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.

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...

Modeling electrostatic and heterogeneity effects on proton dissociation from humic substances

USGS Publications Warehouse

Tipping, E.; Reddy, M.M.; Hurley, M.A.

1990-01-01

The apparent acid dissociation constant of humic substances increases by 2-4 pK units as ionization of the humic carboxylate groups proceeds. This change in apparent acid strength is due in part to the increase in electrical charge on the humic molecules as protons are shed. In addition, proton dissociation reactions are complicated because humic substances are heterogeneous with respect to proton dissociating groups and molecular size. In this paper, we use the Debye-Hu??ckel theory to describe the effects of electrostatic interactions on proton dissociation of humic substances. Simulations show that, for a size-heterogeneous system of molecules, the weight-average molecular weight is preferable to the number-average value for averaging the effects of electrostatic interactions. Analysis of published data on the proton dissociation of fulvic acid from the Suwannee River shows that the electrostatic interactions can be satisfactorily described by a hypothetical homogeneous compound having a molecular weight of 1000 (similar to the experimentally determined weight-average value). Titration data at three ionic strengths, for several fulvic acid concentrations, and in the pH range from 2.9 to 6.4 can be fitted with three adjustable parameters (pK??int values), given information on molecular size and carboxylate group content. ?? 1990 American Chemical Society.

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.

Polymeric heat pipe wick

NASA Technical Reports Server (NTRS)

Seidenberg, Benjamin

1988-01-01

A wick for use in a capillary loop pump heat pipe is described. The wick material is an essentially uniformly porous, permeable, open-cell, polyethylene thermoplastic foam having an ultrahigh average molecular weight of from approximately 1 to 5 million, and an average pore size of about 10 to 12 microns. A representative material having these characteristics is POREX UF, which has an average molecular weight of about 3 million. This material is fully compatible with the FREONs and anhydrous ammonia and allows for the use of these very efficient working fluids in capillary loops.

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

DTIC Science & Technology

2012-10-25

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

Correlation of the protein structure and gelling properties in dried egg white products.

PubMed

Handa, A; Hayashi, K; Shidara, H; Kuroda, N

2001-08-01

The relationship between protein structure and aggregation, as well as heat-induced gelling properties, of seven dried egg white (DEW) products was investigated. Strong correlations were found between average molecular weight and hydrophobicity plus surface SH groups of DEW-soluble protein aggregate (SPA). This suggests that hydrophobic interactions and disulfide bond formation between protein molecules were involved in the aggregation. The average molecular weight of DEW products with alkaline pHs was relatively higher than those with neutral pHs and the same degree of protein unfolding, probably because of more disulfide bond formation between protein molecules. In addition, strong correlations were found between hydrophobicity, surface SH groups plus average molecular weight of DEW-SPA, and physical properties of the gels from DEW products. These data indicated that controlling the aggregation of DEW proteins in the dry state is crucial to controlling the gelling properties of DEW.

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.

Method of generating hydrocarbon reagents from diesel, natural gas and other logistical fuels

DOEpatents

Herling, Darrell R [Richland, WA; Aardahl, Chris L [Richland, WA; Rozmiarek, Robert T [Middleton, WI; Rappe, Kenneth G [Richland, WA; Wang, Yong [Richland, WA; Holladay, Jamelyn D [Kennewick, WA

2010-06-29

The present invention provides a process for producing reagents for a chemical reaction by introducing a fuel containing hydrocarbons into a flash distillation process wherein the fuel is separated into a first component having a lower average molecular weight and a second component having a higher average molecular weight. The first component is then reformed to produce synthesis gas wherein the synthesis gas is reacted catalytically to produce the desire reagent.

Method of Generating Hydrocarbon Reagents from Diesel, Natural Gas and Other Logistical Fuels

DOEpatents

Herling, Darrell R [Richland, WA; Aardahl, Chris L [Richland, WA; Rozmiarek, Robert T [Middleton, WI; Rappe, Kenneth G [Richland, WA; Wang, Yong [Richland, WA; Holladay, Jamelyn D [Kennewick, WA

2008-10-14

The present invention provides a process for producing reagents for a chemical reaction by introducing a fuel containing hydrocarbons into a flash distillation process wherein the fuel is separated into a first component having a lower average molecular weight and a second component having a higher average molecular weight. The first component is then reformed to produce synthesis gas wherein the synthesis gas is reacted catalytically to produce the desire reagent.

Surface segregation and surface tension of polydisperse polymer melts.

PubMed

Minnikanti, Venkatachala S; Qian, Zhenyu; Archer, Lynden A

2007-04-14

The effect of polydispersity on surface segregation of a lower molecular weight polymer component in a higher molecular weight linear polymer melt host is investigated theoretically. We show that the integrated surface excess zM of a polymer component of molecular weight M satisfies a simple relation zM=2Ue(M/Mw-1)phiM, where Mw is the weight averaged molecular weight, phiM is the polymer volume fraction, and Ue is the attraction of polymer chain ends to the surface. Ue is principally of entropic origin, but also reflects any energetic preference of chain ends to the surface. We further show that the surface tension gammaM of a polydisperse melt of high molar mass components depends on the number average degree of polymerization Mn as, gammaM=gammainfinity+2UerhobRT/Mn. The parameter gammainfinity is the asymptotic surface tension of an infinitely long polymer of the same chemistry, rhob is the bulk density of the polymer, R is the universal gas constant, and T is the temperature. The predicted gammaM compare favorably with surface tension values obtained from self-consistent field theory simulations that include equation of state effects, which account for changes in polymer density with molecular weight. We also compare the predicted surface tension with available experimental data.

Raman analysis of polyethylene glycols and polyethylene oxides

NASA Astrophysics Data System (ADS)

Sagitova, E. A.; Prokhorov, K. A.; Nikolaeva, G. Yu; Baimova, A. V.; Pashinin, P. P.; Yarysheva, A. Yu; Mendeleev, D. I.

2018-04-01

We present Raman study of commercial liquids and powders of polyethylene glycols and polyethylene oxides with the average molecular weight from 400 Da to 10000 kDa. The most significant spectral changes were observed for the range of the molecular weights, where the liquid/semisolid transition has occurred. For the powders we revealed increase in the content of the molecules in the helical conformation and in the content of the monoclinic crystalline phase with growth of the molecular weight.

21 CFR 177.1680 - Polyurethane resins.

Code of Federal Regulations, 2012 CFR

2012-04-01

...′,α″-1,2,3-Propanetriyltris [omega-hydroxypoly (oxypropylene) (15-18 moles)], average molecular weight 3,000. Propylene glycol. α,α′,α″-[Propylidynetris (methylene)] tris [omega-hydroxypoly (oxypropylene) (minimum 1.5 moles)], minimum molecular weight 400. α-[ρ(1,1,3,3-Tetramethylbutyl) - phenyl]-omega...

21 CFR 177.1680 - Polyurethane resins.

Code of Federal Regulations, 2011 CFR

2011-04-01

...′,α″-1,2,3-Propanetriyltris [omega-hydroxypoly (oxypropylene) (15-18 moles)], average molecular weight 3,000. Propylene glycol. α,α′,α″-[Propylidynetris (methylene)] tris [omega-hydroxypoly (oxypropylene) (minimum 1.5 moles)], minimum molecular weight 400. α-[ρ(1,1,3,3-Tetramethylbutyl) - phenyl]-omega...

21 CFR 177.1680 - Polyurethane resins.

Code of Federal Regulations, 2010 CFR

2010-04-01

...′,α″-1,2,3-Propanetriyltris [omega-hydroxypoly (oxypropylene) (15-18 moles)], average molecular weight 3,000. Propylene glycol. α,α′,α″-[Propylidynetris (methylene)] tris [omega-hydroxypoly (oxypropylene) (minimum 1.5 moles)], minimum molecular weight 400. α-[ρ(1,1,3,3-Tetramethylbutyl) - phenyl]-omega...

21 CFR 177.1680 - Polyurethane resins.

Code of Federal Regulations, 2013 CFR

2013-04-01

...′,α″-1,2,3-Propanetriyltris [omega-hydroxypoly (oxypropylene) (15-18 moles)], average molecular weight 3,000. Propylene glycol. α,α′,α″-[Propylidynetris (methylene)] tris [omega-hydroxypoly (oxypropylene) (minimum 1.5 moles)], minimum molecular weight 400. α-[ρ(1,1,3,3-Tetramethylbutyl) - phenyl]-omega...

Volatilization of organic compounds from streams

USGS Publications Warehouse

Rathburn, R.E.; Tai, D.Y.

1982-01-01

Mass-transfer coefficients for the volatilization of ethylene and propane were correlated with the hydraulic and geometric properties of seven streams, and predictive equations were developed. The equations were evaluated using a normalized root-mean-square error as the criterion of comparison. The two best equations were a two-variable equation containing the energy dissipated per unit mass per unit time and the average depth of flow and a three-variable equation containing the average velocity, the average depth of flow, and the slope of the stream. Procedures for adjusting the ethylene and propane coefficients for other organic compounds were evaluated. These procedures are based on molecular diffusivity, molecular diameter, or molecular weight. Because of limited data, none of these procedures have been extensively verified. Therefore, until additional data become available, it is suggested that the mass-transfer coefficient be assumed to be inversely proportional to the square root of the molecular weight.

21 CFR 177.1680 - Polyurethane resins.

Code of Federal Regulations, 2014 CFR

2014-04-01

...′-(Isopropylidenedi-p-phenylene)bis[omega-hydroxypoly (oxy-pro-pylene)(3-4 moles)], average molecular weight 675... propylene oxide). Polypropylene glycol. α,α′,α″-1,2,3-Propanetriyltris [omega-hydroxypoly (oxypropylene) (15...)] tris [omega-hydroxypoly (oxypropylene) (minimum 1.5 moles)], minimum molecular weight 400. α-[ρ(1,1,3,3...

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.

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

PubMed

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

2017-01-20

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

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

PubMed

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

2011-12-05

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

Effect of ring-opening polymerization condition on the characteristic and mechanical properties of hydroxyapatite/poly(ethylene glutarate) biomaterials.

PubMed

Monvisade, Pathavuth; Siriphannon, Punnama; Tapcharoen, Walailak

2009-09-01

Preparation of hydroxyapatite/poly(ethylene glutarate) (HAp/PEG) composites was carried out by ring-opening polymerization (ROP) of cyclic oligo(ethylene glutarate) in porous HAp scaffolds using various reaction temperatures and times. The content of ROP-PEG interpenetrated into the porous HAp scaffold was about 13-18 wt % with the values of number average molecular weight (overline_M{n}) and weight average molecular weight (overline_M{W}) of 2120-3630 and 2760-5250 g/mol, respectively. The increase in polymerization time and temperature brought about increase in molecular weight of ROP-PEG, but decrease in its content. Compressive strength and compressive modulus of the HAp/PEG composites were about 5.8-20.1 and 105-208 MPa, respectively. These mechanical properties depend upon the effects of distribution, content, and molecular weight of ROP-PEG in the composites. In vitro bioactivity of the HAp/PEG composites was studied by soaking them in simulated body fluid (SBF) for 28 days. The formation of HAp nanocrystal on the composite surfaces through the consumption of calcium and phosphorus from the SBF solution was observed after soaking, indicating the bioactivity of these HAp/PEG composites.

Effect of molecular weight of starch on the properties of cassava starch microspheres prepared in aqueous two-phase system.

PubMed

Xia, Huiping; Li, Bing-Zheng; Gao, Qunyu

2017-12-01

Starch microspheres (SMs) were fabricated in an aqueous two-phase system (ATPS). A series of starch samples with different molecular weight were prepared by acid hydrolysis, and the effect of molecular weight of starch on the fabrication of SMs were investigated. Scanning electron microscopy (SEM) showed that the morphologies of SMs varied with starch molecular weight, and spherical SMs with sharp contours were obtained while using starch samples with weight-average molecular weight (M¯w)≤1.057×10 5 g/mol. X-ray diffraction (XRD) results revealed that crystalline structure of SMs were different from that of native cassava starch, and the relative crystallinity of SMs increased with the molecular weight of starch decreasing. Differential scanning calorimetry (DSC) results showed peak gelatinization temperature (T p ) and enthalpy of gelatinization (ΔH) of SMs increased with decreased M¯wof starch. Stability tests indicated that the SMs were stable under acid environment, but not stable under α-amylase hydrolysis. Copyright © 2017. Published by Elsevier Ltd.

In situ upgrading of whole biomass to biofuel precursors with low average molecular weight and acidity by the use of zeolite mixture

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

Ben, Haoxi; Huang, Fang; Li, Liwei

2015-09-09

The pyrolysis of whole biomass—pine wood and bark—with mordenite (M), beta (β) and Y zeolites has been examined at 600°C. The GPC results indicated that the pyrolysis oils upgraded by Y and β zeolites have a very low average molecular weight range (70–170 g mol –1). Several NMR methods have been employed to characterize the whole portion of pyrolysis products. After the use of these two zeolites (Y and β), the two main products from the pyrolysis of cellulose—levoglucosan and HMF—were eliminated; this indicates a significant deoxygenation process. When a mixture of zeolites (Y and M) was used, the upgradedmore » pyrolysis oil exhibited advantages provided by both zeolites; this pyrolysis oil represents a biofuel precursor that has a very low average molecular weight and a relatively low acidity. Finally, this study opens up a new way to upgrade pyrolysis oils by employing mixtures of different functional zeolites to produce biofuel/biochemical precursors from whole biomass.« less

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

21 CFR 177.2415 - Poly(aryletherketone) resins.

Code of Federal Regulations, 2014 CFR

2014-04-01

..., and have a minimum weight-average molecular weight of 12,000, as determined by gel permeation...: Distilled water, 50 percent (by volume) ethanol in distilled water, 3 percent acetic acid in distilled water...

Antioxidant and antibacterial activities of polysaccharides isolated and purified from Diaphragma juglandis fructus.

PubMed

Meng, Qingran; Li, Yinghao; Xiao, Tiancun; Zhang, Lianfu; Xu, Dan

2017-12-01

A water-soluble polysaccharide fraction (DJP-2) isolated from Diaphragma juglandis was successfully purified by ion-exchange chromatography (DEAE-cellulose) and gel-permeation chromatography (Sephadex G-100). The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of DJP-2 were 4.95 and 3.99kDa, respectively. Monosaccharide component analysis indicated that DJP-2 comprised arabinose, galactose, glucose, xylose, and mannose in a molar ratio of 0.27:0.55:1:0.14:0.08. The evaluation of the antioxidant and antibacterial activities of polysaccharides from Diaphragma juglandis fructus indicated that they could be explored as promising natural antioxidant and bacteriostatic agents in the food and pharmaceutical industries. Copyright © 2017 Elsevier B.V. All rights reserved.

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

ERIC Educational Resources Information Center

Wackerly, Jay Wm.; Dunne, James F.

2017-01-01

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

Influence of excess diamine on properties of PMR polyimide resins and composites

NASA Technical Reports Server (NTRS)

Hurwitz, F. I.

1980-01-01

By varying the stoichiometry of the reactants in the preparation of PMR polyimide resin, changes occur in molecular weight distribution which influence the rheological properties and thus the processability of the resin, as well as the mechanical properties of the composite. The influence of 1-10 percent molar excess MDA on the molecular weight distribution and rheological properties of an imidized PMR system were exposed. Molecular weight distribution is characterized by gel permeation chromatography of the imidized molding compound; shear viscosity is related to changes in average molecular weight. The thermo-oxidative stability at 600 F, glass transition temperature, flexural and interlaminar shear properties of PMR polyimide/Celion 6000 graphite fiber composites are compared as a function of the percent excess MDA in the monomer reactant mixture.

Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol.

PubMed

Yuan, Zhongshun; Cheng, Shuna; Leitch, Mathew; Xu, Chunbao Charles

2010-12-01

Alkaline lignin of a very high molecular weight was successfully degraded into oligomers in a hot-compressed water-ethanol medium with NaOH as the catalyst and phenol as the capping agent at 220-300 degrees C. Under the optimal reaction conditions, i.e., 260 degrees C, 1 h, with the lignin/phenol ratio of 1:1 (w/w), almost complete degradation was achieved, producing <1% solid residue and negligible gas products. The obtained degraded lignin had a number-average molecular weight M(n) and weight-average molecular weight M(w) of 450 and 1000 g/mol respectively, significantly lower than the M(n) and M(w) of 10,000 and 60,000 g/mol of the original lignin. A higher temperature and a longer reaction time favoured phenol combination, but increased the formation of solid residue due to the condensation reactions of the degradation intermediates/products. The degraded lignin products were soluble in organic solvents (such as THF), and were characterized by HPLC/GPC, IR and NMR. A possible mechanism for lignin hydrolytic degradation was also proposed in this study. 2010 Elsevier Ltd. All rights reserved.

Multicolor Electrochromic Displays Exploratory Development

DTIC Science & Technology

1989-07-01

Electrodes with PEG Plasticizers in KCI ...................... 42 6. Electrodes in KCI-AMPS and KCI-PolyAMPS Electrolytes .. 43 7. Orange/Blue Cycling...ethylene glycol) ( PEG ) preparations with average molecular weights of 300 and 3350 were from J.T. Baker Chemical Co. 3. Conductive Substrates Most of...crystallization of the dye. Poly(ethylene glycols) of molecular weights 300 and 3350 were introduced by incorporating them in the IM KCI electrolyte

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

An improved correlation to predict molecular weight between crosslinks based on equilibrium degree of swelling of hydrogel networks.

PubMed

Jimenez-Vergara, Andrea C; Lewis, John; Hahn, Mariah S; Munoz-Pinto, Dany J

2018-04-01

Accurate characterization of hydrogel diffusional properties is of substantial importance for a range of biotechnological applications. The diffusional capacity of hydrogels has commonly been estimated using the average molecular weight between crosslinks (M c ), which is calculated based on the equilibrium degree of swelling. However, the existing correlation linking M c and equilibrium swelling fails to accurately reflect the diffusional properties of highly crosslinked hydrogel networks. Also, as demonstrated herein, the current model fails to accurately predict the diffusional properties of hydrogels when polymer concentration and molecular weight are varied simultaneously. To address these limitations, we evaluated the diffusional properties of 48 distinct hydrogel formulations using two different photoinitiator systems, employing molecular size exclusion as an alternative methodology to calculate average hydrogel mesh size. The resulting data were then utilized to develop a revised correlation between M c and hydrogel equilibrium swelling that substantially reduces the limitations associated with the current correlation. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1339-1348, 2018. © 2017 Wiley Periodicals, Inc.

In vivo oxidation in remelted highly cross-linked retrievals.

PubMed

Currier, B H; Van Citters, D W; Currier, J H; Collier, J P

2010-10-20

Elimination of free radicals to prevent oxidation has played a major role in the development and product differentiation of the latest generation of highly cross-linked ultra-high molecular weight polyethylene bearing materials. In the current study, we (1) examined oxidation in a series of retrieved remelted highly cross-linked ultra-high molecular weight polyethylene bearings from a number of device manufacturers and (2) compared the retrieval results with findings for shelf-stored control specimens. The hypothesis was that radiation-cross-linked remelted ultra-high molecular weight polyethylene would maintain oxidative stability in vivo comparable with the stability during shelf storage and in published laboratory aging tests. Fifty remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners and nineteen remelted highly cross-linked ultra-high molecular weight polyethylene tibial inserts were received after retrieval from twenty-one surgeons from across the U.S. Thirty-two of the retrievals had been in vivo for two years or more. Each was measured for oxidation with use of Fourier transform infrared spectroscopy. A control series of remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners from three manufacturers was analyzed with electron paramagnetic resonance spectroscopy to measure free radical content and with Fourier transform infrared spectroscopy to measure oxidation initially and after eight to nine years of shelf storage in air. The never-implanted, shelf-aged controls had no measurable free-radical content initially or after eight to nine years of shelf storage. The never-implanted controls showed no increase in oxidation during shelf storage. Oxidation measurements showed measurable oxidation in 22% of the retrieved remelted highly cross-linked liners and inserts after an average of two years in vivo. Because never-implanted remelted highly cross-linked ultra-high molecular weight polyethylene materials had no measurable free-radical concentration and no increase in oxidation during shelf storage, these materials were expected to be oxidation-resistant in vivo. However, some remelted highly cross-linked ultra-high molecular weight polyethylene retrievals showed measurable oxidation after an average of more than two years in vivo. This apparent departure from widely expected behavior requires continued study of the process of in vivo oxidation of ultra-high molecular weight polyethylene materials.

Understanding gas-surface interactions from direct force measurements using a specialized torsion balance

NASA Technical Reports Server (NTRS)

Cook, S. R.; Hoffbauer, M. A.

1996-01-01

The first comprehensive measurements of the magnitude and direction of the forces exerted on surfaces by molecular beams are discussed and used to obtain information about the microscopic properties of the gas-surface interactions. This unique approach is not based on microscopic measurements of the scattered molecules. The reduced force coefficients are introduced as a new set of parameters that completely describe the macroscopic average momentum transfer to a surface by an incident molecular beam. By using a specialized torsion balance and molecular beams of N2, CO, CO2, and H2, the reduced force coefficients are determined from direct measurements of the force components exerted on surface of a solar panel array material, Kapton, SiO2-coated Kapton, and Z-93 as a function of the angle of incidence ranging from 0 degrees to 85 degrees. The absolute flux densities of the molecular beams were measured using a different torsion balance with a beam-stop that nullified the force of the scattered molecules. Standard time-of-flight techniques were used to determine the flux-weighted average velocities of the various molecular beams ranging from 1600 m/s to 4600 m/s. The reduced force coefficients can be used to directly obtain macroscopic average properties of the scattered molecules, such as the flux-weighted average velocity and translational energy, that can then be used to determine microscopic details concerning gas-surface interactions without the complications associated with averaging microscopic measurements.

Mirrored continuum and molecular scale simulations of the ignition of high-pressure phases of RDX

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

Lee, Kibaek; Stewart, D. Scott, E-mail: santc@illinois.edu, E-mail: dss@illinois.edu; Joshi, Kaushik

2016-05-14

We present a mirrored atomistic and continuum framework that is used to describe the ignition of energetic materials, and a high-pressure phase of RDX in particular. The continuum formulation uses meaningful averages of thermodynamic properties obtained from the atomistic simulation and a simplification of enormously complex reaction kinetics. In particular, components are identified based on molecular weight bin averages and our methodology assumes that both the averaged atomistic and continuum simulations are represented on the same time and length scales. The atomistic simulations of thermally initiated ignition of RDX are performed using reactive molecular dynamics (RMD). The continuum model ismore » based on multi-component thermodynamics and uses a kinetics scheme that describes observed chemical changes of the averaged atomistic simulations. Thus the mirrored continuum simulations mimic the rapid change in pressure, temperature, and average molecular weight of species in the reactive mixture. This mirroring enables a new technique to simplify the chemistry obtained from reactive MD simulations while retaining the observed features and spatial and temporal scales from both the RMD and continuum model. The primary benefit of this approach is a potentially powerful, but familiar way to interpret the atomistic simulations and understand the chemical events and reaction rates. The approach is quite general and thus can provide a way to model chemistry based on atomistic simulations and extend the reach of those simulations.« less

Cells of pea (Pisum sativum) that differentiate from G2 phase have extrachromosomal DNA.

PubMed Central

Van't Hof, J; Bjerknes, C A

1982-01-01

Velocity sedimentation in an alkaline sucrose gradient of newly replicated chromosomal DNA revealed the presence of extrachromosomal DNA that was not replicated by differentiating cells in the elongation zone. The extrachromosomal DNA had a number average molecular weight of 12 X 10(6) to 15 X 10(6) and a weight average molecular weight of 25 X 10(6), corresponding to about 26 X 10(6) and 50 X 10(6) daltons, respectively, of double-stranded DNA. The molecules were stable, lasting at least 72 h after being formed. Concurrent measurements by velocity sedimentation, autoradiography, and cytophotometry of isolated nuclei indicated that the extrachromosomal molecules were associated with root-tip cells that stopped dividing and differentiated from G2 phase but not with those that stopped dividing and differentiated from G1 phase. PMID:7110135

Fossil fuel combined cycle power generation method

DOEpatents

Labinov, Solomon D [Knoxville, TN; Armstrong, Timothy R [Clinton, TN; Judkins, Roddie R [Knoxville, TN

2008-10-21

A method for converting fuel energy to electricity includes the steps of converting a higher molecular weight gas into at least one mixed gas stream of lower average molecular weight including at least a first lower molecular weight gas and a second gas, the first and second gases being different gases, wherein the first lower molecular weight gas comprises H.sub.2 and the second gas comprises CO. The mixed gas is supplied to at least one turbine to produce electricity. The mixed gas stream is divided after the turbine into a first gas stream mainly comprising H.sub.2 and a second gas stream mainly comprising CO. The first and second gas streams are then electrochemically oxidized in separate fuel cells to produce electricity. A nuclear reactor can be used to supply at least a portion of the heat the required for the chemical conversion process.

Viscosity Relaxation in Molten HgZnTe

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Lehoczky, S. L.; Kim, Yeong Woo; Baird, James K.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Rotating cup measurements of the viscosity of the pseudo-binary melt, HgZnTe have shown that the isothermal liquid with zinc mole fraction 0.16 requires tens of hours of equilibration time before a steady viscous state can be achieved. Over this relaxation period, the viscosity at 790 C increases by a factor of two, while the viscosity at 810 C increases by 40%. Noting that the Group VI elements tend to polymerize when molten, we suggest that the viscosity of the melt is enhanced by the slow formation of Te atom chains. To explain the build-up of linear Te n-mers, we propose a scheme, which contains formation reactions with second order kinetics that increase the molecular weight, and decomposition reactions with first order kinetics that inactivate the chains. The resulting rate equations can be solved for the time dependence of each molecular weight fraction. Using these molecular weight fractions, we calculate the time dependence of the average molecular weight. Using the standard semi-empirical relation between polymer average molecular weight and viscosity, we then calculate the viscosity relaxation curve. By curve fitting, we find that the data imply that the rate constant for n-mer formation is much smaller than the rate constant for n-mer deactivation, suggesting that Te atoms only weakly polymerize in molten HgZnTe. The steady state toward which the melt relaxes occurs as the rate of formation of an n-mer becomes exactly balanced by the sum of the rate for its deactivation and the rate for its polymerization to form an (n+1)-mer.

Preparing oxidized fractions of polyvinyl alcohol of a given molecular mass

NASA Astrophysics Data System (ADS)

Zimin, Yu. S.; Kutlugil'dina, G. G.; Mustafin, A. G.

