing potential health hazards to humans due to exposure to BBQ fumes, but have not been examined adequately. To address this issue, particle and gaseous samples were collected at 2-m and 10-m distances from a cluster of four BBQ stoves. Personal samplers and cotton clothes were carried by volunteers sitting near the BBQ stoves. Particle-bound PAHs (especially 4-6 rings) derived from BBQ fumes were mostly affiliated with fine particles in the size range of 0.18-1.8 μm. High molecular-weight PAHs were mostly unimodal peaking in fine particles and consequently had small geometric mean diameters and standard deviations. Source diagnostics indicated that particle-bound PAHs in BBQ fumes were generated primarily by combustion of charcoal, fat content in food, and oil. The influences of BBQ fumes on the occurrence of particle-bound PAHs decreased with increasing distance from BBQ stoves, due to increased impacts of ambient sources, especially by petrogenic sources and to a lesser extent by wind speed and direction. Octanol-air and clothing-air partition coefficients of PAHs obtained from personal air samples were significantly correlated to each other. High molecular-weight PAHs had higher area-normalized clothing-air partition coefficients in cotton clothes, i.e., cotton fabrics may be a significant reservoir of higher molecular-weight PAHs. Particle-bound PAHs from barbecue fumes are generated largely from charcoal combustion and food-charred emissions and mainly affiliated with fine particles. Copyright © 2018. Published by Elsevier B.V.

Molecular Sieving by the Bacillus megaterium Cell Wall and Protoplast

PubMed Central

Scherrer, Rene; Gerhardt, Philipp

1971-01-01

Passive permeabilities of the cell wall and protoplast of Bacillus megaterium strain KM were characterized by use of 50 hydrophilic probing molecules (tritiated water, sugars, dextrans, glycols, and polyglycols) which varied widely in size. Weight per cent uptake values (Rw) were measured at diffusional equilibrium under conditions that negated the influences of adsorption or active transport. Plots of Rw for intact cells as a function of number-average molecular weight (¯Mn) or Einstein-Stokes hydrodynamic radius (¯rES) of the solutes showed three phases: a protoplast uptake phase with a polydisperse exclusion threshold of ¯Mn = 0.6 × 103 to 1.1 × 103, ¯rES = 0.6 to 1.1 nm; a cell wall uptake phase with a polydisperse exclusion threshold of ¯Mn = 0.7 × 105 to 1.2 × 105, ¯rES ≅ 8.3 nm; and a total exclusion phase. Isolated cell walls showed only the latter two phases. However, it became evident that the cell wall selectively passed only the smallest molecules in a heterodisperse polymer sample. When the molecular-weight distributions of polyglycol samples (¯Mn = 1,000, 1,450, and 3,350) were determined by analytical gel chromatography before and after uptake by intact cells or isolated cell walls, a quasi-monodisperse exclusion threshold was obtained corresponding to Mn = 1,200, rES = 1.1 nm. The permeability of isolated protoplasts was assessed by the relative ability of solutes to effect osmotic stabilization. An indefinite exclusion threshold, evident even with monodisperse sugars, was attributed to lengthwise orientation of the penetrating rod-shaped molecules. Altogether, the best estimate of the limiting equivalent porosity of the protoplast was 0.4 to 0.6 nm in radius and of the cell wall, 1.1 nm. PMID:4999413

Separation, identification, quantification, and method validation of anthocyanins in botanical supplement raw materials by HPLC and HPLC-MS.

PubMed

Chandra, A; Rana, J; Li, Y

2001-08-01

A method has been established and validated for identification and quantification of individual, as well as total, anthocyanins by HPLC and LC/ES-MS in botanical raw materials used in the herbal supplement industry. The anthocyanins were separated and identified on the basis of their respective M(+) (cation) using LC/ES-MS. Separated anthocyanins were individually calculated against one commercially available anthocyanin external standard (cyanidin-3-glucoside chloride) and expressed as its equivalents. Amounts of each anthocyanin calculated as external standard equivalent were then multiplied by a molecular-weight correction factor to afford their specific quantities. Experimental procedures and use of a molecular-weight correction factors are substantiated and validated using Balaton tart cherry and elderberry as templates. Cyanidin-3-glucoside chloride has been widely used in the botanical industry to calculate total anthocyanins. In our studies on tart cherry and elderberry, its use as external standard followed by use of molecular-weight correction factors should provide relatively accurate results for total anthocyanins, because of the presence of cyanidin as their major anthocyanidin backbone. The method proposed here is simple and has a direct sample preparation procedure without any solid-phase extraction. It enables selection and use of commercially available anthocyanins as external standards for quantification of specific anthocyanins in the sample matrix irrespective of their commercial availability as analytical standards. It can be used as a template and applied for similar quantification in several anthocyanin-containing raw materials for routine quality control procedures, thus providing consistency in analytical testing of botanical raw materials used for manufacturing efficacious and true-to-the-label nutritional supplements.

Textile wastewater reuse after additional treatment by Fenton's reagent.

PubMed

Ribeiro, Marília Cleto Meirelles; Starling, Maria Clara V M; Leão, Mônica Maria Diniz; de Amorim, Camila Costa

2017-03-01

This study verifies textile wastewater reuse treated by the conventional activated sludge process and subjected to further treatment by advanced oxidation processes. Three alternative processes are discussed: Fenton, photo-Fenton, and UV/H 2 O 2 . Evaluation of treatments effects was based on factorial experiment design in which the response variables were the maximum removal of COD and the minimum concentration of residual H 2 O 2 in treated wastewater. Results indicated Fenton's reagent, COD/[H 2 O 2 ]/[Fe 2+ ] mass ratio of 1:2:2, as the best alternative. The selected technique was applied to real wastewater collected from a conventional treatment plant of a textile mill. The quality of the wastewater before and after the additional treatment was monitored in terms of 16 physicochemical parameters defined as suitable for the characterization of waters subjected to industrial textile use. The degradation of the wastewater was also evaluated by determining the distribution of its molecular weight along with the organic matter fractionation by ultrafiltration, measured in terms of COD. Finally, a sample of the wastewater after additional treatment was tested for reuse at pilot scale in order to evaluate the impact on the quality of dyed fabrics. Results show partial compliance of treated wastewater with the physicochemical quality guidelines for reuse. Removal and conversion of high and medium molecular weight substances into low molecular weight substances was observed, as well as the degradation of most of the organic matter originally present in the wastewater. Reuse tests indicated positive results, confirming the applicability of wastewater reuse after the suggested additional treatment. Graphical abstract Textile wastewater samples after additional treatment by Fenton's reagent, photo-Fenton and H 2 O 2 /UV tested in different conditions.

Molecular weight profiles of proanthocyanidin polymers

Treesearch

Vincent M. Williams; Lawrence J. Porter; Richard W. Hemingway

1983-01-01

The MW profiles of proanthocyanidin polymers (condensed tannins) from 32 samples representing a wide range of plant tissues of many different species have been obtained by gel permeation chromatography of the peracetate derivatives. The tannins vary widely in MW, with M values for the peracetates in the range 1600-5500. The MW profiles vary greatly from those with...

Background photobleaching in raman spectra of aqueous solutions of plant toxins

NASA Astrophysics Data System (ADS)

Brandt, Nikolai N.; Chikishev, Andrey Y.; Tonevitsky, Alexander G.

2002-05-01

Kinetics of background photobleaching in Raman spectra of aqueous solutions of ricin, ricin agglutinin and ricin binding subunit were measured. It was found that the spectrum of Raman background changes upon laser irradiation. Background intensity is lower for the samples with lower molecular weight. Photobleaching is characterized by oscillations in the multi exponentially decaying intensity.

Investigation of Deviations from Ideality in the Two Liquid Phase Region of Systems of Medium Molecular Weight Hydrocarbon Mixtures and Water.

DTIC Science & Technology

1986-02-01

determined by refractometry using a Bausch and Lomb Refractometer (Abbe 3-L). Refractive index calibrations for the binary mixtures examined are given in...mixture sample was taken and analyzed by refractometry . b. Results The results of the vapor pressure experiments and the Redlich- Kister coefficients

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

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.

Hydrodynamic size-based separation and characterization of protein aggregates from total cell lysates

PubMed Central

Tanase, Maya; Zolla, Valerio; Clement, Cristina C; Borghi, Francesco; Urbanska, Aleksandra M; Rodriguez-Navarro, Jose Antonio; Roda, Barbara; Zattoni, Andrea; Reschiglian, Pierluigi; Cuervo, Ana Maria; Santambrogio, Laura

2016-01-01

Herein we describe a protocol that uses hollow-fiber flow field-flow fractionation (FFF) coupled with multiangle light scattering (MALS) for hydrodynamic size-based separation and characterization of complex protein aggregates. The fractionation method, which requires 1.5 h to run, was successfully modified from the analysis of protein aggregates, as found in simple protein mixtures, to complex aggregates, as found in total cell lysates. In contrast to other related methods (filter assay, analytical ultracentrifugation, gel electrophoresis and size-exclusion chromatography), hollow-fiber flow FFF coupled with MALS allows a flow-based fractionation of highly purified protein aggregates and simultaneous measurement of their molecular weight, r.m.s. radius and molecular conformation (e.g., round, rod-shaped, compact or relaxed). The polyethersulfone hollow fibers used, which have a 0.8-mm inner diameter, allow separation of as little as 20 μg of total cell lysates. In addition, the ability to run the samples in different denaturing and nondenaturing buffer allows defining true aggregates from artifacts, which can form during sample preparation. The protocol was set up using Paraquat-induced carbonylation, a model that induces protein aggregation in cultured cells. This technique will advance the biochemical, proteomic and biophysical characterization of molecular-weight aggregates associated with protein mutations, as found in many CNS degenerative diseases, or chronic oxidative stress, as found in aging, and chronic metabolic and inflammatory conditions. PMID:25521790

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)

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, chitosan membranes shave the potential to be a suitable matrix for the development of glucose biosensors.

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 the potential to be a suitable matrix for the development of glucose biosensors. PMID:23940599

Silk-Elastinlike Copolymers for Breast Cancer Gene Therapy

DTIC Science & Technology

2005-05-01

linearized expression vector were mixed hydrolysis of the sample in 6 N HCI at 110 ’C for 20 h. at a high monomer-to-vector molar ratio in the presence of...measurements were taken for each sample GAGTA(GA(GTGC(GGTGTA(GAGTTCCTGCGATrT’GC( for calculation of q. TAcCAC(;AGTA(;(;CGTACCGCGAGG’AGGAGTGCC(;,GGTC The...P (Pro), proline ; Q (Gln), steps are to examine the influence of polymer molecular glutamine; Q, weight equilibrium swelling ratios of hydrogels

Prediction of stream volatilization coefficients

USGS Publications Warehouse

Rathbun, Ronald E.

1990-01-01

Equations are developed for predicting the liquid-film and gas-film reference-substance parameters for quantifying volatilization of organic solutes from streams. Molecular weight and molecular-diffusion coefficients of the solute are used as correlating parameters. Equations for predicting molecular-diffusion coefficients of organic solutes in water and air are developed, with molecular weight and molal volume as parameters. Mean absolute errors of prediction for diffusion coefficients in water are 9.97% for the molecular-weight equation, 6.45% for the molal-volume equation. The mean absolute error for the diffusion coefficient in air is 5.79% for the molal-volume equation. Molecular weight is not a satisfactory correlating parameter for diffusion in air because two equations are necessary to describe the values in the data set. The best predictive equation for the liquid-film reference-substance parameter has a mean absolute error of 5.74%, with molal volume as the correlating parameter. The best equation for the gas-film parameter has a mean absolute error of 7.80%, with molecular weight as the correlating parameter.

Melting of superheated molecular crystals

NASA Astrophysics Data System (ADS)

Cubeta, Ulyana; Bhattacharya, Deepanjan; Sadtchenko, Vlad

2017-07-01

Melting dynamics of micrometer scale, polycrystalline samples of isobutane, dimethyl ether, methyl benzene, and 2-propanol were investigated by fast scanning calorimetry. When films are superheated with rates in excess of 105 K s-1, the melting process follows zero-order, Arrhenius-like kinetics until approximately half of the sample has transformed. Such kinetics strongly imply that melting progresses into the bulk via a rapidly moving solid-liquid interface that is likely to originate at the sample's surface. Remarkably, the apparent activation energies for the phase transformation are large; all exceed the enthalpy of vaporization of each compound and some exceed it by an order of magnitude. In fact, we find that the crystalline melting kinetics are comparable to the kinetics of dielectric α-relaxation in deeply supercooled liquids. Based on these observations, we conclude that the rate of non-isothermal melting for superheated, low-molecular-weight crystals is limited by constituent diffusion into an abnormally dense, glass-like, non-crystalline phase.

Dynamics in supercooled polyalcohols: Primary and secondary relaxation

NASA Astrophysics Data System (ADS)

Döß, A.; Paluch, M.; Sillescu, H.; Hinze, G.

2002-10-01

We have studied details of the molecular dynamics in a series of pure polyalcohols by means of dielectric spectroscopy and 2H nuclear magnetic resonance (NMR). From glycerol to threitol, xylitol and sorbitol a systematic change in the dynamics of the primary and secondary relaxation is found. With increasing molecular weight and fragility an increase in the width of the α-peak is observed. Details of the molecular reorientation process responsible for the α-relaxation were exploited by two-dimensional NMR experiments. It is found that in the same sequence of polyalcohols the appearance of the secondary relaxation changes gradually from a wing type scenario to a pronounced β-peak. From NMR experiments using selectively deuterated samples the molecular origin of the secondary relaxation could be elucidated in more detail.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Guanguang; Chen, Baowei; Zhang, Rui

In this work, new strategies involving organic bases were evaluated to depolymerize lignin to reduced molecular fragments in aqueous medium. NaOH as an inorganic base was also investigated as a reference. Full nature lignin samples are used for the study. As research tools to unravel the complexity of the macro lignin structure and bulky molecular size under this study, size exclusion chromatography and high resolution mass spectrometric analysis, typically used for protein characterizations, were used to follow the progress of lignin depolymerisation by measuring the molecular weight distribution of the products and determining the key molecular fingerprints, respectively. The resultsmore » show that sodium phenoxide and guanidine carbonate are effective catalysts for lignin depolymerization. It is observed that there exists a synergism between H2O2 and the organic base, which is strongest with guanidine carbonate.« less

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.

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.

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.

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.

Sample Desorption/Onization From Mesoporous Silica

DOEpatents

Iyer, Srinivas; Dattelbaum, Andrew M.

2005-10-25

Mesoporous silica is shown to be a sample holder for laser desorption/ionization of mass spectrometry. Supported mesoporous silica was prepared by coating an ethanolic silicate solution having a removable surfactant onto a substrate to produce a self-assembled, ordered, nanocomposite silica thin film. The surfactant was chosen to provide a desired pore size between about 1 nanometer diameter and 50 nanometers diameter. Removal of the surfactant resulted in a mesoporous silica thin film on the substrate. Samples having a molecular weight below 1000, such as C.sub.60 and tryptophan, were adsorbed onto and into the mesoporous silica thin film sample holder and analyzed using laser desorption/ionization mass spectrometry.

Direct and comprehensive analysis of dyes based on integrated molecular and structural information via laser desorption laser postionization mass spectrometry.

PubMed

Liu, Rong; Yin, Zhibin; Leng, Yixin; Hang, Wei; Huang, Benli

2018-01-01

Laser desorption laser postionization time-of-flight mass spectrometry (LDPI-TOFMS) was employed for direct analysis and determination of typical basic dyes. It was also used for the analysis and comprehensive understanding of complex materials such as blue ballpoint pen inks. Simultaneous emergences of fragmental and molecular information largely simplify and facilitate unambiguous identification of dyes via variable energy of 266nm postionization laser. More specifically, by optimizing postionization laser energy with the same energy of desorption laser, the structurally significant results show definite differences in the fragmentation patterns, which offer opportunities for discrimination of isomeric species with identical molecular weight. Moreover, relatively high spectra resolution can be acquired without the expense of sensitivity. In contrast to laser desorption/ionization mass spectrometry (LDI-MS), LDPI-MS simultaneously offers valuable molecular information about dyes in traces, solvents and additives about inks, thereby offering direct determination and comprehensive understanding of blue ballpoint inks and giving a high level of confidence to discriminate the complicated evidentiary samples. In addition, direct analysis of the inks not only allows the avoidance of the tedious sample preparation processes, significantly shortening the overall analysis time and improving throughput, but allows minimized sample consumption which is important for rare and precious samples. Copyright © 2017 Elsevier B.V. All rights reserved.

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 the changing additions. Polyethylene oxide, in combination with polyethylene glycol, did show an increase in green strength versus the polyethylene oxide alone. Strengths were still lower than those displayed by the polyethylene glycols alone. Reductions or degradations in molecular weight of the polymers due to mixing and extrusion processes may account for lower green strength of bodies, especially those containing polyethylene oxides.

Gamma radiation effects on random copolymers based on poly(butylene succinate) for packaging applications

NASA Astrophysics Data System (ADS)

Negrin, M.; Macerata, E.; Consolati, G.; Quasso, F.; Genovese, L.; Soccio, M.; Giola, M.; Lotti, N.; Munari, A.; Mariani, M.

2018-01-01

Within the context of new bioplastic materials, poly(butylene succinate) (PBS) and four novel poly(butylene/thiodiethylene succinate) random copolymers (PBS-PTDGS), in sheets as well as in films, were exposed to gamma radiation, in air and in water, and their behavior along with the effect on their biodegradability was investigated. The molecular weight data obtained from gel permeation chromatography indicate that the sensibility to radiation increases with the amount of sulfur-containing co-unit (TDGS). At 200 kGy the average molecular weight of PBS film halves, while for P(BS60TDGS40) the residual molecular weight is about 20%. The calculated intermolecular crosslink Gx and scissioning Gs yields confirmed that degradation is predominant over crosslink for all the aliphatic systems. As shown by thermal analyses, gamma radiation affects the thermal properties, leading to an increased crystallinity of the systems, remarkable for PBS, and lower decomposition temperatures. Variations of crystallinity with the increasing absorbed dose were confirmed also by PALS analyses. Water contact angle measurements revealed post-irradiation wettability alterations that could positively affect polymer biodegradability. In particular, when irradiated in water at 100 kGy PBS film exhibits a water contact angle decrease of about 17%, indicating an enhanced wettability. After degradation in compost, changes in the surface morphology were observed by means of SEM and sample weight losses were determined, at different extent, according to the irradiation environment. Interestingly, after 52 days in compost PBS films, both pristine and irradiated in air at 25 kGy, showed a residual weight of about 60%, while the ones irradiated in water at 25 kGy of about 44%. Experimental data confirmed that gamma irradiation could represent a viable treatment to enhance biodegradation in compost of PBS and PBS-based copolymers.

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.

Role of modifiers for analytical-scale supercritical fluid extraction of environmental samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langenfeld, J.J.; Hawthorne, S.B.; Miller, D.J.

1994-03-15

Supercritical fluid extraction (SFE) using eight different CO[sub 2] + organic modifier mixtures and one ternary mixture (CO[sub 2] + methanol/toluene) at two different concentrations (1 and 10% v/v) was performed on two certified reference materials including polychlorinated biphenyls (PCBs) from river sediment and polycyclic aromatic hydrocarbons (PAHs) from urban air particulate matter. The modifier identity was more important than modifier concentration for increasing extraction efficiencies. Acidic/basic modifiers including methanol, acetic acid, and aniline greatly enhanced the extraction of PCBs. Low molecular weight PAHs were best extracted with modifiers including aniline, acetic acid, acetonitrile, methanol/toluene, hexane, and diethylamine. In contrast,more » modifiers capable of dipole-induced dipole interactions and [pi]-[pi] interactions such as toluene, diethylamine, and methylene chloride were the best modifiers to use for SFE of high molecular weight PAHs from air particulates. 37 refs., 6 tabs.« less

Manufacture and prebiotic potential of oligosaccharides derived from industrial solid wastes.

PubMed

Gullón, Patricia; González-Muñoz, María Jesús; Parajó, Juan Carlos

2011-05-01

The solid waste obtained in malting industries when dehulling barley grains, which was mainly made up of barley husks, spent grains and grain fragments, was subjected to a double hydrothermal processing under selected conditions. The liquor from the second stage (containing xylooligosaccharides, XOS) was refined by membrane and ion exchange processing (with or without a previous endoxylanase treatment to reduce the XOS molecular weight). Three XOS concentrates with different purity and/or molecular weight distribution were fermented in vitro with faecal inocula to assess their prebiotic potential. Succinate, lactate, formiate, acetate, propionate and butyrate were generated in fermentations, confirming the prebiotic potential of the various products assayed. The purity of XOS concentrates did not play a significant role in fermentation, whereas the sample with shorter average degree of polymerization presented a faster fermentation kinetics and led to the highest concentration of lactic acid. Copyright © 2011 Elsevier Ltd. All rights reserved.

X-ray diffraction, IR spectroscopy and thermal characterization of partially hydrolyzed guar gum.

PubMed

Mudgil, Deepak; Barak, Sheweta; Khatkar, B S

2012-05-01

Guar gum was hydrolyzed using cellulase from Aspergillus niger at 5.6 pH and 50°C temperature. Hydrolyzed guar gum sample was characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, dilute solution viscometry and rotational viscometry. Viscometry analysis of native guar gum showed a molecular weight of 889742.06, whereas, after enzymatic hydrolysis, the resultant product had a molecular weight of 7936.5. IR spectral analysis suggests that after enzymatic hydrolysis of guar gum there was no major transformation of functional group. Thermal analysis revealed no major change in thermal behavior of hydrolyzed guar gum. It was shown that partial hydrolysis of guar gum could be achieved by inexpensive and food grade cellulase (Aspergillus niger) having commercial importance and utilization as a functional soluble dietary fiber for food industry. Copyright © 2012 Elsevier B.V. All rights reserved.

[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.

Fluorescent characteristics of estrogenic compounds in landfill leachate.