2016-10-01

The effect of two oxidizers (an oxygen-ozone mixture and hydrogen peroxide) on the kinetics of the oxidative degradation of polyvinyl alcohol in aqueous solutions is studied. Degradation of the polymer is proved not only by a reduction in the weight of oxidized fractions, but in the intrinsic viscosity of their aqueous solutions as well (and thus the average molecular weight of the resulting fractions). It is shown that the degree of the destructive reactions of polyvinyl alcohol grows along with the duration of the process, increasing the initial concentrations of H2O2 and raising the temperature. These results can be used in obtaining oxidized fractions of polyvinyl alcohol that have predetermined molecular weights.

Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) of low molecular weight organic compounds and synthetic polymers using zinc oxide (ZnO) nanoparticles.

PubMed

Watanabe, Takehiro; Kawasaki, Hideya; Yonezawa, Tetsu; Arakawa, Ryuichi

2008-08-01

We have developed surface-assisted laser desorption/ionization mass spectrometry using zinc oxide (ZnO) nanoparticles with anisotropic shapes (ZnO-SALDI-MS). The mass spectra showed low background noises in the low m/z, i.e. less than 500 u region. Thus, we succeeded in SALDI ionization on low molecular weight organic compounds, such as verapamil hydrochloride, testosterone, and polypropylene glycol (PPG) (average molecular weight 400) without using a liquid matrix or buffers such as citric acids. In addition, we found that ZnO-SALDI has advantages in post-source decay (PSD) analysis and produced a simple mass spectrum for phospholipids. The ZnO-SALDI spectra for synthetic polymers of polyethylene glycol (PEG), polystyrene (PS) and polymethylmethacrylate (PMMA) showed the sensitivity and molecular weight distribution to be comparable to matrix-assisted laser desorption/ionization (MALDI) spectra with a 2,5-dihydroxybenzoic acid (DHB) matrix. ZnO-SALDI shows good performance for synthetic polymers as well as low molecular weight organic compounds. Copyright (c) 2008 John Wiley & Sons, Ltd.

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.

Polyacrylamide medium for the electrophoretic separation of biomolecules

DOEpatents

Madabhushi, Ramakrishna S.; Gammon, Stuart A.

2003-11-11

A polyacryalmide medium for the electrophoretic separation of biomolecules. The polyacryalmide medium comprises high molecular weight polyacrylamides (PAAm) having a viscosity average molecular weight (M.sub.v) of about 675-725 kDa were synthesized by conventional red-ox polymerization technique. Using this separation medium, capillary electrophoresis of BigDye DNA sequencing standard was performed. A single base resolution of .about.725 bases was achieved in .about.60 minute in a non-covalently coated capillary of 50 .mu.m i.d., 40 cm effective length, and a filed of 160 V/cm at 40.degree. C. The resolution achieved with this formulation to separate DNA under identical conditions is much superior (725 bases vs. 625 bases) and faster (60 min. vs. 75 min.) to the commercially available PAAm, such as supplied by Amersham. The formulation method employed here to synthesize PAAm is straight-forward, simple and does not require cumbersome methods such as emulsion polymerizaiton in order to achieve very high molecular weights. Also, the formulation here does not require separation of PAAm from the reaction mixture prior to reconstituting the polymer to a final concentration. Furthermore, the formulation here is prepared from a single average mol. wt. PAAm as opposed to the mixture of two different average mo. wt. PAAm previously required to achieve high resolution.

Low-molecular-weight hydroxyacids in marine atmospheric aerosol: evidence of a marine microbial origin

NASA Astrophysics Data System (ADS)

Miyazaki, Y.; Sawano, M.; Kawamura, K.

2014-04-01

Lactic acid (LA) and glycolic acid (GA), which are low-molecular-weight hydroxyacids, were identified in the particle and gas phases within the marine atmospheric boundary layer over the western subarctic North Pacific. Major portion of LA (81%) and GA (57%) were present in the particulate phase, which is consistent with the presence of a hydroxyl group in these molecules leading to the low volatility of the compounds. The average concentration of LA in more biologically influenced marine aerosols (average 33 ± 58 ng m-3) was substantially higher than that in less biologically influenced aerosols (average 11 ± 12 ng m-3). Over the oceacnic region of phytoplankton blooms, the concentration of aerosol LA was comparable to that of oxalic acid, which was the most abundant diacid during the study period. A positive correlation was found between the LA concentrations in more biologically influenced aerosols and chlorophyll a in seawater (r2 = 0.56), suggesting an important production of aerosol LA possibly associated with microbial (e.g., lactobacillus) activity in seawater and/or aerosols. Our finding provides a new insight into the poorly quantified microbial sources of marine organic aerosols (OA) because such low-molecular-weight hydroxyacids are key intermediates for OA formation.

Production and structural analysis of the polysaccharide secreted by Trametes (Coriolus) versicolor ATCC 200801.

PubMed

Rau, Udo; Kuenz, Anja; Wray, Victor; Nimtz, Manfred; Wrenger, Julika; Cicek, Hasan

2009-01-01

Trametes versicolor ATCC 200801 secretes 4.1 g L(-1) of exopolysaccharide (EPS) when synthetic minimal medium and low-shear bioreactor cultivation technique are used. Structural and compositional analyses by thin layer chromatography, gas chromatography-mass spectrometry, electrospray ionization tandem mass spectrometry, and nuclear magnetic resonance spectroscopy yielded predominantly glucose and small amounts of galactose, mannose, arabinose, and xylose. The main EPS is composed of beta-1,3/beta-1,6-linked D-glucose molecules which is identical with Schizophyllan but does not possess a triple helical arrangement as secondary structure. Two molar mass fractions were detected by size exclusion chromatography yielding weight-average molecular weights of 4,100 and 2.6 kDa. Protein content varies between 2-3.6% (w/w). The exopolysaccharide is different in the nature of the glycosidic linkage, composition of monosaccharides, protein content, and weight-average molecular weight compared to the well-known polysaccharopeptide (PSP) and polysaccharopeptide Krestin (PSK).

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.

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.

21 CFR 177.1990 - Vinylidene chloride/methyl acrylate copolymers.

Code of Federal Regulations, 2014 CFR

2014-04-01

... Methyl Acrylate and Vinylidene Chloride Monomers in Saran MA/VDC Resins and Pellets by Headspace Gas... copolymer is not less than 50,000 when determined by gel permeation chromatography using tetrahydrofuran as... Weight Averages and Molecular Weight Distribution of Polystyrene by Liquid Exclusion Chromatography (Gel...

Polyhedral oligomeric silsesquioxane grafted polymer in polymeric foam

DOEpatents

King, Bruce A.; Patankar, Kshitish A.; Costeux, Stephane; Jeon, Hyun K.

2017-01-17

A polymeric foam article with a polymer matrix defining multiple cells therein has a polymer component with a first polymer that is a polyhedral oligomeric silsesquioxane grafted polymer that has a weight-average molecular weight of two kilograms per mole or higher and 200 kilograms per mole or lower.

21 CFR 172.260 - Oxidized polyethylene.

Code of Federal Regulations, 2010 CFR

2010-04-01

... HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION... polyethylene has a minimum number average molecular weight of 1,200, as determined by high temperature vapor pressure osmometry; contains a maximum of 5 percent by weight of total oxygen; and has an acid value of 9...

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.

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

NASA Technical Reports Server (NTRS)

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

1997-01-01

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

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

PubMed

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

2014-10-15

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

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

PubMed

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

2014-02-18

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

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.

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

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

21 CFR 178.3860 - Release agents.

Code of Federal Regulations, 2011 CFR

2011-04-01

...-octadecylcarbamate) (CAS Reg. No. 70892-21-6) produced by the reaction between stoichiometrically equivalent amounts of octadecyl isocyanate and vinyl alcohol/vinyl acetate copolymer; minimum average molecular weight...

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.

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.

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

PubMed

Lee, H G; Cowman, M K

1994-06-01

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

Divalent cation interactions with oligogalacturonides.

PubMed

Cescutti, P; Rizzo, R

2001-07-01

The conformational properties of high and low molecular weight galacturonides were investigated in relation to the ability of oligomers with degree of polymerization >10 to act as elicitors of plant defense mechanisms. Oligomers from polygalacturonate were obtained by means of enzymatic hydrolysis. Two fractions exhibiting high and low average degrees of polymerization were isolated by solvent fractionation and characterized by means of electrospray mass spectrometry. The conformational behaviors of the two fractions were investigated in the presence of different divalent cations using circular dichroism. Calcium, copper, and zinc ions were able to induce a conformational transition in both fractions. When in the presence of the high molecular weight fraction, copper and zinc ions were much more effective than calcium ions, whereas the efficiency was much reduced with low molecular weight oligomers.

21 CFR 172.260 - Oxidized polyethylene.

Code of Federal Regulations, 2014 CFR

2014-04-01

... ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Coatings, Films and Related Substances... average molecular weight of 1,200, as determined by high temperature vapor pressure osmometry; contains a maximum of 5 percent by weight of total oxygen; and has an acid value of 9 to 19. (b) The additive is used...

Separation of water-soluble polysaccharides from Cyclocarya paliurus by ultrafiltration process.

PubMed

Xie, Jian-Hua; Shen, Ming-Yue; Nie, Shao-Ping; Zhao, Qiang; Li, Chang; Xie, Ming-Yong

2014-01-30

In this study, ultrafiltration membrane process was employed to separate polysaccharides from Cyclocarya paliurus (Batal.) Iljinskaja (C. paliurus) to simulate industrial production. Meanwhile, the molecular weight distribution of C. paliurus polysaccharides was investigated by gel permeation chromatography. Four fractions were obtained and named as CPPS-A, CPPS-B, CPPS-C and CPPS-D, respectively. CPPS-A and CPPS-B contained approximately 69.5% and 12.7% of polysaccharides, whose molecular weight were in the range of 100-300 kDa and 120 kDa, respectively. CPPS-C was comprised of two polysaccharides with average molecular weight of 40 kDa and 15 kDa. Results showed that ultrafiltration resulted in the removal of parts of small molecule weight polysaccharides, the increase of proportion of high molecule weight ones and the obvious improvement of quality of products. Compared with ethanol precipitation and gel permeation chromatography techniques, ultrafiltration showed many advantages, and also provided theoretical support for industrial manufacturing of C. paliurus polysaccharides in separation. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

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.

Model-based intensification of a fed-batch microbial process for the maximization of polyhydroxybutyrate (PHB) production rate.

PubMed

Penloglou, Giannis; Vasileiadou, Athina; Chatzidoukas, Christos; Kiparissides, Costas

2017-08-01

An integrated metabolic-polymerization-macroscopic model, describing the microbial production of polyhydroxybutyrate (PHB) in Azohydromonas lata bacteria, was developed and validated using a comprehensive series of experimental measurements. The model accounted for biomass growth, biopolymer accumulation, carbon and nitrogen sources utilization, oxygen mass transfer and uptake rates and average molecular weights of the accumulated PHB, produced under batch and fed-batch cultivation conditions. Model predictions were in excellent agreement with experimental measurements. The validated model was subsequently utilized to calculate optimal operating conditions and feeding policies for maximizing PHB productivity for desired PHB molecular properties. More specifically, two optimal fed-batch strategies were calculated and experimentally tested: (1) a nitrogen-limited fed-batch policy and (2) a nitrogen sufficient one. The calculated optimal operating policies resulted in a maximum PHB content (94% g/g) in the cultivated bacteria and a biopolymer productivity of 4.2 g/(l h), respectively. Moreover, it was demonstrated that different PHB grades with weight average molecular weights of up to 1513 kg/mol could be produced via the optimal selection of bioprocess operating conditions.

Some physico-chemical properties of Prunus armeniaca L. gum exudates.

PubMed

Fathi, Morteza; Mohebbi, Mohebbat; Koocheki, Arash

2016-01-01

The objectives of this paper were to investigate some physicochemical properties of Prunus armeniaca L. gum exudates (PAGE). PAGE had, on average, 66.89% carbohydrate, 10.47% uronic acids, 6.9% moisture (w.b.), 2.91% protein, 4% ash and 1.59% fat. PAGE was composed of monosaccharides including l-arabinose, d-galactose, xylose, mannose and rhamnose in molar percentages of 41.52%, 23.72%, 17.82%, 14.40% and 2.54%, respectively. Elemental analysis showed that PAGE had high values of nutrients. FTIR analysis demonstrated the presence of carboxyl, hydroxyl and methyl groups and glycoside bonds. The weight average molecular weight, number average molecular weight and polydispersity index were found to be approximately 5.69 × 10(5)g/mol, 4.33 g/mol and 1.31, respectively. Rheological measurement of PAGE solutions as a function of concentration (8, 10 and 12% (w/w)) and temperature (10, 20, 30 and 40°C) demonstrated that the gum solutions had a non Newtonian shear thinning behaviour. Intrinsic viscosity for PAGE in deionized water was 3.438 dl/g based on Kramer equation. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

Kawahigashi, Masayuki; Sumida, Hiroaki; Yamamoto, Kazuhiko

2005-04-15

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

Synthesis and Characterisation of Photocrosslinked poly(ethylene glycol) diacrylate Implants for Sustained Ocular Drug Delivery.

PubMed

McAvoy, Kathryn; Jones, David; Thakur, Raghu Raj Singh

2018-01-16

To investigate the sustained ocular delivery of small and large drug molecules from photocrosslinked poly(ethylene glycol) diacrylate (PEGDA) implants with varying pore forming agents. Triamcinolone acetonide and ovalbumin loaded photocrosslinked PEGDA implants, with or without pore-forming agents, were fabricated and characterised for chemical, mechanical, swelling, network parameters, as well as drug release and biocompatibility. HPLC-based analytical methods were employed for analysis of two molecules; ELISA was used to demonstrate bioactivity of ovalbumin. Regardless of PEGDA molecular weight or pore former composition all implants loaded with triamcinolone acetonide released significantly faster than those loaded with ovalbumin. Higher molecular weight PEGDA systems (700 Da) resulted in faster drug release of triamcinolone acetonide than their 250 Da counterpart. All ovalbumin released over the 56-day time period was found to be bioactive. Increasing PEGDA molecular weight resulted in increased system swelling, decreased crosslink density (Ve), increased polymer-water interaction parameter (χ), increased average molecular weight between crosslinks (Mc) and increased mesh size (ε). SEM studies showed the porosity of implants increased with increasing PEGDA molecular weight. Biocompatibility showed both PEGDA molecular weight implants were non-toxic when exposed to retinal epithelial cells over a 7-day period. Photocrosslinked PEGDA implant based systems are capable of controlled drug release of both small and large drug molecules through adaptations in the polymer system network. We are currently continuing evaluation of these systems as potential sustained drug delivery devices.

Synthesis and characterization of functional acrylic copolymers via RAFT mini-emulsion polymerization

NASA Astrophysics Data System (ADS)

Yılmaz, Onur; Özkan, ćiǧdem Kılıçarislan; Yılmaz, Catalina N.; Yorgancıoǧlu, Ali; Özgünay, Hasan; Karavana, Hüseyin Ata

2017-12-01

Copolymers bearing reactive functional groups with controlled molecular weights are of importance since they can be used in many fields such as composites, coatings, membranes, catalysis, biology, optoelectronics, pharmaceuticals, etc. In the present study low molecular weight copolymers based on butyl acrylate (BA) and methyl methacrylate (MMA) in combination with reactive functional monomers of vinyl trietoxysilane (VTES), 3-trimetoxysilylpropyl methacrylate (TMSPMA) and glycidyl methacrylate (GMA) were synthesized via RAFT mini-emulsion technique using 2-cyano 2-propyldodecyldithiocarbonate as CTA agent. The results showed that the average molecular weights of copolymers were close to the theoretical values. On the other hand, PDI values were found to be higher than conventional RAFT polymers. The particle sizes of the latexes were small with very homogenous distributions and good stability. FTIR, H-NMR and TGA results verified the success of copolymer syntheses.

Coordination Polymerization of Renewable 3-Methylenecyclopentene with Rare-Earth-Metal Precursors.

PubMed

Liu, Bo; Li, Shihui; Wang, Meiyan; Cui, Dongmei

2017-04-10

Coordination polymerization of renewable 3-methylenecyclopentene has been investigated for the first time using rare-earth metal-based precursors bearing various bulky ligands. All the prepared complexes catalyze controllable polymerization of 3-methylenecyclopentene into high molecular weight polymers, of which the NPN- and NSN-tridentate non-Cp ligated lutetium-based catalytic systems exhibited extremely high activities up to 11 520 kg/(mol Lu ⋅h) in a dilute toluene solution (3.2 g/100 mL) at room temperature. The resultant polymers have pure 1,4-regioregularity (>99 %) and tailorable number average molecular weights (1-20×10 4 ) with narrow molecular weight distributions (polydispersity index (PDI)=1.45-1.79). DFT simulations were employed to study the polymerization mechanism and stereoregularity control. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Distribution of Chains in Polymer Brushes Produced by a “Grafting From” Mechanism

DOE PAGES

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.; ...

2016-01-11

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

Tannins from Hamamelis virginiana bark extract: characterization and improvement of the antiviral efficacy against influenza A virus and human papillomavirus.

PubMed

Theisen, Linda L; Erdelmeier, Clemens A J; Spoden, Gilles A; Boukhallouk, Fatima; Sausy, Aurélie; Florin, Luise; Muller, Claude P

2014-01-01

Antiviral activity has been demonstrated for different tannin-rich plant extracts. Since tannins of different classes and molecular weights are often found together in plant extracts and may differ in their antiviral activity, we have compared the effect against influenza A virus (IAV) of Hamamelis virginiana L. bark extract, fractions enriched in tannins of different molecular weights and individual tannins of defined structures, including pseudotannins. We demonstrate antiviral activity of the bark extract against different IAV strains, including the recently emerged H7N9, and show for the first time that a tannin-rich extract inhibits human papillomavirus (HPV) type 16 infection. As the best performing antiviral candidate, we identified a highly potent fraction against both IAV and HPV, enriched in high molecular weight condensed tannins by ultrafiltration, a simple, reproducible and easily upscalable method. This ultrafiltration concentrate and the bark extract inhibited early and, to a minor extent, later steps in the IAV life cycle and tannin-dependently inhibited HPV attachment. We observed interesting mechanistic differences between tannin structures: High molecular weight tannin containing extracts and tannic acid (1702 g/mol) inhibited both IAV receptor binding and neuraminidase activity. In contrast, low molecular weight compounds (<500 g/mol) such as gallic acid, epigallocatechin gallate or hamamelitannin inhibited neuraminidase but not hemagglutination. Average molecular weight of the compounds seemed to positively correlate with receptor binding (but not neuraminidase) inhibition. In general, neuraminidase inhibition seemed to contribute little to the antiviral activity. Importantly, antiviral use of the ultrafiltration fraction enriched in high molecular weight condensed tannins and, to a lesser extent, the unfractionated bark extract was preferable over individual isolated compounds. These results are of interest for developing and improving plant-based antivirals.

Tannins from Hamamelis virginiana Bark Extract: Characterization and Improvement of the Antiviral Efficacy against Influenza A Virus and Human Papillomavirus

PubMed Central

Theisen, Linda L.; Erdelmeier, Clemens A. J.; Spoden, Gilles A.; Boukhallouk, Fatima; Sausy, Aurélie; Florin, Luise; Muller, Claude P.

2014-01-01

Antiviral activity has been demonstrated for different tannin-rich plant extracts. Since tannins of different classes and molecular weights are often found together in plant extracts and may differ in their antiviral activity, we have compared the effect against influenza A virus (IAV) of Hamamelis virginiana L. bark extract, fractions enriched in tannins of different molecular weights and individual tannins of defined structures, including pseudotannins. We demonstrate antiviral activity of the bark extract against different IAV strains, including the recently emerged H7N9, and show for the first time that a tannin-rich extract inhibits human papillomavirus (HPV) type 16 infection. As the best performing antiviral candidate, we identified a highly potent fraction against both IAV and HPV, enriched in high molecular weight condensed tannins by ultrafiltration, a simple, reproducible and easily upscalable method. This ultrafiltration concentrate and the bark extract inhibited early and, to a minor extent, later steps in the IAV life cycle and tannin-dependently inhibited HPV attachment. We observed interesting mechanistic differences between tannin structures: High molecular weight tannin containing extracts and tannic acid (1702 g/mol) inhibited both IAV receptor binding and neuraminidase activity. In contrast, low molecular weight compounds (<500 g/mol) such as gallic acid, epigallocatechin gallate or hamamelitannin inhibited neuraminidase but not hemagglutination. Average molecular weight of the compounds seemed to positively correlate with receptor binding (but not neuraminidase) inhibition. In general, neuraminidase inhibition seemed to contribute little to the antiviral activity. Importantly, antiviral use of the ultrafiltration fraction enriched in high molecular weight condensed tannins and, to a lesser extent, the unfractionated bark extract was preferable over individual isolated compounds. These results are of interest for developing and improving plant-based antivirals. PMID:24498245

Demulsification of oil-in-water emulsions

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

Roark, D.N.

1986-09-30

This patent describes a process of demulsifying an oil-in-water emulsion which comprises admixing with the emulsion a water-soluble polymer of monoallylamine that causes formation of and separation between an oil phase and an aqueous phase to occur. The emulsion has a pH in the range of about 5 to about 10 and the polymer has a weight average molecular weight of at least 1000 and contains at least 95% by weight of monoallylamine.

40 CFR 60.564 - Test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

.... If the carrier component of the gas stream is nitrogen, then an average molecular weight of 28 g/g... from materials balance by good engineering practice. (i) The owner or operator shall determine...

40 CFR 60.564 - Test methods and procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

.... If the carrier component of the gas stream is nitrogen, then an average molecular weight of 28 g/g... from materials balance by good engineering practice. (i) The owner or operator shall determine...

40 CFR 60.564 - Test methods and procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

.... If the carrier component of the gas stream is nitrogen, then an average molecular weight of 28 g/g... from materials balance by good engineering practice. (i) The owner or operator shall determine...

40 CFR 60.564 - Test methods and procedures.

Code of Federal Regulations, 2011 CFR

2011-07-01

.... If the carrier component of the gas stream is nitrogen, then an average molecular weight of 28 g/g... from materials balance by good engineering practice. (i) The owner or operator shall determine...

Single-particle characterization of biomass burning organic aerosol (BBOA): evidence for non-uniform mixing of high molecular weight organics and potassium

NASA Astrophysics Data System (ADS)

Lee, Alex K. Y.; Willis, Megan D.; Healy, Robert M.; Wang, Jon M.; Jeong, Cheol-Heon; Wenger, John C.; Evans, Greg J.; Abbatt, Jonathan P. D.

2016-05-01

Biomass burning organic aerosol (BBOA) can be emitted from natural forest fires and human activities such as agricultural burning and domestic energy generation. BBOA is strongly associated with atmospheric brown carbon (BrC) that absorbs near-ultraviolet and visible light, resulting in significant impacts on regional visibility degradation and radiative forcing. The mixing state of BBOA can play a critical role in the prediction of aerosol optical properties. In this work, single-particle measurements from a Soot-Particle Aerosol Mass Spectrometer coupled with a light scattering module (LS-SP-AMS) were performed to examine the mixing state of BBOA, refractory black carbon (rBC), and potassium (K, a tracer for biomass burning aerosol) in an air mass influenced by wildfire emissions transported from northern Québec to Toronto, representing aged biomass burning plumes. Cluster analysis of single-particle measurements identified five BBOA-related particle types. rBC accounted for 3-14 wt % of these particle types on average. Only one particle type exhibited a strong ion signal for K+, with mass spectra characterized by low molecular weight organic species. The remaining four particle types were classified based on the apparent molecular weight of the BBOA constituents. Two particle types were associated with low potassium content and significant amounts of high molecular weight (HMW) organic compounds. Our observations indicate non-uniform mixing of particles within a biomass burning plume in terms of molecular weight and illustrate that HMW BBOA can be a key contributor to low-volatility BrC observed in BBOA particles. The average mass absorption efficiency of low-volatility BBOA is about 0.8-1.1 m2 g-1 based on a theoretical closure calculation. Our estimates indicate that low-volatility BBOA contributes ˜ 33-44 % of thermo-processed particle absorption at 405 nm; and almost all of the BBOA absorption was associated with low-volatility organics.

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 Isolated Fractions of Aloe vera Gel Materials on Indinavir Pharmacokinetics: In vitro and in vivo Studies.

PubMed

Wallis, Lonette; Malan, Maides; Gouws, Chrisna; Steyn, Dewald; Ellis, Suria; Abay, Efrem; Wiesner, Lubbe; Otto, Daniel P; Hamman, Josias

2016-01-01

Aloe vera is a plant with a long history of traditional medicinal use and is consumed in different products, sometimes in conjunction with prescribed medicines. A. vera gel has shown the ability to modulate drug absorption in vitro. The aim of this study was to fractionate the precipitated polysaccharide component of A. vera gel based on molecular weight and to compare their interactions with indinavir pharmacokinetics. Crude polysaccharides were precipitated from a solution of A. vera gel and was fractionated by means of centrifugal filtration through membranes with different molecular weight cut-off values (i.e. 300 KDa, 100 KDa and 30 KDa). Marker molecules were quantified in the aloe leaf materials by means of nuclear magnetic resonance spectroscopy and the average molecular weight was determined by means of gel filtration chromatography linked to multi-angle-laser-light scattering and refractive index detection. The effect of the aloe leaf materials on the transepithelial electrical resistance (TEER) of Caco-2 cell monolayers as well as indinavir metabolism in LS180 cells was measured. The bioavailability of indinavir in the presence and absence of the aloe leaf materials was determined in Sprague-Dawley rats. All the aloe leaf materials investigated in this study reduced the TEER of Caco-2 cell monolayers, inhibited indinavir metabolism in LS 180 cells to different extents and changed the bioavailability parameters of indinavir in rats compared to that of indinavir alone. These indinavir pharmacokinetic modulation effects were not dependent on the presence of aloverose and also not on the average molecular weight of the isolated fractions.

[Preparation of clear thermosetting resin for veneered crown from several bisMEPP monomers (author's transl)].

PubMed

Tanaka, T; Nakabayashi, N; Masuhara, E

1978-07-01

The whitish translucent shade of a thermosetting resin cured from a mixture of a 2,2-Bis (p-methacryloxy (ethoxy)1-2 phenyl)-propane monomer and PMMA pearls makes it difficult to reconstruct a shade of the natural tooth. The attempt to improve the transparency of the mixed polymer was made in this study. Varying the molecular weight of BisMEPP monomer, PMMA polymer and curing temperature, cured specimens were prepared and their transparency was measured with a spectrophotometer. The results obtained are as follows. 1) In any molecular weight of PMMA, BisMEPP with 2.3 to 3.3 average number of ethylene oxide linkage showed the highest transpalency on the specimen. 2) With increasing the curing temperature, transpalency of the specimens made from BisME4.0 PP increased. With another molecular of BisMEPP, transpalency of the cured specimens showed the highest transpalency at the curing temperature of 120 degrees C. 3) With increasing the molecular weight of PMMA, the transpalency increased.

Optoelectronic devices incorporating fluoropolymer compositions for protection

DOEpatents

Chen, Xuming; Chum, Pak-Wing S.; Howard, Kevin E.; Lopez, Leonardo C.; Sumner, William C.; Wu, Shaofu

2015-12-22

The fluoropolymer compositions of the present invention generally incorporate ingredients comprising one or more fluoropolymers, an ultraviolet light protection component (hereinafter UV protection component), and optionally one or more additional ingredients if desired. The UV protection component includes a combination of at least one hindered tertiary amine (HTA) compound having a certain structure and a weight average molecular weight of at least 1000. This tertiary amine is used in combination with at least one organic, UV light absorbing compound (UVLA compound) having a weight average molecular weight greater than 500. When the HTA compound and the UVLA compound are selected according to principles of the present invention, the UV protection component provides fluoropolymer compositions with significantly improved weatherability characteristics for protecting underlying materials, features, structures, components, and/or the like. In particular, fluoropolymer compositions incorporating the UV protection component of the present invention have unexpectedly improved ability to resist blackening, coloration, or other de gradation that may be caused by UV exposure. As a consequence, devices protected by these compositions would be expected to have dramatically improved service life. The compositions have a wide range of uses but are particularly useful for forming protective layers in optoelectronic devices.

Altering surface fluctuations by blending tethered and untethered chains

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

Lee, J. K.; Akgun, B.; Jiang, Z.

"Partially tethering" a thin film of a polymer melt by covalently attaching to the substrate a fraction of the chains in an unentangled melt dramatically increases the relaxation time of the surface height fluctuations. This phenomenon is observed even when the film thickness, h, is 20 times the unperturbed chain radius, R g,tethered, of the tethered chains, indicating that partial tethering is more influential than any physical attraction with the substrate. Furthermore, a partially tethered layer of a low average molecular weight of 5k showed much slower surface fluctuations than did a reference layer of pure untethered chains of muchmore » greater molecular weight (48k), so the partial tethering effect is stronger than the effects of entanglement and increase in glass transition temperature, Tg, with molecular weight. Partial tethering offers a means of tailoring these fluctuations which influence wetting, adhesion, and tribology of the surface.« less

Altering surface fluctuations by blending tethered and untethered chains

DOE PAGES

Lee, J. K.; Akgun, B.; Jiang, Z.; ...

2017-10-16

"Partially tethering" a thin film of a polymer melt by covalently attaching to the substrate a fraction of the chains in an unentangled melt dramatically increases the relaxation time of the surface height fluctuations. This phenomenon is observed even when the film thickness, h, is 20 times the unperturbed chain radius, R g,tethered, of the tethered chains, indicating that partial tethering is more influential than any physical attraction with the substrate. Furthermore, a partially tethered layer of a low average molecular weight of 5k showed much slower surface fluctuations than did a reference layer of pure untethered chains of muchmore » greater molecular weight (48k), so the partial tethering effect is stronger than the effects of entanglement and increase in glass transition temperature, Tg, with molecular weight. Partial tethering offers a means of tailoring these fluctuations which influence wetting, adhesion, and tribology of the surface.« less

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

PubMed

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

2008-09-15

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

The Influence of Polyethylene Glycol Solution on the Dissolution Rate of Sustained Release Morphine.

PubMed

Hodgman, Michael; Holland, Michael G; Englich, Ulrich; Wojcik, Susan M; Grant, William D; Leitner, Erich

2016-12-01

Whole bowel irrigation (WBI) is a management option for overdose of medications poorly adsorbed to activated charcoal, with modified release properties, or for body packers. Polyethylene glycol (PEG) is a mixture of ethylene oxide polymers of varying molecular weight. PEG with an average molecular weight of 3350 g/mol is used for WBI. PEG electrolyte lavage solution has been shown in vitro to hasten the dissolution of acetaminophen. The impact of PEG on the pharmacokinetics of extended release pharmaceuticals is unknown. Lower average molecular weight PEG mixtures are used as solvents and excipients. We sought to investigate the impact of PEG on the release of morphine from several extended release morphine formulations. An in vitro gastric model was developed. To test the validity of our model, we first investigated the previously described interaction of ethanol and Avinza®. Once demonstrated, we then investigated the effect of PEG with several extended release morphine formulations. In the validation portion of our study, we confirmed an ethanol Avinza® interaction. Subsequently, we did not observe accelerated release of morphine from Avinza® or generic extended release morphine in the presence of PEG. The use of PEG for gastric decontamination following ingestion of these extended release morphine formulations is unlikely to accelerate morphine release and aggravate intoxication.

40 CFR 180.1022 - Iodine-detergent complex; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2014 CFR

2014-07-01

... the surfactants (a) polyoxypropylene-polyoxyethylene glycol nomionic block polymers (minimum average... molecular weight of 748 and in which the nonyl group is a propylene trimer isomer, is exempted from the...

40 CFR 180.1022 - Iodine-detergent complex; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2013 CFR

2013-07-01

... the surfactants (a) polyoxypropylene-polyoxyethylene glycol nomionic block polymers (minimum average... molecular weight of 748 and in which the nonyl group is a propylene trimer isomer, is exempted from the...

40 CFR 180.1022 - Iodine-detergent complex; exemption from the requirement of a tolerance.

Code of Federal Regulations, 2012 CFR

2012-07-01

... the surfactants (a) polyoxypropylene-polyoxyethylene glycol nomionic block polymers (minimum average... molecular weight of 748 and in which the nonyl group is a propylene trimer isomer, is exempted from the...

Characterisation of pectins extracted from banana peels (Musa AAA) under different conditions using an experimental design.

PubMed

Happi Emaga, Thomas; Ronkart, Sébastien N; Robert, Christelle; Wathelet, Bernard; Paquot, Michel

2008-05-15

An experimental design was used to study the influence of pH (1.5 and 2.0), temperature (80 and 90°C) and time (1 and 4h) on extraction of pectin from banana peels (Musa AAA). Yield of extracted pectins, their composition (neutral sugars, galacturonic acid, and degree of esterification) and some macromolecular characteristics (average molecular weight, intrinsic viscosity) were determined. It was found that extraction pH was the most important parameter influencing yield and pectin chemical composition. Lower pH values negatively affected the galacturonic acid content of pectin, but increased the pectin yield. The values of degree of methylation decreased significantly with increasing temperature and time of extraction. The average molecular weight ranged widely from 87 to 248kDa and was mainly influenced by pH and extraction time. Copyright © 2007 Elsevier Ltd. All rights reserved.

Fast pyrolysis of palm kernel shells: influence of operation parameters on the bio-oil yield and the yield of phenol and phenolic compounds.

PubMed

Kim, Seon-Jin; Jung, Su-Hwa; Kim, Joo-Sik

2010-12-01

Palm kernel shells were pyrolyzed in a pyrolysis plant equipped with a fluidized-bed reactor and a char-separation system. The influence of reaction temperature, feed size and feed rate on the product spectrum was also investigated. In addition, the effect of reaction temperature on the yields of phenol and phenolic compounds in the bio-oil was examined. The maximum bio-oil yield was 48.7 wt.% of the product at 490 degrees C. The maximum yield of phenol plus phenolic compounds amounted to about 70 area percentage at 475 degrees C. The yield of pyrolytic lignin after its isolation from the bio-oil was approximately 46 wt.% based on the water and ash free oil. The pyrolytic lignin was mainly composed of phenol, phenolic compounds and oligomers of coniferyl, sinapyl and p-coumaryl alcohols. From the result of a GPC analysis, the number average molecular weight and the weight average molecular weight were 325 and 463 g/mol, respectively. 2010 Elsevier Ltd. All rights reserved.

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.

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

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

1992-05-19

A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, T.J.; Ijadi-Maghsooodi, S; Yi Pang.

1993-10-19

A polymeric material is described which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6].

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, T.J.; Ijadi-Maghsoodi, S.; Pang, Y.

1992-05-19

A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl[sub 5] or W(CO)[sub 6]/hv.

Nonlinear optical and conductive polymeric material

DOEpatents

Barton, Thomas J.; Ijadi-Maghsoodi, Sina; Pang, Yi

1993-10-19

A polymeric material which exhibits nonlinear optical properties if undoped and conductive properties if doped. The polymer is prepared by polymerizing diethynylsilane compositions, the resulting polymeric material having a weight average molecular weight between about 20,000 and about 200,000 grams per mole. The polymer is prepared and catalytically polymerized by exposure to a catalyst, such as MoCl.sub.5 or W(CO).sub.6 /hv.

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...

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

PubMed

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

2013-01-01

Mucilaginous polysaccharide extracted from Dalbergia sissoo Roxb. leaves has a number of medicinal applications. Molecular weight studies and correlation analysis of the structure of polysaccharide with oligosaccharides can be helpful for further utilisation, modification and structure-activity relationship for biological applications. To determine molecular weight of medicinally important polysaccharide. To establish an unequivocal correlation of the polysaccharide monosugars with constituting oligosaccharides and glucuronic acid content based on gas-liquid chromatography (GLC) with the spectrophotometric method. Complete and partial hydrolytic studies of pure polysaccharide yielded constituting monosugars and oligosaccharides. The ratio of sugars in polysaccharide and oligosaccharides was studied by preparation of alditol acetates and analysed using GLC. The uronic acid content was studied by GLC analysis and spectrophotometry. Molecular weight of the polysaccharide was determined using the viscometric method. Dalbergia sissoo leaves yielded 14.0% pure polysaccharide, containing 15.7% of glucuronic acid. Complete hydrolysis and GLC analysis of alditol acetate derivatives of reduced and unreduced monosugars indicated the presence of L-rhamnose, D-glucuronic acid, D-galactose and D-glucose in 1.00:1.00:2.00:2.33 molar ratios. Partial hydrolysis followed by monosugar analysis of oligosaccharides established the monosugar ratio in complete agreement with polysaccharide, thereby corroborating the sugar ratio. Similar uronic acid content was obtained by GLC and spectrophotometry. The polysaccharide had an average molecular weight of 1.5 × 10⁵  Da. The study has established an obvious correlation of the structure of polysaccharide with oligosaccharides, leading to unambiguous identification of monosaccharides, which normally is not studied conclusively while reporting the polysaccharide structure. The molecular weight of the polysaccharide was determined. Copyright © 2012 John Wiley & Sons, Ltd.

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.

Association of Many Regions of the Bacillus subtilis Chromosome with the Cell Membrane

PubMed Central

Ivarie, Robert D.; Pène, Jacques J.

1973-01-01

Unsheared lysates of Bacillus subtilis 168T− containing uniformly labeled deoxyribonucleic acid (DNA) were exposed to varying doses of gamma rays to introduce double-strand scissions in the chromosome. From an estimate of the number-average molecular weight and the amount of DNA bound to membrane after irradiation, about 70 to 90 regions of the bacterial chromosome were detected in membrane fractions. Since this number was independent of the molecular weight of the DNA (i.e., the extent of fragmentation of the chromosome), it is thought to represent an upper limit in the number of membrane-binding sites per chromosome. PMID:4196245

A kinetic study of hydrolysis of polyester elastomer in magnetic tape

NASA Technical Reports Server (NTRS)

Yamamoto, K.; Watanabe, H.

1994-01-01

A useful method for kinetic study of the hydrolysis of polyester elastomer is established which uses the number-average molecular weight. The reasonableness of this method is confirmed and the effect of magnetic particles on hydrolysis is considered.

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

PubMed

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

2009-05-01

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

The effect of conjugation to gold nanoparticles on the ability of low molecular weight chitosan to transfer DNA vaccine.

PubMed

Zhou, Xianfeng; Zhang, Xizhen; Yu, Xianghui; Zha, Xiao; Fu, Qiuan; Liu, Bin; Wang, Xueyun; Chen, Yan; Chen, Yue; Shan, Yaming; Jin, Yinghua; Wu, Yongge; Liu, Junqiu; Kong, Wei; Shen, Jiacong

2008-01-01

Nonviral gene delivery systems based on conventional high molecular weight chitosans are efficient as DNA vaccine delivery system, but have poor physical properties such as aggregated shapes, low solubility at neutral pH, high viscosity at concentrations used for in vivo delivery and a slow onset of action. Furthermore, Chitosan oligomers shorter than 14 monomers units were recently found to form only weak complexes with DNA, resulting in physically unstable polyplexes in vitro and in vivo. Here, low molecular weight chitosans with an average molecular mass of 6kDa (Chito6) have been covalently attached to gold nanoparticles (GNPs), and the potency of the resulting Chito6-GNPs conjugates as vectors for the delivery of plasmid DNA has been investigated in vitro and in vivo. After delivery by intramuscular immunization in BALB/c mice, the Chito6-GNPs conjugates induced an enhanced serum antibody response 10 times more potent than naked DNA vaccine. Additionally, in contrast to naked DNA, the Chito6-GNPs conjugates induced potent cytotoxic T lymphocyte responses at a low dose.

Effect of cotton bollworm (Helicoverpa armigera Hübner) caused injury on maize grain content, especially regarding to the protein alteration.

PubMed

Keszthelyi, S; Pál-Fám, F; Kerepesi, I

2011-03-01

The cotton bollworm (Helicoverpa armigera Hübner), which migrated in the Carpathian-basin from Mediterraneum in the last decades, is becoming an increasingly serious problem for maize producers in Hungary. In several regions the damage it causes has reached the threshold of economic loss, especially in the case of the sweet maize cultivation. The aim of the research was to determine the changing of ears weights and in-kernel accumulation and alteration in grain as a function of cotton bollworm mastication.Our investigation confirmed that there is an in-kernel and protein pattern change of maize grain by cotton bollworm. Our results proved the significant damaging of each part of ears by cotton bollworm masticating (the average weight loss of ears: 13.99%; the average weight loss of grains: 14.03%; the average weight loss of cobs: 13.74%), with the exception of the increasing of the grain-cob ratio. Our examinations did not prove the water loss - that is the "forced maturing" - caused by the damage. Decreasing of raw fat (control: 2.8%; part-damaged: 2.6%; damaged: 2.4%) and starch content (control: 53.1%; part-damaged: 46.6%; damaged: 44.7%) were registered as a function of injury. In contrast, the raw protein content was increased (control: 4.7%; part-damaged: 5.3%; damaged: 7.4%) by maize ear masticating. The most conspicuous effect on protein composition changing was proved by comparison of damaged grain samples by SDS PAGE. Increased amounts of 114, 50, 46 and 35 kDa molecular mass proteins were detected which explained the more than 50% elevation of raw protein content. The statistical analysis of molecular weights proved the protein realignment as a function of the pest injuries, too.

Molecular Weights of Bovine and Porcine Heparin Samples: Comparison of Chromatographic Methods and Results of a Collaborative Survey.

PubMed

Bertini, Sabrina; Risi, Giulia; Guerrini, Marco; Carrick, Kevin; Szajek, Anita Y; Mulloy, Barbara

2017-07-19

In a collaborative study involving six laboratories in the USA, Europe, and India the molecular weight distributions of a panel of heparin sodium samples were determined, in order to compare heparin sodium of bovine intestinal origin with that of bovine lung and porcine intestinal origin. Porcine samples met the current criteria as laid out in the USP Heparin Sodium monograph. Bovine lung heparin samples had consistently lower average molecular weights. Bovine intestinal heparin was variable in molecular weight; some samples fell below the USP limits, some fell within these limits and others fell above the upper limits. These data will inform the establishment of pharmacopeial acceptance criteria for heparin sodium derived from bovine intestinal mucosa. The method for MW determination as described in the USP monograph uses a single, broad standard calibrant to characterize the chromatographic profile of heparin sodium on high-resolution silica-based GPC columns. These columns may be short-lived in some laboratories. Using the panel of samples described above, methods based on the use of robust polymer-based columns have been developed. In addition to the use of the USP's broad standard calibrant for heparin sodium with these columns, a set of conditions have been devised that allow light-scattering detected molecular weight characterization of heparin sodium, giving results that agree well with the monograph method. These findings may facilitate the validation of variant chromatographic methods with some practical advantages over the USP monograph method.

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.

Simultaneous determination of molecular weights and contents of water-soluble polysaccharides and their fractions from Lycium barbarum collected in China.

PubMed

Wu, Ding-Tao; Lam, Shing-Chung; Cheong, Kit-Leong; Wei, Feng; Lin, Peng-Cheng; Long, Ze-Rong; Lv, Xiao-Jie; Zhao, Jing; Ma, Shuang-Cheng; Li, Shao-Ping

2016-09-10

Molecular weights and contents of water-soluble polysaccharides and their fractions in fifty batches of fruits of Lycium barbarum (wolfberry) collected from different regions of China, including Qinghai, Ningxia, Inner Mongolia, Xinjiang, and Gansu, were simultaneously determined using high performance size exclusion chromatography (HPSEC) coupled with multi angle laser light scattering (MALLS) and refractive index detector (RID) with the refractive index increment (dn/dc). Results showed that HPSEC chromatograms and molecular weight distributions of polysaccharides in L. barbarum collected from different regions of China were similar. Furthermore, the average contents of each polysaccharide fraction (peaks 1, 2, and 3) in crude polysaccharides of L. barbarum collected from Ningxia were similar with those of Inner Mongolia, Xinjiang, and Gansu, respectively. However, significant difference was found between polysaccharides in L. barbarum collected from Ningxia and Qinghai. Moreover, the average amounts of total polysaccharide fractions (peaks 1, 2, and 3) in the raw material of L. barbarum collected from Ningxia were significantly higher than that of Qinghai. These results may contribute to the rational usage of L. barbarum produced in China, and are beneficial for the improvement of their quality control. Results suggested that HPSEC-MALLS-RID with the dn/dc method could be used as a routine method for the quality evaluation of polysaccharides from natural resources and their products. Copyright © 2016 Elsevier B.V. All rights reserved.

Reversed-phase ion-pair ultra-high-performance-liquid chromatography-mass spectrometry for fingerprinting low-molecular-weight heparins.

PubMed

Langeslay, Derek J; Urso, Elena; Gardini, Cristina; Naggi, Annamaria; Torri, Giangiacomo; Larive, Cynthia K

2013-05-31

Heparin is a complex mixture of sulfated linear carbohydrate polymers. It is widely used as an antithrombotic drug, though it has been shown to have a myriad of additional biological activities. Heparin is often partially depolymerized in order to decrease the average molecular weight, as it has been shown that low molecular weight heparins (LMWH) possess more desirable pharmacokinetic and pharmacodynamic properties than unfractionated heparin (UFH). Due to the prevalence of LMWHs in the market and the emerging availability of generic LMWH products, it is important that analytical methods be developed to ensure the drug quality. This work explores the use of tributylamine (TrBA), dibutylamine (DBA), and pentylamine (PTA) as ion-pairing reagents in conjunction with acetonitrile and methanol modified mobile phases for reversed-phase ion-pairing ultraperformance liquid chromatography coupled to mass spectrometry (RPIP-UPLC-MS) for fingerprint analysis of LMWH preparations. RPIP-UPLC-MS fingerprints are presented and compared for tinzaparinand enoxaparin. Copyright © 2013 Elsevier B.V. All rights reserved.

Depolymerization and hydrodeoxygenation of switchgrass lignin with formic acid.

PubMed

Xu, Weiyin; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

2012-04-01

Organosolv switchgrass lignin is depolymerized and hydrodeoxygenated with a formic acid hydrogen source, 20 wt % Pt/C catalyst, and ethanol solvent. The combination of formic acid and Pt/C is found to promote production of higher fractions of lower molecular weight compounds in the liquid products. After 4 h of reaction, all of the switchgrass lignin is solubilized and 21 wt % of the biomass is shown to be converted into seven prominent molecular species that are identified and quantified. Reaction time is shown to be an important variable in affecting changes in product distributions and bulk liquid product properties. At 20 h of reaction, the lignin is significantly depolymerized to form liquid products with a 76 % reduction in the weighted average molecular weight. Elemental analysis also shows that the resultant liquid products have a 50 % reduction in O/C and 10 % increase in H/C molar ratios compared to the switchgrass lignin after 20 h. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodegradability relationships among propylene glycol substances in the Organization for Economic Cooperation and Development ready- and seawater biodegradability tests.

PubMed

West, Robert J; Davis, John W; Pottenger, Lynn H; Banton, Marcy I; Graham, Cynthia

2007-05-01

Eight propylene glycol substances, ranging from 1,2-propanediol to a poly(propylene glycol) (PPG) having number-average molecular weight (M(n)) of 2,700 (i.e., PPG 2700), were evaluated in the Organization for Economic Cooperation and Development (OECD) ready- and seawater biodegradability tests. Uniformity in test parameters, such as inoculum source/density and test substance concentrations, combined with frequent measurements of O2 consumption and CO2 evolution, revealed unexpected biodegradability trends across this family of substances. Biodegradability in both tests decreased with increased number of oxy-propylene repeating units (n = 1, 2, 3, 4) of the oligomeric propylene glycols (PGs). However, this trend was reversed for the PPG polymers, and increased biodegradability was observed with increases of average n to seven, 17, and 34 (M(n) = 425, 1,000, and 2,000, respectively). This relationship between molecular weight and biodegradability was reversed again when average n was incremented from 34 (PPG 2000) to 46 (PPG 2700). Six of the tested substances (n = 1, 2, 3, 7, 17, and 34) met the OECD-specified criteria for "ready biodegradability," whereas the tetrapropylene glycol (n = 4) and PPG 2700 substances failed to meet these criteria. Biodegradation half-lives for these eight substances ranged from 3.8 d (PPG 2000) to 33.2 d (PPG 2700) in the ready test, and from 13.6 (PG) to 410 d (PPG 2700) in seawater. Biodegradation half-lives in seawater were significantly correlated with half-lives determined in the ready test. However, half-lives in both tests were correlated poorly with molecular weight, water solubility, and log K(ow). It is speculated that the molecular conformation of these substances, perhaps more so than these other physicochemical properties, has an important role in influencing biodegradability of the propylene glycol substances.

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

PubMed

Bidzińska, Ewa; Michalec, Marek; Pawcenis, Dominika

2015-12-01

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

Cold and warm atomic gas around the Perseus molecular cloud. I. Basic properties

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

Stanimirović, Snežana; Murray, Claire E.; Miller, Jesse

2014-10-01

Using the Arecibo Observatory, we have obtained neutral hydrogen (HI) absorption and emission spectral pairs in the direction of 26 background radio continuum sources in the vicinity of the Perseus molecular cloud. Strong absorption lines were detected in all cases, allowing us to estimate spin temperature (T{sub s} ) and optical depth for 107 individual Gaussian components along these lines of sight. Basic properties of individual H I clouds (spin temperature, optical depth, and the column density of the cold and warm neutral medium (CNM and WNM), respectively) in and around Perseus are very similar to those found for randommore » interstellar lines of sight sampled by the Millennium H I survey. This suggests that the neutral gas found in and around molecular clouds is not atypical. However, lines of sight in the vicinity of Perseus have, on average, a higher total H I column density and the CNM fraction, suggesting an enhanced amount of cold H I relative to an average interstellar field. Our estimated optical depth and spin temperature are in stark contrast with the recent attempt at using Planck data to estimate properties of the optically thick H I. Only ∼15% of lines of sight in our study have a column density weighted average spin temperature lower than 50 K, in comparison with ≳ 85% of Planck's sky coverage. The observed CNM fraction is inversely proportional to the optical depth weighted average spin temperature, in excellent agreement with the recent numerical simulations by Kim et al. While the CNM fraction is, on average, higher around Perseus relative to a random interstellar field, it is generally low, between 10%-50%. This suggests that extended WNM envelopes around molecular clouds and/or significant mixing of CNM and WNM throughout molecular clouds are present and should be considered in the models of molecule and star formation. Our detailed comparison of H I absorption with CO emission spectra shows that only 3 of the 26 directions are clear candidates for probing the CO-dark gas as they have N(H I)>10{sup 21} cm{sup –2} yet no detectable CO emission.« less

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.

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

Cellulosic nanowhiskers. Theory and application of light scattering from polydisperse spheroids in the Rayleigh-Gans-Debye regime.

PubMed

Braun, Birgit; Dorgan, John R; Chandler, John P

2008-04-01

Mathematical treatment of light scattering within the Rayleigh-Gans-Debye limit for spheroids with polydispersity in both length and diameter is developed and experimentally tested using cellulosic nanowhiskers (CNW). Polydispersity indices are obtained by fitting the theoretical formfactor to experimental data. Good agreement is achieved using a polydispersity of 2.3 for the length, independent of the type of acid used. Diameter polydispersities are 2.1 and 3.0 for sulfuric and hydrochloric acids, respectively. These polydispersities allow the determination of average dimensions from the z-average mean-square radius (z) and the weight-average molecular weight (M w) easily obtained from Berry plots. For cotton linter hydrolyzed by hydrochloric acid, the average length and diameter are 244 and 22 nm. This compares to average length and diameter of 272 and 13 nm for sulfuric acid. This study establishes a new light-scattering methodology as a quick and robust tool for size characterization of polydisperse spheroidal nanoparticles.

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.

Product Differences in Intra-articular Hyaluronic Acids for Osteoarthritis of the Knee.