PubMed

Zhanga, Hua; Changb, Cheng-Hsuan; Lü, Fan; Su, Ay; Lee, Duu-Jong; He, Pin-Jing; Shao, Li-Ming

2009-08-01

Estrogens in landfill leachate could probably contaminate receiving water sources if not properly polished before discharge. This work measured, using an estrogen receptor-alpha competitor screening assay, the estrogenic potentials of leachate samples collected at a local sanitary landfill in Shanghai, China and their compounds fractionated by molecular weights. The chemical structures of the constituent compounds were characterized using fluorescence excitation and emission matrix (EEM). The organic matters of molecular weight <600 Da and of 3000-14,000 Da contributed most of the estrogenic potentials of the raw leachates. The former were considered as the typical endocrine disrupting compounds in dissolved state; while the latter the fulvic acids with high aromaticity that were readily adsorbed with estrogens (bound state). Statistical analysis on EEM peaks revealed that the chemical structures of noted estrogens in dissolved state and in bound state were not identical. Aerobic treatment effectively removed dissolved estrogens, but rarely removed those bound estrogens.

Microdisc gel electrophoresis in sodium dodecyl sulfate of organic material from rat otoconial complexes

NASA Technical Reports Server (NTRS)

Ross, M. D.; Pote, K. G.; Rarey, K. E.; Verma, L. M.

1981-01-01

The gravity receptors of all vertebrates utilize a 'test mass' consisting of a complex arrangement of mineral and organic substance that lies over the sensory receptor areas. In most vertebrates, the mineral is a polymorph of calcium carbonate in the form of minute, single crystals called otoconia. An investigation is conducted to determine the number of proteins in otoconial complexes and their molecular weights. The investigation makes use of a microdisk gel electrophoresis method reported by Gainer (1971). The most important finding of the reported research is that analysis of the proteins of the organic material of the otoconial complexes is possible when sensitive microanalytical methods are employed. Further modification of the basic technique employed and the inclusion of other sensitive staining methods should mean that, in the future, protein separation by molecular weight will be possible in sample pools containing only two otoconial masses.

Conjugation of Specifically Developed Antibodies for High- and Low-Molecular-Weight Glutenins with Fluorescent Quantum Dots as a Tool for Their Detection in Wheat Flour Dough.

PubMed

Bonilla, Jose C; Ryan, Valerie; Yazar, Gamze; Kokini, Jozef L; Bhunia, Arun K

2018-04-25

The importance of gluten proteins, gliadins and glutenins, is well-known in the quality of wheat products. To gain more specific information about the role of glutenins in wheat dough, the two major subunits of glutenin, high- and low-molecular-weight (HMW and LMW) glutenins, were extracted, isolated, and identified by mass spectrometry. Antibodies for HMW and LMW glutenins were developed using the proteomic information on the characterized glutenin subunits. The antibodies were found to be specific to each subunit by western immunoblots and were then conjugated to quantum dots (QDs) using site-click conjugation, a new method to keep antibody integrity. A fluorescence-link immunosorbent assay tested the successful QD conjugation. The QD-conjugated antibodies were applied to dough samples, where they recognized glutenin subunits and were visualized using a confocal laser scanning microscope.

Branched chain amino acids maintain the molecular weight of poly(γ-glutamic acid) of Bacillus licheniformis ATCC 9945 during the fermentation.

PubMed

Mitsunaga, Hitoshi; Meissner, Lena; Büchs, Jochen; Fukusaki, Eiichiro

2016-10-01

Poly(γ-glutamic acid) mainly produced by Bacillus spp. is an industrially important compound due to several useful features. Among them, molecular weight is an important characteristic affecting on the physical properties such as viscosities and negative charge densities. However, it is difficult to control the molecular size of PGA since it decreases during fermentation. Previous study reported that PGA produced in the media containing different carbon sources such as glucose and glycerol showed differences in molecular weight. Therefore in this study, the effect of carbon source on the PGA molecular weight was examined; with the aim of developing a strategy to maintain the high molecular weight of PGA during fermentation. Our result showed that the weight average molecular weight (Mw) of PGA of Bacillus licheniformis ATCC 9945 cultivated in the media containing PTS-sugars were higher than the medium containing glycerol (non-PTS). The result of metabolome analysis indicated the possibility of CodY (a global regulator protein) activation in the cells cultivated in the media containing PTS-sugars. To mimic this effect, branched-chain amino acids (BCAAs), which are activators of CodY, were added to a medium containing glycerol. As the result, the Mw of PGA in the BCAAs-supplemented media were maintained and high during the early production phase compared to the non BCAAs-supplemented medium. These results indicate that BCAAs can repress the PGA molecular weight reduction during fermentation in B. licheniformis ATCC 9945. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

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.

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.

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.

Seed gum of Stryphnodendron barbatiman (Barbatimao)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reicher, F.; Leitner, S.C.S.; Fontana, J.D.

1991-12-31

Stryphnodendron barbatiman (barbatimao) is a native tree that is found throughout the {open_quotes}Cerrados,{close_quotes} a region of Central Brazil. Plant seeds, on water extraction, furnished 28 g% galactomannan (dry-weight basis), the monosaccharide composition of which (galactose to mannose ratio, 1.0:1.5) fits in the legume heteromannan group. This seed gum, after Sevag deproteinization, still retained 6 g% of associated protein and had a molecular weight of about 1.8 MD on gel filtration. A high intrinsic viscosity (1300 cP) was observed for the polysaccharide sample obtained after reflux of the crushed seeds in 80% aqueous methanol.

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.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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.

Molecular Adsorber Coating

NASA Technical Reports Server (NTRS)

Straka, Sharon; Peters, Wanda; Hasegawa, Mark; Hedgeland, Randy; Petro, John; Novo-Gradac, Kevin; Wong, Alfred; Triolo, Jack; Miller, Cory

2011-01-01

A document discusses a zeolite-based sprayable molecular adsorber coating that has been developed to alleviate the size and weight issues of current ceramic puck-based technology, while providing a configuration that more projects can use to protect against degradation from outgassed materials within a spacecraft, particularly contamination-sensitive instruments. This coating system demonstrates five times the adsorption capacity of previously developed adsorber coating slurries. The molecular adsorber formulation was developed and refined, and a procedure for spray application was developed. Samples were spray-coated and tested for capacity, thermal optical/radiative properties, coating adhesion, and thermal cycling. Work performed during this study indicates that the molecular adsorber formulation can be applied to aluminum, stainless steel, or other metal substrates that can accept silicate-based coatings. The coating can also function as a thermal- control coating. This adsorber will dramatically reduce the mass and volume restrictions, and is less expensive than the currently used molecular adsorber puck design.

[The value of low-molecular-weight DNA of blood plasma in the diagnostic of the patological processes of different genesis].

PubMed

Vasil'eva, I N; Zinkin, V N

2013-01-01

The low-molecular-weight DNA appears in blood plasma of irradiated rats, and its content correlates directly with the irradiation dose. Cloning has shown, that enrichment of low-molecular-weight DNA with G+C content and features of its nucleotide sequences point to its ability to form rather stable nucleosomes. DNA obtained after irradiation of rats with principally different doses 8 and 100 Gy differed not only quantitatively, but also by content of the dinucleotides CpG and CpT; this suggests their origin from different sites of genome. For the first time it has been shown that exposure to low-frequency noise results in an increase of the contents of blood plasma low-molecular-weight DNA. In stroke patients blood concentrations of this DNA increased 3 days after the beginning of the acute period, and dynamics of its excretion differs in ischemic and hemorrhagic forms; in the case of ischemia low-molecular-weight DNA appears in cerebrospinal fluid. The chronic obstructive pulmonary disease in the state of remission is characterized by the decline of the level of low-molecular-weight DNA in the blood plasma unlike in the case of the chronic nonobstructive bronchitis. The clear dependence between formation and special features of the low-molecular-weight DNA fraction in blood plasma makes it possible to consider the low-molecular fraction as an universal index of apoptosis, which allows to distinguish basically different conditions of the body.

Ultraviolet-B radiation induced crosslinking improves physical properties of cold- and warm-water fish gelatin gels and films

USDA-ARS?s Scientific Manuscript database

Cold- and warm-water fish gelatin granules were exposed to ultraviolet-B radiation for doses up to 29.7 J/cm2. Solutions and films were prepared from the granules. Gel electrophoresis and refractive index were used to examine changes in molecular weight of the samples. Also, the gel strength and rhe...

Quick detection of Leifsonia xyli subsp. xyli by PCR and necleotide sequence analysis of PCR amplicons from Chinese Leifsonia xyli subsp. xyli isolates

USDA-ARS?s Scientific Manuscript database

A quick polymerase chain reaction (PCR) assay was developed for the detection of Leifsonia xyli subsp. xyli (Lxx), the bacterial causal agent of ratoon stunting disease (RSD) of sugarcane, in crude juice samples from stalks. After removal of abiotic impurities and large molecular weight microorgani...

Measuring the molecular dimensions of wine tannins: comparison of small-angle X-ray scattering, gel-permeation chromatography and mean degree of polymerization.

PubMed

McRae, Jacqui M; Kirby, Nigel; Mertens, Haydyn D T; Kassara, Stella; Smith, Paul A

2014-07-23

The molecular size of wine tannins can influence astringency, and yet it has been unclear as to whether the standard methods for determining average tannin molecular weight (MW), including gel-permeation chromatography (GPC) and depolymerization reactions, are actually related to the size of the tannin in wine-like conditions. Small-angle X-ray scattering (SAXS) was therefore used to determine the molecular sizes and corresponding MWs of wine tannin samples from 3 and 7 year old Cabernet Sauvignon wine in a variety of wine-like matrixes: 5-15% and 100% ethanol; 0-200 mM NaCl and pH 3.0-4.0, and compared to those measured using the standard methods. The SAXS results indicated that the tannin samples from the older wine were larger than those of the younger wine and that wine composition did not greatly impact on tannin molecular size. The average tannin MWs as determined by GPC correlated strongly with the SAXS results, suggesting that this method does give a good indication of tannin molecular size in wine-like conditions. The MW as determined from the depolymerization reactions did not correlate as strongly with the SAXS results. To our knowledge, SAXS measurements have not previously been attempted for wine tannins.

The effect of the molecular orientation on the release of antimicrobial substances from uniaxially drawn polymer matrixes.

PubMed

Iconomopoulou, S M; Voyiatzis, G A

2005-03-21

A new method of controlled release of low molecular weight biocides incorporated in polymer matrixes is described. The molecular orientation of uniaxially drawn biocide doped polymer films is suggested as a significant parameter for controlled release monitoring. Triclosan, a well-established widespread antibacterial agent, has been incorporated into high density polyethylene (HDPE) films that have been subsequently uniaxially drawn at different draw ratios. The molecular orientation developed was estimated utilizing polarized mu-Raman spectra. Biocide incorporated polymer films, drawn at different draw ratios, have been immersed in ethanol-water solutions (EtOH) and in physiological saline. The release of Triclosan out of the polymer matrix was probed with UV-Vis absorption spectroscopy for a period of time up to 15 months. In all cases, although the film surface of the drawn samples exposed to the liquid solution was higher than the undrawn one, the relevant release rate from the drawn specimens was lower than the non-stretched samples depending on the molecular orientation developed during the drawing process. A note is made of the fact that no significant molecular orientation relaxation of the polyethylene films has been observed even after such a long time of immersion of the drawn films in the liquid solutions.

Solid-phase microextraction for qualitative and quantitative determination of migrated degradation products of antioxidants in an organic aqueous solution.

PubMed

Burman, Lina; Albertsson, Ann-Christine; Höglund, Anders

2005-07-08

Low molecular weight aromatic substances may migrate out from plastic packaging to their contents, especially if they consist of organic aqueous solutions or oils. It is, therefore, extremely important to be able to identify and quantify any migrated substances in such solutions, even at very low concentrations. We have in this work investigated and evaluated the use of solid-phase microextraction for the specific task of extraction from an organic aqueous solution such as a simulated pharmaceutical solution consisting of 10 vol.% ethanol in water. The goal was furthermore to investigate the possibility of simultaneously identifying and quantifying the substances in spite of differences in their chemical structures. Methods were developed and evaluated for extraction both with direct sampling and with headspace sampling. Difficulties appeared due to the ethanol in the solution and the minute amounts of substances present. We have shown that a simultaneous quantification of migrated low molecular weight degradation products of antioxidants using only one fibre is possible if the extraction method and temperature are adjusted in relation to the concentration levels of the analytes. Comparions were made with solid-phase extraction.

Weathering Patterns of Forensic Biomarker Compounds and PAHs in Coastal Marsh Sediment Samples since the 2010 Deepwater Horizon Oil Spill

NASA Astrophysics Data System (ADS)

Overton, E. B.; Meyer, B.; Miles, S.; Olson, G.; Adhikari, P. L.

2016-02-01

It has been well established that the composition of oil, when spilled into the marine environment, undergoes substantial changes caused by weathering. The general sequence of this compositional change begins with straight chain alkanes (the fastest to degrade), followed by low molecular weight branched and cyclic alkanes and, finally the aromatics. Most resistant to weathering are the higher molecular weight cyclic and branched alkanes (i.e., the "forensic biomarker compounds" such as the hopanes and steranes) and tri-aromatic ringed steroids. The composition of these biomarker compounds is particularly resistant to change because they are not affected by evaporative weathering, are not water soluble, and are not readily degraded by microbial and/or photo-oxidation. However, after extensive time in the environment, being subjected to numerous weathering factors, biomarker compositional patterns are beginning to exhibit significant changes. This presentation will describe the general weathering patterns of petroleum residues in sediment samples collected from marsh areas of coastal Louisiana over a five year period. Particular attention will focus on compositional changes that have been observed in the steranes and diasteranes compounds that traditionally have been considered the most resistant to compositional changes due to weathering.

Elucidating Adsorptive Fractions of Natural Organic Matter on Carbon Nanotubes.

PubMed

Ateia, Mohamed; Apul, Onur G; Shimizu, Yuta; Muflihah, Astri; Yoshimura, Chihiro; Karanfil, Tanju

2017-06-20

Natural organic matter (NOM) is a heterogeneous mixture of organic compounds that is omnipresent in natural waters. To date, the understanding of the adsorption of NOM components by carbon nanotubes (CNTs) is limited because of the limited number of comprehensive studies in the literature examining the adsorption of NOM by CNTs. In this study, 11 standard NOM samples from various sources were characterized, and their adsorption behaviors on four different CNTs were examined side-by-side using total organic carbon, fluorescence, UV-visible spectroscopy, and high-performance size-exclusion chromatography (HPSEC) analysis. Adsorption was influenced by the chemical properties of the NOM, including aromaticity, degree of oxidation, and carboxylic acidity. Fluorescence excitation-emission matrix (EEM) analysis showed preferential adsorption of decomposed and terrestrial-derived NOM compared to freshly produced and microbial-derived NOM. HPSEC analysis revealed preferential adsorption of fractions in the molecular weight range of 0.5-2 kDa for humic acids but in the molecular weight range of 1-3 kDa for all fulvic acids and reverse-osmosis isolates. However, the smallest characterized fraction (MW < 0.4 kDa) in all samples did not adsorb on the CNTs.

Simultaneous determination of low-molecular-weight organic acids and chlorinated acid herbicides in environmental water by a portable CE system with contactless conductivity detection.

PubMed

Xu, Yan; Wang, Weilong; Li, Sam Fong Yau

2007-05-01

This report describes a method to simultaneously determine 11 low-molecular-weight (LMW) organic acids and 16 chlorinated acid herbicides within a single run by a portable CE system with contactless conductivity detection (CCD) in a poly(vinyl alcohol) (PVA)-coated capillary. Under the optimized condition, the LODs of CE-CCD ranged from 0.056 to 0.270 ppm, which were better than for indirect UV (IUV) detection of the 11 LMW organic acids or UV detection of the 16 chlorinated acid herbicides. Combined with an on-line field-amplified sample stacking (FASS) procedure, sensitivity enhancement of 632- to 1078-fold was achieved, with satisfactory reproducibility (RSDs of migration times less than 2.2%, and RSDs of peak areas less than 5.1%). The FASS-CE-CCD method was successfully applied to determine the two groups of acidic pollutants in two kinds of environmental water samples. The portable CE-CCD system shows advantages such as simplicity, cost effectiveness, and miniaturization. Therefore, the method presented in this report has great potential for onsite analysis of various pollutants at the trace level.

Characterization of pitch prepared from pyrolysis fuel oil via electron beam irradiation

NASA Astrophysics Data System (ADS)

Kim, Hong Gun; Park, Mira; Kim, Hak-Yong; Kwac, Lee Ku; Shin, Hye Kyoung

2017-06-01

Pitch samples were obtained from pyrolysis fuel oil by thermal treatment for 2 h at 300 °C after electron beam irradiation (EBI) treatment and by thermal treatment alone for different temperature of 250 °C, 300 °C, and 350 °C. EBI treatment was found to be an effective treatment for preparing pitch compare to the pitch obtained without EBI treatment. These results were confirmed by Fourier transform infrared spectroscopy (FT-IR) and Carbon-13 nuclear magnetic resonance (13C NMR) analyses, which showed the increase in the intensities of peaks corresponding to aromatic compounds. In the matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) spectra, the amount of components with medium molecular weights in the pitch was found to increase with the temperature; likewise, in the case of the pitch obtained via EBI treatment, we found that the amount of components with higher molecular weight over 1000 (m/v) similarly increased. Further, the thermal stability and carbon yield at 850 °C of the pitch obtained by EBI were greater than those of samples subjected to thermal treatment at 250 and 300 °C.

Quantification of low molecular weight selenium metabolites in human plasma after treatment with selenite in pharmacological doses by LC-ICP-MS.

PubMed

Flouda, Konstantina; Dersch, Julie Maria; Gabel-Jensen, Charlotte; Stürup, Stefan; Misra, Sougat; Björnstedt, Mikael; Gammelgaard, Bente

2016-03-01

The paper presents an analytical method for quantification of low molecular weight (LMW) selenium compounds in human plasma based on liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS) and post column isotope dilution-based quantification. Prior to analysis, samples were ultrafiltrated using a cut-off value of 3000 Da. The method was validated in aqueous solution as well as plasma using standards of selenomethionine (SeMet), Se-methylselenocysteine (MeSeCys), selenite, and the selenosugar Se-methylseleno-N-acetylgalactosamine (SeGal) for linearity, precision, recoveries, and limits of detection and quantitation with satisfactory results. The method was applied for analysis of a set of plasma samples from cancer patients receiving selenite treatment in a clinical trial. Three LMW selenium compounds were observed. The main compounds, SeGal and selenite were tentatively identified by retention time matching with standards in different chromatographic systems, while the third minor compound was not identified. The identity of the selenosugar was verified by ESI-MS-MS product ion scanning, while selenite was identified indirectly as the glutathione (GSH) reaction product, GS-Se-SG.

Fossil fuel combined cycle power system

DOEpatents

Labinov, Solomon Davidovich; Armstrong, Timothy Robert; Judkins, Roddie Reagan

2006-10-10

A system for converting fuel energy to electricity includes a reformer for converting a higher molecular weight gas into at least one lower molecular weight gas, at least one turbine to produce electricity from expansion of at least one of the lower molecular weight gases, and at least one fuel cell. The system can further include at least one separation device for substantially dividing the lower molecular weight gases into at least two gas streams prior to the electrochemical oxidization step. A nuclear reactor can be used to supply at least a portion of the heat the required for the chemical conversion process.

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.

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.

Efficiently sampling conformations and pathways using the concurrent adaptive sampling (CAS) algorithm

NASA Astrophysics Data System (ADS)

Ahn, Surl-Hee; Grate, Jay W.; Darve, Eric F.

2017-08-01

Molecular dynamics simulations are useful in obtaining thermodynamic and kinetic properties of bio-molecules, but they are limited by the time scale barrier. That is, we may not obtain properties' efficiently because we need to run microseconds or longer simulations using femtosecond time steps. To overcome this time scale barrier, we can use the weighted ensemble (WE) method, a powerful enhanced sampling method that efficiently samples thermodynamic and kinetic properties. However, the WE method requires an appropriate partitioning of phase space into discrete macrostates, which can be problematic when we have a high-dimensional collective space or when little is known a priori about the molecular system. Hence, we developed a new WE-based method, called the "Concurrent Adaptive Sampling (CAS) algorithm," to tackle these issues. The CAS algorithm is not constrained to use only one or two collective variables, unlike most reaction coordinate-dependent methods. Instead, it can use a large number of collective variables and adaptive macrostates to enhance the sampling in the high-dimensional space. This is especially useful for systems in which we do not know what the right reaction coordinates are, in which case we can use many collective variables to sample conformations and pathways. In addition, a clustering technique based on the committor function is used to accelerate sampling the slowest process in the molecular system. In this paper, we introduce the new method and show results from two-dimensional models and bio-molecules, specifically penta-alanine and a triazine trimer.

Correlation of transarterial transport of various dextrans with their physicochemical properties.

PubMed

Elmalak, O; Lovich, M A; Edelman, E

2000-11-01

Local vascular drug delivery provides elevated concentrations of drug in the target tissue while minimizing systemic side effects. To better characterize local pharmacokinetics we examined the arterial transport of locally applied dextran and dextran derivatives in vivo. Using a two-compartment pharmacokinetic model to correct the measured transmural flux of these compounds for systemic redistribution and elimination as delivered from a photopolymerizable hydrogel surrounding rat carotid arteries, we found that the diffusivities and the transendothelial permeabilities were strongly dependent on molecular weight and charge. For neutral dextrans, the effective diffusive resistance in the media increased with molecular weight approximately 4.1-fold between the molecular weights of 10 and 282 kDa. Similarly, endothelial resistance increased 28-fold over the same molecular weight range. The effective medial diffusive resistance was unaffected by cationic charge as such molecules moved identically to neutral compounds, but increased approximately 40% when dextrans were negatively charged. Transendothelial resistance was 20-fold lower for the cationic dextrans, and 11-fold higher for the anionic dextrans, when both were compared to neutral counterparts. These results suggest that, while low molecular weight drugs will rapidly traverse the arterial wall with the endothelium posing a minimal barrier, the reverse is true for high molecular weight agents. With these data, the deposition and distribution of locally released vasotherapeutic compounds might be predicted based upon chemical properties, such as molecular weight and charge.