PubMed

Altman, Roy D; Bedi, Asheesh; Karlsson, Jon; Sancheti, Parag; Schemitsch, Emil

2016-08-01

Knee osteoarthritis (OA) is a common and often disabling joint disorder among adults that may result in impaired activity and daily function. A variety of treatment options are currently available and prescribed for knee OA depending on the severity of the disorder and physician preference. Intra-articular hyaluronic acid (IA-HA) injection is a treatment for knee OA that reportedly provides numerous biochemical and biological benefits, including shock absorption, chondroprotection, and anti-inflammatory effects within the knee. Clarity is needed as to whether the available IA-HA products should be considered for therapy as a group or whether there are significant differences in the products that need to be considered in treatment of OA of the knee. To determine whether there are differences in efficacy and safety with respect to intrinsic properties of available IA-HA injections for knee OA. Meta-analysis. A comprehensive literature search of the Medline, EMBASE, and PubMed databases was conducted for all existing randomized trials of IA-HA. The primary outcome measure analyzed was the mean pain score at the reported follow-up nearest to 26 weeks after injection. Pooled efficacy and safety results were recorded for subgroupings of HA product characteristics. A total of 68 studies were included for analysis. Products with an average molecular weight ≥3000 kDa provided favorable efficacy results when compared with products of an average molecular weight <3000 kDa. Products with a molecular weight ≥3000 kDa demonstrated significantly fewer discontinuations due to treatment-related adverse events than did ≤1500 kDa counterparts, while trial discontinuation rates were similar between biological fermentation-derived HA products and avian-derived HA. The results did not demonstrate a significant difference in the occurrence of effusion across molecular weight subgroups. Additionally, biological fermentation-derived HA had a significantly smaller incidence of effusion than did avian-derived HA. Biological fermentation-derived HA demonstrated fewer acute flare-ups at the injection site than did avian-derived HA products, while high-molecular-weight products demonstrated the highest rate of injection site flare-up. Despite similarities, IA-HA products should not be treated as a group, as there are differences in IA-HA products that influence both efficacy and safety. In the available literature, IA-HA products with a molecular weight ≥3000 kDa and those derived from biological fermentation relate to superior efficacy and safety-factors that may influence selection an IA-HA product for OA of the knee. © 2015 The Author(s).

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.

Biocatalytic Synthesis of Poly(δ-Valerolactone) Using a Thermophilic Esterase from Archaeoglobus fulgidus as Catalyst

PubMed Central

Cao, Hong; Han, Haobo; Li, Guangquan; Yang, Jiebing; Zhang, Lingfei; Yang, Yan; Fang, Xuedong; Li, Quanshun

2012-01-01

The ring-opening polymerization of δ-valerolactone catalyzed by a thermophilic esterase from the archaeon Archaeoglobus fulgidus was successfully conducted in organic solvents. The effects of enzyme concentration, temperature, reaction time and reaction medium on monomer conversion and product molecular weight were systematically evaluated. Through the optimization of reaction conditions, poly(δ-valerolactone) was produced in 97% monomer conversion, with a number-average molecular weight of 2225 g/mol, in toluene at 70 °C for 72 h. This paper has produced a new biocatalyst for the synthesis of poly(δ-valerolactone), and also deeper insight has been gained into the mechanism of thermophilic esterase-catalyzed ring-opening polymerization. PMID:23202895

Effect of molecular weight and concentration of legume condensed tannins on in vitro larval migration inhibition of Haemonchus contortus.

PubMed

Naumann, H D; Armstrong, S A; Lambert, B D; Muir, J P; Tedeschi, L O; Kothmann, M M

2014-01-17

The effect of molecular weight of condensed tannins (CT) from a variety of warm-season perennial legumes commonly consumed by sheep and goats on anthelmintic activity has not been previously explored. The objectives of this study were to determine if molecular weight of CT from warm-season perennial legumes could predict the biological activity of CT relative to anthelmintic activity against ivermectin resistant L3 stage Haemonchus contortus (HC) using a larval migration inhibition (LMI) assay. A second objective was to determine if CT from warm-season perennial legumes possess anthelmintic properties against L3 stage (HC). Lespedeza stuevei had the greatest concentration of total condensed tannin (TCT; 11.7%), whereas, with the exception of Arachis glabrata, a CT-free negative control, Leucaena retusa had the least TCT (3.3%). Weight-average molecular weight of CT ranged from 552 Da for L. stuevei to 1483 Da for Lespedeza cuneata. The treatments demonstrating the greatest percent LMI were L. retusa, L. stuevei and Acacia angustissima var. hirta (65.4%, 63.1% and 42.2%, respectively). The ivermectin treatment had the smallest percent LMI (12.5%) against ivermectin resistant L3 HC. There was a weak correlation (R(2)=0.34; P=0.05) between CT MW and percent LMI, suggesting that molecular weight of CT is a weak contributing factor to CT biological activity as it relates to LMI of L3 stage HC. L. stuevei, L. retusa and A. angustissima var. hirta STP5 warrant further evaluation of anthelmintic properties in vivo. Copyright © 2013 Elsevier B.V. All rights reserved.

Viscoelastic properties of cationic starch adsorbed on quartz studied by QCM-D.

PubMed

Tammelin, Tekla; Merta, Juha; Johansson, Leena-Sisko; Stenius, Per

2004-12-07

The adsorption and viscoelastic properties of layers of a cationic polyelectrolyte (cationic starch, CS, with 2-hydroxy-3-trimethylammoniumchloride as the substituent) adsorbed from aqueous solutions (pH 7.5, added NaCl 0, 1, 100, and 500 mM) on silica were studied with a quartz crystal microbalance with dissipation (QCM-D). Three different starches were investigated (weight-average molecular weights M(w) approximately 8.7 x 10(5) and 4.5 x 10(5) with degree of substitution DS = 0.75 and M(w) approximately 8.8 x 10(5) with DS = 0.2). At low ionic strength, the adsorbed layers are thin and rigid and the amount adsorbed can be calculated using the Sauerbrey equation. When the ionic strength is increased, significant changes take place in the amount of adsorbed CS and the viscoelasticity of the adsorbed layer. These changes were analyzed assuming that the layer can be described as a Voigt element on a rigid surface in contact with purely viscous solvent. It was found that CS with low charge density forms a thicker and more mobile layer with higher viscosity and elasticity than CS with high charge density. The polymers adsorbed on the silica even when the ionic strength was so high that electrostatic interactions were effectively screened. At this high ionic strength, it was possible to study the effect of molecular weight and molecular weight distribution of the CS on the properties of the adsorbed film. Increasing the molecular weight of CS resulted in a larger hydrodynamic thickness. CS with a narrow molecular weight distribution formed a more compact and rigid layer than broadly distributed CS, presumably due to the better packing of the molecules.

Probing the effect of polymer molecular weight on penetration into the wood cell wall using polyethylenimine (PEI) as a model compound.

PubMed

Dorvel, Brian; Boopalachandran, Praveenkumar; Chen, Ida; Bowling, Andrew; Williams, Kerry; King, Steve

2018-05-01

Decking is one of the largest applications for the treated wood market. The most challenging property to obtain for treated wood is dimensional stability, which can be achieved, in part, by cell wall bulking, cell wall polymer crosslinking and removal of hygroscopic components in the cell wall. A commonly accepted key requirement is for the actives to infuse through the cell wall, which has a microporosity of ∼5-13 nm. Equally as challenging is being able to measure and quantify the cell wall penetration. Branched polyethylenimine (PEI) was studied as a model polymer for penetration due to its water solubility, polarity, variable molecular weight ranges, and ability to form a chelation complex with preservative metals to treat lumbers. Two different molecular weight polyethylenimines (PEI), one with a weight average molecular weight (Mw) equal to 800 Da and the other 750 000 Da, were investigated for penetration by microscopy and spectroscopy techniques. Analytical methods were developed to both create smooth interfaces and for relative quantitation and visualisation of PEI penetration into the wood. The results showed both PEI with Mw of 800 Da and PEI with Mw of 750 000 Da coated the lumens in high density. However, only the PEI with Mw of 800 appeared to penetrate the cell walls in sufficient levels. Literature has shown the hydrodynamic radii of PEI 750 000 is near 29 nm, whereas a smaller PEI at 25 K showed 4.5 nm. Most importantly the results, based on methods developed, show how molecular weight and tertiary structure of the polymer can affect its penetration, with the microporosity of the wood being the main barrier. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Gene expression profiling in the Cynomolgus macaque Macaca fascicularis shows variation within the normal birth range

PubMed Central

2011-01-01

Background Although an adverse early-life environment has been linked to an increased risk of developing the metabolic syndrome, the molecular mechanisms underlying altered disease susceptibility as well as their relevance to humans are largely unknown. Importantly, emerging evidence suggests that these effects operate within the normal range of birth weights and involve mechanisms of developmental palsticity rather than pathology. Method To explore this further, we utilised a non-human primate model Macaca fascicularis (Cynomolgus macaque) which shares with humans the same progressive history of the metabolic syndrome. Using microarray we compared tissues from neonates in the average birth weight (50-75th centile) to those of lower birth weight (5-25th centile) and studied the effect of different growth trajectories within the normal range on gene expression levels in the umbilical cord, neonatal liver and skeletal muscle. Results We identified 1973 genes which were differentially expressed in the three tissue types between average and low birth weight animals (P < 0.05). Gene ontology analysis identified that these genes were involved in metabolic processes including cellular lipid metabolism, cellular biosynthesis, cellular macromolecule synthesis, cellular nitrogen metabolism, cellular carbohydrate metabolism, cellular catabolism, nucleotide and nucleic acid metabolism, regulation of molecular functions, biological adhesion and development. Conclusion These differences in gene expression levels between animals in the upper and lower percentiles of the normal birth weight range may point towards early life metabolic adaptations that in later life result in differences in disease risk. PMID:21999700

Characterization of oxidized tannins: comparison of depolymerization methods, asymmetric flow field-flow fractionation and small-angle X-ray scattering.

PubMed

Vernhet, Aude; Dubascoux, Stéphane; Cabane, Bernard; Fulcrand, Hélène; Dubreucq, Eric; Poncet-Legrand, Céline

2011-09-01

Condensed tannins are a major class of plant polyphenols. They play an important part in the colour and taste of foods and beverages. Due to their chemical reactivity, tannins are not stable once extracted from plants. A number of chemical reactions can take place, leading to structural changes of the native structures to give so-called derived tannins and pigments. This paper compares results obtained on native and oxidized tannins with different techniques: depolymerization followed by high-performance liquid chromatography analysis, small-angle X-ray scattering (SAXS) and asymmetric flow field-flow fractionation (AF4). Upon oxidation, new macromolecules were formed. Thioglycolysis experiments showed no evidence of molecular weight increase, but thioglycolysis yields drastically decreased. When oxidation was performed at high concentration (e.g., 10 g L(-1)), the weight average degree of polymerization determined from SAXS increased, whereas it remained stable when oxidation was done at low concentration (0.1 g L(-1)), indicating that the reaction was intramolecular, yet the conformations were different. Differences in terms of solubility were observed; ethanol being a better solvent than water. We also separated soluble and non-water-soluble species of a much oxidized fraction. Thioglycolysis showed no big differences between the two fractions, whereas SAXS and AF4 showed that insoluble macromolecules have a weight average molecular weight ten times higher than the soluble ones.

Preparation of Pure and Stable Chitosan Nanofibers by Electrospinning in the Presence of Poly(ethylene oxide)

PubMed Central

Mengistu Lemma, Solomon; Bossard, Frédéric; Rinaudo, Marguerite

2016-01-01

Electrospinning was employed to obtain chitosan nanofibers from blends of chitosans (CS) and poly(ethylene oxide) (PEO). Blends of chitosan (MW (weight-average molecular weight) = 102 kg/mol) and PEO (M (molecular weight) = 1000 kg/mol) were selected to optimize the electrospinning process parameters. The PEO powder was solubilized into chitosan solution at different weight ratios in 0.5 M acetic acid. The physicochemical changes of the nanofibers were determined by scanning electron microscopy (SEM), swelling capacity, and nuclear magnetic resonance (NMR) spectroscopy. For stabilization, the produced nanofibers were neutralized with K2CO3 in water or 70% ethanol/30% water as solvent. Subsequently, repeated washings with pure water were performed to extract PEO, potassium acetate and carbonate salts formed in the course of chitosan nanofiber purification. The increase of PEO content in the blend from 20 to 40 w% exhibited bead-free fibers with average diameters 85 ± 19 and 147 ± 28 nm, respectively. Their NMR analysis proved that PEO and the salts were nearly completely removed from the nanostructure of chitosan, demonstrating that the adopted strategy is successful for producing pure chitosan nanofibers. In addition, the nanofibers obtained after neutralization in ethanol-aqueous solution has better structural stability, at least for six months in aqueous solutions (phosphate buffer (PBS) or water). PMID:27792192

Receptors and aging: structural selectivity of the rhamnose-receptor on fibroblasts as shown by Ca(2+)-mobilization and gene-expression profiles.

PubMed

Faury, G; Molinari, J; Rusova, E; Mariko, B; Raveaud, S; Huber, P; Velebny, V; Robert, A M; Robert, L

2011-01-01

Qualitative and quantitative modifications of receptors were shown to play a key role in cell and tissue aging. We recently described the properties of a rhamnose-recognizing receptor on fibroblasts involved in the mediation of age-dependent functions of these cells. Using Ca(2+)-mobilization and DNA-microarrays we could show in the presence of rhamnose-rich oligo- and polysaccharides (RROPs) Ca(2+)-mobilization and changes in gene regulation. Here, we compared the effects of several RROPs, differing in their carbohydrate sequence and molecular weights, in normal human dermal fibroblasts (NHDFs). It appeared that different structural features were required for maximal effects on Ca(2+)-mobilization and gene-expression profiles. Maximal effect on Ca(2+) influx and intracellular free calcium regulation was exhibited by RROP-1, a 50 kDa average molecular weight polysaccharide, and RROP-3, a 5 kDa average molecular weight oligosaccharide with a different carbohydrate sequence. Maximal effect on gene-expression profiles was obtained with RROP-3. These results suggest the possibility of several different transmission pathways from the rhamnose-receptor to intracellular targets, differentially affecting these two intracellular functions, with potential consequences on aging. Although of only relative specificity, this receptor site exhibits a high affinity for rhamnose, absent from vertebrate glycoconjugates. The rhamnose-receptor might well represent an evolutionary conserved conformation of a prokaryote lectin. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

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.

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

Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir; Roghani-Mamaqani, Hossein

Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presencemore » of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric analysis shows that thermal stability of the nanocomposites increases by adding nanoparticles content. Decrease of glass transition temperature is also demonstrated by the addition of 3 wt% of silica nanoparticles according to the differential scanning calorimetry results.« less

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.

Treatment of wet blue with fillers produced from quebracho-modified gelatin

USDA-ARS?s Scientific Manuscript database

Gelatin modified with quebracho to produce high molecular weight, high viscosity products was investigated as a filler in leather processing. The uptake of quebracho/gelatin product by the wet blue was on the average about 55% of the 10% gelatin/quebracho product offered; the reaction appeared to be...

Characteristics and DBP formation of dissolved organic matter from leachates of fresh and aged leaf litter.

PubMed

Jian, Qianyun; Boyer, Treavor H; Yang, Xiuhong; Xia, Beicheng; Yang, Xin

2016-06-01

Dissolved organic matter (DOM) was leached from leaves of two trees commonly grown in subtropical regions, Pinus elliottii (commonly known as slash pine) and Schima superba (S. superba), and its degradation pattern and potential for forming disinfection byproducts (DBPs) were evaluated. The leaves were exposed in the field for up to one year before leaching. The DOM leached from slash pine litter contained on average 10.4 mg of dissolved organic carbon (DOC) per gram of dry weight; for S. superba the average was 37.2 mg-DOC/g-dry weight. Ultraviolet and visible light absorbance, fluorescence, and molecular weight analysis indicated that more aromatic/humic and higher molecular weight compounds are formed as leaf litter ages. A 4-component parallel factor analysis of the fluorescence data showed that the intensity of peaks related with protein-like components decreased gradually during biodegradation, while that of peaks attributed to humic-acid-like components increased continuously. Fresh slash pine leachates formed on average 40.0 μg of trihalomethane (THM) per milligram of DOC, while S. superba leachates formed 45.6 μg. THM formation showed peak values of 55.7 μg/mg DOC for slash pine and 74.9 μg/mg DOC for S. superba after 8 months of aging. The formation of haloacetonitrile (HAN) and trichloronitromethane (TCNM) increased with increasing leaf age, while chloral hydrate (CH) formation did not show such a trend. Specific UV absorbance showed some positive correlation with DBPs, but humic-acid-like and protein-like absorbance peaks correlated with CH and TCNM yields in only some leaf samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

In vivo cleavage rate of a dextran-bound magnetic resonance imaging contrast agent: preparation and intravascular pharmacokinetic characteristics in the rabbit.

PubMed

Hals, Petter Arnt; Sontum, Per Christian; Holtz, Eckart; Klaveness, Jo; Rongved, Pål

2013-02-01

Earlier described dextran-based contrast agents for magnetic resonance imaging (MRI) comprising the gadolinium chelate diethylenetriamine pentaacetic acid (GdDTPA, 1) have shown significantly shorter in vivo contrast duration in rat than what would be expected from the initial average molecular weight (Mw) of the dextran fraction (71.4 kD). To investigate this further, four dextran fractions with given initial average molecular weight (Mw) of 10.4, 41.0, 71.4 and 580 kD were used as starting material to prepare products 2-5 where one of the carboxylic acid functionalities in GdDTPA was used as a direct covalent ester linker to hydroxyl groups in dextrans. A fifth derivative (6) was an amide-ester bound β-alanine-DTPAGd conjugate with dextran having Mw 71.4 kD. The reference compound GdDTPA (1) and gadoliniumlabelled dextran derivatives 2-6 were injected intravenously in rabbits. Pharmacokinetic parameters showed that when GdDTPA is ester-bound directly to dextran hydroxyls, the cleavage rates of 2-5 were only moderately dependent on the molecular weights of the dextrans, having blood pool half-lives comparable to the low-molecular reference compound (t 1/2,β 0.3 - 0.5 hrs.). Presence of a β-alanine spacer in 6 prolonged the plasma half-life t 1/2,β to 6.9 hours, rendering a blood residence time suitable for blood pool slow release of GdDTPA. Biological cleavage regenerates the clinically acceptable carrier dextran and the β-alanine derivative of GdDTPA, pointing at a clinically acceptable product class for blood-pool contrast in MRI.

Polyhydroxyalkanoate recovery and effect of in situ extracellular polymeric substances removal from aerobic granules.

PubMed

Gobi, K; Vadivelu, V M

2015-01-01

Polyhydroxyalkanoate (PHA) recovery from aerobic granules was investigated using four cell digestion agents, namely, sodium hypochlorite, sodium hydroxide, acetone and sodium chloride. Simultaneously, the removal of extracellular polymeric substances (EPS) and its effect on PHA yield were investigated. The highest PHA recovery yield was obtained using sodium hypochlorite, accounting for 89% cell dry weight (CDW). The highest PHA was recovered after the sodium hypochlorite completely removed the EPS from the aerobic granules. The average molecular weight (Mw) of the PHA recovered using sodium hypochlorite was 5.31 × 10(5)g/mol with only 1.8% molecular weight degradation. The energy and duration analysis for PHA recovery revealed that the sodium hypochlorite method required the least amount of energy and time at 0.0561 MJ/g PHA and 26 h, respectively. The PHA that was recovered was a P3(HB-co-HV) co-polymer. Copyright © 2015 Elsevier Ltd. All rights reserved.

Direct analysis in real time mass spectrometry (DART-MS) of highly non-polar low molecular weight polyisobutylenes.

PubMed

Nagy, Lajos; Nagy, Tibor; Deák, György; Kuki, Ákos; Antal, Borbála; Zsuga, Miklós; Kéki, Sándor

2015-09-01

Low molecular weight polyisobutylenes (PIB) with chlorine, olefin and succinic acid end-groups were studied using direct analysis in real time mass spectrometry (DART-MS). To facilitate the adduct ion formation under DART conditions, NH 4 Cl as an auxiliary reagent was deposited onto the PIB surface. It was found that chlorinated adduct ions of olefin and chlorine telechelic PIBs, i.e. [M + Cl] - up to m/z 1100, and the deprotonated polyisobutylene succinic acid [MH] - were formed as observed in the negative ion mode. In the positive ion mode formation of [M + NH 4 ] + , adduct ions were detected. In the tandem mass (MS/MS) spectra of [M + Cl] - , product ions were absent, suggesting a simple dissociation of the precursor [M + Cl] - into a Cl - ion and a neutral M without fragmentation of the PIB backbones. However, structurally important product ions were produced from the corresponding [M + NH 4 ] + ions, allowing us to obtain valuable information on the arm-length distributions of the PIBs containing aromatic initiator moiety. In addition, a model was developed to interpret the oligomer distributions and the number average molecular weights observed in DART-MS for PIBs and other polymers of low molecular weight. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Chemical characterization, antioxidant and antitumor activity of sulfated polysaccharide from Sargassum horneri.

PubMed

Shao, Ping; Chen, Xiaoxiao; Sun, Peilong

2014-05-25

Three water-soluble polysaccharide fractions (SHP30, SHP60, and SHP80) extracted from the Sargassum horneri were obtained by water extraction and radial flow chromatography. The high-performance gel-permeation chromatography analysis showed that the average molecular weight (Mw) of three polysaccharides were approximately 1.58×10(3), 1.92×10(3) and 11.2KDa, respectively. Their in vitro antioxidant activities, antitumor activities were investigated and compared. Among these three polysaccharides, SHP30 with the highest sulfate content and intermediate molecular weight exhibited excellent antioxidant and antitumor activities in the superoxide radical assay, hydroxyl radical assay, reducing power assay, and MTT assay. Then, flow cytometry assay and quantitative real-time reverse transcription-PCR analysis suggested that the accumulation of cells in G0/G1 and S phase effecting apoptosis-associated gene expressions such as Bcl-2 and Bax might account for the growth inhibition of DLD cells by SHP30. Based on these results, we have inferred that sulfate content and molecular weight were the factors influencing antioxidant and antitumor activities. Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.

Effect of Silk Protein Processing on Drug Delivery from Silk Films

PubMed Central

Pritchard, Eleanor M.; Hu, Xiao; Finley, Violet; Kuo, Catherine K.; Kaplan, David L.

2013-01-01

Sericin removal from the core fibroin protein of silkworm silk is a critical first step in the use of silk for biomaterial-related applications, but degumming can affect silk biomaterial properties, including molecular weight, viscosity, diffusivity and degradation behavior. Increasing the degumming time (10, 30, 60 and 90 min) decreases the average molecular weight of silk protein in solution, silk solution viscosity, and silk film glass transition temperature, and increases the rate of degradation of silk film by protease. Model compounds spanning a range of physical-chemical properties generally showed an inverse relationship between degumming time and release rate through a varied degumming time silk coating. Degumming provides a useful control point to manipulate silk’s material properties. PMID:23349062

Plastic degradation by thermophilic Bacillus sp. BCBT21 isolated from composting agricultural residual in Vietnam

NASA Astrophysics Data System (ADS)

Dang, Thi Cam Ha; Thang Nguyen, Dang; Thai, Hoang; Chinh Nguyen, Thuy; Thu Hien Tran, Thi; Le, Viet Hung; Huynh Nguyen, Van; Bach Tran, Xuan; Phuong Thao Pham, Thi; Giang Nguyen, Truong; Nguyen, Quang Trung

2018-03-01

Three different kinds of plastic bags HL, VHL, and VN1 with different chemical nature were degraded by a novel thermophilic bacterial strain isolated from composting agricultural residual in Vietnam in shaking liquid medium at 55 °C after 30 d. The new strain was classified in the Bacillus genus by morphological property and sequence of partial 16Sr RNA coding gene and named as Bacillus sp. BCBT21. This strain could produce extracellular hydrolase enzymes including lipase, CMCase, xylanase, chitinase, and protease with different level of activity in the same media. After a 30-d treatment at 55 °C with Bacillus sp. BCBT21, all characteristics including properties and morphology of treated plastic bags had been significantly changed. The weight loss, structure and surface morphology of these bags as well as the change in the average molecular weight of VHL bag were detected. Especially, the average molecular weight of VHL bag was significantly reduced from 205 000 to 116 760. New metabolites from the treated bags indicated biodegradation occurring with the different pathways. This finding suggests that there is high potential to develop an effective integrated method for plastic bags degradation by a combination of extracellular enzymes from bacteria and fungi existing in the composting process.

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.

Supercritical multicomponent solvent coal extraction

NASA Technical Reports Server (NTRS)

Corcoran, W. H.; Fong, W. S.; Pichaichanarong, P.; Chan, P. C. F.; Lawson, D. D. (Inventor)

1983-01-01

The yield of organic extract from the supercritical extraction of coal with larger diameter organic solvents such as toluene is increased by use of a minor amount of from 0.1 to 10% by weight of a second solvent such as methanol having a molecular diameter significantly smaller than the average pore diameter of the coal.

Correlations between the average molecular weight and viscosity of soybean polymercaptan

USDA-ARS?s Scientific Manuscript database

Polymercaptanized soybean oil (PMSO), the product of a thiol-ene reaction between soybean oil and hydrogen sulfide, is a material of interest as a lubricant additive and polymer precursor. We investigated, with GPC, NMR (1D and 2D), GC-MS, and viscometry, the changes that occur with PMSO upon heatin...

1H and 13C-NMR studies on phenol-formaldehyde prepolymers for tannin-based adhesives

Treesearch

Gerald W. McGraw; Lawerence L. Lanucci; Seiji Ohara; Richard W. Hemingway

1989-01-01

The number average structure and the molecular weight distribution of phenol-formaldehyde prepolymers for use in synthesis of tannin-based adhesive resins were determined with 1H and 13C-NMR spectroscopy and gel permeation chromatography of acetylated resins. These methods were used to determine differences in phenol-...

40 CFR 180.960 - Polymers; exemptions from the requirement of a tolerance.

Code of Federal Regulations, 2013 CFR

2013-07-01

...-hydroxypoly (oxypropylene) and/or poly (oxyethylene) polymers where the alkyl chain contains a minimum of six... (oxypropylene) poly(oxyethylene) block copolymer; the minimum poly(oxypropylene) content is 27 moles and the... number average molecular weight (in amu), 900,000 62386-95-2 Monophosphate ester of the block copolymer α...

Semi-empirical estimation of organic compound fugacity ratios at environmentally relevant system temperatures.

PubMed

van Noort, Paul C M

2009-06-01

Fugacity ratios of organic compounds are used to calculate (subcooled) liquid properties, such as solubility or vapour pressure, from solid properties and vice versa. They can be calculated from the entropy of fusion, the melting temperature, and heat capacity data for the solid and the liquid. For many organic compounds, values for the fusion entropy are lacking. Heat capacity data are even scarcer. In the present study, semi-empirical compound class specific equations were derived to estimate fugacity ratios from molecular weight and melting temperature for polycyclic aromatic hydrocarbons and polychlorinated benzenes, biphenyls, dibenzo[p]dioxins and dibenzofurans. These equations estimate fugacity ratios with an average standard error of about 0.05 log units. In addition, for compounds with known fusion entropy values, a general semi-empirical correction equation based on molecular weight and melting temperature was derived for estimation of the contribution of heat capacity differences to the fugacity ratio. This equation estimates the heat capacity contribution correction factor with an average standard error of 0.02 log units for polycyclic aromatic hydrocarbons, polychlorinated benzenes, biphenyls, dibenzo[p]dioxins and dibenzofurans.

Microbial production of polyhydroxybutyrate with tailor-made properties: an integrated modelling approach and experimental validation.

PubMed

Penloglou, Giannis; Chatzidoukas, Christos; Kiparissides, Costas

2012-01-01

The microbial production of polyhydroxybutyrate (PHB) is a complex process in which the final quantity and quality of the PHB depend on a large number of process operating variables. Consequently, the design and optimal dynamic operation of a microbial process for the efficient production of PHB with tailor-made molecular properties is an extremely interesting problem. The present study investigates how key process operating variables (i.e., nutritional and aeration conditions) affect the biomass production rate and the PHB accumulation in the cells and its associated molecular weight distribution. A combined metabolic/polymerization/macroscopic modelling approach, relating the process performance and product quality with the process variables, was developed and validated using an extensive series of experiments and measurements. The model predicts the dynamic evolution of the biomass growth, the polymer accumulation, the consumption of carbon and nitrogen sources and the average molecular weights of the PHB in a bioreactor, under batch and fed-batch operating conditions. The proposed integrated model was used for the model-based optimization of the production of PHB with tailor-made molecular properties in Azohydromonas lata bacteria. The process optimization led to a high intracellular PHB accumulation (up to 95% g of PHB per g of DCW) and the production of different grades (i.e., different molecular weight distributions) of PHB. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis and Characterization of Solution and Melt Processible Poly(Acrylonitrile-Co-Methyl Acrylate) Statistical Copolymers

NASA Astrophysics Data System (ADS)

Pisipati, Padmapriya

Polyacrylonitrile (PAN) and its copolymers are used in a wide variety of applications ranging from textiles to purification membranes, packaging material and carbon fiber precursors. High performance polyacrylonitrile copolymer fiber is the most dominant precursor for carbon fibers. Synthesis of very high molecular weight poly(acrylonitrile-co-methyl acrylate) copolymers with weight average molecular weights of at least 1.7 million g/mole were synthesized on a laboratory scale using low temperature, emulsion copolymerization in a closed pressure reactor. Single filaments were spun via hybrid dry-jet gel solution spinning. These very high molecular weight copolymers produced precursor fibers with tensile strengths averaging 954 MPa with an elastic modulus of 15.9 GPa (N = 296). The small filament diameters were approximately 5 im. Results indicated that the low filament diameter that was achieved with a high draw ratio, combined with the hybrid dry-jet gel spinning process lead to an exponential enhancement of the tensile properties of these fibers. Carbon fibers for polymer matrix composites are currently derived from polyacrylonitrile copolymer fiber precursors where solution spinning accounts for ˜40 % of the total fiber production cost. To expand carbon fiber applications into the automotive industry, the cost of the carbon fiber needs to be reduced from 8 to ˜3-5. In order to develop an alternative melt processing route several benign plasticizers have been investigated. A low temperature, persulfate-metabisulfite initiated emulsion copolymerization was developed to synthesize poly(acrylonitrile-co-methyl acrylate) copolymers with acrylonitrile contents between 91-96 wt% with a molecular weight range of 100-200 kg/mol. This method was designed for a potential industrial scale up. Furthermore, water was investigated as a potential melting point depressant for these copolymers. Twenty-five wt% water lead to a decrease in the Tm of a 93/7 wt/wt % poly(acrylonitrile-co-methyl acrylate) of Mw = 200 kg/mol to 160 0C as measured via DSC. Glycerin, ethylene glycol and glycerin/water combinations were investigated as potential plasticizers for high molecular weight (˜200,000 g/mol), high acrylonitrile (93-96 mole:mole %) content poly(acrylonitrile-co-methyl acrylate) statistical copolymers. Pure glycerin (25 wt %) induced crystallization followed by a reduced "Tm" of about 213 0C via DSC. However this composition did not melt process well. A lower M W (˜35 kg/mol) copolymer did extrude with no apparent degradation. Our hypothesis is that the hydroxyl groups in glycerin (or water) disrupt the strong dipole-dipole interactions between the chains enabling the copolymer endothermic transition (Tm) to be reduced and enable melting before the onset of degradation. Additionally high molecular weight (Mw = 200-230 kg/mol) poly(acrylonitrile-co-methyl acrylate) copolymers with lower acrylonitrile content (82-85 wt %) were synthesized via emulsion copolymerization and successfully melt pressed. These materials will be further investigated for their utility in packaging applications.

Advantages and risks of using steel slag in preparing composts from raw organic waste.

PubMed

Tu, Xuefei; Aneksampant, Apichaya; Kobayashi, Shizusa; Tanaka, Atsushi; Nishimoto, Ryo; Fukushima, Masami

2017-01-02

It had been reported that iron and manganese oxides in steel slag enhanced the production of humic acid (HA) from low-molecular-weight compounds, such as phenolic acids, amino acids, and saccharides. In the present study, this function of steel slag was applied to the composting of raw organic wastes (ROWs). The degree of humification of HAs is an important factor in evaluating compost quality. Thus, HAs were extracted from the prepared composts and the humification parameters were determined, in terms of elemental compositions, acidic functional group contents, molecular weights, spectroscopic parameters from UV-vis absorption and 13 C NMR spectra. The timing for adding steel slag affected the degree of humification of HAs in the composts. The weight average molecular weight of a HA when slag was added initially (29 kDa) was significantly higher than when slag was added after elevating the temperature of the compost pile (17-18 kDa). These results show that ROWs are decomposed to low-molecular-weight compounds after the pile temperature is elevated and the presence of slag enhances the polycondensation of these compounds to produce HAs with a higher degree of humification. Because the slag used in the present study contained several-tens ng g -1 to several μg g -1 of toxic elements (B, Cu, Cr, and Zn), leaching tests for these elements from the prepared composts were carried out. Levels for leaching boron from composts prepared by adding slag (0.2-0.4 mg L -1 ) were obviously higher than the corresponding levels without slag (0.05 mg L -1 ).

Proteomic analysis of albumin and globulin fractions of pea (Pisum sativum L.) seeds.

PubMed

Dziuba, Jerzy; Szerszunowicz, Iwona; Nałęcz, Dorota; Dziuba, Marta

2014-01-01

Proteomic analysis is emerging as a highly useful tool in food research, including studies of food allergies. Two-dimensional gel electrophoresis involving isoelectric focusing and sodium dodecyl sulfate polyacrylamide gel electrophoresis is the most effective method of separating hundreds or even thousands of proteins. In this study, albumin and globulin tractions of pea seeds cv. Ramrod were subjected to proteomic analysis. Selected potentially alergenic proteins were identified based on their molecular weights and isoelectric points. Pea seeds (Pisum sativum L.) cv. Ramrod harvested over a period of two years (Plant Breeding Station in Piaski-Szelejewo) were used in the experiment. The isolated albumins, globulins and legumin and vicilin fractions of globulins were separated by two-dimensional gel electrophoresis. Proteomic images were analysed in the ImageMaster 2D Platinum program with the use of algorithms from the Melanie application. The relative content, isoelectric points and molecular weights were computed for all identified proteins. Electrophoregrams were analysed by matching spot positions from three independent replications. The proteomes of albumins, globulins and legumin and vicilin fractions of globulins produced up to several hundred spots (proteins). Spots most characteristic of a given fraction were identified by computer analysis and spot matching. The albumin proteome accumulated spots of relatively high intensity over a broad range of pi values of ~4.2-8.1 in 3 molecular weight (MW) ranges: I - high molecular-weight albumins with MW of ~50-110 kDa, II - average molecular-weight albumins with MW of ~20-35 kDa, and III - low molecular-weight albumins with MW of ~13-17 kDa. 2D gel electrophoregrams revealed the presence of 81 characteristic spots, including 24 characteristic of legumin and 14 - of vicilin. Two-dimensional gel electrophoresis proved to be a useful tool for identifying pea proteins. Patterns of spots with similar isoelectric points and different molecular weights or spots with different isoelectric points and similar molecular weights play an important role in proteome analysis. The regions characteristic of albumin, globulin and legumin and vicilin fractions of globulin with typical MW and pi values were identified as the results of performed 2D electrophoretic separations of pea proteins. 2D gel electrophoresis of albumins and the vicilin fraction of globulins revealed the presence of 4 and 2 spots, respectively, representing potentially allergenic proteins. They probably corresponded to vicilin fragments synthesized during post-translational modification of the analysed protein.

Ultrasound effects on the degradation kinetics, structure and rheological properties of apple pectin.

PubMed

Zhang, Lifen; Ye, Xinqian; Ding, Tian; Sun, Xiaoyang; Xu, Yuting; Liu, Donghong

2013-01-01

The effects of ultrasound on the molecular weight of apple pectin were investigated. The structure and rheological properties of the degradation products were also tentatively identified by High Performance Liquid Chromatography-Photodiode Array Detector (HPLC-PAD), Infrared spectroscopy (IR), Nuclear Magnetic Resonance spectroscopy (NMR) and Rheometer. The results indicated that the weight-average molecular weight of apple pectin decreased obviously after ultrasound treatment. The molecular weight of degradation products had a uniform and narrow distribution. Ultrasound intensity and temperature play an important role in the degradation reaction. Degradation kinetics model of apple pectin fitted to 1/M(t) - 1/M(0) = kt from 5 to 45 °C. The degree of methylation of apple pectin reduced according to IR analysis when ultrasound was applied. Ultrasound treatment could not alter the primary structure of apple pectin according to the results determined by HPLC, IR and NMR. Meanwhile, the viscosity of apple pectin was 10(3) times as large as that of ultrasound-treated apple pectin. The ultrasound-treated apple pectin showed predominantly viscous responses (G' < G") over the same frequency range. The results suggested that ultrasound provided a viable alternative method for the modification of pectin. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

High-resolution crystal structure of copper amine oxidase from Arthrobacter globiformis: assignment of bound diatomic molecules as O2.

PubMed

Murakawa, Takeshi; Hayashi, Hideyuki; Sunami, Tomoko; Kurihara, Kazuo; Tamada, Taro; Kuroki, Ryota; Suzuki, Mamoru; Tanizawa, Katsuyuki; Okajima, Toshihide

2013-12-01

The crystal structure of a copper amine oxidase from Arthrobacter globiformis was determined at 1.08 Å resolution with the use of low-molecular-weight polyethylene glycol (LMW PEG; average molecular weight ∼200) as a cryoprotectant. The final crystallographic R factor and Rfree were 13.0 and 15.0%, respectively. Several molecules of LMW PEG were found to occupy cavities in the protein interior, including the active site, which resulted in a marked reduction in the overall B factor and consequently led to a subatomic resolution structure for a relatively large protein with a monomer molecular weight of ∼70,000. About 40% of the presumed H atoms were observed as clear electron densities in the Fo - Fc difference map. Multiple minor conformers were also identified for many residues. Anisotropic displacement fluctuations were evaluated in the active site, which contains a post-translationally derived quinone cofactor and a Cu atom. Furthermore, diatomic molecules, most likely to be molecular oxygen, are bound to the protein, one of which is located in a region that had previously been proposed as an entry route for the dioxygen substrate from the central cavity of the dimer interface to the active site.

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.

Single processing step toward injectable sustained-release formulations of Triptorelin based on a novel degradable semi-solid polymer.

PubMed

Asmus, Lutz R; Kaufmann, Béatrice; Melander, Louise; Weiss, Torsten; Schwach, Grégoire; Gurny, Robert; Möller, Michael

2012-08-01

Poly(lactic acid) is a widely used polymer for parenteral sustained-release formulations. But its solid state at room-temperature complicates the formulation process, and elaborate formulation systems like microparticles and self-precipitating implants are required for administration. In contrast, hexylsubstituted poly(lactic acid) (hexPLA) is a viscous, biodegradable liquid, which can simply be mixed with the active compound. In this study, the feasibility to prepare injectable suspension formulations with peptides was addressed on the example of the GnRH-agonist Triptorelin. Two formulation procedures, of which one was a straight forward one-step cryo-milling-mixing process, were compared regarding the particle size of the peptide in the polymer matrix, distribution, and drug release. This beneficial method resulted in a homogeneous formulation with an average particle diameter of the incorporated Triptorelin of only 4.1 μm. The rheological behavior of the Triptorelin-hexPLA formulations was assessed and showed thixotropic and shear-thinning behavior. Viscosity and injectability were highly dependent on the drug loading, polymer molecular weight, and temperature. Nine formulations with drug loadings from 2.5% to 10% and hexPLA molecular weights between 1500 and 5000 g/mol were investigated in release experiments, and all displayed a long-term release for over 3 months. Formulations with hexPLA of 1500 g/mol showed a viscosity-dependent release and hexPLA-Triptorelin formulations of over 2500 g/mol a molecular weight-dependent release profile. In consequence, the burst release and rate of release were controllable by adapting the drug loading and the molecular weight of the hexPLA. The degradation characteristics of the hexPLA polymer during the in vitro release experiment were studied by following the molecular weight decrease and weight loss. Triptorelin-hexPLA formulations had interesting sustained-release characteristics justifying further investigations in the drug-polymer interactions and the in vivo behavior. Copyright © 2012 Elsevier B.V. All rights reserved.

Persistent organic pollutants and porphyrins biomarkers in penguin faeces from Kopaitic Island and Antarctic Peninsula.

PubMed

Rudolph, Ignacio; Chiang, Gustavo; Galbán-Malagón, Cristóbal; Mendoza, Rafael; Martinez, Miguel; Gonzalez, Carlos; Becerra, José; Servos, Mark R; Munkittrick, Kelly R; Barra, Ricardo

2016-12-15

Polychlorinated biphenyl (PCB) levels were determined in the faeces of three Antarctic Peninsula penguin species to assess viability as a non-invasive approach for sampling PCBs in Antarctic biota. These determinations were complemented with stable isotope and porphyrins assessments, and together this methodology determined the role of diet and metabolic disruption in penguins. Up to 60% of the collected faecal samples evidenced low molecular weight PCBs, of which, the more volatile compounds were predominant, in agreement with previous results. The highest PCB levels were reported in the gentoo penguin (Pygoscelis papua; 35.3ngg -1 wet weight average), followed by the chinstrap (Pygoscelis antarctica; 6.4ngg -1 wet weight average) and Adélie penguins (Pygoscelis adeliae; 12.9ngg -1 wet weight average). Stable isotope analyses (δ 15 N and δ 13 C) demonstrated that gentoo feeding and foraging habits differed from those of Adélie and chinstrap penguins. A strong positive correlation was found between PCB concentrations and δ 15 N, indicating the role of diet on the observed pollutant levels. Porphyrins metabolite levels were also directly correlated with PCB concentrations. These results suggest that PCB levels impair the health of Antarctic penguins. Copyright © 2016 Elsevier B.V. All rights reserved.

Studies on Acetone Powder and Purified Rhus Laccase Immobilized on Zirconium Chloride for Oxidation of Phenols

PubMed Central

Lu, Rong; Miyakoshi, Tetsuo

2012-01-01

Rhus laccase was isolated and purified from acetone powder obtained from the exudates of Chinese lacquer trees (Rhus vernicifera) from the Jianshi region, Hubei province of China. There are two blue bands appearing on CM-sephadex C-50 chromatography column, and each band corresponding to Rhus laccase 1 and 2, the former being the major constituent, and each had an average molecular weight of approximately 110 kDa. The purified and crude Rhus laccases were immobilized on zirconium chloride in ammonium chloride solution, and the kinetic properties of free and immobilized Rhus laccase, such as activity, molecular weight, optimum pH, and thermostability, were examined. In addition, the behaviors on catalytic oxidation of phenols also were conducted. PMID:22545205

Polypyrrole-based nanotheranostics for activatable fluorescence imaging and chemo/photothermal dual therapy of triple-negative breast cancer

NASA Astrophysics Data System (ADS)

Park, Dongjin; Ahn, Kyung-Ohk; Jeong, Kyung-Chae; Choi, Yongdoo

2016-05-01

Here, we fabricated polypyrrole nanoparticles (PPys) (termed HA10-PPy, HA20-PPy, and HA40-PPy) doped with different average molecular weight hyaluronic acids (HAs) (10, 20, and 40 kDa, respectively), and evaluated the effect of molecular weight of doped HA on photothermal induction, fluorescence quenching, and drug loading efficiencies. Doxorubicin-loaded HA-doped PPys (DOX@HA-PPys) could be used for imaging and therapy of triple-negative breast cancer (TNBC). Fluorescence turn-on, stimuli-responsive drug release, and photo-induced heating of DOX@HA-PPys enabled not only activatable fluorescence imaging but also subsequent chemo/photothermal dual therapy for TNBC. In particular, we illustrated the potential usefulness of the photothermal effect of the nanoparticles for overcoming chemoresistance in TNBC.

Low-molecular-weight lignin-rich fraction in the extract of cultured Lentinula edodes mycelia attenuates carbon tetrachloride-induced toxicity in primary cultures of rat hepatocytes.

PubMed

Yoshioka, Yasuko; Kojima, H; Tamura, A; Tsuji, K; Tamesada, M; Yagi, K; Murakami, N

2012-01-01

The extract of cultured Lentinula edodes mycelia (LEM) is a medicinal food ingredient that has hepatoprotective effects. In this study, we fractionated the LEM extract to explore novel active compounds related to hepatoprotection by using primary cultures of rat hepatocytes exposed to carbon tetrachloride (CCl(4)). The LEM extract and the fractions markedly inhibited the release of alanine aminotransferase (ALT) from hepatocytes damaged by CCl(4) into the culture medium. The strongest hepatocyte-protective activity was seen in a fraction (Fr. 2) in which a 50% ethanol extract was further eluted with 50% methanol and separated using reverse-phase HPLC. Fr. 2 had an average molecular weight of 2753, and the main components are lignin (49%) and saccharides (36%, of which xylose comprises 41%). Therefore, Fr. 2 was presumed to be a low-molecular-weight compound consisting mainly of lignin and xylan-like polysaccharides. The hepatocyte-protective activity was observed even after digestion of xylan-like polysaccharides in Fr.2 and confirmed with low-molecular-weight lignin (LM-lignin) alone. In addition, Fr. 2, the xylan-digested Fr. 2 and LM-lignin showed higher superoxide dismutase (SOD)-like activity than the LEM extract. These results suggested that the effective fraction in the LEM extract related to hepatocyte protection consisted mainly of LM-lignin, and its antioxidant activity partially contributes to the hepatocyte-protective activity of the LEM extract.

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.

Polymer Characterization by 13C Nuclear Magnetic Resonance (NMR) spectroscopy: Acryloid K125-EA and High Molecular Weight PIBM

DTIC Science & Technology

1980-02-01

average sequence length Butyl acrylate Methyl methacrylate PIBM Carbon-13 Monomer distribution PMMA (Continued on reverse side) 120. ASTACT (VC•T e m...TACTEC Attic SARPH.FTA 1 505 KIng Avenue Ihlle ithlt, AR 71611 Columbus, OH 43201 US ARMY TRAINING & DOCTRINE COMMAND Director or Toxicology

Stabilization and Carbonization of Gel Spun Polyacrylonitrile/Single Wall Carbon Nanotube Composite Fibers

DTIC Science & Technology

2007-02-01

elsewhere[9]. PAN was supplied by Exlan, Co. ( Japan ) and the viscosity average molecular weight was 250,000 g/mol. SWNTs (lot number XO1 PPP) were...200 kV). For TEM specimen preparation, the carbonized fibers were ground using pestle and mortar into very fine powder. The ground powder was collected

Characterization of novolac type liquefied wood/phenol/formaldehyde (LWPF) resin

Treesearch

Hui Pan; Todd F. Shupe; Chung-Yun Hse

2009-01-01

Novolac type liquefied wood/phenol/formaldehyde (LWPF) resins were synthesized from liquefied wood and formaldehyde. The average molecular weight of the LWPF resin made from the liquefied wood reacted in an atmospheric three neck flask increased with increasing P/W ratio. However, it decreased with increasing phenol/wood ratio when using a sealed Parr reactor. On...

Preparation and mass spectrometric study of egg yolk antibody (IgY) against rabies virus.

PubMed

Sun, S; Mo, W; Ji, Y; Liu, S

2001-01-01

Rabies virus was used as the antigen to immunize laying chickens. Anti-rabies virus immunoglobulin Y(IgY) was isolated from yolks of the eggs laid by these chickens using a two-step salt precipitation and one-step gel filtration protocol. The purified IgY was reduced with dithiothreitol, and heavy chains (HC) and light chains (LC) were obtained. In addition, the purified IgY was digested with pepsin and the fragment with specific antigen binding properties (Fab) was produced. Using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOFMS), the average molecular weights of IgY, HC, LC, and Fab were determined as 167 250, 65 105, 18 660, and 45,359 Da, respectively. IgY has two structural differences compared with mammalian IgGs. First, the molecular weight of the heavy chain of IgY is larger than that of its mammalian counterpart, while the molecular weight of the light chain of IgY is smaller. Second, upon pepsin digestion, anti-rabies virus IgY is degraded into Fab, in contrast to mammalian IgG, which has been reported to be degraded into F(ab')(2) under the same conditions. Copyright 2001 John Wiley & Sons, Ltd.

Effect of initiators on synthesis of poly(L-lactide) by ring opening polymerization

NASA Astrophysics Data System (ADS)

Pholharn, D.; Srithep, Y.; Morris, J.

2017-06-01

We studied the effect of several aliphatic alcohols, including1-dodecanol, 1-octanol and methanol, as initiators on synthesis of poly(L-lactide) (PLLA) by ring opening polymerization. The reaction starts with L-lactide monomer and uses stannous octoate as catalyst. Fourier transform infrared spectroscopy and X-ray diffraction analysis verified that PLLAs were produced successfully. Weight, number average molecular weight and polydispersity index of PLLAs were measured by gel permeation chromatography. The PLLA initiated by methanol (PLLA-Meth) presented the highest molecular weight and yield percent. From differential scanning calorimetry, PLLA-Meth showed the highest melting temperature at ∼167°C, crystallization temperature at 110°C and degree of crystallinity 80%. The thermal stability was assessed by thermogravimetric analysis: this confirmed that PLLA-Meth was superior with the highest degradation temperature compared to PLLA initiated by other initiators. We concluded that methanol was the most appropriate initiator for PLLA synthesis by ring opening polymerization.

Climate-Induced Changes in the Chemical Characteristics of Natural Organic Matter at a Small Freshwater Wetland

NASA Astrophysics Data System (ADS)

Maurice, P. A.; Cabaniss, S. E.; Drummond, J.

2001-12-01

This study investigated the spatiotemporal variability in dissolved organic carbon concentration (DOC), natural organic matter (NOM) weight average molecular weight (Mw), and absorptivity at 280 nm (e280, an estimator of aromaticity) at McDonalds Branch, a first-order stream that is a fen wetland. When ground-water discharge to the stream was predominant, the DOC, the Mw, and the e280 were all relatively low. When soil porewater was more important, not only was the DOC higher, but also the Mw and e280. Hence, the contribution of soil pore water relative to ground water controlled not only the concentration but also the average physicochemical characteristics of the NOM. Results from this small watershed study provide insight into climatic effects on surface-water NOM characteristics in a small freshwater fen. Low-flow periods resulted in lower Mw, more aliphatic NOM derived primarily from ground-water discharge to the stream whereas higher flow periods resulted in a higher Mw(by 150-500 Da), more aromatic downstream surface-water NOM pool. Hence, during future summer drought periods, as suggested by climate-change models for much of North America, surface-water NOM likely will be lower molecular weight, more aliphatic, and more hydrophilic with lesser metal binding and HOC uptake abilities, along with decreased ability to attenuate UV radiation.

Brief communication: Preoperative anticoagulant activity after bridging low-molecular-weight heparin for temporary interruption of warfarin.

PubMed

O'Donnell, Martin J; Kearon, Clive; Johnson, Judy; Robinson, Marlene; Zondag, Michelle; Turpie, Irene; Turpie, Alexander G

2007-02-06

Preoperative low-molecular-weight heparin (LMWH) is often used when warfarin therapy is interrupted for surgery. To determine the preoperative anticoagulant activity of LMWH following a standardized "bridging" regimen. Prospective cohort study. Single university hospital. Consecutive patients who had warfarin therapy interrupted before an invasive procedure. Enoxaparin, 1 mg/kg of body weight, twice daily. The last dose was administered the evening before surgery. Blood anti-factor Xa heparin levels measured shortly before surgery. Preoperative anti-Xa heparin levels were obtained in 80 patients at an average of 14 hours after the last dose of enoxaparin was administered. The average anti-Xa heparin level was 0.6 U/mL. The anti-Xa heparin level, measured shortly before surgery, was 0.5 U/mL or greater in 54 (68%) patients and 1.0 U/mL or greater in 13 (16%) patients. A shorter interval since the last dose (P < 0.001) and a higher body mass index (P = 0.001) were associated with higher preoperative anti-Xa heparin levels. The small sample size limits accurate estimates of the frequency of the clinical outcomes. A single regimen of LMWH was evaluated. Anti-Xa heparin levels often remain high at the time of surgery if a last dose of a twice-daily regimen of LMWH is given the evening before surgery.

Polysaccharides from Smilax glabra inhibit the pro-inflammatory mediators via ERK1/2 and JNK pathways in LPS-induced RAW264.7 cells.

PubMed

Lu, Chuan-li; Wei, Zhu; Min, Wang; Hu, Meng-mei; Chen, Wen-long; Xu, Xiao-jie; Lu, Chuan-jian

2015-05-20

The rhizomes of Smilax glabra have been used as both food and folk medicine in many countries for a long time. However, little research has been reported on polysaccharides of S. glabra. In the present study, two polysaccharide fractions, SGP-1 and SGP-2, were isolated from the rhizomes of S. glabra with the number average molecular weights of 1.72 × 10(2)kDa and 1.31 × 10(2)kDa, and the weight average molecular weights of 1.31 × 10(5)kDa and 1.18 × 10(5)kDa, respectively, and their mainly monosaccharide compositions were both galactose and rhamnose (2.5:1). Both SGP-1 and SGP-2 significantly suppressed the release of nitric oxide (NO), tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) from LPS-induced RAW 264.7 cells, as well as the mRNA expression of inducible nitric oxide synthase (iNOS), TNF-α and IL-6. Additionally, SGP-1 and SGP-2 repressed the extracellular signal-regulated kinase (ERK) and c-Jun NH2-terminal kinase (JNK). These findings strongly suggested polysaccharides were also the anti-inflammatory active ingredient for S. glabra, and the potential of SGP-1 and SGP-2 as the anti-inflammatory agents. Copyright © 2015. Published by Elsevier Ltd.