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.

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Polychlorinated biphenyls and polybrominated biphenyl ethers in adipose tissue and matched serum from an E-waste recycling area (Wenling, China).

PubMed

Lv, Quan-Xia; Wang, Wenyue; Li, Xing-Hong; Yu, Lianlian; Zhang, Yun; Tian, Yuan

2015-04-01

To Date, the knowledge on relationship between PCBs/PBDEs exposure and thyroid hormones (THs) levels during pregnancy still needs to be extended. Meanwhile, studies on congener-specific adipose-serum ratios for PCBs/PBDEs were limited. This study reports the levels of PCBs/PBDEs in serum-adipose tissue samples (n = 64) from expectant women living surrounding e-waste recycling sites in Wenling, China. Their concentrations varied from several to hundreds of ng g(-1) lipid. Maternal exposure to PCBs was associated with lower TSH during pregnancy, suggesting possible implication for maternal health and fetal development. The compound levels between the adipose tissue and matched serum samples were highly correlated (p < 0.001), generating a predicted adipose-serum partitioning relationship for individual PCB congener and PBDE congener. Molecular characteristics, such as Kow value, molecular weight and molecular volume, may play a key role in the variable partitioning of some compounds between serum and adipose tissue. Copyright © 2015 Elsevier Ltd. All rights reserved.

Titanium compounds as catalysts of higher alpha-olefin-based super-high-molecular polymers synthesis

NASA Astrophysics Data System (ADS)

Konovalov, K. B.; Kazaryan, M. A.; Manzhay, V. N.; Vetrova, O. V.

2016-01-01

The synthesis of polymers of 10 million or more molecular weight is a difficult task even in a chemical lab. Higher α-olefin-based polymer agents of such kind have found a narrow but quite important niche, the reduction of drag in the turbulent flow of hydrocarbon fluids such as oil and oil-products. In its turn, searching for a catalytic system capable to produce molecules of such a high length and to synthesize polymers of a low molecular-mass distribution is part of a global task of obtaining a high-quality product. In this paper we had observed a number of industrial catalysts with respect to their suitability for higher poly-α- olefins synthesis. A number samples representing copolymers of 1-hexene with 1-decene obtained on a previous generation catalyst, a microsphere titanium chloride catalytic agent had been compared to samples synthesized using a titanium-magnesium catalyst both in solution and in a polymer medium.

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.

GOM Deepwater Horizon Oil Spill: A Time Series Analysis of Variations in Spilled Hydrocarbons

NASA Astrophysics Data System (ADS)

Palomo, C. M.; Yan, B.

2013-12-01

An estimated amount of 210 million gallons of crude oil was released into the Gulf of Mexico (GOM) from April 20th to July 15th 2010 during the Deepwater Horizon oil rig explosion. The spill caused a tremendous financial, ecological, environmental and health impact and continues to affect the GOM today. Variations in hydrocarbons including alkanes, hopanes and poly-cyclic aromatic hydrocarbons (PAHs) can be analyzed to better understand the oil spill and assist in oil source identification. Twenty-one sediment samples*, two tar ball samples and one surface water oil sample were obtained from distinct locations in the GOM and within varying time frames from May to December 2010. Each sample was extracted through the ASE 200 solvent extractor, concentrated down under nitrogen gas, purified through an alumina column, concentrated down again with nitrogen gas and analyzed via GC X GC-TOF MS. Forty-one different hydrocarbons were quantified in each sample. Various hydrocarbon 'fingerprints,' such as parental :alkylate PAH ratios, high molecular weight PAHs: low molecular weight alkane ratios, and carbon preference index were calculated. The initial objective of this project was to identify the relative hydrocarbon contributions of petrogenic sources and combustion sources. Based on the calculated ratios, it is evident that the sediment core taken in October of 2010 was greatly affected by combustion sources. Following the first month of the spill, oil in the gulf was burned in attempts to contain the spill. Combustion related sources have quicker sedimentation rates, and hydrocarbons from a combustion source essentially move into deeper depths quicker than those from a petrogenic source, as was observed in analyses of the October 2010 sediment. *Of the twenty-one sediment samples prepared, nine were quantified for this project.

Characterization of citrus pectin samples extracted under different conditions: influence of acid type and pH of extraction

PubMed Central

Kaya, Merve; Sousa, António G.; Crépeau, Marie-Jeanne; Sørensen, Susanne O.; Ralet, Marie-Christine

2014-01-01

Background and Aims Pectin is a complex macromolecule, the fine structure of which is influenced by many factors. It is used as a gelling, thickening and emulsifying agent in a wide range of applications, from food to pharmaceutical products. Current industrial pectin extraction processes are based on fruit peel, a waste product from the juicing industry, in which thousands of tons of citrus are processed worldwide every year. This study examines how pectin components vary in relation to the plant source (orange, lemon, lime, grapefruit) and considers the influence of extraction conditions on the chemical and macromolecular characteristics of pectin samples. Methods Citrus peel (orange, lemon, lime and grapefruit) from a commercial supplier was used as raw material. Pectin samples were obtained on a bulk plant scale (kilograms; harsh nitric acid, mild nitric acid and harsh oxalic acid extraction) and on a laboratory scale (grams; mild oxalic acid extraction). Pectin composition (acidic and neutral sugars) and physicochemical properties (molar mass and intrinsic viscosity) were determined. Key Results Oxalic acid extraction allowed the recovery of pectin samples of high molecular weight. Mild oxalic acid-extracted pectins were rich in long homogalacturonan stretches and contained rhamnogalacturonan I stretches with conserved side chains. Nitric acid-extracted pectins exhibited lower molecular weights and contained rhamnogalacturonan I stretches encompassing few and/or short side chains. Grapefruit pectin was found to have short side chains compared with orange, lime and lemon. Orange and grapefruit pectin samples were both particularly rich in rhamnogalacturonan I backbones. Conclusions Structural, and hence macromolecular, variations within the different citrus pectin samples were mainly related to their rhamnogalacturonan I contents and integrity, and, to a lesser extent, to the length of their homogalacturonan domains. PMID:25081519

Recognition pattern of thyroglobulin autoantibody from hypothyroid dogs to tryptic peptides of canine thyroglobulin.

PubMed

Tani, Hiroyuki; Shimizu, Reiko; Sasai, Kazumi; Baba, Eiichiroh

2003-10-01

Circulating thyroglobulin autoantibody (TgAA) was analyzed using the Western immunoblot for determination of the dominant epitopes recognized by TgAA on tryptic peptides of canine thyroglobulin (cTg) in hypothyroid dogs. TgAA was measured in hypothyroid dogs, non-hypothyroid dogs with skin diseases and clinically normal dogs. Five of the 7 hypothyroid dogs, 1 of the 8 dogs with skin diseases and 1 of the 4 normal dogs were positive for TgAA. Four of the 5 TgAA-positive hypothyroid dogs were Golden Retrievers, and 3 of them showed high antibody titers. The sera of TgAA positive-dogs reacted to several peptides, and their patterns varied from sample to sample. Sera from 3 dogs with high titers of TgAA reacted broadly to high molecular weight peptides ranging from 45 to 90 kDa. These Western immunoblot patterns of the sera were disappeared after pretreatment with sufficient amount of intact cTg. All serum samples of both TgAA positive dogs and negative controls reacted to low molecular weight peptides ranging from 15 to 20 kDa. These immunoblot patterns of the sera were not disappeared even after pretreatment with sufficient amount of intact cTg. These findings show the possibility that the epitopes recognized by TgAA depend upon individual dogs with hypothyroidism and these autoantibodies recognize conformational epitopes on the cTg molecule.

Chemical Degradation of Polyacrylamide during Hydraulic Fracturing

NASA Astrophysics Data System (ADS)

Xiong, B.; Tasker, T.; Miller, Z.; Roman-White, S.; Farina, B.; Piechowicz, B.; Burgos, W.; Joshi, P.; Zhu, L.; Gorski, C.; Zydney, A.; Kumar, M.

2017-12-01

Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus shale outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by two orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluid. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-M hydroxyl radical concentrations. The shale sample adsorbed some PAM ( 30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe2+ at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

Chemical Degradation of Polyacrylamide during Hydraulic Fracturing.

PubMed

Xiong, Boya; Miller, Zachary; Roman-White, Selina; Tasker, Travis; Farina, Benjamin; Piechowicz, Bethany; Burgos, William D; Joshi, Prachi; Zhu, Liang; Gorski, Christopher A; Zydney, Andrew L; Kumar, Manish

2018-01-02

Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including decisions on strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by 2 orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluids. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-μM hydroxyl radical concentrations. The shale sample adsorbed some PAM (∼30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe 2+ at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

Absence of differences among low, middle, and high molecular weight hyaluronan in activating murine immune cells in vitro.

PubMed

Šafránková, Barbora; Hermannová, Martina; Nešporová, Kristina; Velebný, Vladimír; Kubala, Lukáš

2018-02-01

Hyaluronan (HA) effects on immune response are suggested to be dependent on HA molecular weight (MW), as low MW HA should activate immune cells in contrast to high MW HA. However, some current studies do not support this conception and emphasize the importance of the form of preparation of HA, particularly with respect to its purity and origin. We compared the activation of mouse immune cells by HA samples (100kDa, 500kDa, and 997kDa) prepared from HA originating from rooster comb, and HA samples (71kDa, 500kDa, and 1000kDa) prepared from pharmacological grade HA originating from Streptococcus equi. Interestingly, in contrast to established theory, only middle and high MW HA originating from rooster comb induced the production of tumor necrosis factor-α by macrophages and in whole blood. Further, all tested preparations of HA failed to induce the expression of inducible nitric oxide synthase, the production of nitric oxide, or the expression of cyclooxygenase 2 in macrophages and splenocytes. Importantly, all HA samples originating from rooster comb were found to be contaminated by endotoxin (up to 1.23EU/ml). Hence, low MW HA did not reveal itself to have significantly higher immunostimulatory activity compared to HA of higher MW. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Low molecular weight salts combined with fluorinated solvents for electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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.

Detection of over 100 selenium metabolites in selenized yeast by liquid chromatography electrospray time-of-flight mass spectrometry.

PubMed

Gilbert-López, Bienvenida; Dernovics, Mihaly; Moreno-González, David; Molina-Díaz, Antonio; García-Reyes, Juan F

2017-08-15

The characterization of the selenometabolome of Selenized(Se)-yeast, that is the fraction of water soluble low-molecular weight Se-metabolites produced in Se-yeast is of paramount interest to expand the knowledge on the composition of this food supplement. In this work, we have applied liquid chromatography electrospray time-of-flight mass spectrometry (LC-TOFMS) to search for Se-species from the low molecular weight range fraction of the selenized yeast used for food supplements. Prior to LC-TOFMS, sample treatment consisted of ultrasound assisted water extraction followed by size exclusion fractionation assisted with off-line inductively coupled plasma mass spectrometry detection of isotope 82 Se. The fraction corresponding to low-molecular weight species was subjected to LC-TOFMS using electrospray ionization in the positive ion mode. The detection of the suspected selenized species has been based on the information obtained from accurate mass measurements of both the protonated molecules and fragments from in-source CID fragmentation; along with the characteristic isotope pattern exhibited by the presence of Se. The approach enables the detection of 103 selenized species, most of them not previously reported, in the range from ca. 300-650Da. Besides the detection of selenium species, related sulphur derivate metabolites were detected based on the accurate mass shift due to the substitution of sulphur and selenium. Copyright © 2017. Published by Elsevier B.V.

Analysis of iminosugars and other low molecular weight carbohydrates in Aglaonema sp. extracts by hydrophilic interaction liquid chromatography coupled to mass spectrometry.

PubMed

Rodríguez-Sánchez, S; García-Sarrió, M J; Quintanilla-López, J E; Soria, A C; Sanz, M L

2015-12-04

A method by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry (HILIC-MS(2)) has been successfully developed for the simultaneous analysis of bioactive iminosugars and other low molecular weight carbohydrates in Aglaonema leaf extracts. Among other experimental chromatographic conditions, mobile phase eluents, additives and column temperature were evaluated in terms of retention time, resolution, peak width and symmetry provided for target carbohydrates. In general, narrow peaks (wh: 0.2-0.6min) with good symmetry (As: 0.9-1.3) and excellent resolution (Rs>1.8) were obtained for iminosugars using an acetonitrile:water gradient with 5mM ammonium acetate in both eluents at 55°C. Tandem mass spectra were used to confirm the presence of previously detected iminosugars in Aglaonema extracts and to tentatively identify for the first time others such as miglitol isomer, glycosyl-miglitol isomers and glycosyl-DMDP isomers. Concentration of total iminosugars varied from 1.35 to 2.84mgg(-1) in the extracts of the different Aglaonema samples analyzed. To the best of our knowledge, this is the first time that a HILIC-MS(2) method has been proposed for the simultaneous analysis of iminosugars and other low molecular weight carbohydrates of Aglaonema sp. extracts. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of Low Molecular Weight Fractions of Humic Substances on Their Reducing Capacities and Distribution of Redox Functional Groups.

NASA Astrophysics Data System (ADS)

Yang, Z.; Jiang, J.

2015-12-01

Humic substances (HS) are redox-active organic compounds and their reducing capacities depend on molecule structure and distribution of redox functional groups (RFG). During dialysis experiments, initial HS were separated into low molecular weight fractions (LMWF, molecular weight <3,500 Da or <14,000 Da) and retentate. LMWF accounts for only 2% in TOC contents of HS molecules, while their reducing capacities are up to 33 times greater than those of initial HA. However, great amount of reducing capacities of LMWF does not cause decreasing reducing capacities of retentate relative to those of initial HA. Total reducing capacities of whole dialysis device were calculated for initial HA, retentate and LMWF in native and reduced state, and result suggests that releasing of LMWF leads to production and explosion of RFG. LWMF have great fluorescence intensities for protein-like fluorophores and humic acids-like fluorophores (quinone-like functional groups), where quinonoid π-π* transition is responsible for the great reducing capacities of LMWF. The 3,500 Da molecules (0.25 nm diameter) of HS are capable of stimulating transformation of redox-active metals or potential pollutants trapped in soil micropores (< 2 nm diameter). A development of relationship between reducing capacity and Ex / Em position provides a possibility to predicate relative reducing capacities of HS in treated raw water sample.

Effects of Co-Processing Sewage Sludge in the Cement Kiln on PAHs, Heavy Metals Emissions and the Surrounding Environment.

PubMed

Lv, Dong; Zhu, Tianle; Liu, Runwei; Li, Xinghua; Zhao, Yuan; Sun, Ye; Wang, Hongmei; Zhang, Fan; Zhao, Qinglin

2018-04-08

To understand the effects of co-processing sewage sludge in the cement kiln on non-criterion pollutants emissions and its surrounding environment, the flue gas from a cement kiln stack, ambient air and soil from the background/downwind sites were collected in the cement plant. Polycyclic aromatic hydrocarbons (PAHs) and heavy metals of the samples were analyzed. The results show that PAHs in flue gas mainly exist in the gas phase and the low molecular weight PAHs are the predominant congener. The co-processing sewage sludge results in the increase in PAHs and heavy metals emissions, especially high molecular weight PAHs and low-volatile heavy metals such as Cd and Pb in the particle phase, while it does not change their compositions and distribution patterns significantly. The concentrations and their distributions of the PAHs and heavy metals between the emissions and ambient air have a positive correlation and the co-processing sewage sludge results in the increase of PAHs and heavy metals concentrations in the ambient air. The PAHs concentration level and their distribution in soil are proportional to those in the particle phase of flue gas, and the co-processing sewage sludge can accelerate the accumulation of the PAHs and heavy metals in the surrounding soil, especially high/middle molecular weight PAHs and low-volatile heavy metals.

Histidinoalanine, a naturally occurring cross-link derived from phosphoserine and histidine residues in mineral-binding phosphoproteins.

PubMed

Marsh, M E

1986-05-06

Native mineral-containing phosphoprotein particles were isolated from the Heterodont bivalve Macrocallista nimbosa. The native particles are discrete structures about 40 nm in diameter which migrate as a single band during electrophoresis in agarose gels. Removal of the mineral component with ethylenediaminetetraacetic acid dissociates the native protein into nonidentical subunits. The lower molecular weight subunits, representing 8% of the total protein, were obtained by differential centrifugation. The native protein is characterized by a high content of aspartic acid, phosphoserine, phosphothreonine, histidine, and the bifunctional cross-linking residue histidinoalanine. The low molecular weight subunits have the same amino acid composition except for a reduction in histidinoalanine and a corresponding increase in phosphoserine and histidine residues, demonstrating that the alanine portion of the cross-link is derived from phosphoserine residues. Ion-exchange chromatography and molecular sieve chromatography show that the low molecular weight subunits have a similar charge density but differ in molecular weight, and the relative mobilities of the subunits on agarose gels indicate that they are polymers of a single phosphoprotein molecule. The minimum molecular weight of the monomer is about 140 000 on the basis of the amino acid composition. The high molecular weight subunits are rich in histidinoalanine and too large to be resolved by either molecular sieve chromatography or gel electrophoresis. On the basis of the ultrastructural, electrophoretic, chromatographic, and compositional evidence, native phosphoprotein particles are composed of subunits ionically cross-linked via divalent cations. These subunits are variable molecular weight aggregates of a single phosphoprotein molecule covalently cross-linked via histidinoalanine residues. Evidence for a nonenzymatic cross-linking mechanism is discussed.

WESTPA: An interoperable, highly scalable software package for weighted ensemble simulation and analysis

PubMed Central

Zwier, Matthew C.; Adelman, Joshua L.; Kaus, Joseph W.; Pratt, Adam J.; Wong, Kim F.; Rego, Nicholas B.; Suárez, Ernesto; Lettieri, Steven; Wang, David W.; Grabe, Michael; Zuckerman, Daniel M.; Chong, Lillian T.

2015-01-01

The weighted ensemble (WE) path sampling approach orchestrates an ensemble of parallel calculations with intermittent communication to enhance the sampling of rare events, such as molecular associations or conformational changes in proteins or peptides. Trajectories are replicated and pruned in a way that focuses computational effort on under-explored regions of configuration space while maintaining rigorous kinetics. To enable the simulation of rare events at any scale (e.g. atomistic, cellular), we have developed an open-source, interoperable, and highly scalable software package for the execution and analysis of WE simulations: WESTPA (The Weighted Ensemble Simulation Toolkit with Parallelization and Analysis). WESTPA scales to thousands of CPU cores and includes a suite of analysis tools that have been implemented in a massively parallel fashion. The software has been designed to interface conveniently with any dynamics engine and has already been used with a variety of molecular dynamics (e.g. GROMACS, NAMD, OpenMM, AMBER) and cell-modeling packages (e.g. BioNetGen, MCell). WESTPA has been in production use for over a year, and its utility has been demonstrated for a broad set of problems, ranging from atomically detailed host-guest associations to non-spatial chemical kinetics of cellular signaling networks. The following describes the design and features of WESTPA, including the facilities it provides for running WE simulations, storing and analyzing WE simulation data, as well as examples of input and output. PMID:26392815

Molecular evidence of heavy-oil weathering following the M/V Cosco Busan spill: insights from Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Lemkau, Karin L; McKenna, Amy M; Podgorski, David C; Rodgers, Ryan P; Reddy, Christopher M

2014-04-01

Recent studies have highlighted a critical need to investigate oil weathering beyond the analytical window afforded by conventional gas chromatography (GC). In particular, techniques capable of detecting polar and higher molecular weight (HMW; > 400 Da) components abundant in crude and heavy fuel oils (HFOs) as well as transformation products. Here, we used atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI FT-ICR MS) to identify molecular transformations in oil-residue samples from the 2007 M/V Cosco Busan HFO spill (San Francisco, CA). Over 617 days, the abundance and diversity of oxygen-containing compounds increased relative to the parent HFO, likely from bio- and photodegradation. HMW, highly aromatic, alkylated compounds decreased in relative abundance concurrent with increased relative abundance of less alkylated stable aromatic structures. Combining these results with GC-based data yielded a more comprehensive understanding of oil spill weathering. For example, dealkylation trends and the overall loss of HMW species observed by FT-ICR MS has not previously been documented and is counterintuitive given losses of lower molecular weight species observed by GC. These results suggest a region of relative stability at the interface of these techniques, which provides new indicators for studying long-term weathering and identifying sources.

Photothermal optical coherence tomography of epidermal growth factor receptor in live cells using immunotargeted gold nanospheres

NASA Astrophysics Data System (ADS)

Skala, Melissa C.; Crow, Matthew J.; Wax, Adam; Izatt, Joseph A.

2009-02-01

Molecular imaging is a powerful tool for investigating disease processes and potential therapies in both in vivo and in vitro systems. However, high resolution molecular imaging has been limited to relatively shallow penetration depths that can be accessed with microscopy. Optical coherence tomography (OCT) is an optical analogue to ultrasound with relatively good penetration depth (1-2 mm) and resolution (~1-10 μm). We have developed and characterized photothermal OCT as a molecular contrast mechanism that allows for high resolution molecular imaging at deeper penetration depths than microscopy. Our photothermal system consists of an amplitude-modulated heating beam that spatially overlaps with the focused spot of the sample arm of a spectral-domain OCT microscope. Validation experiments in tissue-like phantoms containing gold nanospheres that absorb at 532 nm revealed a sensitivity of 14 parts per million nanospheres (weight/weight) in a tissue-like environment. The nanospheres were then conjugated to anti-EGFR, and molecular targeting was confirmed in cells that over-express EGFR (MDA-MB-468) and cells that express low levels of EGFR (MDA-MB-435). Molecular imaging in three-dimensional tissue constructs was confirmed with a significantly lower photothermal signal (p<0.0001) from the constructs composed of cells that express low levels of EGFR compared to the over-expressing cell constructs (300% signal increase). This technique could potentially augment confocal and multiphoton microscopy as a method for deep-tissue, depth-resolved molecular imaging with relatively high resolution and target sensitivity, without photobleaching or cytotoxicity.