Preparation of enhanced hydrophobic poly(L-lactide-co-ɛ-caprolactone) films surface and its blood compatibility

NASA Astrophysics Data System (ADS)

Kim, Seung Il; Lim, Jin Ik; Jung, Youngmee; Mun, Cho Hay; Kim, Ji Heung; Kim, Soo Hyun

2013-07-01

Hydrophobicity-enhanced poly(L-lactide-co-ɛ-caprolactone) (PLCL) (50:50) films were cast by using the solvent-nonsolvent casting method. PLCL (50:50) was synthesized by the well-known random copolymerization process and confirmed by 1H NMR analysis. The molecular weight of the synthesized PLCL was measured by gel permeation chromatography (GPC). Number-average (Mn), weight-average (Mw) molecular weights and polydispersity (Mw/Mn) were 7 × 104, 1.2 × 105, and 1.7, respectively. PLCL films were cast in vacuum condition with various nonsolvents and nonsolvent ratios. Tetrahydrofuran (THF) was used as the solvent and three different alcohols were used as the nonsolvent: methanol, ethanol, and isopropyl alcohol (IPA). Surface hydrophobicity was confirmed by water contact angle. The water contact angle was increased from 81° ± 2° to 107° ± 2°. Water contact angle was influenced by surface porosity and topography. The prepared film surfaces were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The change of crystalline property was characterized by X-ray diffraction (XRD). Platelet adhesion tests on the modified PLCL film surfaces were evaluated by platelet-rich plasma (PRP). The modified film surface exhibited enhanced hydrophobicity and reduced platelet adhesion ratio depending on the surface topography. One of the candidate products proposed as a potential blood compatible material showed a markedly reduced platelet adhesion property.

Study of Hyperbranched Poly(ethyleneimine) Polymers of Different Molecular Weight and Their Interaction with Epoxy Resin

PubMed Central

2018-01-01

Two different commercial hyperbranched poly(ethyleneimine)s (HBPEI), with molecular weights (MW) of 800 and 25,000 g/mol, and denoted as PEI800 and PEI25000, respectively, as well as the mixtures with a Diglycidyl Ether of Bisphenol-A (DGEBA) epoxy resin, have been studied using thermal analysis techniques (DSC, TGA), dielectric relaxation spectroscopy (DRS), and dynamic mechanical analysis (DMA). Only a single glass transition is observed in these mixtures by DSC. DRS of the HBPEIs shows three dipolar relaxations: γ, β, and α. The average activation energy for the γ-relaxation is similar for all HBPEIs and is associated with the motion of the terminal groups. The β-relaxation has the same average activation energy for both PEI800 and PEI25000; this relaxation is attributed to the mobility of the branches. The α-relaxation peak for all the HBPEIs is an asymmetric peak with a shoulder on the high temperature side. This shoulder suggests the existence of ionic charge trapped in the PEI. For the mixtures, the γ- and β-relaxations follow the behaviour of the epoxy resin alone, indicating that the epoxy resin dominates the molecular mobility. The α-relaxation by DRS is observed only as a shoulder, as a consequence of an overlap with conductivity effects, whereas by DMA, it is a clear peak. PMID:29522480

Surface accumulation of low molecular weight dissolved organic matter in surface waters and horizontal off-shelf spreading of nutrients and humic-like fluorescence in the Chukchi Sea of the Arctic Ocean.

PubMed

Chen, Meilian; Jung, Jinyoung; Lee, Yun Kyung; Hur, Jin

2018-05-23

Polar regions play unique roles in global overturning circulation, carbon cycling, and climate change. In this study, seawater dissolved organic matter (DOM) was characterized for the Chukchi Sea in the Arctic Ocean in the summer season. The seawater generally contains high concentrations of dissolved organic carbon (DOC, up to 92 μM C) and tyrosine-like fluorescence (up to 0.21 RU), and it was enriched with heteroatomic molecular formula with nitrogen-containing and sulfur-containing formulas counting 2246 (~41% of total identified molecular formula) and 1838 (~34%), respectively. Significant correlations were observed between salinity and the absorption coefficient at 254 nm, between chlorophyll-a and DOC as well as the tyrosine-like component, C 270/302 (C ex/em maxima), and between biological index and two protein-like components, C 275/338 and C 305/344 . A comparison between surface waters and close-to-seafloor deep waters suggested a trend of the accumulation of low molecular weight (LMW) fraction (~54-74%, nominal average molecular weight M n  < ~350 Da) in the surface waters. Another interesting finding from spatial data was an obvious horizontal off-shelf spreading of nutrients and humic-like fluorescence. This study sheds novel insights of DOM characteristics and dynamics in the highly productive polar sea. Copyright © 2018 Elsevier B.V. All rights reserved.

Degradation of Lignin by Cyathus Species

PubMed Central

Abbott, Thomas P.; Wicklow, Donald T.

1984-01-01

The ability of 12 Cyathus species to degrade 14C-labeled lignin in kenaf was studied. The sum of 14C released into solution plus 14C released into the gas phase over a 32-day fermentation period was used to determine average daily rates of lignin biodegradation. Cyathus pallidus. C. africanus, and C. berkeleyanus delignified kenaf most rapidly. C. canna showed the greatest preference for lignin degradation over other plant components, and its rate of lignin degradation was only slightly lower than the three most active species. The apparent ability of fungi to metabolize low-molecular-weight lignin breakdown products correlated well with their overall delignification rates. C. stercoreus metabolized degradation products of lignin from wheat straw better than those from kenaf lignin, based on the amount of low-molecular-weight products left in solution. PMID:16346497

ENZYMATIC POLYMERIZATION OF PHENOLS IN ROOM TEMPERATURE IONIC LIQUIDS

PubMed Central

Eker, Bilge; Zagorevski, Dmitri; Zhu, Guangyu; Linhardt, Robert J.; Dordick, Jonathan S.

2009-01-01

Soybean peroxidase (SBP) was used to catalyze the polymerization of phenols in room-temperature ionic liquids (RTILs). Phenolic polymers with number average molecular weights ranging from 1200 to 4100 D were obtained depending on the composition of the reaction medium and the nature of the phenol. Specifically, SBP was highly active in methylimidazolium-containing RTILs, including 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(BF4)), and 1-butyl-3-methylpyridinium tetrafluoroborate (BMPy(BF4)) with the ionic liquid content as high as 90% (v/v); the balance being aqueous buffer. Gel permeation chromatography and MALDI-TOF analysis indicated that higher molecular weight polymers can be synthesized in the presence of higher RTIL concentrations, with selective control over polymer size achieved by varying the RTIL concentration. The resulting polyphenols exhibited high thermostability and possessed thermosetting properties. PMID:20161409

Functional Aromatic Poly(1,3,4-Oxadiazole-Ether)s with Benzimidazole Pendants: Synthesis, Thermal and Dielectric Studies

PubMed Central

Ganesh, Shimoga D.; Pai, Vasantakumar K.; Kariduraganavar, Mahadevappa Y.; Jayanna, Madhu B.

2014-01-01

Poly(1,3,4-oxadiazole-ether) with reactive carboxylic acid pendants was synthesized from solution polymerization via nucleophilic displacement polycondensation among 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole (BFPOx) and 4,4′-bis(4-hydroxyphenyl) valeric acid (BHPA). Without altering the polymeric segments, benzimidazole modified poly(1,3,4-oxadiazole-ether)s were prepared by varying stoichiometric ratios of 1,2-phenylenediamine. The molecular structural characterization of these polymers was achieved by, FT-IR, NMR, TGA, elemental analysis, and analytical techniques. The weight-average molecular weight of virgin polymer with carboxylic acid functionality was determined by gel permeation chromatography (GPC) and was found to be 22400 (Mw/Mn = 2.07). All the synthesized polyethers were compressed into pellets and electrical contacts were established to perform dielectric properties. PMID:27437448

Characterization and migration of oil and solids in oily sludge during centrifugation.

PubMed

Wang, Jun; Han, Xu; Huang, Qunxing; Ma, Zengyi; Chi, Yong; Yan, Jianhua

2018-05-01

The migration behaviors of oil, water and solids in sludge during centrifugation were elaborated. Size distribution, surface topography and lypohydrophilic properties were studied in detail. The average size of solids was 61 μm in original sludge, 31 μm in upper layer and 235 μm in bottom layer. The result shows that solvent is essential to separate oil phase into molecular light and weight fractions during centrifugation. With solvent/oil ratio increases from 1:2, 1:1, 2:1 to 5:1, molecular weight in upper layer decreases from 1044, 1043, 1020 to 846 combined with that in bottom layer increases. A model was proposed to calculate the oil residue content in solid phases after sedimentation. The findings of this paper provide information for optimizing the oil recovery and clean treatment.

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.

Particulate sulfur-containing lipids: Production and cycling from the epipelagic to the abyssopelagic zone

NASA Astrophysics Data System (ADS)

Gašparović, Blaženka; Penezić, Abra; Frka, Sanja; Kazazić, Saša; Lampitt, Richard S.; Holguin, F. Omar; Sudasinghe, Nilusha; Schaub, Tanner

2018-04-01

There are major gaps in our understanding of the distribution and role of lipids in the open ocean especially with regard to sulfur-containing lipids (S-lipids). Here, we employ a powerful analytical approach based on high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to elucidate depth-related S-lipid production and molecular transformations in suspended particulate matter from the Northeast Atlantic Ocean in this depth range. We show that within the open-ocean environment S-lipids contribute up to 4.2% of the particulate organic carbon, and that up to 95% of these compounds have elemental compositions that do not match those found in the Nature Lipidomics Gateway database (termed "novel"). Among the remaining 5% of lipids that match the database, we find that sulphoquinovosyldiacylglycerol (SQDG) are efficiently removed while sinking through the mesopelagic zone. The relative abundance of other assigned lipids (sulphoquinovosylmonoacylglycerol (SQMG), sulfite and sulfate lipids, Vitamin D2 and D3 derivatives, and sphingolipids) did not change substantially with depth. The novel S-lipids, represented by hundreds of distinct elemental compositions (160-300 molecules at any one depth), contribute increasingly to the lipid and particulate organic matter pools with increased depth. Depth-related transformations cause (i) incomplete degradation/transformation of unsaturated S-lipids which leads to the depth-related accumulation of the refractory saturated compounds with reduced molecular weight (average 455 Da) and (ii) formation of highly unsaturated S-lipids (average abyssopelagic molecular double bond equivalents, DBE=7.8) with lower molecular weight (average 567 Da) than surface S-lipids (average 592 Da). A depth-related increase in molecular oxygen content is observed for all novel S-lipids and indicates that oxidation has a significant role in their transformation while (bio)hydrogenation possibly impacts the formation of saturated compounds. The instrumentation approach applied here represents a step change in our comprehension of marine S-lipid diversity and the potential role of these compounds in the oceanic carbon cycle. We describe a very much higher number of compounds than previously reported, albeit at the level of elemental composition and fold-change quantitation with depth, rather than isomeric confirmation and absolute quantitation of individual lipids. We emphasize that saturated S-lipids have the potential to transfer carbon from the upper ocean to depth and hence are significant vectors for carbon sequestration.

Using [superscript 1]H NMR Spectra of Polymers and Polymer Products to Illustrate Concepts in Organic Chemistry

ERIC Educational Resources Information Center

Harrell, Mary L.; Bergbreiter, David E.

2017-01-01

The use of [superscript 1]H NMR spectroscopy to analyze the number-average molecular weight of a methoxy poly(ethylene glycol) (MPEG) and an acetate derivative of this MPEG is described. These analyses illustrate NMR principles associated with the chemical shift differences of protons in different environments, NMR integration, and the effect of…

Communication: Smoothing out excited-state dynamics: Analytical gradients for dynamically weighted complete active space self-consistent field

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

Glover, W. J., E-mail: williamjglover@gmail.com

2014-11-07

State averaged complete active space self-consistent field (SA-CASSCF) is a workhorse for determining the excited-state electronic structure of molecules, particularly for states with multireference character; however, the method suffers from known issues that have prevented its wider adoption. One issue is the presence of discontinuities in potential energy surfaces when a state that is not included in the state averaging crosses with one that is. In this communication I introduce a new dynamical weight with spline (DWS) scheme that mimics SA-CASSCF while removing energy discontinuities due to unweighted state crossings. In addition, analytical gradients for DWS-CASSCF (and other dynamically weightedmore » schemes) are derived for the first time, enabling energy-conserving excited-state ab initio molecular dynamics in instances where SA-CASSCF fails.« less

Data on the synthesis and mechanical characterization of polysiloxane-based urea-elastomers prepared from amino-terminated polydimethylsiloxanes and polydimethyl-methyl-phenyl-siloxane-copolymers.

PubMed

Riehle, Natascha; Götz, Tobias; Kandelbauer, Andreas; Tovar, Günter E M; Lorenz, Günter

2018-06-01

This article contains data on the synthesis and mechanical characterization of polysiloxane-based urea-elastomers (PSUs) and is related to the research article entitled "Influence of PDMS molecular weight on transparency and mechanical properties of soft polysiloxane-urea-elastomers for intraocular lens application" (Riehle et al., 2018) [1]. These elastomers were prepared by a two-step polyaddition using the aliphatic diisocyanate 4,4'-Methylenbis(cyclohexylisocyanate) (H 12 MDI), a siloxane-based chain extender 1,3-Bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (APTMDS) and amino-terminated polydimethylsiloxanes (PDMS) or polydimethyl-methyl-phenyl-siloxane-copolymers (PDMS-Me,Ph), respectively. (More details about the synthesis procedure and the reaction scheme can be found in the related research article (Riehle et al., 2018) [1]). Amino-terminated polydimethylsiloxanes with varying molecular weights and PDMS-Me,Ph-copolymers were prepared prior by a base-catalyzed ring-chain equilibration of a cyclic siloxane and the endblocker APTMDS. This DiB article contains a procedure for the synthesis of the base catalyst tetramethylammonium-3-aminopropyl-dimethylsilanolate and a generic synthesis procedure for the preparation of a PDMS having a targeted number average molecular weight M ¯ n of 3000 g mol -1 . Molecular weights and the amount of methyl-phenyl-siloxane within the polysiloxane-copolymers were determined by 1 H NMR and 29 Si NMR spectroscopy. The corresponding NMR spectra and data are described in this article. Additionally, this DiB article contains processed data on in line and off line FTIR-ATR spectroscopy, which was used to follow the reaction progress of the polyaddition by showing the conversion of the diisocyanate. All relevant IR band assignments of a polydimethylsiloxane-urea spectrum are described in this article. Finally, data on the tensile properties and the mechanical hysteresis-behaviour at 100% elongation of PDMS-based polyurea-elastomers are shown in dependence to the PDMS molecular weight.

A RCT study of Rivaroxaban, low-molecular-weight heparin, and sequential medication regimens for the prevention of venous thrombosis after internal fixation of hip fracture.

PubMed

Tang, Yilun; Wang, Kunzheng; Shi, Zhibin; Yang, Pei; Dang, Xiaoqian

2017-08-01

The guidelines for the prevention of venous thromboembolism in orthopedic surgeries have reached a consensus on the postoperative conventional anticoagulation. However, the choice of anticoagulant drugs is yet controversial. The use of the drug rivaroxaban is expensive. Since the compliance of patients with low-molecular-weight heparin is considerably low, a cost-effective, efficacious and convenient anticoagulant program is essential. The present study investigated the efficacy, safety, patient compliance, and cost-effectiveness of low-molecular-weight heparin with sequential Rivaroxaban anticoagulant therapy in patients with a hip fracture, following internal fixation. A total of 287 patients with hip fractures were randomized into three groups: Rivaroxaban alone, Enoxaparin alone, and Enoxaparin followed by Rivaroxaban. The primary endpoint was the incidence of postoperative VTE, whereas the secondary endpoints were the compliance and treatment costs. Adverse reactions included bleeding and wound complications. The incidences of VTE were 5.21%, 14.74%, and 10.42% in the Rivaroxaban, low-molecular-weight heparin, and sequential therapy groups, respectively. The VTE-related mortality rates were 0%, 1.05%, and 1.04%. The average hospital stay was 12±8,15±7, and 11±5d, whereas the compliance rates of the three groups were 82.3%, 71.6%, and 88.5%, respectively. The incidences of adverse incisions were 14.6%, 4.2%, and 6.3% for the three groups examined. The effects and the incidence of postoperative bleeding in the treatment of low-molecular-weight heparin followed by Rivaroxaban did not differ significantly from that of Rivaroxaban alone. However, the postoperative drainage, the cost of treatment and the incidence of VTE reduced significantly, whereas the incidences of adverse incisions and the patient compliance were increased. ChiCTR-INR-17010495. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

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.

A universal reduced glass transition temperature for liquids

NASA Technical Reports Server (NTRS)

Fedors, R. F.

1979-01-01

Data on the dependence of the glass transition temperature on the molecular structure for low-molecular-weight liquids are analyzed in order to determine whether Boyer's reduced glass transition temperature (1952) is a universal constant as proposed. It is shown that the Boyer ratio varies widely depending on the chemical nature of the molecule. It is pointed out that a characteristic temperature ratio, defined by the ratio of the sum of the melting temperature and the boiling temperature to the sum of the glass transition temperature and the boiling temperature, is a universal constant independent of the molecular structure of the liquid. The average value of the ratio obtained from data for 65 liquids is 1.15.

Molecular Characteristics of Kraft-AQ Pulping Lignin Fractionated by Sequential Organic Solvent Extraction

PubMed Central

Wang, Kun; Xu, Feng; Sun, Runcang

2010-01-01

Kraft-AQ pulping lignin was sequentially fractionated by organic solvent extractions and the molecular properties of each fraction were characterized by chemical degradation, GPC, UV, FT-IR, 13C-NMR and thermal analysis. The average molecular weight and polydispersity of each lignin fraction increased with its hydrogen-bonding capacity (Hildebrand solubility parameter). In addition, the ratio of the non-condensed guaiacyl/syringyl units and the content of β-O-4 linkages increased with the increment of the lignin fractions extracted successively with hexane, diethylether, methylene chloride, methanol, and dioxane. Furthermore, the presence of the condensation reaction products was contributed to the higher thermal stability of the larger molecules. PMID:21152286

Surface temperatures and glassy state investigations in tribology, part 4

NASA Technical Reports Server (NTRS)

Bair, S. S.; Winer, W. O.

1981-01-01

Measurements were made of the limiting shear stress for two naphthenic oils of differing molecular weight and three blends of the lower molecular weight oil and polyalkylmethacrylate polymers of differing molecular weight. The two base oils reached the same limiting shear stress for the same temperature and pressure. This was also true for all the polymer solutions although the polymer reduced the limiting shear stress by about 15 percent. It is shown that limiting stress is more a function of material type than viscosity or molecular weight. A new falling body viscometer was constructed to operate to 230 C and 0.6 GPa. Another viscometer was constructed to extend the pressure range to 1.1 GPa. A concentrated contact simulator was developed which allows recording of the traction force while the slide-roll ratio is continuously varied and the rolling speed is maintained essentially constant by a single drive motor. The configuration is that of a crowned roller against a disk. Measurement of lubricant minimum film thickness of elliptical EHD contacts of various aspect ratios were made by optical interferometry. The data collected were used to evaluate the Hamrock and Dowson minimum film thickness model over a range of contract ellipticity ratio where the major axis of the contact ellipse was aligned both parallel and perpendicular to the direction of motion. A statistical analysis of the measured film thickness data showed that on the average the experimental data were 30 percent greater than the film thickness predicted by the model. Preliminary development of the application of a scanning infrared radiation system to a tribo-system was completed.

Polyethylenimine Interfacial Layers in Inverted Organic Photovoltaic Devices: Effects of Ethoxylation and Molecular Weight on Efficiency and Temporal Stability.

PubMed

Courtright, Brett A E; Jenekhe, Samson A

2015-12-02

We report a comparative study of polyethylenimine (PEI) and ethoxylated-polyethylenimine (PEIE) cathode buffer layers in high performance inverted organic photovoltaic devices. The work function of the indium-tin oxide (ITO)/zinc oxide (ZnO) cathode was reduced substantially (Δφ = 0.73-1.09 eV) as the molecular weight of PEI was varied from 800 g mol(-1) to 750 000 g mol(-1) compared with the observed much smaller reduction when using a PEIE thin film (Δφ = 0.56 eV). The reference inverted polymer solar cells based on the small band gap polymer PBDTT-FTTE (ITO/ZnO/PBDTT-FTTE:PC70BM/MoO3/Ag), without a cathode buffer layer, had an average power conversion efficiency (PCE) of 6.06 ± 0.22%. Incorporation of a PEIE cathode buffer layer in the same PBDTT-FTTE:PC70BM blend devices gave an enhanced performance with a PCE of 7.37 ± 0.53%. In contrast, an even greater photovoltaic efficiency with a PCE of 8.22 ± 0.10% was obtained in similar PBDTT-FTTE:PC70BM blend solar cells containing a PEI cathode buffer layer. The temporal stability of the inverted polymer solar cells was found to increase with increasing molecular weight of the cathode buffer layer. The results show that PEI is superior to PEIE as a cathode buffer layer in high performance organic photovoltaic devices and that the highest molecular weight PEI interlayer provides the highest temporal stability.

Ultraviolet-B radiation mobilizes uranium from uranium-dissolved organic carbon complexes in aquatic systems, demonstrated by asymmetrical flow field-flow fractionation.

PubMed

Nehete, Sachin Vilas; Christensen, Terje; Salbu, Brit; Teien, Hans-Christian

2017-05-05

Humic substances have a tendency to form complexes with metal ions in aquatic medium, impacting the metal mobility, decreasing bioavailability and toxicity. Ultraviolet-B (UV-B) radiation exposure degrades the humic substance, changes their molecular weight distribution and their metal binding capacity in aquatic medium. In this study, we experimented the effect of UV-B radiation on the uranium complexed with fulvic acids and humic acids in a soft water system at different pH, uranium concentrations and radiant exposure. The concentration and distribution of uranium in a complexed form were investigated by asymmetrical flow field-flow fractionation coupled to multi detection technique (AsFlFFF-UV-ICP-MS). The major concentration of uranium present in complexes was primarily associated with average and higher molecular weight fulvic and humic acids components. The concentration of uranium in a complexed form increased with increasing fulvic and humic acid concentrations as well as pH of the solution. The higher molecular weight fraction of uranium was degraded due to the UV-B exposure, transforming about 50% of the uranium-dissolved organic carbon complexes into low molecular weight uranium species in complex form with organic ligands and/or free form. The result also suggests AsFlFFF-UV-ICP-MS to be an important separation and detection technique for understanding the interaction of radionuclides with dissolved organic matter, tracking size distribution changes during degradation of organic complexes for understanding mobility, bioavailability and ecosystem transfer of radionuclides as well as metals. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Action of polysaccharides of similar average mass but differing molecular volume and charge on fluid drainage through synovial interstitium in rabbit knees

PubMed Central

Scott, D; Coleman, P J; Mason, R M; Levick, J R

2000-01-01

Hyaluronan (HA), an anionic polysaccharide of synovial fluid, attenuates fluid loss from joints as joint pressure is raised (‘outflow buffering’). The buffering is thought to depend on the expanded molecular domain of the polymer, which causes reflection by synovial extracellular matrix, leading to flow-dependent concentration polarization. We therefore assessed the effects of polysaccharides of differing average molecular volume and charge. Trans-synovial fluid drainage(Q̇s) was measured at controlled joint fluid pressure (Pj) in knees of anaesthetized rabbits. The joints were infused with polydisperse HA of weight-average mass 2100 kDa (4 mg ml−1, n = 17), with polydisperse neutral dextran of similar average mass (2000 kDa; n = 7) or with Ringer solution vehicle (n = 2). The role of polymer charge was assessed by infusions of neutral or sulphated dextran of average molecular mass 500 kDa (n = 6). When HA was present, Q̇s increased little with pressure, forming a virtual plateau of ∼4 μl min−1 from 10 to 25 cmH2O. Neutral dextran 2000 failed to replicate this effect. Instead, Q̇s increased steeply with Pj, reaching eight times the HA value by 20 cmH2O (P = 0.0001, ANOVA). Dextran 2000 reduced flows in comparison with Ringer solution. Analysis of the aspirated joint fluid showed that 31 ± 0.07 % (s.e.m.) of dextran 2000 in the filtrand was reflected by synovium, compared with ≥ 79 % for HA. The viscometric molecular radius of the dextran, ∼31 nm, was smaller than that of HA (101–181 nm), as was its osmotic pressure. Anionic dextran 500 failed to buffer fluid drainage, but it reduced fluid escape and synovial conductance dQ̇s/dPj more than neutral dextran 500 (P < 0.0001, ANOVA). The anionic charge increased the molecular volume and viscosity of dextran 500. The results support the hypothesis that polymer molecular volume influences its reflection by interstitial matrix and outflow buffering. Polymer charge influences flow through an effect on viscosity and possibly electrostatic interactions with negatively charged interstitial matrix. PMID:11060134

PETROLEUM RESIDUA SOLUBILITY PARAMETER/POLARITY MAP: STABILITY STUDIES OF RESIDUA PYROLYSIS

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

John F. Schabron; A. Troy Pauli; Joseph F. Rovani, Jr.

1999-04-30

A new molecular weight/polarity map based on the Scatchard-Hildebrand solubility equation has been developed for petroleum residua. A series of extractions are performed with solvents of increasing solubility parameter, and the fractions are analyzed by vapor pressure osmometry for number average molecular weight and by analytical-scale size exclusion chromatography for molecular weight spread. Work was performed for a heavy oil material subjected to three increasing severities of thermal treatment prior to and through the onset of coke formation. The results are diagnostic of the layers of solvations by resin-type molecules around a central asphaltene core. Two additional stability diagnostic methodsmore » were also used. These were the Heithaus titration ''P-index'' and Gaestel ''G'' index, which have been applied to paving asphalts for decades. The Heithaus titration involves the titration of three toluene solutions of a residuum at three concentrations with a poor solvent, such as isooctane, to the point of asphaltene flocculation. In the present work, the significance of the data are developed in terms of the Hildebrand solubility parameter. The Heithaus results are combined with data from the new molecular weight/polarity map. The solubility parameters for the toluene-soluble asphaltene components are measured, and the solubility parameters of the maltenes can be calculated. As thermal treatment progresses, the solubility parameters of asphaltene materials increase and the molecular weights decrease. A new coking index is proposed based on Heithaus titration data. Preliminary results suggest that an alternative, simpler coking index may be developed by measuring the weight percent of cyclohexane solubles in heptane asphaltenes. Coking onset appears to coincide with the depletion of these resin-type asphaltene solubilizing components of residua. The objective of the present study was to develop a mapping tool that will enhance understanding of the changes that occur in residua during upgrading and support the industry-sponsored work in which Western Research Institute is engaged. WRI performs proprietary industry-sponsored residua and heavy oil upgrading process development and optimization research. The new mapping tool can be used for evaluating heavy oils and residua in both upstream and downstream operations.« less

Functionalized polycarbonate derived from tartaric acid: enzymatic ring-opening polymerization of a seven-membered cyclic carbonate.

PubMed

Wu, Ruizhi; Al-Azemi, Talal F; Bisht, Kirpal S

2008-10-01

Enantiomerically pure functional polycarbonate was synthesized from a novel seven-membered cyclic carbonate monomer derived from naturally occurring L-tartaric acid. The monomer was synthesized in three steps and screened for polymerization with four commercially available lipases from different sources at 80 degrees C, in bulk. The ring-opening polymerization (ROP) was affected by the source of the enzyme; the highest number-average molecular weight, M(n) = 15500 g/mol (PDI = 1.7; [alpha]D(20) = +77.8, T(m) = 58.8 degrees C) optically active polycarbonate was obtained with lipase Novozyme-435. The relationship between monomer conversion, reaction time, molecular weight, and molecular weight distribution were investigated for Novozyme-435 catalyzed ROP. Deprotection of the ketal groups was achieved with minimal polymer chain cleavage (M(n) = 10000 g/mol, PDI = 2.0) and resulted in optically pure polycarbonate ([alpha]D(20) = +56) bearing hydroxy functional groups. Deprotected poly(ITC) shows T(m) of 60.2 degrees C and DeltaH(f) = 69.56 J/g and similar to that of the poly(ITC), a glass transition temperature was not found. The availability of the pendant hydroxyl group is expected to enhance the biodegradability of the polymer and serves in a variety of potential biomedical applications such as polymeric drug delivery systems.

Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Li, Hui; ...

2015-01-14

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Low-molecular-weight hydroxyacids in marine atmospheric aerosol: evidence of a marine microbial origin

NASA Astrophysics Data System (ADS)

Miyazaki, Y.; Sawano, M.; Kawamura, K.

2014-08-01

Lactic acid (LA) and glycolic acid (GA), which are low-molecular-weight hydroxyacids, were identified in the particle and gas phases within the marine atmospheric boundary layer over the western subarctic North Pacific. A major portion of LA (81%) and GA (57%) was present in the particulate phase, which is consistent with the presence of a hydroxyl group in these molecules leading to the low volatility of the compounds. The average concentration (±SD) of LA in more biologically influenced marine aerosols (33 ± 58 ng m-3) was substantially higher than that in less biologically influenced aerosols (11 ± 12 ng m-3). Over the oceanic region of phytoplankton blooms, the concentration of aerosol LA was comparable to that of oxalic acid, which was the most abundant diacid during the study period. A positive correlation was found between the LA concentrations in more biologically influenced aerosols and chlorophyll a in seawater (r2 = 0.56), suggesting an important production of aerosol LA possibly associated with microbial (e.g., lactobacillus) activity in seawater and/or aerosols. Our finding provides a new insight into the poorly quantified microbial sources of marine organic aerosols (OAs) because such low-molecular-weight hydroxyacids are key intermediates for OA formation.

Microtubule protein ADP-ribosylation in vitro leads to assembly inhibition and rapid depolymerization

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

Scaife, R.M.; Wilson, L.; Purich, D.L.

1992-01-14

Bovine brain microtubule protein, containing both tubulin and microtubule-associated proteins, undergoes ADP-ribosylation in the presence of ({sup 14}C)NAD{sup +} and a turkey erythrocyte mono-ADP-ribosyltransferase in vitro. The modification reaction could be demonstrated in crude brain tissue extracts where selective ADP-ribosylation of both the {alpha} and {beta} chains of tubulin and of the high molecular weight microtubule-associated protein MAP-2 occurred. In experiments with purified microtubule protein, tubulin dimer, the high molecular weight microtubule-associated protein MAP-2, and another high molecular weight microtubule-associated protein which may be a MAP-1 species were heavily labeled. Tubulin and MAP-2 incorporated ({sup 14}C)ADP-ribose to an average extentmore » of approximately 2.4 and 30 mol of ADP-ribose/mol of protein, respectively. Assembly of microtubule protein into microtubules in vitro was inhibited by ADP-ribosylation, and incubation of assembled steady-state microtubules with ADP-ribosyltransferase and NAD{sup +} resulted in rapid depolymerization of the microtubules. Thus, the eukaryotic enzyme can ADP-ribosylate tubulin and microtubule-associated proteins to much greater extents than previously observed with cholera and pertussis toxins, and the modification can significantly modulate microtubule assembly and disassembly.« less

Inhibitory effect of konjac glucomanan on pitting corrosion of AA5052 aluminium alloy in NaCl solution.

PubMed

Zhang, Kegui; Yang, Wenzhong; Xu, Bin; Chen, Yun; Yin, Xiaoshuang; Liu, Ying; Zuo, Huanzhen

2018-05-01

A natural carbohydrate polymer, konjac glucomanan, has been extracted from commercial product and studied as a green corrosion inhibitor for AA5052 aluminium alloy in 3.5 wt% NaCl solution by high-performance gel permeation chromatography (GPC), thermo gravimetric analysis (TGA), Fourier-transform infrared (FT-IR) spectra, electrochemical measurement and surface characterization techniques. The results of GPC measurements suggest the weight-average molecular weight and the number-average molecular weight of KGM with 98.2% purity are 1.61 × 10 5  g/mol and 1.54 × 10 5  g/mol, respectively. Potentiodynamic polarization curves show konjac glucomanan behaves as a mixed-type inhibitor with dominant anodic effect and that its maximum efficiency at 200 ppm is 94%. Electrochemical impedance spectroscopy (EIS) studies reveal the resistance of oxide film is approximately two orders of magnitude greater than the resistance of adsorbed inhibitor layer and that they both increase with KGM concentration. Moreover, in-situ electrochemical noise (EN) detection demonstrates that the growth and propagation stages of the pitting corrosion germinating on metal surface are blocked by polysaccharide additive, which is confirmed by the surface analysis of aluminium alloy using scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and Raman spectroscopy. At last, it is found that the addition of KGM makes it harder for water droplet containing NaCl to wet the metallic substrate. Copyright © 2018 Elsevier Inc. All rights reserved.

Morphology, directed self-assembly and pattern transfer from a high molecular weight polystyrene-block-poly(dimethylsiloxane) block copolymer film

NASA Astrophysics Data System (ADS)

Cheng, Li-Chen; Bai, Wubin; Fernandez Martin, Eduardo; Tu, Kun-Hua; Ntetsikas, Konstantinos; Liontos, George; Avgeropoulos, Apostolos; Ross, C. A.

2017-04-01

The self-assembly of block copolymers with large feature sizes is inherently challenging as the large kinetic barrier arising from chain entanglement of high molecular weight (MW) polymers limits the extent over which long-range ordered microdomains can be achieved. Here, we illustrate the evolution of thin film morphology from a diblock copolymer of polystyrene-block-poly(dimethylsiloxane) exhibiting total number average MW of 123 kg mol-1, and demonstrate the formation of layers of well-ordered cylindrical microdomains under appropriate conditions of binary solvent mix ratio, commensurate film thickness, and solvent vapor annealing time. Directed self-assembly of the block copolymer within lithographically patterned trenches occurs with alignment of cylinders parallel to the sidewalls. Fabrication of ordered cobalt nanowire arrays by pattern transfer was also implemented, and their magnetic properties and domain wall behavior were characterized.

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.

Organosiloxane working fluids for the liquid droplet radiator

NASA Technical Reports Server (NTRS)

Buch, R. R.; Huntress, A. R.

1985-01-01

Siloxane-based working fluids for advanced space radiators requiring direct fluid exposure to the space environment are evaluated. Isolation of five candidate fluids by vacuum distillation from existing siloxane polymers is discussed. The five fluids recovered include a polydimethylsiloxane, three phenyl-containing siloxanes, and a methylhexylsiloxane. Vapor pressures and viscosities for the five fluids are reported over the temperature range of 250 to 400 K. Use of thermal-gravimetric analysis to reliably estimate vapor pressures of 10 to the -8 power Pascals is described. Polydimethylsiloxane (PDMS) and polymethylphenylsiloxane (PMPS) are selected from the five candidate fluids based on favorable vapor pressure and viscosity, as well as perceived stability in low-Earth orbit environments. Characterization of these fluids by infrared spectroscopy, Si-29 NMR, gel-permeation chromatography, and liquid chromatography is presented. Both fluids consist of narrow molecular weight distributions, with average molecular weights of about 2500 for PDMS and 1300 for PMPS.

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.

Nature of alpha and beta particles in glycogen using molecular size distributions.

PubMed

Sullivan, Mitchell A; Vilaplana, Francisco; Cave, Richard A; Stapleton, David; Gray-Weale, Angus A; Gilbert, Robert G

2010-04-12

Glycogen is a randomly hyperbranched glucose polymer. Complex branched polymers have two structural levels: individual branches and the way these branches are linked. Liver glycogen has a third level: supramolecular clusters of beta particles which form larger clusters of alpha particles. Size distributions of native glycogen were characterized using size exclusion chromatography (SEC) to find the number and weight distributions and the size dependences of the number- and weight-average masses. These were fitted to two distinct randomly joined reference structures, constructed by random attachment of individual branches and as random aggregates of beta particles. The z-average size of the alpha particles in dimethylsulfoxide does not change significantly with high concentrations of LiBr, a solvent system that would disrupt hydrogen bonding. These data reveal that the beta particles are covalently bonded to form alpha particles through a hitherto unsuspected enzyme process, operative in the liver on particles above a certain size range.

Extraction and physicochemical characterization of broiler (Gallus gallus domesticus) skin gelatin compared to commercial bovine gelatin.

PubMed

Aykin-Dinçer, E; Koç, A; Erbas, M

2017-09-01

Gelatin was extracted from broiler (Gallus gallus domesticus) skins and analyzed to compare its physicochemical properties with those of commercial bovine gelatin. The average yield of broiler skin gelatin was 6.5% on a wet weight basis. Broiler skin gelatin had more α1-and α2-chains than β-chain and contained high molecular weight (γ-chain) polymers. Glycine was the dominant amino acid in broiler skin gelatin (20.26%), followed by proline (Pro) (15.12%) then hydroxyproline (Hyp) (11.36%). Compared to commercial bovine gelatin, broiler skin gelatin had less total imino acids (Pro and Hyp) but a higher (33.65 vs. 31.38°C) melting temperature (P < 0.01). The differences in physical properties between the broiler and commercial bovine gelatins appeared to be associated with differences in their amino acid composition and molecular weight distribution. The sensory evaluation results revealed that broiler skin gelatin could be a potential alternative to commercial bovine gelatin, useful in various food products. © 2017 Poultry Science Association Inc.

Synchrotron-based X-ray Fluorescence Microscopy in Conjunction with Nanoindentation to Study Molecular-Scale Interactions of Phenol-Formaldehyde in Wood Cell Walls

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

Jakes, Joseph E.; Hunt, Chris G.; Yelle, Daniel J.

Understanding and controlling molecular-scale interactions between adhesives and wood polymers are critical to accelerate the development of improved adhesives for advanced wood-based materials. The submicrometer resolution of synchrotron-based X-ray fluorescence microscopy (XFM) was found capable of mapping and quantifying infiltration of Br-labeled phenolformaldehyde (BrPF) into wood cell walls. Cell wall infiltration of five BrPF adhesives with different average molecular weights (MWs) was mapped. Nanoindentation on the same cell walls was performed to assess the effects of BrPF infiltration on cell wall hygromechanical properties. For the same amount of weight uptake, lower MW BrPF adhesives were found to be more effectivemore » at decreasing moisture-induced mechanical softening. This greater effectiveness of lower MW phenolic adhesives likely resulted from their ability to more intimately associate with water sorption sites in the wood polymers. Evidence also suggests that a BrPF interpenetrating polymer network (IPN) formed within the wood polymers, which might also decrease moisture sorption by mechanically restraining wood polymers during swelling.« less

Characterization of a Chitosanase from Jelly Fig (Ficus awkeotsang Makino) Latex and Its Application in the Production of Water-Soluble Low Molecular Weight Chitosans.

PubMed

Chang, Chen-Tien; Lin, Yen-Lu; Lu, Shu-Wei; Huang, Chun-Wei; Wang, Yu-Ting; Chung, Yun-Chin

2016-01-01

A chitosanase was purified from jelly fig latex by ammonium sulfate fractionation (50-80% saturation) and three successive column chromatography steps. The purified enzyme was almost homogeneous, as determined by SDS-polyacrylamide gel electrophoresis (SDS-PAGE) and gel activity staining. The molecular mass of the enzyme was 20.5 kDa. The isoelectric point (pI) was <3.5, as estimated by isoelectric focusing electrophoresis on PhastGel IEF 3-9. Using chitosan as the substrate, the optimal pH for the enzyme reaction was 4.5; the kinetic parameters Km and Vmax were 0.089 mg mL-1 and 0.69 μmol min-1 mg-1, respectively. The enzyme showed activity toward chitosan polymers which exhibited various degrees of deacetylation (21-94%). The enzyme hydrolyzed 70-84% deacetylated chitosan polymers most effectively. Substrate specificity analysis indicated that the enzyme catalyzed the hydrolysis of chitin and chitosan polymers and their derivatives. The products of the hydrolysis of chitosan polymer derivatives, ethylene glycol (EG) chitosan, carboxymethyl (CM) chitosan and aminoethyl (AE) chitosan, were low molecular weight chitosans (LMWCs); these products were referred to as EG-LMWC, CM-LMWC and AE-LMWC, respectively. The average molecular weights of EG-LMWC, CM-LMWC and AE-LMWC were 11.2, 11.2 and 8.89 kDa, respectively. All of the LMWC products exhibited free radical scavenging activities toward ABTS•+, superoxide and peroxyl radicals.

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.)

21 CFR 173.315 - Chemicals used in washing or to assist in the peeling of fruits and vegetables.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Chemicals used in washing or to assist in the... alkyl alcohols consisting of: α-alkyl (C12-C18)-omega-hydroxy-poly (oxyethylene) (7.5-8.5 moles)/poly (oxypropylene) block copolymer having an average molecular weight of 810; α-alkyl (C12-C18)-omega-hydroxy-poly...

21 CFR 173.315 - Chemicals used in washing or to assist in the peeling of fruits and vegetables.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Chemicals used in washing or to assist in the... alkyl alcohols consisting of: α-alkyl (C12-C18)-omega-hydroxy-poly (oxyethylene) (7.5-8.5 moles)/poly (oxypropylene) block copolymer having an average molecular weight of 810; α-alkyl (C12-C18)-omega-hydroxy-poly...

21 CFR 173.315 - Chemicals used in washing or to assist in the peeling of fruits and vegetables.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Chemicals used in washing or to assist in the... alkyl alcohols consisting of: α-alkyl (C12-C18)-omega-hydroxy-poly (oxyethylene) (7.5-8.5 moles)/poly (oxypropylene) block copolymer having an average molecular weight of 810; α-alkyl (C12-C18)-omega-hydroxy-poly...

21 CFR 173.315 - Chemicals used in washing or to assist in the peeling of fruits and vegetables.

Code of Federal Regulations, 2014 CFR

2014-04-01

... (C12-C18)-omega-hydroxy-poly (oxyethylene) (7.5-8.5 moles)/poly (oxypropylene) block copolymer having an average molecular weight of 810; α-alkyl (C12-C18)-omega-hydroxy-poly (oxyethylene) (3.3-3.7 moles... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Chemicals used in washing or to assist in the...

21 CFR 173.315 - Chemicals used in washing or to assist in the peeling of fruits and vegetables.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Chemicals used in washing or to assist in the... alkyl alcohols consisting of: α-alkyl (C12-C18)-omega-hydroxy-poly (oxyethylene) (7.5-8.5 moles)/poly (oxypropylene) block copolymer having an average molecular weight of 810; α-alkyl (C12-C18)-omega-hydroxy-poly...

Sedimentation, viscosity and partial specific volumes of membrane proteins and lipoproteins

PubMed Central

Brown, A. D.; Netschey, A.

1967-01-01

1. Lipoproteins or defatted proteins from the membrane of Halobacterium halobium were dissolved in 0·02m-phosphate buffer, pH7·4, with or without urea (8m). Physicochemical measurements were made on these solutions with and without addition of sodium chloride. 2. In the presence of 8m-urea the lipoproteins could be resolved into two sedimenting groups. The faster group had an average apparent molecular weight of 390 000; sedimentation coefficients of the slower group could not be determined. 3. Proteins that had been defatted by extraction with a chloroform–methanol mixture could also be resolved into two groups distinguished by their sedimentation velocities. Sedimentation coefficients of both groups were readily determined. The average apparent molecular weight of the faster group of defatted proteins in 8m-urea was 340 000 and that of the slower group was 97 000. It is concluded that attachment of lipid does not affect the state of aggregation of the proteins in 8m-urea. 4. Intrinsic viscosities of lipoproteins and defatted proteins were higher than is customary for globular proteins and suggest expanded highly-solvated molecules, consistent with the `denaturing' action on the proteins of solutions of low ionic strength. ImagesFig. 1. PMID:6033765

Purification and characterization of two polyhydroxyalcanoates from Bacillus cereus.

PubMed

Zribi-Maaloul, Emna; Trabelsi, Imen; Elleuch, Lobna; Chouayekh, Hichem; Ben Salah, Riadh

2013-10-01

This work aimed to study the potential of 155 strains of Bacillus sp., isolated from a collection of Tunisian microorganisms, for polyhydroxyalcanoates production. The strains were submitted to a battery of standard tests commonly used for determining bioplastic properties. The findings revealed that two of the isolates, namely Bacillus US 163 and US 177, provided red excitations at a wavelength of approximately 543 nm. The polyhydroxyalcanoates produced by the two strains were purified. Gas chromatography-mass spectroscopy (GC-MS), Fourier transformed infrared spectroscopy (FTIR), and gel permeation chromatography (GPC) were used to characterize the two biopolymers. Bacillus US 163 was noted to produce a poly methyl-3-hydroxy tetradecanoic acid (P-3HTD) with an average molecular weight of 455 kDa, a completely amorphous homopolymer without crystallinity. The US 177 strain produced a homopolymer of methyl-3-hydroxy octadecanoic acid (P3-HOD) with an average molecular weight of 555 kDa. Exhibiting the highest performance, US 163 and US 177 were submitted to 16S rRNA gene sequencing, and the results revealed that they belonged to the Bacillus cereus species. Overall, the findings indicated that the Bacilli from petroleum soil have a number of promising properties that make them promising candidates for bioplastic production. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Fractionation of Organosolv Lignin Using Acetone:Water and Properties of the Obtained Fractions

DOE PAGES

Sadeghifar, Hasan; Wells, Tyrone; Le, Rosemary Khuu; ...

2016-11-07

In this study, lignin fractions with different molecular weight were prepared using a simple and almost green method from switchgrass and pine organosolv lignin. Different proportions of acetone in water, ranging from 30 to 60%, were used for lignin fractionation. A higher concentration of acetone dissolved higher molecular weight fractions of the lignin. Fractionated organosolv lignin showed different molecular weight and functional groups. Higher molecular weight fractions exhibited more aliphatic and less phenolic OH than lower molecular weight fractions. Lower molecular weight fractions lead to more homogeneous structure compared to samples with a higher molecular weight. In conclusion, all fractionsmore » showed strong antioxidant activity.« less

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.

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.

Aqueous self-assembly of poly(ethylene oxide)-block-poly(ε-caprolactone) (PEO-b-PCL) copolymers: disparate diblock copolymer compositions give rise to nano- and meso-scale bilayered vesicles

NASA Astrophysics Data System (ADS)

Qi, Wei; Ghoroghchian, P. Peter; Li, Guizhi; Hammer, Daniel A.; Therien, Michael J.

2013-10-01

Nanoparticles formed from diblock copolymers of FDA approved PEO and PCL have generated considerable interest as in vivo drug delivery vehicles. Herein, we report the synthesis of the most extensive family PEO-b-PCL copolymers that vary over the largest range of number-average molecular weights (Mn: 3.6-57k), PEO weight fractions (fPEO: 0.08-0.33), and PEO chain lengths (0.75-5.8k) reported to date. These polymers were synthesized in order to establish the full range of aqueous phase behaviours of these diblock copolymers and to specifically identify formulations that were able to generate bilayered vesicles (polymersomes). Cryogenic transmission electron microscopy (cryo-TEM) was utilized in order to visualize the morphology of these structures upon aqueous self-assembly of dry polymer films. Nanoscale polymersomes were formed from PEO-b-PCL copolymers over a wide range of PEO weight fractions (fPEO: 0.14-0.27) and PEO molecular weights (0.75-3.8k) after extrusion of aqueous suspensions. Comparative morphology diagrams, which describe the nature of self-assembled structures as a function of diblock copolymer molecular weight and PEO weight fraction, show that in contrast to micron-scale polymersomes, which form only from a limited range of PEO-b-PCL diblock copolymer compositions, a multiplicity of PEO-b-PCL diblock copolymer compositions are able to give rise to nanoscale vesicles. These data underscore that PEO-b-PCL compositions that spontaneously form micron-sized polymersomes, as well as those that have previously been reported to form polymersomes via a cosolvent fabrication system, provide only limited insights into the distribution of PEO-b-PCL diblocks that give rise to nanoscale vesicles. The broad range of polymersome-forming PEO-b-PCL compositions described herein suggest the ability to construct extensive families of nanoscale vesicles of varied bilayer thickness, providing the ability to tune the timescales of vesicle degradation and encapsulant release based on the intended in vivo application.Nanoparticles formed from diblock copolymers of FDA approved PEO and PCL have generated considerable interest as in vivo drug delivery vehicles. Herein, we report the synthesis of the most extensive family PEO-b-PCL copolymers that vary over the largest range of number-average molecular weights (Mn: 3.6-57k), PEO weight fractions (fPEO: 0.08-0.33), and PEO chain lengths (0.75-5.8k) reported to date. These polymers were synthesized in order to establish the full range of aqueous phase behaviours of these diblock copolymers and to specifically identify formulations that were able to generate bilayered vesicles (polymersomes). Cryogenic transmission electron microscopy (cryo-TEM) was utilized in order to visualize the morphology of these structures upon aqueous self-assembly of dry polymer films. Nanoscale polymersomes were formed from PEO-b-PCL copolymers over a wide range of PEO weight fractions (fPEO: 0.14-0.27) and PEO molecular weights (0.75-3.8k) after extrusion of aqueous suspensions. Comparative morphology diagrams, which describe the nature of self-assembled structures as a function of diblock copolymer molecular weight and PEO weight fraction, show that in contrast to micron-scale polymersomes, which form only from a limited range of PEO-b-PCL diblock copolymer compositions, a multiplicity of PEO-b-PCL diblock copolymer compositions are able to give rise to nanoscale vesicles. These data underscore that PEO-b-PCL compositions that spontaneously form micron-sized polymersomes, as well as those that have previously been reported to form polymersomes via a cosolvent fabrication system, provide only limited insights into the distribution of PEO-b-PCL diblocks that give rise to nanoscale vesicles. The broad range of polymersome-forming PEO-b-PCL compositions described herein suggest the ability to construct extensive families of nanoscale vesicles of varied bilayer thickness, providing the ability to tune the timescales of vesicle degradation and encapsulant release based on the intended in vivo application. Electronic supplementary information (ESI) available: Materials and methods, characterization data. See DOI: 10.1039/c3nr03250g

Storm impacts upon the composition of organic matrices in Nagara River--a study based on molecular weight and activated carbon adsorbability.

PubMed

Li, Fusheng; Yuasa, Akira; Chiharada, Hajime; Matsui, Yoshihiko

2003-09-01

The impacts of a heavy storm of rain on the composition of natural organic matter (NOM) in Nagara River water were studied in terms of molecular weights (MWs) and activated carbon (AC) adsorbabilities using six water samples collected during a critical Typhoon weather condition. The composition in MWs was analyzed using a HPSEC system and that in adsorbabilities was characterized using parameters devised to reflect NOMs average adsorptive strength (K(M)), adsorptive strength polydispersity (sigma), affinity to AC (1/n) and non-adsorbable fraction (C(non)/C(T0)), respectively. These parameters were determined by model description of observed isotherms with a distributed fictive component method. The heavy storm of rain brought higher content of larger organic components into the river source, thus causing changes of NOMs weight-averaged MWs in the range of 2962-3495 Dalton and MW polydispersity in the narrow range of 1.153-1.226. Comparison of K(M) and sigma values for all samples assessed with both indices of TOC and UV260 showed that large proportions of the storm-induced organic components had adsorptive strengths similar to those existent before the storm, with the presence levels for components revealing much strong and weak adsorbabilities being low. Among all organic components brought into the river by the storm of rain, the percentages of non-adsorbable ones was lower (smaller C(non)/C(T0) values); and the adsorbable ones had generally more affinity to the adsorbents used (smaller 1/n values).

Synthesis, characterization, conductivity and antimicrobial study of a novel thermally stable polyphenol containing azomethine group

NASA Astrophysics Data System (ADS)

Yılmaz Baran, Nuray; Karakışla, Meral; Demir, Hacı Ökkeş; Saçak, Mehmet

2016-11-01

Poly(4-[[(4-methylphenyl)methylene]amino]phenol) (P(4-MMAP)), which is a Schiff base polymer, was synthesized by an oxidative polycondensation reaction of 4-[[(4-methylphenyl)methylene]amino]phenol (4-MMAP) with the oxidants NaOCl, H2O2 and O2 in an aqueous alkaline medium. The polymerizations were carried out at various temperatures and times, and the highest polymer yield could be obtained when using 37% with NaOCl oxidant. The structures of the monomer and polymer were characterized by UV-Vis, FTIR 1H NMR and X-ray diffraction techniques. The thermal behaviors of the monomer and polymer were identified by the TG and DTG techniques. The thermal degradation of the polymer which was observed thermally stable up to 1000 °C, was also supported by the Thermo-IR spectra recorded in the temperature range of 25-800 °C. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (PDI) of the polymer were found to be 16682, 57796 g/mol and 3.4, respectively. The highest electrical conductivity value of P(4-MMAP) doped with iodine vapor at different temperatures and times was measured to be 7.8 × 10-5 Scm-1 after doping for 48 h at 60 °C. The antibacterial and antifungal activities of 4-MMAP and P(4-MMAP) were also assayed against the bacteria Sarcina lutea, Enterobacter aerogenes, Escherichia coli, Enterococcus faecalis, Klebsiella pneumoniae, Bacillus subtilis and the fungi Candida albicans, Saccharomyces cerevisiae, respectively.