Drop-on-demand drop formation of polyethylene oxide solutions

NASA Astrophysics Data System (ADS)

Yan, Xuejia; Carr, Wallace W.; Dong, Hongming

2011-10-01

The dynamics of drop-on-demand (DOD) drop formation for solutions containing polyethylene oxide (PEO) have been studied experimentally. Using a piezoelectrical actuated inkjet printhead with the nozzle orifice diameter of 53 μm, experiments were conducted for a series of PEO aqueous solutions with molecular weights ranging from 14 to 1000 kg/mol, polydispersity from 1.02 to 2.5, and concentrations from 0.005 to 10 wt. %. The addition of a small amount of PEO can have a significant effect on the DOD drop formation process, increasing breakup time, decreasing primary drop speed, and decreasing the number of satellite drops in some cases. The effects depend on both molecular weight and concentration. At lower molecular weights (14 and 35 kg/mol), the effect of PEO over the dilute solution regime is insignificant even at concentrations large enough that the solution does not fall in the dilute regime. As PEO molecular weight increased, the effects became significant. For monodispersed PEO solutions, breakup time and primary drop speed closely correlated with effective relaxation time but not for polydispersed PEO. Effective relaxation time depended greatly on molecular weight distribution. Viscosity-average molecular weight, used in calculating effective relaxation time for polydispersed PEO solutions, did not adequately account for high molecular fractions in the molecular weight distribution of the polydispersed PEOs. A mixture rule was developed to calculate the effective relaxation times for aqueous solutions containing mixtures of monodispersed PEO, and breakup times and primary drop speeds correlated well with effective relaxation times. For our experiments, DOD drop formation was limited to Deborah number ≲ 23.

Overview of the TREC 2009 Chemical IR Track

DTIC Science & Technology

2009-11-01

several classes have been identified. 3 methods for controlling molecular weight of polyhydroxyalkanoate organic, high molecular weight We are a group of...researchers in an university/company. We want to start a project and, before starting, we want more informations about polyhydroxyalkanoate and about...methods for controlling molecular weight of polyhydroxyalkanoate constituted of units containing residue of phenyl-, thienyl-, or cyclohexyl-structure

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.

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

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.

The Presence Of Strange Males' Odor Induces Behavioral Responses And Elevated Levels Of Low Molecular Weight Proteins Excreted In The Urine Of Mature Water Vole Males (Arvicola amphibius L).

PubMed

Nazarova, Galina G; Proskurniak, Lyudmila P; Yuzhik, Ekaterina I

2016-03-01

We hypothesized that low molecular weight urinary proteins play a role in male-male chemical communication in the water vole, Arvicola ampibius L. We studied the effect of placing soiled litter from strange males into the cage of another sexually mature male on the intensity of its digging and scattering, urination on the litter, and alteration in the levels of low molecular weight proteins (15-25 kDa) excreted in the urine before and after 4 days of exposure as determined by chip electrophoresis. The intensity of digging and scattering was positively correlated with levels of testosterone in serum of males exposed to strange male odors (r = 0.56; P < 0.01), as well as with the concentration of low molecular weight proteins in the donor's urine (r = 0.52, P < 0.05). At the end of the experiment, the level of low molecular weight protein in excreted urine was elevated in the males exposed to the strange male's litter. These results highlight the importance of quantitative inter-individual variation of low molecular weight urinary proteins in the modulation of the physiology and behavior of conspecifics.

Study on the behavior and mechanism of polycarbonate with hot-water aging

NASA Astrophysics Data System (ADS)

Kong, L. P.; Zhao, Y. X.; Zhou, C. H.; Huang, Y. H.; Tang, M.; Gao, J. G.

2016-07-01

The present work was concerned with hot-water aging behavior and mechanism of Bisphenol A polycarbonate (PC) used as food and packaging materials. It indicated that with the aging time prolonged, PC sample had internal defects and the mechanical properties of PC materials changed not too much, molecular weight decreased, thermal stability declined. Phenolic hydroxyl absorption intensity enhanced in IR spectra and the maximum absorption wavelength red shift of benzene in UV-Vis spectra, the level of BPA increased. The color change of PC sample was not apparent.

Magic Angle Spinning NMR Metabolomics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhi Hu, Jian

Nuclear Magnetic Resonance (NMR) spectroscopy is a non-destructive, quantitative, reproducible, untargeted and unbiased method that requires no or minimal sample preparation, and is one of the leading analytical tools for metabonomics research [1-3]. The easy quantification and the no need of prior knowledge about compounds present in a sample associated with NMR are advantageous over other techniques [1,4]. 1H NMR is especially attractive because protons are present in virtually all metabolites and its NMR sensitivity is high, enabling the simultaneous identification and monitoring of a wide range of low molecular weight metabolites.

Space Shuttle solid rocket motor exposure monitoring

NASA Technical Reports Server (NTRS)

Brown, S. W.

1993-01-01

During the processing of the Space Shuttle Solid Rocket Booster (SRB), segments at the Kennedy Space Center, an odor was detected around the solid propellant. An Industrial Hygiene survey was conducted to determine the chemical identity of the SRB offgassing constituents. Air samples were collected inside a forward SRB segment and analyzed to determine chemical composition. Specific chemical analysis for suspected offgassing constituents of the propellant indicated ammonia to be present. A gas chromatograph mass spectroscopy (GC/MS) analysis of the air samples detected numerous high molecular weight hydrocarbons.

Effects of Molecular Structure in Macroscopic Mechanical Properties of an Advanced Polymer (LARC(sup TM)-SI)

NASA Technical Reports Server (NTRS)

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

2004-01-01

Mechanical testing of an advanced polymer resin with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. The elastic properties, inelastic elongation behavior, and notched tensile strength all as a function of molecular weight and test temperature were determined. 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.

Extraction of hyaluronic acid (HA) from rooster comb and characterization using flow field-flow fractionation (FlFFF) coupled with multiangle light scattering (MALS).

PubMed

Kang, Dong Young; Kim, Won-Suk; Heo, In Sook; Park, Young Hun; Lee, Seungho

2010-11-01

Hyaluronic acid (HA) was extracted in a relatively large scale from rooster comb using a method similar to that reported previously. The extraction method was modified to simplify and to reduce time and cost in order to accommodate a large-scale extraction. Five hundred grams of frozen rooster combs yielded about 500 mg of dried HA. Extracted HA was characterized using asymmetrical flow field-flow fractionation (AsFlFFF) coupled online to a multiangle light scattering detector and a refractive index detector to determine the molecular size, molecular weight (MW) distribution, and molecular conformation of HA. For characterization of HA, AsFlFFF was operated by a simplified two-step procedure, instead of the conventional three-step procedure, where the first two steps (sample loading and focusing) were combined into one to avoid the adsorption of viscous HA onto the channel membrane. The simplified two-step AsFlFFF yielded reasonably good separations of HA molecules based on their MWs. The weight average MW (M(w) ) and the average root-mean-square (RMS) radius of HA extracted from rooster comb were 1.20×10(6) and 94.7 nm, respectively. When the sample solution was filtered through a 0.45 μm disposable syringe filter, they were reduced down to 3.8×10(5) and 50.1 nm, respectively. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular forms of C-type natriuretic peptide in cerebrospinal fluid and plasma reflect differential processing in brain and pituitary tissues.

PubMed

Wilson, Michele O; Barrell, Graham K; Prickett, Timothy C R; Espiner, Eric A

2018-01-01

C-type natriuretic peptide (CNP) is a paracrine growth factor widely expressed within tissues of the central nervous system. Consistent with this is the high concentration of CNP in cerebrospinal fluid (CSF), exceeding levels in the systemic circulation. CNP abundance is high in hypothalamus and especially enriched in pituitary tissue where - in contrast to hypothalamus - processing to CNP-22 is minimal. Recently we have shown that dexamethasone acutely raises CNP peptides throughout the brain as well as in CSF and plasma. Postulating that molecular forms of CNP would differ in central tissues compared to forms in pituitary and plasma, we have characterized the molecular forms of CNP in tissues (hypothalamus, anterior and posterior pituitary gland) and associated fluids (CSF and plasma) using size-exclusion high performance liquid chromatography (SE-HPLC) and radioimmunoassay in control (saline-treated) and dexamethasone-treated adult sheep. Three immunoreactive-CNP components were identified which were consistent with proCNP (1-103), CNP-53 and CNP-22, but the presence and proportions of these different fragments differed among tissues. Peaks consistent with CNP-53 were the dominant form in all tissues and fluids. Peaks consistent with proCNP, conspicuous in hypothalamic extracts, were negligible in CSF whereas proportions of low molecular weight immunoreactivity (IR) consistent with CNP-22 were similar in hypothalamus, posterior pituitary gland and CSF. In contrast, in both plasma and the anterior pituitary gland, proportions of higher molecular weight IR, consistent with CNP-53 and proCNP, predominated, and low molecular weight IR consistent with CNP-22 was very low. After dexamethasone, proCNP like material - but not other forms - was increased in all samples except CSF, consistent with increased synthesis and secretion. In conclusion, immunoreactive forms of CNP in central tissues differ from those identified in anterior pituitary tissue and plasma - suggesting that the anterior pituitary gland may contribute to systemic levels of CNP in some physiological settings. Copyright © 2017 Elsevier Inc. All rights reserved.

Concentrations of polynuclear aromatic hydrocarbons and inorganic constituents in ambient surface soils, Chicago, Illinois, 2001-02

USGS Publications Warehouse

Kay, Robert T.; Arnold, Terri L.; Cannon, William F.; Graham, David; Morton, Eric; Bienert, Raymond

2003-01-01

Polynuclear aromatic hydrocarbon (PAH) compounds are ubiquitous in ambient surface soils in the city of Chicago, Illinois. PAH concentrations in samples collected in June 2001 and January 2002 were typically in the following order from highest to lowest: fluoranthene, pyrene, benzo(b)fluoranthene, phenanthrene, benzo(a)pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, dibenzo(a,h)anthracene, and anthracene. Naphthalene, acenaphthene, acenaphthylene, and fluorene were consistently at the lowest concentrations in each sample. Concentrations of the PAH compounds showed variable correlation. Concentrations of PAH compounds with higher molecular weights typically show a higher degree of correlation with other PAH compounds of higher molecular weight, whereas PAH compounds with lower molecular weights tended to show a lower degree of correlation with all other PAH compounds. These differences indicate that high and low molecular-weight PAHs behave differentl y once released into the environment. Concentrations of individual PAH compounds in soils typically varied by at least three orders of magnitude across the city and varied by more than an order of magnitude over a distance of about 1,000 feet. Concentrations of a given PAH in ambient surface soils are affected by a variety of site-specific factors, and may be affected by proximity to industrial areas. Concentrations of a given PAH in ambient surface soils did not appear to be affected the organic carbon content of the soil, proximity to non-industrial land use, or proximity to a roadway. The concentration of the different PAH compounds in ambient surface soils appears to be affected by the propensity for the PAH compound to be in the vapor or particulate phase in the atmosphere. Lower molecular-weight PAH compounds, which are primarily in the vapor phase in the atmosphere, were detected in lower concentrations in the surface soils. Higher molecular-weight PAH compounds, which are present primarily in the particulate phase in the atmosphere, tended to be in higher concentrations in the surface soils. The apparent effect of the PAH phase in the atmosphere on the concentration of a PAH in ambient surface soils indicates that atmospheric settling of particulate matter is an important source of the PAH compounds in ambient surface soils in Chicago. The distribution of PAH compounds within the city was complex. Comparatively high concentrations were detected near Lake Michigan in the northern part of the city, in much of the western part of the city, and in isolated areas in the southern part of the city. Concentrations were lower in much of the northwestern, south-central, southwestern, and far southern parts of the city. The arithmetic mean concentration of arsenic, mercury, calcium, magnesium, phosphorus, copper, molybdenum, zinc, and selenium was from 2 to 6 times higher in ambient surface soils in the city of Chicago than in soils from surrounding agricultural areas. The arithmetic mean concentration of lead in Chicago soils was about 20 times higher. Concentrations of calcium and magnesium above those of surrounding agricultural areas appear to be related to the effects of dolomite bedrock on the chemical composition of the soil. Elevated concentrations of the remaining elements listed above indicate a potential anthropogenic source(s) of these elements in Chicago soils.

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.

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.

Effect of polyethylene glycols on the trans-ungual delivery of terbinafine.

PubMed

Nair, Anroop B; Chakraborty, Bireswar; Murthy, S Narasimha

2010-12-01

Topical nail drug delivery could be improved by identifying potent chemical penetration enhancers. The purpose of this study was to assess the effect of polyethylene glycols (PEGs) on the trans-ungual delivery of terbinafine. In vitro permeation studies were carried out by passive and iontophoresis (0.5 mA/cm2) processes for a period of 1 h using gel formulations containing different molecular weight PEGs (30%w/w). The release of drug from the loaded nail plates and the possible mechanisms for the enhanced delivery was studied. Passive delivery using formulation with low molecular weight PEGs (200 and 400 MW) indicated moderate enhancement in the permeation and drug load in the nail plate, compared to the control formulation. However, the effect of low molecular weight PEGs was predominant during iontophoresis process with greater amount of terbinafine being permeated (≈35 µg/cm2) and loaded into the nail plate (≈2.7 µg/mg). However, little or no effect on drug delivery was observed with high molecular weight PEGs (1000- 3350 MW) in passive and iontophoresis processes. Release of drug from the nail plates loaded by iontophoresis using low molecular weight PEG (400 MW) exhibited sustain effect which continued over a period of 72 days. The enhancement in drug permeation by low molecular weight PEGs is likely due to their ability to lead to greater water uptake and swelling of nail. This study concluded that the low molecular weight PEGs are indeed a promising trans-ungual permeation enhancer.

Study of the Molecular Dynamics of Multiarm Star Polymers with a Poly(ethyleneimine) Core and Poly(lactide) Multiarms

PubMed Central

Román, Frida; Colomer, Pere; Calventus, Yolanda; Hutchinson, John M.

2017-01-01

Multiarm star polymers, denoted PEIx-PLAy and containing a hyperbranched poly(ethyleneimine) (PEI) core of different molecular weights x and poly(lactide) (PLA) arms with y ratio of lactide repeat units to N links were used in this work. Samples were preconditioned to remove the moisture content and then characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The glass transition temperature, Tg, is between 48 and 50 °C for all the PEIx-PLAy samples. The dielectric curves show four dipolar relaxations: γ, β, α, and α′ in order of increasing temperature. The temperatures at which these relaxations appear, together with their dependence on the frequency, allows relaxation maps to be drawn, from which the activation energies of the sub-Tg γ- and β-relaxations and the Vogel–Fulcher–Tammann parameters of the α-relaxation glass transition are obtained. The dependence of the characteristic features of these relaxations on the molecular weight of the PEI core and on the ratio of lactide repeat units to N links permits the assignation of molecular motions to each relaxation. The γ-relaxation is associated with local motions of the –OH groups of the poly(lactide) chains, the β-relaxation with motions of the main chain of poly(lactide), the α-relaxation with global motions of the complete assembly of PEI core and PLA arms, and the α′-relaxation is related to the normal mode relaxation due to fluctuations of the end-to-end vector in the PLA arms, without excluding the possibility that it could be a Maxwell–Wagner–Sillars type ionic peak because the material may have nano-regions of different conductivity. PMID:28772486

Study of the Molecular Dynamics of Multiarm Star Polymers with a Poly(ethyleneimine) Core and Poly(lactide) Multiarms.

PubMed

Román, Frida; Colomer, Pere; Calventus, Yolanda; Hutchinson, John M

2017-02-04

Multiarm star polymers, denoted PEI x -PLA y and containing a hyperbranched poly(ethyleneimine) (PEI) core of different molecular weights x and poly(lactide) (PLA) arms with y ratio of lactide repeat units to N links were used in this work. Samples were preconditioned to remove the moisture content and then characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The glass transition temperature, T g , is between 48 and 50 °C for all the PEI x -PLA y samples. The dielectric curves show four dipolar relaxations: γ, β, α, and α' in order of increasing temperature. The temperatures at which these relaxations appear, together with their dependence on the frequency, allows relaxation maps to be drawn, from which the activation energies of the sub- T g γ- and β-relaxations and the Vogel-Fulcher-Tammann parameters of the α-relaxation glass transition are obtained. The dependence of the characteristic features of these relaxations on the molecular weight of the PEI core and on the ratio of lactide repeat units to N links permits the assignation of molecular motions to each relaxation. The γ-relaxation is associated with local motions of the -OH groups of the poly(lactide) chains, the β-relaxation with motions of the main chain of poly(lactide), the α-relaxation with global motions of the complete assembly of PEI core and PLA arms, and the α'-relaxation is related to the normal mode relaxation due to fluctuations of the end-to-end vector in the PLA arms, without excluding the possibility that it could be a Maxwell-Wagner-Sillars type ionic peak because the material may have nano-regions of different conductivity.

Thermal Cracking of Tars in a Continuously Fed Reactor with Steam

DTIC Science & Technology

2011-05-01

Fluidized Bed using biomass 8 Tars  Mixture of organic components present in gasification product gas with high molecular weight hydrocarbons [MW...Disable sulfur removal systems FoulingPlugging [Ref. 3: Biomass Gasification – Tar and Particles in Product Gases Sampling and Analysis”, European...P., and Nussbaumer T., “Gas Cleaning Requirements for Internal Combustion Engine Applications of Fixed Bed Biomass Gasification ”, Biomass and

Species identification refined by molecular scatology in a community of sympatric carnivores in Xinjiang, China.

PubMed

Laguardia, Alice; Wang, Jun; Shi, Fang-Lei; Shi, Kun; Riordan, Philip

2015-03-18

Many ecological studies and conservation management plans employ noninvasive scat sampling based on the assumption that species' scats can be correctly identified in the field. However, in habitats with sympatric similarly sized carnivores, misidentification of scats is frequent and can lead to bias in research results. To address the scat identification dilemma, molecular scatology techniques have been developed to extract DNA from the donor cells present on the outer lining of the scat samples. A total of 100 samples were collected in the winter of 2009 and 2011 in Taxkorgan region of Xinjiang, China. DNA was extracted successfully from 88% of samples and genetic species identification showed that more than half the scats identified in the field as snow leopard (Panthera uncia) actually belonged to fox (Vulpes vulpes). Correlation between scat characteristics and species were investigated, showing that diameter and dry weight of the scat were significantly different between the species. However it was not possible to define a precise range of values for each species because of extensive overlap between the morphological values. This preliminary study confirms that identification of snow leopard feces in the field is misleading. Research that relies upon scat samples to assess distribution or diet of the snow leopard should therefore employ molecular scatology techniques. These methods are financially accessible and employ relatively simple laboratory procedures that can give an indisputable response to species identification from scats.

Efficient exploration of chemical space by fragment-based screening.

PubMed

Hall, Richard J; Mortenson, Paul N; Murray, Christopher W

2014-01-01

Screening methods seek to sample a vast chemical space in order to identify starting points for further chemical optimisation. Fragment based drug discovery exploits the superior sampling of chemical space that can be achieved when the molecular weight is restricted. Here we show that commercially available fragment space is still relatively poorly sampled and argue for highly sensitive screening methods to allow the detection of smaller fragments. We analyse the properties of our fragment library versus the properties of X-ray hits derived from the library. We particularly consider properties related to the degree of planarity of the fragments. Copyright © 2014 Elsevier Ltd. All rights reserved.

40 CFR Table A-7 to Subpart A of... - Data Elements That Are Inputs to Emission Equations and for Which the Reporting Deadline Is March...

Code of Federal Regulations, 2012 CFR

2012-07-01

... mass balance equation. K 98.116(b) Only annual production by product from each EAF (No CEMS). K 98.116... carbon content values, molecular weights for gaseous feedstocks, molecular weights for gaseous products... of gas flared, average molecular weight, carbon content of the flare, and molar volume conversion...

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.

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.

Design and Testing of a Linear Ion Trap for the Mars Organic Molecule Analyzer (MOMA) Investigation on the 2018 ExoMars Rover

NASA Astrophysics Data System (ADS)

Brinckerhoff, W. B.; van Amerom, F.; Danell, R.; Pinnick, V. T.; Arevalo, R. D.; Li, X.; Hovmand, L.; Siljestrom, S.; Mahaffy, P. R.; Goetz, W.; Goesmann, F.; Steininger, H.

2013-12-01

The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. MOMA includes an ion trap mass spectrometer (ITMS) that is designed to analyze molecular composition of (i) gas evolved from pyrolyzed powder samples and separated on a gas chromatograph and (ii) ions directly desorbed from solid samples at Mars ambient pressure using a pulsed laser and a fast-valve capillary ion inlet system. This 'dual source' approach gives MOMA unprecedented breadth of detection over a wide range of molecular weights and volatilities. Analysis of nonvolatile, higher-molecular weight organics such as carboxylic acids and peptides even in the presence of significant perchlorate concentrations is enabled by the extremely short (~1 ns) pulses of the desorption laser. Use of the ion trap's tandem mass spectrometry mode permits selective focus on key species for isolation and controlled fragmentation, providing structural analysis capabilities. The flight-like engineering test unit (ETU) of the ITMS, now under construction, will be used to verify breadboard performance with high fidelity, while simultaneously supporting the development of analytical scripts and spectral libraries using synthetic and natural Mars analog samples guided by current results from MSL. ETU campaign data will strongly advise the specifics of the calibration applied to the MOMA flight model as well as the science operational procedures during the mission.

Glass transition-related thermorheological complexity in polystyrene melts

NASA Astrophysics Data System (ADS)

Lin, Y.-H.

2007-11-01

The relaxation-modulus G(t) functional forms covering the whole time range are given by incorporating a stretched exponential for the structural- (glassy-) relaxation process into the extended reptation theory (ERT; for entangled systems) or the Rouse theory (for entanglement-free systems). The creep compliance J(t) curves of two entangled (A and B) and one entanglement-free (C) polystyrene samples (Plazek) as well as the viscoelastic spectra G*(ω) of four entanglement-free polystyrene samples (Inoue et al) have been quantitatively analyzed in terms of the given G(t) functional forms. In such quantitatively successful analyses, the ERT or the Rouse theory works as the frame of reference in both the line shape and timescale. The thermorheological complexity in the J(t) curves is explained naturally and precisely by the temperature dependence of the energetic-interaction-derived structural relaxation being stronger than that of the entropic ERT or Rouse dynamics in a simple way. Structural-relaxation times τS (= 18s'K') of all the studied samples are equally well separated into two decoupled quantities: the structural-growth parameter s' and the frictional factor K' (for the Rouse-Mooney or Rouse modes of motion). The separation is fundamentally a clean-cut process: s' is determined entirely by the line shape of J(t) or G*(ω) while K' is calculated from the timescale shifting factor obtained from the superposition of the calculated curves onto the measured. The glassy-relaxation strength AGf and the stretching parameter β extracted from the J(t) and G*(ω) results over the glassy-relaxation region are in good agreement. The glass-transition temperature Tg is defined as corresponding to τS = 1000 s for all the studied samples. The τS, s' and K' data points of samples A, B and C extracted from their J(t) curves individually fall closely on the same curves when expressed as a function of ΔT = T-Tg, revealing a Tg-related universality within the polystyrene system, entangled or not. The revealed universality confirms the previously derived conclusion that the ERT and the Rouse theory have the same footing at the Rouse-segmental level. Representing important physical features of the universality, the length-scale of the structural relaxation increases as ΔT diminishes and reaches the value of ~3 nm at ΔT = 0 (or at Tg) for all three samples, A, B and C. Extracted from the G*(ω) results, the τS, s' and K' data of samples with molecular weights just below and well below entanglement molecular weight Me (13 500) are found to deviate more from the respective universal curves with decreasing molecular weight. Deviation is estimated to start occurring at Mw = 12 000.

[Crosslinking sodium hyaluronate gel with different ratio of molecular weight for subcutaneous injection: animal experimental study and clinical trials subcutaneous injection].

PubMed

Ran, Weizhi; Wang, Xiaoli; Hu, Yuefei; Gao, Songying; Yang, Yahong; Sun, Jian; Sun, Shuming; Liu, Zhongmei; Wang, Jiangling

2015-05-01

To investigate the biocompatibility and degradation rate of crosslinking sodium hyaluronate gel with different ratio of molecular weight, so as to choose the effective, safe and totally degraded hyaluronate gel for aesthetic injection. (1) Compound colloid was formed by cross-linking the divinyl sulphone and sodium hyaluronate with different molecular weight (4 x 10(5), 8 x 10(5), 10 x 10(5), 12 x 10(5)). (2) Healthy level KM mice was randomly divided into two groups to receive hyaluronic acid gel or liquid injection. Each group was subdivided into three subgroup to receive hyaluronic acid with different molecular weight. The biocompatibility and degradation rate, of hyaluronate were observed at 7, 90, 180 days after injection. At the same time, different molecular weight of sodium hyaluronate gel is sealed or exposed respectively under the low temperature preservation to observe its natural degradation rate. (3) The most stable colloid was selected as aesthetic injector for volunteers to observe the aesthetic effect. The sodium hyaluronate gel with molecular of 4 x 10(5) was completely degraded 90 days later. The sodium hyaluronate gel with molecular of 8 x 10(5) was completely degraded 180 days later. The sodium hyaluronate gel with molecular of 10 x 10(5) was degraded to 90.0% after 180 days. The sodium hyaluronate liquid can be degraded completely within 7 days. The colloid could be kept for at least 12 months when sealed under low temperature, but was totally degraded when exposed for I d. Sodium hyaluronate gel with molecular 10 x 10(5) was confirmed to be kept for at least 6 months in animal experiment and clinical trials. Under the same condition of material ratio, the higher the molecular weight is, the lower the degradation rate is. But the liquidity of gel is not good for injection when molecular weight is too large. It suggests that Sodium hyaluronate gel with molecular 10 x 10(5) maybe the best choice in cosmetic injections.

Temporal change in molecular weight distribution of hot-water extractable organic nitrogen from cattle manure compost buried in soil using high-performance size exclusion chromatography with chemiluminescent nitrogen detection

NASA Astrophysics Data System (ADS)

Moriizumi, M.; Mutsunaga, T.

2012-04-01

The application of compost can improve the fertility of the agricultural soils. The compost organic nitrogen is absorbed by plants after degradation and mineralization. To investigate the degradation process of compost organic nitrogen in soil, we conducted soil burial test of compost and observed the molecular weight distribution of hot-water extractable organic nitrogen from the compost. The cattle manure compost (1g) was mixed with soil (25g), put into glass fiber-filter paper bag and buried in 15 cm under surface of the ground for 6 months. The soils used were Andosol, Gray Lowland soil, and Yellow soil without organic matter application for 25 years in Tsukuba, Japan. Organic matter was extracted from the buried sample with 80° C of water for 16 hours. The molecular weight distribution of the hot-water extractable organic matter (HWEOM) was measured by high-performance size exclusion chromatography and chemiluminescent nitrogen detection (HPSEC/CLND). In this system, N-containing compound eluted from a SEC column was introduced into a furnace at 1050° C, and N in the compound was oxidized to nitric oxide and then detected using a chemiluminescent reaction with ozone. The N chromatogram showed that N in the HWEOM from the soil with compost had various molecular weights ranging from 0.1 to 100 kDa. A void peak (>100 kDa), a broad peak around 30 kDa, and several sharp peaks less than 30 kDa were observed in the chromatogram. The broad peak (~ 30kDa) was likely to be derived from the compost, because it was not observed in the chromatogram of HWEOM from soil alone. The N intensities of all peaks decreased with burial time, especially, the broad peak (~30 kDa) intensity rapidly decreased by 10 - 50 % in only first 2 months. The decreasing rates of the broad peak were higher than that of the sharp peaks, indicating that the organic nitrogen with a larger molecular weight decomposed faster. The broad peak (~ 30 kDa) had visible (420nm) absorption and less fulvic acid like florescence (Ex340nm, Em440 nm). The several sharp peaks had small visible absorption and intense florescence. Further studies are needed to assign the chemical forms for each peak.

Using pulse field gradient NMR diffusion measurements to define molecular size distributions in glycan preparations.

PubMed

Miller, Michelle C; Klyosov, Anatole; Platt, David; Mayo, Kevin H

2009-07-06

Glycans comprise perhaps the largest biomass in nature, and more and more glycans are used in a number of applications, including those as pharmaceutical agents in the clinic. However, defining glycan molecular weight distributions during and after their preparation is not always straightforward. Here, we use pulse field gradient (PFG) (1)H NMR self-diffusion measurements to assess molecular weight distributions in various glycan preparations. Initially, we derived diffusion coefficients, D, on a series of dextrans with reported weight-average molecular weights from about 5 kDa to 150 kDa. For each dextran sample, we analyzed 15 diffusion decay curves, one from each of the 15 major (1)H resonance envelopes, to provide diffusion coefficients. By measuring D as a function of dextran concentration, we determined D at infinite dilution, D(inf), which allowed estimation of the hydrodynamic radius, R(h), using the Stokes-Einstein relationship. A plot of log D(inf) versus log R(h) was linear and provided a standard calibration curve from which R(h) is estimated for other glycans. We then applied this methodology to investigate two other glycans, an alpha-(1-->2)-L-rhamnosyl-alpha-(1-->4)-D-galacturonosyl with quasi-randomly distributed, mostly terminal beta(1-->4)-linked galactose side-chains (GRG) and an alpha(1-->6)-D-galacto-beta(1-->4)-D-mannan (Davanat), which is presently being tested against cancer in the clinic. Using the dextran-derived calibration curve, we find that average R(h) values for GRG and Davanat are 76+/-6 x 10(-10) m and 56+/-3 x 10(-10) m, with GRG being more polydispersed than Davanat. Results from this study will be useful to investigators requiring knowledge of polysaccharide dispersity, needing to study polysaccharides under various solution conditions, or wanting to follow degradation of polysaccharides during production.

Improved synthesis with high yield and increased molecular weight of poly(alpha,beta-malic acid) by direct polycondensation.

PubMed

Kajiyama, Tetsuto; Kobayashi, Hisatoshi; Taguchi, Tetsushi; Kataoka, Kazunori; Tanaka, Junzo

2004-01-01

The development of synthetic biodegradable polymers, such as poly(alpha-hydroxy acid), is particularly important for constructing medical devices, including scaffolds and sutures, and has attracted growing interest in the biomedical field. Here, we report a novel approach to preparing high molecular weight poly(malic acid) (HMW--PMA) as a biodegradable and bioabsorbable water-soluble polymer. We investigated in detail the reaction conditions for the simple direct polycondensation of l-malic acid, including the reaction times, temperatures, and catalysts. The molecular weight of synthesized alpha,beta-PMA is dependent on both the reaction temperature and time. The optimum reaction condition to obtain alpha,beta-PMA by direct polycondensation using tin(II) chloride as a catalyst was thus determined to be 110 degrees C for 45 h with a molecular weight of 5300. The method for alpha,beta-PMA synthesis established here will facilitate production of alpha,beta-PMA of various molecular weights, which may have a potential utility as biomaterials.

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.

The polysaccharide and low molecular weight components of Opuntia ficus indica cladodes: Structure and skin repairing properties.

PubMed

Di Lorenzo, Flaviana; Silipo, Alba; Molinaro, Antonio; Parrilli, Michelangelo; Schiraldi, Chiara; D'Agostino, Antonella; Izzo, Elisabetta; Rizza, Luisa; Bonina, Andrea; Bonina, Francesco; Lanzetta, Rosa

2017-02-10

The Opuntia ficus-indica multiple properties are reflected in the increasing interest of chemists in the identification of its natural components having pharmaceutical and/or cosmetical applications. Here we report the structural elucidation of Opuntia ficus-indica mucilage that highlighted the presence of components differing for their chemical nature and the molecular weight distribution. The high molecular weight components were identified as a linear galactan polymer and a highly branched xyloarabinan. The low molecular weight components were identified as lactic acid, D-mannitol, piscidic, eucomic and 2-hydroxy-4-(4'-hydroxyphenyl)-butanoic acids. A wound healing assay was performed in order to test the cicatrizing properties of the various components, highlighting the ability of these latter to fasten dermal regeneration using a simplified in vitro cellular model based on a scratched keratinocytes monolayer. The results showed that the whole Opuntia mucilage and the low molecular weight components are active in the wound repair. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

Rapid and Clean Covalent Attachment of Methylsiloxane Polymers and Oligomers to Silica Using B(C6F5)3 Catalysis.

PubMed

Flagg, Daniel H; McCarthy, Thomas J

2017-08-22

The rapid, room-temperature covalent attachment of alkylhydridosilanes (R 3 Si-H) to silicon oxide surfaces to form monolayers using tris(pentafluorophenyl)borane (B(C 6 F 5 ) 3 , BCF) catalysis has recently been described. This method, unlike alternative routes to monolayers, produces only unreactive H 2 gas as a byproduct and reaches completion within minutes. We report the use of this selective reaction between surface silanols and hydridosilanes to prepare surface-grafted poly(dimethylsiloxane)s (PDMSs) with various graft architectures that are controlled by the placement of hydridosilane functionality at one end, both ends, or along the chain of PDMS samples of controlled molecular weight. We also report studies of model methylsiloxane monolayers prepared from pentamethyldisiloxane, heptamethyltrisiloxane (two isomers), heptamethylcyclotetrasiloxane, and tris(trimethylsiloxy)silane. These modified silica surfaces with structurally defined methylsiloxane groups are not accessible by conventional silane surface chemistry and proved to be useful in exploring the steric limitations of the reaction. Linear monohydride- and dihydride-terminated PDMS-grafted surfaces exhibit increasing thickness and decreasing contact angle hysteresis with increasing molecular weight up to a particular molecular weight value. Above this value, the hysteresis increases with increasing molecular weight of end-grafted polymers. Poly(hydridomethyl-co-dimethylsiloxane)s with varied hydride content (3-100 mol %) exhibit decreasing thickness, decreasing contact angle, and increasing contact angle hysteresis with increasing hydride content. These observations illustrate the importance of molecular mobility in three-phase contact line dynamics on low-hysteresis surfaces. To calibrate our preparative procedure against both monolayers prepared by conventional approaches as well as the recent reports, a series of trialkylsilane (mostly, n-alkyldimethylsilane) monolayers was prepared to determine the reaction time required to achieve the maximum bonding density using dynamic contact angle analysis. Monolayers prepared from hydridosilanes with BCF catalysis have lower bonding densities than those derived from chlorosilanes, and the reactions are more sensitive to alkyl group sterics. This lower bonding density renders greater flexibility to the n-alkyl groups in monolayers and can decrease the contact angle hysteresis.

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.

Retraction Note: Catalytic living ring-opening metathesis polymerization

NASA Astrophysics Data System (ADS)

Nagarkar, Amit A.; Kilbinger, Andreas F. M.

2018-05-01

We the authors are retracting this Article because of our failure to reproduce the molecular weight dispersities (PDI) shown in Fig. 4 using the chain-transfer agent described in the paper (CTA1). While the degenerate chain-transfer mechanism described in Fig. 3 is correct, the best molecular weight dispersities that could be reproduced with the chain-transfer agent shown in the Article are much larger (PDI > 2.0) than reported.We have since studied the kinetics of CTA1 in comparison with several other chain-transfer agents we are currently investigating and we now understand that the reactivity of CTA1 towards propagating ruthenium alkylidene complexes is very low. Very long monomer addition times would therefore have been necessary to gain control over the molecular weight distribution. Such long addition times would exceed the lifetime of the Grubbs catalyst in solution. Faster addition of the monomer has since repeatedly been shown to broaden the molecular weight dispersity.Additionally, the best chain-transfer agents we are currently investigating are orders of magnitude more reactive than CTA1 but give broader molecular weight dispersities than reported in Fig. 4. Molecular weight and dispersity control as shown in Fig. 4 is therefore an inappropriate claim for CTA1.The authors deeply regret these errors and apologize to the community.

Predicting hydration free energies with a hybrid QM/MM approach: an evaluation of implicit and explicit solvation models in SAMPL4

NASA Astrophysics Data System (ADS)

König, Gerhard; Pickard, Frank C.; Mei, Ye; Brooks, Bernard R.

2014-03-01

The correct representation of solute-water interactions is essential for the accurate simulation of most biological phenomena. Several highly accurate quantum methods are available to deal with solvation by using both implicit and explicit solvents. So far, however, most evaluations of those methods were based on a single conformation, which neglects solute entropy. Here, we present the first test of a novel approach to determine hydration free energies that uses molecular mechanics (MM) to sample phase space and quantum mechanics (QM) to evaluate the potential energies. Free energies are determined by using re-weighting with the Non-Boltzmann Bennett (NBB) method. In this context, the method is referred to as QM-NBB. Based on snapshots from MM sampling and accounting for their correct Boltzmann weight, it is possible to obtain hydration free energies that incorporate the effect of solute entropy. We evaluate the performance of several QM implicit solvent models, as well as explicit solvent QM/MM for the blind subset of the SAMPL4 hydration free energy challenge. While classical free energy simulations with molecular dynamics give root mean square deviations (RMSD) of 2.8 and 2.3 kcal/mol, the hybrid approach yields an improved RMSD of 1.6 kcal/mol. By selecting an appropriate functional and basis set, the RMSD can be reduced to 1 kcal/mol for calculations based on a single conformation. Results for a selected set of challenging molecules imply that this RMSD can be further reduced by using NBB to reweight MM trajectories with the SMD implicit solvent model.

Molecular structure of the pyruvate dehydrogenase complex from Escherichia coli K-12.

PubMed

Vogel, O; Hoehn, B; Henning, U

1972-06-01

The pyruvate dehydrogenase core complex from E. coli K-12, defined as the multienzyme complex that can be obtained with a unique polypeptide chain composition, has a molecular weight of 3.75 x 10(6). All results obtained agree with the following numerology. The core complex consists of 48 polypeptide chains. There are 16 chains (molecular weight = 100,000) of the pyruvate dehydrogenase component, 16 chains (molecular weight = 80,000) of the dihydrolipoamide dehydrogenase component, and 16 chains (molecular weight = 56,000) of the dihydrolipoamide dehydrogenase component. Usually, but not always, pyruvate dehydrogenase complex is produced in vivo containing at least 2-3 mol more of dimers of the pyruvate dehydrogenase component than the stoichiometric ratio with respect to the core complex. This "excess" component is bound differently than are the eight dimers in the core complex.

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.

Post-exercise ingestion of a unique, high molecular weight glucose polymer solution improves performance during a subsequent bout of cycling exercise.

PubMed

Stephens, Francis B; Roig, Marc; Armstrong, Gerald; Greenhaff, Paul L

2008-01-15

The aim of the present study was to determine the effect of post-exercise ingestion of a unique, high molecular weight glucose polymer solution, known to augment gastric emptying and post-exercise muscle glycogen re-synthesis, on performance during a subsequent bout of intense exercise. On three randomized visits, eight healthy men cycled to exhaustion at 73.0% (s = 1.3) maximal oxygen uptake (90 min, s = 15). Immediately after this, participants consumed a one-litre solution containing sugar-free flavoured water (control), 100 g of a low molecular weight glucose polymer or 100 g of a very high molecular weight glucose polymer, and rested on a bed for 2 h. After recovery, a 15-min time-trial was performed on a cycle ergometer, during which work output was determined. Post-exercise ingestion of the very high molecular weight glucose polymer solution resulted in faster and greater increases in blood glucose (P < 0.001) and serum insulin (P < 0.01) concentrations than the low molecular weight glucose polymer solution, and greater work output during the 15-min time-trial (164.1 kJ, s = 21.1) than both the sugar-free flavoured water (137.5 kJ, s = 24.2; P < 0.05) and the low molecular weight glucose polymer (149.4 kJ, s = 21.8; P < 0.05) solutions. These findings could be of practical importance for athletes wishing to optimize performance by facilitating rapid re-synthesis of the muscle glycogen store during recovery following prolonged sub-maximal exercise.

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.

Broadband terahertz dynamics of propylene glycol monomer and oligomers

NASA Astrophysics Data System (ADS)

Koda, Shota; Mori, Tatsuya; Kojima, Seiji

2016-12-01

We investigated the broadband terahertz spectra (0.1-5.0 THz) of glass-forming liquids, propylene glycol (PG), its oligomers poly (propylene glycol)s (PPGs), and poly (propylene glycol) diglycidyl ether (PPG-de) using broadband terahertz time-domain spectroscopy and low-frequency Raman scattering. The numerical value of the dielectric loss at around 1.5 THz, which is the peak position of broad peaks in all samples, decreased as the molecular weight increased. Furthermore, the peak at around 1.5 THz is insensitive to the molecular weight. For PPGs, the side chain effect of the oligomer was observed in the terahertz region. Based on the experimental and calculation results for the PPGs and PPG-de, whose end groups are epoxy groups, the beginnings of the increases in the observed dielectric loss above 3.5 THz of the PPGs are assigned to the OH bending vibration. The higher value of the dielectric loss in the terahertz region for the PPG-de can be the tail of a broad peak located in the MHz region. The difference between the Raman susceptibility and dielectric loss reflects the difference in the observable molecular dynamics between the infrared and Raman spectroscopies.

The intrinsic mechanical nonlinearity 3Q0(ω) of linear homopolymer melts

NASA Astrophysics Data System (ADS)

Cziep, Miriam Angela; Abbasi, Mahdi; Wilhelm, Manfred

2017-05-01

Medium amplitude oscillatory shear (MAOS) in combination with Fourier Transformation of the mechanical stress signal (FT rheology) was utilized to investigate the influence of molecular weight, molecular weight distribution and the monomer on the intrinsic nonlinearity 3Q0(ω). Nonlinear master curves of 3Q0(ω) have been created, applying the time-temperature superposition (TTS) principle. These master curves showed a characteristic shape with an increasing slope at small frequencies, a maximum 3Q0,max and a decreasing slope at high frequencies. 3Q0(De) master curves of monodisperse polymers were evaluated and quantified with the help of a semi-empiric equation, derived from predictions from the pom-pom and molecular stress function (MSF) models. This resulted in a monomer independent description of the nonlinear mechanical behavior of linear, monodisperse homopolymer melts, where 3Q0(ω,Z) is only a function of the frequency ω and the number of entanglements Z. For polydisperse samples, 3Q0(ω) showed a high sensitivity within the experimental window towards an increasing PDI. At small frequencies, the slope of 3Q0(ω) decreases until approximately zero as a plateau value is reached, starting at a PDI around 2 and higher.

A single center retrospective cohort study comparing low-molecular-weight heparins to direct oral anticoagulants for the treatment of venous thromboembolism in patients with cancer - A real world experience.

PubMed

Phelps, Megan K; Wiczer, Tracy E; Erdeljac, H Paige; Van Deusen, Kelsey R; Porter, Kyle; Philips, Gary; Wang, Tzu-Fei

2018-01-01

Introduction Low-molecular-weight heparins are the standard treatment for cancer-associated thrombosis. Recently, direct oral anticoagulants are a new option for thrombosis treatment; however, data supporting the use of direct oral anticoagulants for cancer-associated thrombosis are limited. Objectives The primary objective of this study was to determine the rate of recurrent cancer-associated thrombosis and major bleeding within 6 months of starting either low-molecular-weight heparin or direct oral anticoagulant for treatment of cancer-associated thrombosis. Secondary objectives were to determine the rates of clinically relevant-non-major bleeding and all-cause mortality. Patients/methods This is a retrospective cohort study including adults with cancer-associated thrombosis treated with low-molecular-weight heparin or direct oral anticoagulant between 2010 and 2016 at the Ohio State University. Medical records were reviewed for 6 months after initiation of anticoagulation or until the occurrence of recurrent cancer-associated thrombosis, major bleeding, cessation of anticoagulation of interest, or death, whichever occurred first. Results Four hundred and eighty patients were included (290 low-molecular-weight heparin and 190 direct oral anticoagulant). Patients treated with direct oral anticoagulant were found to carry "lower risk" features including cancer with lower VTE risk and lower rate of metastatic disease. After adjustment for baseline differences, there was no significant difference in the rate of recurrent cancer-associated thrombosis (7.2% low-molecular-weight heparin vs 6.3% direct oral anticoagulant, p = 0.71) or major bleeding (7.6% low-molecular-weight heparin vs 2.6% direct oral anticoagulant, p = 0.08). Conclusions Our study demonstrates that in a select population of cancer patients with VTE, direct oral anticoagulant use can be as effective and safe compared to the standard therapy with low-molecular-weight heparin.

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

Analysis of molecular interaction using a pulse-induced ring-down compression ATR-DIRLD step-scan time resolved spectroscopy/2D-IR

NASA Astrophysics Data System (ADS)

Nishikawa, Yuji; Ito, Hiroto; Noda, Isao

2018-03-01

A rheo-optical method, based on pulsed compression ATR dynamic infrared linear dichroism (DIRLD) step scan time-resolved-FT-IR/2D-IR spectroscopy, is further improved. By inserting a tungsten carbide block with massive weight between a film sample and a piezo electric actuator, a ring-down response was successfully generated according to the inertial effect. The improved method is used to analyze molecular interactions in cellulose acetate propionate (CAP) films including tricresyl-phosphate (TCP), as compared with cellulose triacetate (CTA) films with the TCP case. The result suggests that the existence of molecular interaction among propionyl groups in the CAP, the TCP's Methyl, and phenyl rings, which is not observed in the CTA-TCP system.

Variations in organic carbon chemistry in the Gulf Coast and coastal marshes following the Deepwater Horizon oil spill

NASA Astrophysics Data System (ADS)

Holloway, J. M.; Orem, W. H.; Aiken, G.; Varonka, M. S.; Butler, K.; Kokaly, R. F.

2011-12-01

Record volumes of oil released from the Macondo well following the explosion of the Deepwater Horizon offshore oil-drilling platform in the Gulf of Mexico significantly impacted coastal marshes in Barataria Bay, Louisiana. Remote sensing and water sampling was conducted by the U.S. Geological Survey to evaluate the extent of impact. Water samples were collected offshore from near the spill site July 5-10, 2010 to characterize molecular organic carbon chemistry on unfiltered samples and dissolved organic carbon (DOC) on filtered samples. Three field visits were conducted in July 7-10, August 12-14, and August 24-26, 2010, to collect samples from the soil-water interface in coastal marshes along lower Barataria Bay and the Bird's Foot Delta at the distal end of the Mississippi River Delta. Visible oil in the marsh was observed as thick coatings on vegetation and soil and as sheens at the water surface. Samples were extracted for hydrocarbons with dichloromethane, separated into aliphatic, aromatic and polar compound classes using standard column techniques, and analyzed by gas chromatography/mass spectrometry. A significant amount of oil was observed "dissolved" in the water column with a hydrocarbon distribution resembling that of the surface oil slick. While oils maintained many of the more volatile lower molecular weight components near the spill site, these were mostly gone in the onshore Barataria Bay samples, leaving mostly higher molecular weight components. Dissolved organic carbon was characterized using concentration, fluorescence index (FI), specific ultratviolet absorbance (SUVA) and excitation/emission fluorescence (EEM). Offshore samples had distinctive EEMs patterns, SUVA and FI. With few exceptions, marsh samples had EEMs patterns more similar to previously extracted organic matter from the Mississippi River than to the offshore oil. In spite of visible oil sheen in unfiltered water from contaminated shorelines and no visible sign of impact on vegetation in the "control" sites with no visible oil on vegetation, DOC concentrations were similar in impacted and visibly unimpacted sites in Barataria Bay. There was an increase in specific UV absorbance (SUVA), an index of aromaticity, with increasing DOC concentrations at some repeatedly sampled sites, either due to seasonal effects or continued dissolution of petroleum compounds. These data reflect the degradation of oil during transport from the spill site to coastal marshes. Ongoing studies to track oil impacts on coastal marshes included sampling oiled and unimpacted areas in Barataria Bay for extractable hydrocarbons in July 2011, more than a year after the spill.

The effect of multimeric adiponectin isoforms and leptin on the function of rheumatoid fibroblast-like synoviocytes.

PubMed

Kontny, E; Janicka, I; Skalska, U; Maśliński, W

2015-01-01

To evaluate the effects of physiologically relevant concentrations of multimeric adiponectin isoforms and leptin on the function of fibroblast-like synoviocytes (FLS) from patients with rheumatoid arthritis (RA). FLS, isolated from the synovial tissue of 21 RA patients, were stimulated for 24 h with interleukin (IL)-1β (1 ng/mL) and adiponectin isoforms [fraction enriched with high-molecular-weight (HMW) oligomers and middle-molecular-weight (MMW) hexamers or low-molecular-weight (LMW) trimers, 10 μg/mL each], or leptin (10 ng/mL), either separately or in a combination of IL-1β and the respective adipokine. Moreover, cells were pre-treated for 24 h with adipokines, then stimulated for 8 h with IL-1β. The concentrations of IL-6, IL-8, matrix metalloproteinase (MMP)-3, and dickkopf (DKK)-1, an inhibitor of osteoblastogenesis, in culture supernatants, as well as the concentrations of leptin, HMW, MMW, and LMW adiponectin in sera and synovial fluid (SF) samples, were measured by specific enzyme-linked immunosorbent assays (ELISAs). In comparison with sera, SF samples contained similar amounts of leptin, lower amounts of total adiponectin but a higher proportion of the LMW isoform. Separately added IL-1β and HMW/MMW adiponectin, but not LMW adiponectin or leptin, up-regulated the release of IL-6, IL-8, and MMP-3 from FLS but no synergy was observed in co-stimulation experiments. However, pre-treatment of FLS with HMW/MMW or LMW significantly raised the IL-1β-triggered secretion of MMP-3 and IL-6 or MMP-3, respectively. Adiponectin not only triggers pro-inflammatory and pro-destructive activities of rheumatoid FLS but also pre-disposes these cells to a stronger response to IL-1β. Thus, it is likely that adiponectin is more important in the initiation phase than in the chronic phase of RA.

Morphological studies of sulfonated polystyrene and sulfonated EPDM ionomers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jackson, D.A.

1992-12-31

Two ionomer systems have been investigated in this research. Sulfonated polystyrene (SPS) is a typical random ionomer and is a good material for studies into the nature of phase separation in ionomers. A series of narrow molecular weight distribution (MWD) zinc neutralized SPS samples of varying sulfonation levels were prepared and analyzed through small angle x-ray scattering (SAXS). Results indicated that the correlation distance varied with both molecular weight and sulfonation level. Increases in the position of the scattering maximum with sulfonation level is the result of a greater number of ionic groups. Increasing molecular weight led to the movementmore » of the scattering maximum to smaller scattering vectors, an indication of larger distances. It was also observed that ionomer peak occurred at smaller scattering vectors for the narrow MWD samples than in corresponding materials of greater dispersity. SAXS was also used to examine the morphology of zinc stearate (ZnSt) filled sulfonated EPDM (S-EPDM) ionomers and the nature of the interaction between the plasticizer and the ionomer. S-EPDM is a material that may find use as a thermoplastic elastomer, although its melt viscosity is too high to allow for convenient processing. The addition of of ZnSt as a plasticizer greatly reduces the melt viscosity of S-EPDM. ZnSt exists in this system as very small crystallites which are associated with ionic groups. As the temperature is increased, the crystallites anneal briefly into larger crystals before melting and diffusing into the S-EPDM matrix. Above the melting temperature of the ZnSt, it solvates the ionic groups of the ionomer, decreasing their self-association and the viscosity of the system. Increasing ZnSt loading is seen in the SAXS as an increase in scattering in the low angle region. However, this increase in intensity is not linear with concentration, showing that ZnSt exists in different environments at higher concentrations.« less

Relevance of nonfunctional linear polyacrylic acid for the biodegradation of superabsorbent polymer in soils.

PubMed

Bai, Mo; Wilske, Burkhard; Buegger, Franz; Esperschütz, Jürgen; Bach, Martin; Frede, Hans-Georg; Breuer, Lutz

2015-04-01

Biodegradability is a desired characteristic for synthetic soil amendments. Cross-linked polyacrylic acid (PAA) is a synthetic superabsorbent used to increase the water availability for plant growth in soils. About 4% within products of cross-linked PAA remains as linear polyacrylic acid (PAAlinear). PAAlinear has no superabsorbent function but may contribute to the apparent biodegradation of the overall product. This is the first study that shows specifically the biodegradation of PAAlinear in agricultural soil. Two (13)C-labeled PAAlinear of the average molecular weights of 530, 400, and 219,500 g mol(-1) were incubated in soil. Mineralization of PAAlinear was measured directly as the (13)CO2 efflux from incubation vessels using an automatic system, which is based on (13)C-sensitive wavelength-scanned cavity ring-down spectroscopy. After 149 days, the PAAlinear with the larger average molecular weight and chain length showed about half of the degradation (0.91% of the initial weight) of the smaller PAAlinear (1.85%). The difference in biodegradation was confirmed by the δ(13)C signature of the microbial biomass (δ(13)Cmic), which was significantly enriched in the samples with short PAAlinear (-13‰ against reference Vienna Pee Dee Belemnite,VPDB) as compared to those with long PAAlinear (-16‰ VPDB). In agreement with other polymer studies, the results suggest that the biodegradation of PAAlinear in soil is determined by the average molecular weight and occurs mainly at terminal sites. Most importantly, the study outlines that the size of PAA that escapes cross-linking can have a significant impact on the overall biodegradability of a PAA-based superabsorbent.

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…

Determination of pesticides in composite dietary samples by gas chromatography/mass spectrometry in the selected ion monitoring mode by using a temperature-programmable large volume injector with preseparation column.

PubMed

Rosenblum, L; Hieber, T; Morgan, J

2001-01-01

Use of a temperature-programmable preseparation column in the gas chromatographic (GC) injection port permits determination of a wide range of semi-volatile pesticides including organochlorines, organophosphates, triazines, and anilines in fatty composite dietary samples while reducing sample preparation time and solvent consumption. Dietary samples are mixed with diatomaceous earth and are Soxhlet-extracted with an azeotropic solution of hexane and acetone. Sample preparation uses liquid-liquid partitioning over diatomaceous earth followed by normal phase chromatography over partially deactivated alumina. The final cleanup step occurs in a preseparation column in the GC injector, which is able to perform splitless transfer of the analytes to the analytical column and purge 99% of the high molecular weight residue. Detection is performed by GC/mass spectrometry (MS) in the selected ion monitoring mode. Method detection limits were at or below 2 ng/g for 24 of 35 pesticides studied, with recovery between 70 and 125% for 27 pesticides in samples fortified at 10 ng/g. Recovery was not dependent on fat content when measured in laboratory fortified samples containing 1, 5, and 10% fat by weight. Precision over multiple injections was acceptable, with a relative standard deviation of 2.6-15% for 25 analytes.

Alumoxanes: Rationalization of Black Box Materials

DTIC Science & Technology

1993-05-18

complexes for the synthesis of polyketones , ICH2CH(R)C(O)in. The activity observed is comparable to commercial systems but without the instability issues...see below). Commercial samples of polyketones suffer from severe thermal decomposition during melt processing. The Patent literature describes the...as well as the structure and molecular weight of the polymer. We intend to further our work with the catalytic synthesis of polyketones . We will

Cost-Effective, Ultra-Sensitive Groundwater Monitoring for Site Remediation and Management

DTIC Science & Technology

2015-08-01

Micrometer ml Milliliter MS Mass Spectrometry MW Molecular Weight MΩ Mega-ohm NAS Naval Air Station 6 NASNI Naval Air Station North Island...feasibility studies. ..........42 Table 5-2 Compounds screened in the laboratory for IS2 sampling ......................................44 Table 5-3 Mass ...concentration data is derived directly from the mass of analyte recovered from the sorbent cartridge and the known volume of water processed. This

LIGHT SCATTERING PROPERTIES OF GLIADIN AFTER X-RAY IRRADIATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, J.

1962-01-01

The gliadin portion of wheat gluten prepared in 60% ethanol solution was investigated for its light scattering properties after x irradiation. Results show that the effect of irradiation depends on the quality of the sample, such as dry or wet. The average molecular weight of liadin decreased in accordance with the time of irradiation. The longer the irradiated time, the more SH groups were setfree. (P.C.H.)

Synthesis and Characterization of High Molecular Weight Peptide Polymers and Copolymers Containing L-Dopa Residues

DTIC Science & Technology

1988-07-01

polymerize E- aminocaproic acid with DPPA for the S same period of time. Portions of each sample were then mixed together and the polymerization was...copolymers between GLUE polypeptides and poly(?c.-amino caproic acid ). Concurrent enzymatic oxidation studies with GLUE peptidesihas given some...insight into the crosslinking mechanisms which control relative reactivities of specific amino acid residues towards intramolecular or intermolecular bond

Electronic and Ionic Transport in Processable Conducting Polymers

DTIC Science & Technology

1990-04-10

Multiangle laser light scanting molecular weight GPC studies of a number of different samples of poly(3-octylhiophenc) has shown a’variation from...photochemistry at chemically modified electrodes offers a powerful ro ute to catalyst generation at, the surface.( 0!" 20. DISTRIBUTION /AVAILABILITY OF ABSTRACT...unsymmetric molecules. Oxidative polymerization has been accomplished using both chemical (FeC13) and electrochemical methods. In the case of the 2

Analysis of MALDI-TOF Serum Profiles for Biomarker Selection and Sample Classification

DTIC Science & Technology

2005-01-01

these five m/z windows as its inputs yielded 92% sensitivity and 90% specificity in distinguishing hepatocellular carcinoma (HCC) patients from...Cubizolles, I. Laurendeau, and P. Bedossa, "Identification of a new marker of hepatocellular carcinoma by serum protein profiling of patients with chronic...Goldman, "Enrichment of low molecular weight fraction of serum for mass spectrometric analysis of peptides associated with hepatocellular carcinoma ," Submitted

AWE-WQ: fast-forwarding molecular dynamics using the accelerated weighted ensemble.

PubMed

Abdul-Wahid, Badi'; Feng, Haoyun; Rajan, Dinesh; Costaouec, Ronan; Darve, Eric; Thain, Douglas; Izaguirre, Jesús A

2014-10-27

A limitation of traditional molecular dynamics (MD) is that reaction rates are difficult to compute. This is due to the rarity of observing transitions between metastable states since high energy barriers trap the system in these states. Recently the weighted ensemble (WE) family of methods have emerged which can flexibly and efficiently sample conformational space without being trapped and allow calculation of unbiased rates. However, while WE can sample correctly and efficiently, a scalable implementation applicable to interesting biomolecular systems is not available. We provide here a GPLv2 implementation called AWE-WQ of a WE algorithm using the master/worker distributed computing WorkQueue (WQ) framework. AWE-WQ is scalable to thousands of nodes and supports dynamic allocation of computer resources, heterogeneous resource usage (such as central processing units (CPU) and graphical processing units (GPUs) concurrently), seamless heterogeneous cluster usage (i.e., campus grids and cloud providers), and support for arbitrary MD codes such as GROMACS, while ensuring that all statistics are unbiased. We applied AWE-WQ to a 34 residue protein which simulated 1.5 ms over 8 months with peak aggregate performance of 1000 ns/h. Comparison was done with a 200 μs simulation collected on a GPU over a similar timespan. The folding and unfolded rates were of comparable accuracy.

Analysis of PEG oligomers in black gel inks: Discrimination and ink dating.

PubMed

Sun, Qiran; Luo, Yiwen; Xiang, Ping; Yang, Xu; Shen, Min

2017-08-01

Carbon-based black gel inks are common samples in forensic practice of questioned document examination in China, but there are few analytical methods for this type of ink. In this study, a liquid chromatography-.high resolution mass spectrometry (LC-HRMS) method was established for the analysis of PEG oligomers in carbon-based black gel ink entries. The coupled instruments achieve both the identification and quantification of PEG oligomers in ink entries with reproducible results. Twenty carbon-based black gel inks, whose Raman spectra appeared identical, were analyzed using the LC-HRMS method. As a result, the twenty gel inks were classified into four groups according to the distribution of PEG oligomers. Artificially aging of PEG 400 and a gel ink showed that as PEG degraded, the relative amounts of low molecular weight PEG oligomers increased, while those of high molecular weight decreased. The degradation of PEG oligomers in a naturally aged gel ink was consistent with those in the artificially aged samples, but occurred more slowly. This study not only provided a new method for discriminating carbon-based black gel ink entries, but also offered a new approach for studying the relative ink dating of carbon-based black gel ink entries. Copyright © 2017 Elsevier B.V. All rights reserved.

Organic contamination of ground water at Gas Works Park, Seattle, Washington

USGS Publications Warehouse

Turney, G.L.; Goerlitz, D.F.

1990-01-01

Gas Works Park, in Seattle, Washington, is located on the site of a coal and oil gasification plant that ceased operation in 1956. During operation, many types of wastes, including coal, tar, and oil, accumulated on-site. The park soil is currently (1986) contaminated with compounds such as polynuclear aromatic hydrocarbons, volatile organic compounds, trace metals, and cyanide. Analyses of water samples from a network of observation wells in the park indicate that these compounds are also present in the ground water. Polynuclear aromatic hydrocarbons and volatile organic compounds were identified in ground water samples in concentrations as large as 200 mg/L. Concentrations of organic compounds were largest where ground water was in contact with a non-aqueous phase liquid in the soil. Where no non-aqueous phase liquid was present, concentrations were much smaller, even if the ground water was in contact with contaminated soils. This condition is attributed to weathering processes in which soluble, low-molecular-weight organic compounds are preferentially dissolved from the non-aqueous phase liquid into the ground water. Where no non-aqueous phase liquid is present, only stained soils containing relatively insoluble, high-molecular-weight compounds remain. Concentrations of organic contaminants in the soils may still remain large.

Distribution, partition and removal of polycyclic aromatic hydrocarbons (PAHs) during coking wastewater treatment processes.

PubMed

Zhang, Wanhui; Wei, Chaohai; An, Guanfeng

2015-05-01

In this study, we report the performance of a full-scale conventional activated sludge (A-O1-O2) treatment in eliminating polycyclic aromatic hydrocarbons (PAHs). Both aqueous and solid phases along with the coking wastewater treatment processes were analyzed for the presence of 18 PAHs. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent and sludge samples. In the coking wastewater treatment system, 4-5 ring PAHs were the dominant compounds, while 4 rings PAHs predominated in the sludge samples. Over 98% of the PAH removal was achieved in the coking wastewater treatment plant (WWTP), with the total concentration of PAHs being 21.3 ± 1.9 μg L(-1) in the final effluent. During the coking wastewater treatment processes, the association of the lower molecular weight PAH with suspended solids was generally less than 60%, while the association of higher molecular weight PAHs was greater than 90%. High distribution efficiencies (Kdp and Kds) were found, suggesting that adsorption was the potential removal pathway of PAHs. Finally, the mass balances of PAHs in various stages of the coking WWTP were obtained, and the results indicated that adsorption to sludge was the main removal pathway for PAHs in the coking wastewater treatment processes.

Measurements and source apportionment of particle-associated polycyclic aromatic hydrocarbons in ambient air in Riyadh, Saudi Arabia

NASA Astrophysics Data System (ADS)

Bian, Qijing; Alharbi, Badr; Collett, Jeffrey; Kreidenweis, Sonia; Pasha, Mohammad J.

2016-07-01

Ambient air samples were obtained in Riyadh, the capital and largest city of Saudi Arabia, during two measurement campaigns spanning September 2011 to September 2012. Sixteen particle-phase polycyclic aromatic hydrocarbons (PAH) were quantified in 167 samples. Pyrene and fluoranthene were the most abundant PAH, with average of 3.37 ± 14.01 ng m-3 and 8.00 ± 44.09 ng m-3, respectively. A dominant contribution from low molecular weight (LMW) PAH (MW < 228) suggested a large influence of industrial emissions on PAH concentrations. Monte Carlo source apportionment using diagnostic ratios showed that 80 ± 10% of the average LMW PAH concentrations were contributed by petroleum vapor emissions, while 53 ± 19% of high molecular weight (HMW) PAH were from solid fuel combustion emissions. The positive matrix factorization model estimated that oil combustion emissions dominated total PAH concentrations, accounting for on average 96%, likely due to widespread use of oil fuels in energy production (power plants and industries). Our results demonstrate the significant influence of petroleum product production and consumption on particulate-phase PAH concentrations in Riyadh, but also point to the importance of traffic and solid fuel burning, including coke burning and seasonal biomass burning, especially as they contribute to the ambient levels of HMW PAH.

Graphene as a Novel Matrix for the Analysis of Small Molecules by MALDI-TOF MS

PubMed Central

Dong, Xiaoli; Cheng, Jinsheng; Li, Jinghong; Wang, Yinsheng

2010-01-01

Graphene was utilized for the first time as matrix for the analysis of low-molecular weight compounds using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Polar compounds including amino acids, polyamines, anticancer drugs and nucleosides could be successfully analyzed. Additionally, nonpolar compounds including steroids could be detected with high resolution and sensitivity. Compared with conventional matrix, graphene exhibited high desorption/ionization efficiency for nonpolar compounds. The graphene matrix functions as substrate to trap analytes, and it transfers energy to the analytes upon laser irradiation, which allowed for the analytes to be readily desorbed/ionized and interference of intrinsic matrix ions to be eliminated. The use of graphene as matrix avoided the fragmentation of analytes and provided good reproducibility and high salt tolerance, underscoring the potential application of graphene as matrix for MALDI-MS analysis of practical samples in complex sample matrices. We also demonstrated that the use of graphene as adsorbent for the solid-phase extraction of squalene could improve greatly the detection limit. This work not only opens a new field for applications of graphene, but also offers a new technique for high-speed analysis of low-molecular weight compounds in areas such as metabolism research and natural products characterization. PMID:20565059

Modification to AOAC official methods 2009.01 and 2011.25 to allow for minor overestimation of low molecular weight soluble dietary fiber in samples containing starch.

PubMed

Mccleary, Barry V

2014-01-01

AOAC Official Methods 2009.01 and 2011.25 have been modified to allow removal of resistant maltodextrins produced on hydrolysis of various starches by the combination of pancreatic alpha-amylase and amyloglucosidase (AMG) used in these assay procedures. The major resistant maltodextrin, 6(3),6(5)-di-alpha-D-glucosyl maltopentaose, is highly resistant to hydrolysis by microbial alpha-glucosidases, isoamylase, pullulanase, pancreatic, bacterial and fungal alpha-amylase and AMG. However, this oligosaccharide is hydrolyzed by the mucosal alpha-glucosidase complex of the pig small intestine (which is similar to the human small intestine), and thus must be removed in the analytical procedure. Hydrolysis of these oligosaccharides has been by incubation with a high concentration of a purified AMG at 60 degrees C. This incubation results in no hydrolysis or loss of other resistant oligosaccharides such as FOS, GOS, XOS, resistant maltodextrins (e.g., Fibersol 2) or polydextrose. The effect of this additional incubation with AMG on the measured level of low molecular weight soluble dietary fiber (SDFS) and of total dietary fiber in a broad range of samples is reported. Results from this study demonstrate that the proposed modification can be used with confidence in the measurement of dietary fiber.

Extraction, characterization and antioxidant activities of Se-enriched tea polysaccharides.

PubMed

Wang, Yuanfeng; Li, Yongfu; Liu, Yangyang; Chen, Xueqing; Wei, Xinlin

2015-01-01

Se-polysaccharides from Se-enriched tea leaves were purified by DEAE-sepharose fast flow gel column (2.5×60cm) and three polysaccharide fractions (Se-TPS1, Se-TPS2, and Se-TPS3) were isolated and purified with yields of 6.5, 37.14, and 8.57%, respectively. The average sizes of Se-TPS1 and Se-TPS2 were determined by HPGPC system, with molecular weights of 1.1×10(5) and 2.4×10(5)Da, respectively. Se-TPS3 was a polysaccharide polymer with two peaks with molecular weights of 9.2×10(5) and 2.5×10(5)Da. Monosaccharide components analysis by ion chromatography revealed Se-polysaccharides were acidic polysaccharoses and different from each other in monosaccharide kinds and molar ratio. Elements of Se, C, H, N, S, and 14 kinds of mineral elements were analyzed by AFS, EA, and ICP-AES, respectively. Spectral analysis (IR and UV) indicated Se-polysaccharides were typical glycoproteins. Morphological analyses of the samples were determined by SEM and AFM. In addition, the DPPH and superoxide radicals scavenging activities were also discussed to assess antioxidant activities of the samples, and Se-polysaccharides showed higher antioxidant activities compared to the ordinary polysaccharides. Copyright © 2015 Elsevier B.V. All rights reserved.

AWE-WQ: Fast-Forwarding Molecular Dynamics Using the Accelerated Weighted Ensemble

PubMed Central

2015-01-01

A limitation of traditional molecular dynamics (MD) is that reaction rates are difficult to compute. This is due to the rarity of observing transitions between metastable states since high energy barriers trap the system in these states. Recently the weighted ensemble (WE) family of methods have emerged which can flexibly and efficiently sample conformational space without being trapped and allow calculation of unbiased rates. However, while WE can sample correctly and efficiently, a scalable implementation applicable to interesting biomolecular systems is not available. We provide here a GPLv2 implementation called AWE-WQ of a WE algorithm using the master/worker distributed computing WorkQueue (WQ) framework. AWE-WQ is scalable to thousands of nodes and supports dynamic allocation of computer resources, heterogeneous resource usage (such as central processing units (CPU) and graphical processing units (GPUs) concurrently), seamless heterogeneous cluster usage (i.e., campus grids and cloud providers), and support for arbitrary MD codes such as GROMACS, while ensuring that all statistics are unbiased. We applied AWE-WQ to a 34 residue protein which simulated 1.5 ms over 8 months with peak aggregate performance of 1000 ns/h. Comparison was done with a 200 μs simulation collected on a GPU over a similar timespan. The folding and unfolded rates were of comparable accuracy. PMID:25207854

Optimization of high purity chitin and chitosan production from Illex argentinus pens by a combination of enzymatic and chemical processes.

PubMed

Vázquez, José Antonio; Noriega, Diana; Ramos, Patricia; Valcarcel, Jesus; Novoa-Carballal, Ramon; Pastrana, Lorenzo; Reis, Rui L; Pérez-Martín, Ricardo I

2017-10-15

The present report illustrates the optimisation of the experimental conditions for the chemical and enzymatic production of chitin and chitosan from Illex argentinus pen by-products. Optima conditions for chitin isolation were established at 0.82M NaOH/36.4°C, 57.5°C/pH=9.29, 59.6°C/pH=9.30 and 49.6°C/pH=5.91 for chemical, alcalase, esperase and neutrase deproteinization, respectively. Chitin samples were subsequently deacetylated by alkaline treatment reaching the highest degrees of deacetylation (DD>93%) at 61.0-63.7% of NaOH and 14.9-16.4h of hydrolysis depending on the type of process previously performed to the squid pens. Molecular weight (as number average molecular weight, Mn) of chitosan produced in the experimental designs ranged from 143kDa (PDI 2.37) to 339kDa (PDI 2.38). Copyright © 2017 Elsevier Ltd. All rights reserved.

Approaches for the analysis of low molecular weight compounds with laser desorption/ionization techniques and mass spectrometry.

PubMed

Bergman, Nina; Shevchenko, Denys; Bergquist, Jonas

2014-01-01

This review summarizes various approaches for the analysis of low molecular weight (LMW) compounds by different laser desorption/ionization mass spectrometry techniques (LDI-MS). It is common to use an agent to assist the ionization, and small molecules are normally difficult to analyze by, e.g., matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) using the common matrices available today, because the latter are generally small organic compounds themselves. This often results in severe suppression of analyte peaks, or interference of the matrix and analyte signals in the low mass region. However, intrinsic properties of several LDI techniques such as high sensitivity, low sample consumption, high tolerance towards salts and solid particles, and rapid analysis have stimulated scientists to develop methods to circumvent matrix-related issues in the analysis of LMW molecules. Recent developments within this field as well as historical considerations and future prospects are presented in this review.

Concentrations of polycyclic aromatic hydrocarbons (PAHs) and azaarenes in runoff from coal-tar- and asphalt-sealcoated pavement

USGS Publications Warehouse

Mahler, Barbara J.; Van Metre, Peter C.; Foreman, William T.

2014-01-01

Coal-tar-based sealcoat, used extensively on parking lots and driveways in North America, is a potent source of PAHs. We investigated how concentrations and assemblages of PAHs and azaarenes in runoff from pavement newly sealed with coal-tar-based (CT) or asphalt-based (AS) sealcoat changed over time. Samples of simulated runoff were collected from pavement 5 h to 111 d following application of AS or CT sealcoat. Concentrations of the sum of 16 PAHs (median concentrations of 328 and 35 μg/L for CT and AS runoff, respectively) in runoff varied relatively little, but rapid decreases in concentrations of azaarenes and low molecular weight PAHs were offset by increases in high molecular weight PAHs. The results demonstrate that runoff from CT-sealcoated pavement, in particular, continues to contain elevated concentrations of PAHs long after a 24-h curing time, with implications for the fate, transport, and ecotoxicological effects of contaminants in runoff from CT-sealcoated pavement.

An Efficient Method for Genomic DNA Extraction from Different Molluscs Species

PubMed Central

Pereira, Jorge C.; Chaves, Raquel; Bastos, Estela; Leitão, Alexandra; Guedes-Pinto, Henrique

2011-01-01

The selection of a DNA extraction method is a critical step when subsequent analysis depends on the DNA quality and quantity. Unlike mammals, for which several capable DNA extraction methods have been developed, for molluscs the availability of optimized genomic DNA extraction protocols is clearly insufficient. Several aspects such as animal physiology, the type (e.g., adductor muscle or gills) or quantity of tissue, can explain the lack of efficiency (quality and yield) in molluscs genomic DNA extraction procedure. In an attempt to overcome these aspects, this work describes an efficient method for molluscs genomic DNA extraction that was tested in several species from different orders: Veneridae, Ostreidae, Anomiidae, Cardiidae (Bivalvia) and Muricidae (Gastropoda), with different weight sample tissues. The isolated DNA was of high molecular weight with high yield and purity, even with reduced quantities of tissue. Moreover, the genomic DNA isolated, demonstrated to be suitable for several downstream molecular techniques, such as PCR sequencing among others. PMID:22174651

Polycyclic aromatic hydrocarbons in surface soil across the Tibetan Plateau: spatial distribution, source and air-soil exchange.

PubMed

Wang, Chuanfei; Wang, Xiaoping; Gong, Ping; Yao, Tandong

2014-01-01

There are limited data on polycyclic aromatic hydrocarbons (PAHs) in both the atmosphere and soil of the Tibetan Plateau (TP). Concentrations of PAHs were therefore measured in 13 XAD resin-based passive air samplers and 41 surface (0-5 cm) soil samples across the TP. The average concentration of atmospheric PAHs was 5.55 ng/m(3), which was lower than that reported for other background areas, but higher than the Arctic. Concentrations in the soils fell in a wide range from 5.54 to 389 ng/g, with an average of 59.9 ng/g. Elevation was found to play an important role in determining the spatial distribution of soil PAHs. The air-soil exchange state showed that the soils of the TP will likely remain as a sink for high molecular weight PAHs, but may become a potential "secondary source" for low molecular weight PAHs. Copyright © 2013 Elsevier Ltd. All rights reserved.

Quantification and varietal variation of low molecular weight glutenin subunits (LMW-GS) using size exclusion chromatography.

PubMed

Dangi, Priya; Khatkar, B S

2018-03-01

Crude glutenin of four commercial wheat varieties viz. C 306, HI 977, HW 2004 and PBW 550 of diverse origin and breadmaking quality were fractionated by size-exclusion chromatography into three fractions of decreasing molecular weights. The relative quantity of peak II, containing LMW-GS specifically, varied considerably among the varieties as reflected from their discrete SEC profiles. The area % of peak II, containing protein of interest, was maximal for C 306 (22.08%) followed by PBW 550 (15.86%). The least proportion of LMW-GS were recovered from variety HW 2004 (9.68%). As the concentration of the sample extract injected to the column increased, the resolution of the peak declined in association with the slight shifting of retention time to the higher values. The best results were obtained for variety C 306 at 100 mg protein concentration with 3 M urea buffer. Consequently, the optimized conditions for purification of LMW-GS in appreciable amounts using SEC were established.

Effect of gamma-irradiation on degradation of alginate.

PubMed

Lee, Dong Wook; Choi, Won Seok; Byun, Myung Woo; Park, Hyun Jin; Yu, Yong-Man; Lee, Chong M

2003-07-30

The aqueous solution of alginate was irradiated by 60Co gamma-rays in the dose range of 10-500 kGy. To assess the effect of irradiation on the degradation of alginate, the irradiation-induced changes in the viscosity, molecular weight, color, monomer composition, and sequence were measured. The molecular weight of raw alginate was reduced from 300000 to 25000 when irradiated at 100 kGy. The degradation rate decreased and the chain breaks per molecule increased with increasing irradiation dose. The viscosity of irradiated alginate solution reached a near minimum as low as at 10 kGy. No appreciable color changes were observed in the samples irradiated at up to 100 kGy, but intense browning occurred beyond 200 kGy. The 13C NMR spectra showed that homopolymeric blocks, MM and GG, increased and the M/G ratio decreased with irradiation. Considering both the level of degradation and the color change of alginate, the optimum irradiation dose was found to be 100 kGy.

Ozone treatment of polysaccharides from Arthrocnemum indicum: Physico-chemical characterization and antiproliferative activity.

PubMed

Mzoughi, Zeineb; Chakroun, Ibtissem; Hamida, Sarra Ben; Rihouey, Christophe; Mansour, Hedi Ben; Le Cerf, Didier; Majdoub, Hatem

2017-12-01

The isolation, purification and ozone depolymerization of polysaccharides from Arthrocnemum indicum as well as the evaluation of their antiproliferative capacities were investigated. The ozone treatment for various reaction times (0, 15, 30, 45 and 60min) was employed as degradation method in order to attain lower molecular weight product with stronger antiproliferative property. According to FTIR, 1 H NMR and UV-vis analysis, the main chain of ozonolytic degraded polysaccharides could be preserved. The monosaccharide composition, which was determined via GC/MS analysis, showed that extracted polysaccharides were of type of arabinan-rich pectic polysaccharides. Macromolecular characteristics as well as intrinsic viscosity of the degraded polysaccharides were performed by size exclusion chromatography before and after ozone treatment. These experiments showed that intrinsic viscosity and molecular weight (Mn and Mw) of degraded samples decreased with increase in reaction time. Furthermore, preliminary antiproliferative tests indicated that degraded polysaccharide for 1h showed even better antiproliferative capacity. Copyright © 2017 Elsevier B.V. All rights reserved.

Anomalous Micellization of Pluronic Block Copolymers

NASA Astrophysics Data System (ADS)

Leonardi, Amanda; Ryu, Chang Y.

2014-03-01

Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

Innovative thermoplastic chitosan obtained by thermo-mechanical mixing with polyol plasticizers.

PubMed

Matet, Marie; Heuzey, Marie-Claude; Pollet, Eric; Ajji, Abdellah; Avérous, Luc

2013-06-05

Chitosan shows a degradation temperature lower than its melting point, which prevents its development in several applications. One way to overcome this issue is the plasticization of the carbohydrate. In this work plasticized chitosan was prepared by a thermo-mechanical kneading approach. The effects of different non-volatile polyol plasticizers (glycerol, xylitol and sorbitol) were investigated. The microstructure and morphology were determined using FTIR, XRD, TEM and SEM in order to understand the plasticization mechanism. Sorbitol, which is the highest molecular weight polyol used, resulted in plasticized chitosan with the highest thermal, mechanical and rheological properties. On the other hand, the sample plasticized with glycerol, the lowest molecular weight polyol, had the most important amorphous phase content and the lowest thermal, mechanical and rheological properties. Also, when the polyol content increased in the formulation, the plasticized chitosan was more amorphous and consequently its processability easier, while its properties decreased. Copyright © 2013 Elsevier Ltd. All rights reserved.

Separation of three phenolic high-molecular-weight compounds from the crude extract of Terminalia Chebula Retz. by ultrasound-assisted extraction and high-speed counter-current chromatography.

PubMed

Zou, Deng-lang; Chen, Tao; Li, Hong-mei; Chen, Chen; Zhao, Jing-yang; Li, Yu-lin

2016-04-01

This study presents an efficient strategy for separation of three phenolic compounds with high molecular weight from the crude extract of Terminalia chebula Retz. by ultrasound-assisted extraction and high-speed counter-current chromatography. The ultrasound-assisted extraction conditions were optimized by response surface methodology and the results showed the target compounds could be well enriched under the optimized extraction conditions. Then the crude extract was directly separated by high-speed counter-current chromatography without any pretreatment using n-hexane/ethyl acetate/methanol/water (1:7:0.5:3, v/v/v/v) as the solvent system. In 180 min, 13 mg of A, 18 mg of B, and 9 mg of C were obtained from 200 mg of crude sample. Their structures were identified as Chebulagic acid (A, 954 Da), Chebulinic acid (B, 956 Da), and Ellagic acid (C) by (1) H NMR spectroscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Factors that influence the extraction of polycyclic aromatic hydrocarbons from coal

USGS Publications Warehouse

Xue, J.; Liu, Gaisheng; Niu, Z.; Chou, C.-L.; Qi, C.; Zheng, Lingyun; Zhang, H.

2007-01-01

Coal samples and carbonaceous mudstone were collected from the Huaibei coalfield, China, and experiments investigating the factors influencing the extraction of the sixteen US EPA (Environmental Protection Agency) priority polycyclic aromatic hydrocarbons (PAHs) were carried out. Different extraction times, solvents, and methods were used. Major interest was focused on finding optimum conditions for extracting the PAHs from coal. We conclude that (1) coal composition, including the H/C and O/C ratios, is an important factor for the distribution of PAHs in coals; (2) the total amount of EPA priority PAHs increases with increasing extraction time, 30 min being suitable for ultrasonic-assisted extraction and 24 h for Soxhlet extraction; (3) CS2 is effective in extracting low molecular weight PAHs, while CH2Cl2 is better for extracting high molecular weight PAHs (both are excellent extraction solvents vs hexane); (4) both Soxhlet and ultrasonic extraction showed a similar PAH concentration profile, but the ultrasonic method is less efficient. ?? 2007 American Chemical Society.

Gel filtration of sialoglycoproteins.

PubMed Central

Alhadeff, J A

1978-01-01

The role of sialic acid in the gel-filtration behaviour of sialoglycoproteins was investigated by using the separated isoenzymes of purified human liver alpha-L-fucosidase and several other well-known sialic acid-containing glycoproteins (fetuin, alpha1-acid glycoprotein, thyroglobulin and bovine submaxillary mucin). For each glycoprotein studied, gel filtration of its desialylated derivative gave an apparent molecular weights much less than that expected just from removal of sialic acid. For the lower-molecular-weight glycoproteins (fetuin and alpha1-acid glyocprotein), gel filtration of the sialylated molecules led to apparent molecular weights much larger than the known values. The data indicate that gel filtration cannot be used for accurately determining the molecular weights of at least some sialoglycoproteins. Images Fig. 1. PMID:356853

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

Polyimide molding powder, coating, adhesive, and matrix resin

NASA Technical Reports Server (NTRS)

St.clair, Terry L. (Inventor); Progar, Donald J. (Inventor)

1992-01-01

The invention is a polyimide prepared from 3,4'-oxydianiline (3,4'-ODA) and 4,4'-oxydiphthalic anhydride (ODPA), in 2-methoxyethyl ether (diglyme). The polymer was prepared in ultra high molecular weight and in a controlled molecular weight form which has a 2.5 percent offset in stoichiometry (excess diamine) with a 5.0 percent level of phthalic anhydride as an endcap. This controlled molecular weight form allows for greatly improved processing of the polymer for moldings, adhesive bonding, and composite fabrication. The higher molecular weight version affords tougher films and coatings. The overall polymer structure groups in the dianhydride, the diamine, and a metal linkage in the diamine affords adequate flow properties for making this polymer useful as a molding powder, adhesive, and matrix resin.

A study of physical properties of ODPA-p-PDA polyimide films

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Eftekhari, Abe; St.clair, Terry L.

1990-01-01

Physical properties were investigated of ODPA-p-PDA polyimide films, including their lower molecular weight versions with phthalimide endcaps. Free volume, determined by low energy positron annihilation in the test films, was the major parameter of interest since all other physical properties are ostensibly related to it. It affects the dielectric constant as well as the saturation moisture pickup of the test films. An empirical relation was developed between the free volume and molecular weight of the test films, comparable to the Mark-Houwink relation between the polymer solution viscosity and the molecular weight. Development of such a relation constitutes a unique achievement since it enables researchers to estimate the molecular weight of an intractable polymer in solid state for the first time.

Deep proteomic profiling of vasopressin-sensitive collecting duct cells. I. Virtual Western blots and molecular weight distributions.

PubMed

Yang, Chin-Rang; Tongyoo, Pumipat; Emamian, Milad; Sandoval, Pablo C; Raghuram, Viswanathan; Knepper, Mark A

2015-12-15

The mouse mpkCCD cell line is a continuous cultured epithelial cell line with characteristics of renal collecting duct principal cells. This line is widely used to study epithelial transport and its regulation. To provide a data resource useful for experimental design and interpretation in studies using mpkCCD cells, we have carried out "deep" proteomic profiling of these cells using three levels of fractionation (differential centrifugation, SDS-PAGE, and HPLC) followed by tandem mass spectrometry to identify and quantify proteins. The analysis of all resulting samples generated 34.6 gigabytes of spectral data. As a result, we identified 6,766 proteins in mpkCCD cells at a high level of stringency. These proteins are expressed over eight orders of magnitude of protein abundance. The data are provided to users as a public data base (https://helixweb.nih.gov/ESBL/Database/mpkFractions/). The mass spectrometry data were mapped back to their gel slices to generate "virtual Western blots" for each protein. For most of the 6,766 proteins, the apparent molecular weight from SDS-PAGE agreed closely with the calculated molecular weight. However, a substantial fraction (>15%) of proteins was found to run aberrantly, with much higher or much lower mobilities than predicted. These proteins were analyzed to identify mechanisms responsible for altered mobility on SDS-PAGE, including high or low isoelectric point, high or low hydrophobicity, physiological cleavage, residence in the lysosome, posttranslational modifications, and expression of alternative isoforms due to alternative exon usage. Additionally, this analysis identified a previously unrecognized isoform of aquaporin-2 with apparent molecular mass <20 kDa. Copyright © 2015 the American Physiological Society.

Deep proteomic profiling of vasopressin-sensitive collecting duct cells. I. Virtual Western blots and molecular weight distributions

PubMed Central

Yang, Chin-Rang; Tongyoo, Pumipat; Emamian, Milad; Sandoval, Pablo C.; Raghuram, Viswanathan

2015-01-01

The mouse mpkCCD cell line is a continuous cultured epithelial cell line with characteristics of renal collecting duct principal cells. This line is widely used to study epithelial transport and its regulation. To provide a data resource useful for experimental design and interpretation in studies using mpkCCD cells, we have carried out “deep” proteomic profiling of these cells using three levels of fractionation (differential centrifugation, SDS-PAGE, and HPLC) followed by tandem mass spectrometry to identify and quantify proteins. The analysis of all resulting samples generated 34.6 gigabytes of spectral data. As a result, we identified 6,766 proteins in mpkCCD cells at a high level of stringency. These proteins are expressed over eight orders of magnitude of protein abundance. The data are provided to users as a public data base (https://helixweb.nih.gov/ESBL/Database/mpkFractions/). The mass spectrometry data were mapped back to their gel slices to generate “virtual Western blots” for each protein. For most of the 6,766 proteins, the apparent molecular weight from SDS-PAGE agreed closely with the calculated molecular weight. However, a substantial fraction (>15%) of proteins was found to run aberrantly, with much higher or much lower mobilities than predicted. These proteins were analyzed to identify mechanisms responsible for altered mobility on SDS-PAGE, including high or low isoelectric point, high or low hydrophobicity, physiological cleavage, residence in the lysosome, posttranslational modifications, and expression of alternative isoforms due to alternative exon usage. Additionally, this analysis identified a previously unrecognized isoform of aquaporin-2 with apparent molecular mass <20 kDa. PMID:26310816

All-acrylic multigraft copolymers: Effect of side chain molecular weight and volume fraction on mechanical behavior

DOE PAGES

Goodwin, Andrew; Wang, Weiyu; Kang, Nam -Goo; ...

2015-08-21

We present in this paper the synthesis of poly(n-butyl acrylate)-g-poly(methyl methacrylate) (PnBA-g-PMMA) multigraft copolymers via a grafting-through (macromonomer) approach. The synthesis was performed using two controlled polymerization techniques. The PMMA macromonomer was obtained by high-vacuum anionic polymerization followed by the copolymerization of n-butyl acrylate and PMMA macromonomer using reversible addition–fragmentation chain transfer (RAFT) polymerization to yield the desired all-acrylic multigraft structures. The PnBA-g-PMMA multigraft structures exhibit randomly spaced branch points with various PMMA contents, ranging from 15 to 40 vol %, allowing an investigation into how physical properties vary with differences in the number of branch points and molecular weightmore » of grafted side chains. The determination of molecular weight and polydispersity indices of both the PMMA macromonomer and the graft copolymers was carried out using size exclusion chromatography with triple detection, and the structural characteristics of both the macromonomer and PnBA-g-PMMA graft materials were characterized by 1H and 13C NMR. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was employed for monitoring the macromonomer synthesis. Thermal characteristics of the materials were analyzed using differential scanning calorimetry and thermogravimetric analysis. The mechanical performance of the graft materials was characterized by rheology and dynamic mechanical analysis, revealing that samples with PMMA content of 25–40 vol % exhibit superior elastomeric properties as compared to materials containing short PMMA side chains or <25 vol % PMMA. In conclusion, atomic force microscopy showed a varying degree of microphase separation between the glassy and rubbery components that is strongly dependent on PMMA side chain molecular weight.« less

Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs in the coastal seawater, surface sediment and oyster from Dalian, Northeast China.

PubMed

Hong, Wen-Jun; Jia, Hongliang; Li, Yi-Fan; Sun, Yeqing; Liu, Xianjie; Wang, Luo

2016-06-01

A total of 46 polycyclic aromatic hydrocarbons (PAHs, 21 parent and 25 alkylated) were determined in seawater, surface sediment and oyster from coastal area of Dalian, North China. The concentration of Σ46PAHs in seawater, sediment, and oyster were 136-621 ng/L, 172-4700 ng/g dry weight (dw) and 60.0-129 ng/g wet weight (ww) in winter, and 65.0-1130 ng/L, 71.1-1090 ng/g dw and 72.8-216 ng/g ww in summer, respectively. High PAH levels were found in industrial area both in winter and summer. Selected PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism and the results indicate that surface sediment from all sampling sites have a low to medium ecotoxicological risk. Daily intake of PAHs via oyster as seafood by humans were estimated and the results indicated that oyster intake would not pose a health risk to humans even 30 days after a oil spill accident near by. Water-sediment exchange analysis showed that, both in winter and summer, the fluxes for most high molecular weight PAHs were from seawater to sediment, while for low molecular weight PAHs, an equilibrium was reached between seawater and sediment. Copyright © 2016 Elsevier Inc. All rights reserved.

Identification of a Streptococcus agalactiae protein antigen associated with bovine mastitis isolates.

PubMed Central

Wanger, A R; Dunny, G M

1987-01-01

Immunoblotting was used to analyze the immune response of cows to Streptococcus agalactiae. Antibody from the milk of cows immunized (via the superficial inguinal lymph node) with formalinized S. agalactiae cells or from the milk of cows with S. agalactiae mastitis reacted strongly with a group of high-molecular-weight proteinaceous antigens. The two most predominant antigenic polypeptides in this group had apparent molecular weights of 97,000 and 104,000. Because the data indicated that these two antigens, as well as several minor antigens sometimes observed in the 70- to 100-kilodalton size range, seemed to be different forms of the same protein, we refer to the entire group as Sas97/104. A monoclonal antibody that was reactive with Sas97/104 was derived and was used to purify the antigen by affinity chromatography. Whole-cell and colony blot enzyme-linked immunoassays with either the monoclonal antibody or a polyclonal serum sample raised against the affinity-purified antigen indicated that this antigen (or cross-reactive proteins with higher molecular weights) is present on the S. agalactiae strains that were freshly isolated from mastitic cows. However, the antigen was not detected in S. agalactiae of human origin, bovine strains of S. agalactiae maintained for a prolonged period in the laboratory, or other streptococci. The data are consistent with the notion that Sas97/104 is a surface antigen and does not correspond to previously described type-specific antigens of group B streptococci. Images PMID:3552991

Hemorrhagic shock and surgical stress alter distribution of labile zinc within high- and low-molecular-weight plasma fractions.

PubMed

Kelly, Edward; Mathew, Jeff; Kohler, Jonathan E; Blass, Amy L; Soybel, And David I

2012-08-01

Zinc ions (Zn) are essential for tissue repair following injury or stress. We hypothesize that during such stresses Zn is redistributed to labile pools in plasma components. Here we tested this hypothesis using a novel assay to monitor labile Zn in plasma in hemorrhagic shock. Adult rats in the shock group (S group) underwent hemorrhage and resuscitation. Blood samples were drawn at baseline and at 1, 4, and 24 h. The surgical control group (SC group) was anesthetized and instrumented, but not bled. Albumin, total Zn, and labile Zn levels were assayed in plasma. Binding capacity for Zn was assessed in high- and low-molecular-weight pools. Significant decreases in total Zn were observed by 24 h, in both S and SC groups. Albumin levels were significantly reduced in the S group at 1 and 4 h but restored at 24 h; significant changes were not observed in other groups. In whole plasma, labile Zn levels were stable initially in the S and SC groups, but declined at 24 h. In the high-molecular-weight pool, marked and significant impairment of binding was noted throughout all time periods following the shock period in the S group. Such changes were observed in the SC group of less intensity and duration. These experiments suggest that shock alters affinity of plasma proteins for Zn, promoting delivery to peripheral tissues during periods of increased Zn utilization.

Association between arsenic and different-sized dissolved organic matter in the groundwater of black-foot disease area, Taiwan.

PubMed

Chen, Ting-Chien; Hseu, Zeng-Yei; Jean, Jiin-Shuh; Chou, Mon-Lin

2016-09-01

The formation of an arsenic (As)-dissolved organic matter (DOM) complex is important in driving the release of arsenic in groundwater. This study collected groundwater samples from a 20 m deep well throughout 2014 and separated each into three subsamples by ultrafiltration: high molecular weight-DOM (HDOM, 0.45 μm-10 kDa), medium molecular weight-DOM (MDOM, 10-1 kDa), and low molecular weight-DOM (LDOM, <1 kDa) solutions. The fractional DOM was measured with a three-dimensional excitation-emission matrix (EEM) via fluorescence spectroscopy. A fluorescence quenching method was used to calculate the apparent stability constant (Ks) between arsenic and the fractional DOM. Based on the EEM records, three fluorescence indicators were further calculated to characterize the DOM sources, including the fluorescence index (FI), the biological index (BI), and the humification index (HI). The experimental results indicated that arsenic in the groundwater was mainly partitioned into the MDOM and LDOM fractions. All fractional DOMs contained humic acid-like substances and were considered as microbial sources. LDOM had the highest humification degree and aromaticity, followed by MDOM and HDOM. The As and DOM association could be formed by a Fe-bridge, which was demonstrated by the Ks values and fourier transform infrared (FTIR) spectra of the DOM. The formation of AsFe-DOM complex was only significant in the MDOM and LDOM. Copyright © 2016 Elsevier Ltd. All rights reserved.

Recovering the Physical Properties of Molecular Gas in Galaxies from CO SLED Modeling

NASA Astrophysics Data System (ADS)

Kamenetzky, J.; Privon, G. C.; Narayanan, D.

2018-05-01

Modeling of the spectral line energy distribution (SLED) of the CO molecule can reveal the physical conditions (temperature and density) of molecular gas in Galactic clouds and other galaxies. Recently, the Herschel Space Observatory and ALMA have offered, for the first time, a comprehensive view of the rotational J = 4‑3 through J = 13‑12 lines, which arise from a complex, diverse range of physical conditions that must be simplified to one, two, or three components when modeled. Here we investigate the recoverability of physical conditions from SLEDs produced by galaxy evolution simulations containing a large dynamical range in physical properties. These simulated SLEDs were generally fit well by one component of gas whose properties largely resemble or slightly underestimate the luminosity-weighted properties of the simulations when clumping due to nonthermal velocity dispersion is taken into account. If only modeling the first three rotational lines, the median values of the marginalized parameter distributions better represent the luminosity-weighted properties of the simulations, but the uncertainties in the fitted parameters are nearly an order of magnitude, compared to approximately 0.2 dex in the “best-case” scenario of a fully sampled SLED through J = 10‑9. This study demonstrates that while common CO SLED modeling techniques cannot reveal the underlying complexities of the molecular gas, they can distinguish bulk luminosity-weighted properties that vary with star formation surface densities and galaxy evolution, if a sufficient number of lines are detected and modeled.

Selenium bioaccessibility and speciation in biofortified Pleurotus mushrooms grown on selenium-rich agricultural residues.

PubMed

Bhatia, Poonam; Aureli, Federica; D'Amato, Marilena; Prakash, Ranjana; Cameotra, Swaranjit Singh; Nagaraja, Tejo Prakash; Cubadda, Francesco

2013-09-01

Cultivation of saprophytic fungi on selenium-rich substrates can be an effective means to produce selenium-fortified food. Pleurotus florida, an edible species of oyster mushrooms, was grown on wheat straw from the seleniferous belt of Punjab (India) and its potential to mobilize and accumulate selenium from the growth substrate was studied. Selenium concentration in biofortified mushrooms was 800 times higher compared with control samples grown on wheat straw from non selenium-rich areas (141 vs 0.17 μg Se g(-1) dry weight). Seventy-five percent of the selenium was extracted after in vitro simulated gastrointestinal digestion and investigation of the selenium molecular fractions by size exclusion HPLC-ICP-MS revealed that proteins and any other high molecular weight selenium-containing molecule were hydrolyzed to peptides and low molecular weight selenocompounds. Analysis of the gastrointestinal hydrolysates by anion exchange HPLC-ICP-MS showed that the bioaccessible selenium was mainly present as selenomethionine, a good bioavailable source of selenium, which accounted for 73% of the sum of the detected species. This study demonstrates the feasibility of producing selenium-biofortified edible mushrooms using selenium-rich agricultural by-products as growth substrates. The proposed approach can be used to evaluate whether selenium-contaminated plant waste materials harvested from high-selenium areas may be used to produce selenium-biofortified edible mushrooms based on the concentration, bioaccessibility and speciation of selenium in the mushrooms. Copyright © 2013 Elsevier Ltd. All rights reserved.

Formation of porous HPCL/LPCL/HA scaffolds with supercritical CO2 gas foaming method.

PubMed

Moghadam, M Zahedi; Hassanajili, Sh; Esmaeilzadeh, F; Ayatollahi, M; Ahmadi, M

2017-05-01

Scaffold is a 3D porous structure that is made of different materials, such as synthetic and natural polymers. It plays the role of a synthetic extracellular matrix and permits adhesion, proliferation and differentiation of the cells. Porosity and pore size are the important factors for any 3D scaffold used in bone tissue engineering. In this study, porous scaffolds were prepared by adding hydroxyapatite (HA) nanoparticles as filler to the polymeric matrix of polycaprolactone (PCL) blends with two different molecular weight by using supercritical CO 2 (ScCO 2 ) foaming method. The effect of different parameters such as CO 2 pressure, ratios of the polymers and amount of the filler on the scaffold properties was investigated. The results showed that porosity increased with increment of pressure and decreased with increasing the ratio of the high molecular weight PCL to the low molecular weight PCL in the scaffolds and also HA content. Optimum condition for obtaining adequate porous scaffold of HPCL/LPCL/HA occurred at 140bar and 45°C. The physical and mechanical properties of the prepared scaffolds were characterized using DSC, XRD, FTIR, SEM, contact angle and compression test. By analyzing the results of these tests, optimum sample for cell culture was selected. The biocompatibility of the selected HPCL/LPCL/HA scaffold (HPCL/LPCL 60/40 containing 2.5% HA) was assessed in vitro by using human mesenchymal stem cells (hMSCs). Copyright © 2016 Elsevier Ltd. All rights reserved.

Biodegradable in situ gelling delivery systems containing pilocarpine as new antiglaucoma formulations: effect of a mercaptoacetic acid/N-isopropylacrylamide molar ratio

PubMed Central

Lai, Jui-Yang

2013-01-01

Ocular drug delivery is one of the most commonly used treatment modalities in the management of glaucoma. We have recently proposed the use of gelatin and poly(N-isopropylacrylamide) (PNIPAAm) graft copolymers as biodegradable in situ forming delivery systems for the intracameral administration of antiglaucoma medications. In this study, we further investigated the influence of carrier characteristics on drug delivery performance. The carboxyl-terminated PNIPAAm samples with different molecular weights were synthesized by varying the molar ratio of mercaptoacetic acid (MAA)/N-isopropylacrylamide (NIPAAm) from 0.05 to 1.25, and were determined by end-group titration. The preparation of gelatin-g-PNIPAAm (GN) copolymers from these thermoresponsive polymers was achieved using carbodiimide chemistry. Our results showed that the carboxylic end-capped PNIPAAm of high molecular weight may lead to the lower thermal phase transition temperature and slower degradation rate of GN vehicles than its low molecular weight counterparts. With a decreasing MAA/NIPAAm molar ratio, the drug encapsulation efficiency of copolymers was increased due to fast temperature-triggered capture of pilocarpine nitrate. The degradation of the gelatin network could greatly affect the drug release profiles. All of the GN copolymeric carriers demonstrated good corneal endothelial cell and tissue compatibility. It is concluded that different types of GN-based delivery systems exhibit noticeably distinct intraocular pressure-lowering effect and miosis action, thereby reflecting the potential value of a MAA/NIPAAm molar ratio in the development of new antiglaucoma formulations. PMID:24187486

Biodegradable in situ gelling delivery systems containing pilocarpine as new antiglaucoma formulations: effect of a mercaptoacetic acid/N-isopropylacrylamide molar ratio.

PubMed

Lai, Jui-Yang

2013-01-01

Ocular drug delivery is one of the most commonly used treatment modalities in the management of glaucoma. We have recently proposed the use of gelatin and poly(N-isopropylacrylamide) (PNIPAAm) graft copolymers as biodegradable in situ forming delivery systems for the intracameral administration of antiglaucoma medications. In this study, we further investigated the influence of carrier characteristics on drug delivery performance. The carboxyl-terminated PNIPAAm samples with different molecular weights were synthesized by varying the molar ratio of mercaptoacetic acid (MAA)/N-isopropylacrylamide (NIPAAm) from 0.05 to 1.25, and were determined by end-group titration. The preparation of gelatin-g-PNIPAAm (GN) copolymers from these thermoresponsive polymers was achieved using carbodiimide chemistry. Our results showed that the carboxylic end-capped PNIPAAm of high molecular weight may lead to the lower thermal phase transition temperature and slower degradation rate of GN vehicles than its low molecular weight counterparts. With a decreasing MAA/NIPAAm molar ratio, the drug encapsulation efficiency of copolymers was increased due to fast temperature-triggered capture of pilocarpine nitrate. The degradation of the gelatin network could greatly affect the drug release profiles. All of the GN copolymeric carriers demonstrated good corneal endothelial cell and tissue compatibility. It is concluded that different types of GN-based delivery systems exhibit noticeably distinct intraocular pressure-lowering effect and miosis action, thereby reflecting the potential value of a MAA/NIPAAm molar ratio in the development of new antiglaucoma formulations.

Combining experimental and simulation data of molecular processes via augmented Markov models.

PubMed

Olsson, Simon; Wu, Hao; Paul, Fabian; Clementi, Cecilia; Noé, Frank

2017-08-01

Accurate mechanistic description of structural changes in biomolecules is an increasingly important topic in structural and chemical biology. Markov models have emerged as a powerful way to approximate the molecular kinetics of large biomolecules while keeping full structural resolution in a divide-and-conquer fashion. However, the accuracy of these models is limited by that of the force fields used to generate the underlying molecular dynamics (MD) simulation data. Whereas the quality of classical MD force fields has improved significantly in recent years, remaining errors in the Boltzmann weights are still on the order of a few [Formula: see text], which may lead to significant discrepancies when comparing to experimentally measured rates or state populations. Here we take the view that simulations using a sufficiently good force-field sample conformations that are valid but have inaccurate weights, yet these weights may be made accurate by incorporating experimental data a posteriori. To do so, we propose augmented Markov models (AMMs), an approach that combines concepts from probability theory and information theory to consistently treat systematic force-field error and statistical errors in simulation and experiment. Our results demonstrate that AMMs can reconcile conflicting results for protein mechanisms obtained by different force fields and correct for a wide range of stationary and dynamical observables even when only equilibrium measurements are incorporated into the estimation process. This approach constitutes a unique avenue to combine experiment and computation into integrative models of biomolecular structure and dynamics.

Polycyclic aromatic hydrocarbons in the leaves of twelve plant species along an urbanization gradient in Shanghai, China.

PubMed

Liang, Jing; Fang, Hailan; Zhang, Taolin; Wang, Xingxiang

2017-04-01

Plants, particularly their leaves, play an important role in filtering both gas-phase and particle-phase polycyclic aromatic hydrocarbons (PAHs). However, many studies have focused on the accumulation and adsorption functions of plant leaves, possibly underestimating the effects that plants have on air quality. Therefore, eight tree species from different locations in Shanghai were selected to assess PAH filtering (via adsorption and capture) using washed and unwashed plant leaves. The differences in the total PAH contents in the washed leaves were constant for the different species across the different sampling sites. The PAH levels decreased in the following order: industrial areas > traffic areas > urban areas > background area. The PAH compositions in the different plant leaves were dominated by fluorene (Fle), phenanthrene (Phe), anthracene (Ant), chrysene (Chr), fluoranthene (Flu), and pyrene (Pyr); notably, Phe accounted for 49.4-76.7% of the total PAHs. By comparing the PAH contents in the washed leaves with the PAH contents in the unwashed leaves, Pittosporum tobira (P. tobira), Ginkgo biloba (G. biloba), and Platanus acerifolia (P. acerifolia) were found to be efficient species for adsorbing PAHs, while Osmanthus fragrans (O. fragrans), Magnolia grandiflora (M. grandiflora), and Prunus cerasifera Ehrh. (P. cerasifera Ehrh.) were efficient species for capturing PAHs. The efficiencies of the plant leaves for the removal of PAHs from air occurred in the order of low molecular weight > medium molecular weight > high molecular weight PAHs.

Transdermal Protein Delivery Using Choline and Geranate (CAGE) Deep Eutectic Solvent.

PubMed

Banerjee, Amrita; Ibsen, Kelly; Iwao, Yasunori; Zakrewsky, Michael; Mitragotri, Samir

2017-08-01

Transdermal delivery of peptides and other biological macromolecules is limited due to skin's inherent low permeability. Here, the authors report the use of a deep eutectic solvent, choline and geranate (CAGE), to enhance topical delivery of proteins such as bovine serum albumin (BSA, molecular weight: ≈66 kDa), ovalbumin (OVA, molecular weight: ≈45 kDa) and insulin (INS, molecular weight: 5.8 kDa). CAGE enhances permeation of BSA, OVA, and insulin into porcine skin ex vivo, penetrating deep into the epidermis and dermis. Studies using tritium-labeled BSA and fluorescein isothiocyanate labeled insulin show significantly enhanced delivery of proteins into and across porcine skin, penetrating the skin in a time-dependent manner. Fourier transform IR spectra of porcine stratum corneum (SC) samples before and after incubation in CAGE show a reduction in peak area attributed to SC lipid content, suggesting lipid extraction from the SC. Circular dichroism confirms that CAGE does not affect insulin's secondary conformation. In vivo studies in rats show that topical application of 10 U insulin dispersed in CAGE (25 U kg -1 insulin dose) leads to a highly significant 40% drop in blood glucose levels in 4 h that is relatively sustained for 12 h. Taken together, these studies demonstrate that CAGE is a promising vehicle for transdermal delivery of therapeutic proteins; specifically, as a noninvasive delivery alternative to injectable insulin for the treatment of diabetes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.