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.

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.

'Ogura'-based 'CMS' lines with different nuclear backgrounds of cabbage revealed substantial diversity at morphological and molecular levels.

PubMed

Parkash, Chander; Kumar, Sandeep; Singh, Rajender; Kumar, Ajay; Kumar, Satish; Dey, Shyam Sundar; Bhatia, Reeta; Kumar, Raj

2018-01-01

A comprehensive study on characterization and genetic diversity analysis was carried out in 16 'Ogura'-based 'CMS' lines of cabbage using 14 agro-morphological traits and 29 SSR markers. Agro-morphological characterization depicted considerable variations for different horticultural traits studied. The genotype, ZHA-2, performed better for most of the economically important quantitative traits. Further, gross head weight (0.76), head length (0.60) and head width (0.83) revealed significant positive correlation with net head weight. Dendrogram based on 10 quantitative traits exhibited considerable diversity among different CMS lines and principle component analysis (PCA) indicated that net and gross head weight, and head length and width are the main components of divergence between 16 CMS lines of cabbage. In molecular study, a total of 58 alleles were amplified by 29 SSR primers, averaging to 2.0 alleles in each locus. High mean values of Shannon's Information index (0.62), expected (0.45) and observed (0.32) heterozygosity and polymorphic information content (0.35) depicted substantial polymorphism. Dendrogram based on Jaccard's similarity coefficient constructed two major groups and eight sub-groups, which revealed substantial diversity among different CMS lines. In overall, based on agro-morphological and molecular studies genotype RRMA, ZHA-2 and RCA were found most divergent. Hence, they have immense potential in future breeding programs for the high-yielding hybrid development in cabbage.

Osmotic effects of polyethylene glycol.

PubMed

Schiller, L R; Emmett, M; Santa Ana, C A; Fordtran, J S

1988-04-01

Polyethylene glycol (PEG) has been used to increase the osmotic pressure of fluids used to cleanse the gastrointestinal tract. However, little is known about its osmotic activity. To investigate this activity systematically, solutions of PEG of differing molecular weights were made and subjected to measurement of osmolality by both freezing point depression and vapor pressure osmometry. Measured osmolality was increasingly greater than predicted from average molecular weight as PEG concentration increased. Measurement of sodium activity in NaCl/PEG solutions by means of an ion-selective electrode suggested that the higher than expected osmolality could be due in part to interactions that, in effect, sequestered water from the solution. Osmolality was consistently greater by freezing point osmometry than by vapor pressure osmometry. To determine which osmometry method reflected biologically relevant osmolality, normal subjects underwent steady-state total gut perfusion with an electrolyte solution containing 105 g/L of PEG 3350. This produced rectal effluent that was hypertonic by freezing point osmometry but isotonic by vapor pressure osmometry. Assuming that luminal fluid reaches osmotic equilibrium with plasma during total gut perfusion, this result suggests that the vapor pressure osmometer accurately reflects the biologically relevant osmolality of intestinal contents. We conclude that PEG exerts more of an osmotic effect than would be predicted from its molecular weight. This phenomenon may reflect interactions between PEG and water molecules that alter the physical chemistry of the solution and sequester water from the solution.

Use of molecular modeling to determine the interaction and competition of gases within coal for carbon dioxide sequestration

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

Jeffrey D. Evanseck; Jeffry D. Madura; Jonathan P. Mathews

2006-04-21

Molecular modeling was employed to both visualize and probe our understanding of carbon dioxide sequestration within a bituminous coal. A large-scale (>20,000 atoms) 3D molecular representation of Pocahontas No. 3 coal was generated. This model was constructed based on a the review data of Stock and Muntean, oxidation and decarboxylation data for aromatic clustersize frequency of Stock and Obeng, and the combination of Laser Desorption Mass Spectrometry data with HRTEM, enabled the inclusion of a molecular weight distribution. The model contains 21,931 atoms, with a molecular mass of 174,873 amu, and an average molecular weight of 714 amu, with 201more » structural components. The structure was evaluated based on several characteristics to ensure a reasonable constitution (chemical and physical representation). The helium density of Pocahontas No. 3 coal is 1.34 g/cm{sup 3} (dmmf) and the model was 1.27 g/cm{sup 3}. The structure is microporous, with a pore volume comprising 34% of the volume as expected for a coal of this rank. The representation was used to visualize CO{sub 2}, and CH{sub 4} capacity, and the role of moisture in swelling and CO{sub 2}, and CH{sub 4} capacity reduction. Inclusion of 0.68% moisture by mass (ash-free) enabled the model to swell by 1.2% (volume). Inclusion of CO{sub 2} enabled volumetric swelling of 4%.« less

76 FR 28947 - Bus Testing: Calculation of Average Passenger Weight and Test Vehicle Weight, and Public Meeting...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-19

...-0015] RIN 2132-AB01 Bus Testing: Calculation of Average Passenger Weight and Test Vehicle Weight, and... of proposed rulemaking (NPRM) regarding the calculation of average passenger weights and test vehicle... passenger weights and actual transit vehicle loads. Specifically, FTA proposed to change the average...

New polyarylene ethers

NASA Technical Reports Server (NTRS)

Hergenrother, P. M.; Havens, S. J.; Jensen, B. J.

1986-01-01

A series of new polyarylene ethers (PAEs) were prepared from the reaction of activated dihalo compounds with various bisphenols. Measured number average molecular weights for the PAEs ranged from 13,500 to 39,400 g/mole, and glass transition temperatures varied from 152 to 280 C. Ethynyl-terminated polyarylene ethers (ETPAEs) were also prepared by endcapping hydroxy-terminated polyarylene ethers with 4-ethynylbenzoyl chloride. Structure/property relationships for the PAEs, and the advantages offered by the ETPAEs, are discussed.

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.

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.

THE STIMULATING EFFECT OF GLYCOLS AND THEIR POLYMERS ON THE TARSAL RECEPTORS OF BLOWFLIES

PubMed Central

Dethier, V. G.; Chadwick, L. E.

1948-01-01

The rejection thresholds of Phormia regina Meigen for twenty-four glycols have been determined. A definite relationship between the concentration of the test material and the distribution of thresholds has been noted regularly in samples of flies selected at random from a population of known age which had been reared under standard conditions. The scattering of thresholds is normal with respect to the logarithm of concentration. Recalculation of the data of other workers reveals the same sort of relationship with other species of insects and the minnow Phoxinus. The underlying reason for the phenomenon is not known. The glycols in common with other series of homologous alipbatic compounds are rejected at logarithmically decreasing concentrations as the chain length is increased. In general the straight chain diols are more stimulating than the corresponding polyethylene and polypropylene glycols. This difference is related in some manner to the presence of ether linkages in the latter. Polypropylene glycols, with chains of three carbon atoms between the ether linkages are more stimulating than polyethylene glycols, where the spacing is —O—C—C—O—. Unipolymers are more stimulating than mixtures of homologues with the same average molecular weights. Polyethylene glycol 1540 is the largest molecule of measured molecular weight known to stimulate chemoreceptors. The introduction of a second terminal hydroxyl group into the straight hydrocarbon chain reduces the stimulating effect. Alcohols corresponding to the first three diols average about four times as stimulating as the latter while those corresponding to the higher diols average more than one hundred times as stimulating. PMID:18891141

Conformation and activity alteration of horseradish peroxidase induced by the interaction with gene carrier polyethyleneimines

NASA Astrophysics Data System (ADS)

Huang, Aimin; Wei, Bangzhi; Mo, Junyong; Wang, Yajing; Ma, Lin

2018-01-01

Polyethyleneimine (PEI) has long been considered as "golden standard" for polymeric gene delivery carriers. However the molecular basis of the cytotoxicity of PEI is poorly understood. Little is known about the effects of PEI on the structure and functions of biomacromolecules. In this work, fluorescence, UV-vis absorption, circular dichroism spectroscopy were conducted to investigate the influence of PEI of average molecular weight 25, 10 and 1.8 kDa (denoted as PEI25k, PEI10k and PEI1.8k) on the conformation of horseradish peroxidase (HRP) and its catalytic efficiency. Zeta-potential measurement and isothermal titration calorimetry were used to reveal the mechanism of the interaction between PEIs and HRP. PEIs were found to bind onto the surface of HRP predominantly via hydrophobic interaction and hydrogen bond or van der Waals interaction. The complex formation between HRP and PEI induced a more compact conformation of the enzyme and an increased hydrophobicity of the microenvironment surrounding heme pocket. The conformational change of HRP had little impact on the affinity towards H2O2 and phenol. However, the increase in the non-planarity of porphyrin ring in the heme group led to an increase in the exposure degree of the active center and thus an enhancement of catalytic efficiency of HRP in the presence of high molecular weight PEIs (PEI25k and PEI10k). The polymer size played an important role in PEI-HRP interaction. PEI of low molecular weight (PEI1.8k) was less efficient to alter the conformation and catalytic activity of HRP in aqueous solutions.

Effects of interaction with gene carrier polyethyleneimines on conformation and enzymatic activity of pig heart lactate dehydrogenase.

PubMed

Wang, Fan; Mo, Junyong; Huang, Aimin; Zhang, Min; Ma, Lin

2018-06-15

Polyethyleneimine (PEI) has long been considered as "golden standard" for polymeric gene delivery carrier, however also induces cytotoxicity. To make a further insight into the molecular basis of PEI cytotoxicity, fluorescence, absorption and circular dichroism spectroscopy were conducted to investigate the influence of PEI (average molecular weight 25,000 and 1800 Da) on the conformation of pig heart lactate dehydrogenase (LDH) and its catalytic efficiency. Zeta-potential measurement and isothermal titration calorimetry were used to reveal the interaction between PEI and LDH. PEI was found to bind onto the surface of LDH predominantly via hydrophobic interaction, inducing a more compact conformation and an increased surface hydrophobicity of the enzyme. The conformational change of LDH induced by PEI binding had little influence on the complex formation between LDH and reduced nicotinamide adenine dinucleotide (NADH, the co-enzyme). However, the nonspecific binding of PEI on the surface of LDH retarded the turnover of the enzyme. Meanwhile, the large quantity of amine groups on the polymer chain made PEI subject to form complexes with NADH and pyruvate (the substrate) via hydrogen bond and electrostatic interaction, which greatly reduced the binding efficient of LDH. The polymer size played an important role in PEI-LDH interaction. The smaller size of lower molecular weight PEI facilitated the close contact with LDH and consequential reduction of the turnover number of the enzyme. However, higher molecular weight PEI was more favorable for competitive binding with NADH and pyruvate and generally decreased the catalytic efficient of LDH. Copyright © 2018. Published by Elsevier B.V.

THE MITOTIC APPARATUS

PubMed Central

Stephens, R. E.

1967-01-01

The major 22S protein of the hexylene glycol-isolated mitotic apparatus has been characterized from spindle isolates and extracts of whole eggs and acetone powders of eggs from the sea urchins Strongylocentrotus purpuratus, Strongylocentrotus droebachiensis, and Arbacia punctulata. The protein is free of nucleotide, lipid, and ATPase activity. Essentially identical in amino acid composition, proteins from these species show a relatively high content of glutamic and aspartic acids and are fairly rich in hydrophobic amino acids. Optical rotatory dispersion studies indicate a helical content of about 20%, a value consistent with the proline content of the protein. The purified proteins have sedimentation rates in the range of 22–24S, diffusion constants of 2.4–2.5F, intrinsic viscosities of 3.7–4.3 ml/g, a partial specific volume of 0.74, and an average molecular weight of 880,000. Electron microscopy indicates a globular molecule with dimensions of approximately 150 by 200 A; such size and symmetry are consistent with hydrodynamic measurements. The 22S protein yields 6–7S, 9–10S, and 13–14S subunits below pH 4 or above pH 11. The 13–14S component has an estimated molecular weight of 600,000–700,000. A 5–6S particle is formed in 8 M urea or 5 M guanidine hydrochloride, while at pH 12 the 6–7S subunit is seen; each particle has a molecular weight of 230,000–240,000. In 8 M urea plus 2% mercaptoethanol or at pH 13, the molecular weight becomes 105,000–120,000; under these conditions the particle sediments at 2.5–3S and 4S, respectively. On the basis of these molecular weights, the 6–7S, 9–10S, 13–14S, and the parent 22S particle should be dimer, tetramer, hexamer, and octamer, respectively, of the 105,000–120,000 molecular weight subunit. The various subunits will reform the 22S particle when returned to neutral buffer, with the exception of the mercaptoethanol-treated urea subunit where breakage of disulfide bonds results in a polydisperse aggregate. The 22S particle itself is not susceptible to sulfhydryl reagents, implying either that the disulfide bonds are inaccessible or that they are unnecessary for maintenance of tertiary structure once the 22S particle has formed from subunits. PMID:10976220

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…

Incorporating perylene moiety into poly(phenothiazine-co-bithiophene) backbone for higher charge transport.

PubMed

Tang, Weihua; Ke, Lin; Chen, Zhi-Kuan

2008-03-27

Low band gap pi-conjugated polymers composed of phenothiazine, bithiophene, and perylene moieties were prepared in high yields by using a palladium-catalyzed Suzuki coupling reaction. The polymers were characterized by NMR, gel permeation chromatography, and elemental analysis. The characterizations revealed that high-molecular weight (weight-average molecular weight up to 42,400 g/mol) polymers were thermally stable with a decomposition temperature in the region of 338-354 degrees C and their glass transition temperatures (Tg) ranging from 124 to 136 degrees C. All polymers demonstrated broad optical absorption in the region of 300-550 nm with efficient blue-green light emission. The absorption was broadened further (for ca. 50 nm) when the perylene moiety was incorporated. Cyclic voltammograms displayed that the p- and n-doping processes of all the polymers were partially reversible and that electrochemical band gaps were as low as -2.30 eV with the incorporation of a perylene moiety. The hole mobility of polymers was evaluated by using the space-charge-limited current model with a device structure of ITO/PEDOT:PSS/polymer/Ca. The results show that the incorporation of perylene is beneficial for improving the hole mobility of the conjugated polymers.

Chemistry and structure of coal-derived asphaltenes, Phase III. Quarterly progress report, January--March 1978

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

Yen, T. F.

1978-01-01

The solubility limits of Synthoil and PAMCO asphaltenes have been measured as a function of Hildebrand solubility parameters and hydrogen bonding. Solvents with moderate hydrogen bonding capacity such as dioxane, ethyl benzoate and dibutyl phthalate were found to be most effective in dissolving asphaltenes over the widest range of solubility parameters. VPO molecular weight studies of coal liquid derived carbenes, as a function of concentration in the solvent THF, indicate that these fractions are more strongly self-associated than the corresponding asphaltenes, and generally afford high infinite dilution number average molecular weights: Synthoil, 861; HRI H-Coal, 1156; Cat. Inc. SRC, 1228;more » PAMCO SRC, 1054. The variable ESR temperature dependence of the spin intensity for a Synthoil asphaltene-I/sub 2/ charge transfer followed a 1/T (Curie--Weiss) dependence over the temperature range from 25/sup 0/ to -114/sup 0/C suggesting that independent, non-interacting donor and acceptor doublets were formed. Weight percent OH values, determined from 'H NMR analysis of silylated asphaltenes, were found to provide a reasonably linear correlation with the absorbance of the monomeric OH infrared stretching bands of the asphaltenes.« less

Spontaneously formed high-performance charge-transport layers of organic single-crystal semiconductors on precisely synthesized insulating polymers

NASA Astrophysics Data System (ADS)

Makita, Tatsuyuki; Sasaki, Masayuki; Annaka, Tatsuro; Sasaki, Mari; Matsui, Hiroyuki; Mitsui, Chikahiko; Kumagai, Shohei; Watanabe, Shun; Hayakawa, Teruaki; Okamoto, Toshihiro; Takeya, Jun

2017-04-01

Charge-transporting semiconductor layers with high carrier mobility and low trap-density, desired for high-performance organic transistors, are spontaneously formed as a result of thermodynamic phase separation from a blend of π-conjugated small molecules and precisely synthesized insulating polymers dissolved in an aromatic solvent. A crystal film grows continuously to the size of centimeters, with the critical conditions of temperature, concentrations, and atmosphere. It turns out that the molecular weight of the insulating polymers plays an essential role in stable film growth and interfacial homogeneity at the phase separation boundary. Fabricating the transistor devices directly at the semiconductor-insulator boundaries, we demonstrate that the mixture of 3,11-didecyldinaphtho[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene and poly(methyl methacrylate) with the optimized weight-average molecular weight shows excellent device performances. The spontaneous phase separation with a one-step fabrication process leads to a high mobility up to 10 cm2 V-1 s-1 and a low subthreshold swing of 0.25 V dec-1 even without any surface treatment such as self-assembled monolayer modifications on oxide gate insulators.

Increase in 4-coumaryl alcohol units during lignification in alfalfa (Medicago sativa) alters the extractability and molecular weight of lignin.

PubMed

Ziebell, Angela; Gracom, Kristen; Katahira, Rui; Chen, Fang; Pu, Yunqiao; Ragauskas, Art; Dixon, Richard A; Davis, Mark

2010-12-10

The lignin content of biomass can impact the ease and cost of biomass processing. Lignin reduction through breeding and genetic modification therefore has potential to reduce costs in biomass-processing industries (e.g. pulp and paper, forage, and lignocellulosic ethanol). We investigated compositional changes in two low-lignin alfalfa (Medicago sativa) lines with antisense down-regulation of p-coumarate 3-hydroxylase (C3H) or hydroxycinnamoyl-CoA:shikimate hydroxycinnamoyltransferase (HCT). We investigated whether the difference in reactivity during lignification of 4-coumaryl alcohol (H) monomers versus the naturally dominant sinapyl alcohol and coniferyl alcohol lignin monomers alters the lignin structure. Sequential base extraction readily reduced the H monomer content of the transgenic lines, leaving a residual lignin greatly enriched in H subunits; the extraction profile highlighted the difference between the control and transgenic lines. Gel permeation chromatography of isolated ball-milled lignin indicated significant changes in the weight average molecular weight distribution of the control versus transgenic lines (CTR1a, 6000; C3H4a, 5500; C3H9a, 4000; and HCT30a, 4000).

Weighted south-wide average pulpwood prices

Treesearch

James E. Granskog; Kevin D. Growther

1991-01-01

Weighted average prices provide a more accurate representation of regional pulpwood price trends when production volumes valy widely by state. Unweighted South-wide average delivered prices for pulpwood, as reported by Timber Mart-South, were compared to average annual prices weighted by each state's pulpwood production from 1977 to 1986. Weighted average prices...

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.

Studies on production of fructo-oligosaccharides (FOS) by gamma radiation processing of microbial levan.

PubMed

Jalan, N; Varshney, Lalit; Misra, Nilanjal; Paul, Jhimli; Mitra, D; Rairakhwada, D D; Bhathena, Z; Kumar, Virendra

2013-07-01

Microbial levan, a natural polymer of fructose, was produced and purified by alcohol precipitation from culture supernatants of Bacillus megaterium type 1 grown in an optimized liquid sucrose medium. GPC analysis showed that the yield of the major fraction of levan having molecular weight ~5000 D increased with increase in sucrose concentration in the broth. Levan subjected to (60)Co-gamma radiation as well as acid hydrolysis was investigated by rheometry, UV-visible spectrophotometry and gel permeation chromatography (GPC) techniques. Unlike most of the polysaccharides, levan powder exhibited good radiation degradation stability up to 150 kGy. Gamma irradiation of 10% levan aqueous solution at 250 kGy yielded 63.0% fructo-oligosaccharide (FOS) with an average molecular weight of 1250 D. Acid hydrolysis of levan using 0.5 N HCl for 60 min treatment time gave rise to the desired FOS with lower yield (23.1%) as compared to that obtained in gamma radiolysis process. Copyright © 2013 Elsevier Ltd. All rights reserved.

Preparation and physiological activities of carboxymethylated derivative purified from corn bran

NASA Astrophysics Data System (ADS)

Zhu, Linghui; Fang, Miaoli; Ma, Jianjun; Mo, Qing

2017-06-01

Two water-soluble polysaccharides extracted from corn bran were chemically modified to obtain their carboxymethylated derivatives (C-CBP1, C-CBP2). Theresults of degree of substitution and FT-IR analysis showed the carboxymethylation of polysaccharides were successful. The average molecular weight (Mw) of C-CBP1 and C-CBP2 were 368 and 263kDa, respectively. The degree of substitution (DS) of C-CBP1 and C-CBP2 were determined to be 0.44 and 0.46. The results showed that derivatives were effective in antioxidant and bile acidbinding activityin a dose dependent way. And C-CBP2 had the higher activity for hydroxyl radical, superoxide anion scavenging activities and bile acid capacity, as lower molecular weight plays a critical role in antioxidant activities and bile acid capacity. The results suggest that the carboxymethylated derivatives are potential natural antioxidant and blood fat reduce agent that can be used as drugs or functional food ingredients.

Improved antimelanogenesis and antioxidant effects of polysaccharide from Cuscuta chinensis Lam seeds after enzymatic hydrolysis.

PubMed

Liu, Zi-Jun; Wang, Ya-Lan; Li, Qi-Ling; Yang, Liu

2018-01-01

Cuscuta chinensis polysaccharide (CPS) was extracted using hot water and enzymatically hydrolyzed C. chinensis polysaccharide (ECPS) was produced by the mannase enzymatic hydrolysis process. The purpose of this research was to investigate the antimelanogenic activity of ECPS and CPS in B16F10 melanoma cells. The in vitro antioxidant activity was assessed by their ferric iron reducing power and DPPH free radical scavenging activities. The molecular mass distribution of polysaccharides was determined using SEC-MALLS-RI. CPS was successfully enzymatically degraded using mannase and the weighted average molecular weights of CPS and ECPS were 434.6 kDa and 211.7 kDa. The results of biological activity assays suggested that the enzymatically hydrolyzed polysaccharide had superior antimelanogenic activity and antioxidant effect than the original polysaccharide. ECPS exhibited antimelanogenic activity by down-regulating the expression of tyrosinase, MITF, and TRP-1 without cytotoxic effects in B16F10 melanoma cells. In conclusion, ECPS have the potential to become a skin whitening product.

Photo-enhanced performance and photo-tunable degradation in LC ecopolymers

NASA Astrophysics Data System (ADS)

Kaneko, Tatsuo

2007-05-01

Photosensitive, liquid crystalline (LC) polymers were prepared by in-bulk polymerization of phytomonomers such as cinnamic acid derivatives. The p-coumaric acid (4HCA) homopolymer showed a thermotropic LC phase where a photoreaction of [2+2] cycloaddition occurred by ultraviolet irradiation. LC phase was exhibited only in a low molecular weight state but the polymer was too brittle to materialize. Then we copolymerized 4HCA with multifunctional cinnamate, 3,4 dihydroxycinnamic acid (caffeic acid; DHCA), to prepare the hyperbranching architecture. Many branches increased the apparent size of the polymer chain but kept the low number-average molecular weight. P(4HCA-co-DHCA)s showed high performances which may be attained through the entanglement by in-bulk formation of hyperbranching, rigid structures. P(4HCA-co-DHCA)s showed a smooth hydrolysis, an in-soil degradation and a photoreaction cross-linking from conjugated cinnamate esters to aliphatic esters. The change in photoconversion degree tuned the polymer performance and chain hydrolysis.

Development of Noncytotoxic Chitosan–Gold Nanocomposites as Efficient Antibacterial Materials

PubMed Central

2014-01-01

This work describes the synthesis and characterization of noncytotoxic nanocomposites either colloidal or as films exhibiting high antibacterial activity. The biocompatible and biodegradable polymer chitosan was used as reducing and stabilizing agent for the synthesis of gold nanoparticles embedded in it. Herein, for the first time, three different chitosan grades varying in the average molecular weight and deacetylation degree (DD) were used with an optimized gold precursor concentration. Several factors were analyzed in order to obtain antimicrobial but not cytotoxic nanocomposite materials. Films based on chitosan with medium molecular weight and the highest DD exhibited the highest antibacterial activity against biofilm forming strains of Staphylococcus aureus and Pseudomonas aeruginosa. The resulting nanocomposites did not show any cytotoxicity against mammalian somatic and tumoral cells. They produced a disruptive effect on the bacteria wall while their internalization was hindered on the eukaryotic cells. This selectivity and safety make them potentially applicable as antimicrobial coatings in the biomedical field. PMID:25522372

Non-fouling surfaces produced by gas phase pulsed plasma polymerization of an ultra low molecular weight ethylene oxide containing monomer.

PubMed

Wu; Timmons; Jen; Molock

2000-10-01

The pulsed plasma polymerization of low molecular weight molecules containing only one (ethylene oxide vinyl ether) and two (diethylene oxide vinyl ether) ethylene oxide units were investigated. The surface density of EO units retained in the polymer films increases sharply with decreasing average power input during deposition, particularly at very low plasma duty cycles. The protein adsorption properties of these plasma synthesized polymer were investigated using 125I-labeled albumin and fibrinogen. Surprisingly effective, non-fouling surfaces were observed with films synthesized from the monomer containing two ethylene oxide units; however, the monomer containing only one EO unit gave surfaces that were not particularly effective in preventing protein adsorptions. The results obtained show that ultra short chain length PEO modified surfaces can be biologically non-fouling. This, in turn, has interesting consequences in terms of trying to identify the basic reason for the effectiveness of EO units in preventing biomolecule adsorptions on surfaces.

[NH4+-N removal stability of zeolite media packed multistage-biofilm system for coke-plant wastewater treatment].

PubMed

Zhao, Wen-Tao; Huang, Xia; He, Miao; Zhang, Peng-Yi; Zuo, Chen-Yan

2009-02-15

The practical ammonia stripping effectiveness of coke-plant wastewater treatment may vary widely, and high NH4+-N shock loading will lead to the fluctuation of residual NH4+-N concentration of biological effluent. A zeolite media packed multistage-biofilm system (ZMBS) was used for coke-plant wastewater treatment for enhancing the NH4+-N treatment ability of the bio-system to shock loading, as well as achieving high COD removal efficiency. Treatment performance during steady-state and shock loading and transformation of organic pollutants in the system were investigated systematically. The experiment results indicated that when the system was operated at NH4+-N loading 0.21 kg/(m3 x d) and COD loading < or = 1.35 kg/(m3 x d), the average effluent NH4+-N and COD concentrations were (2.2 +/- 1.2) mg/L, (228 +/- 60) mg/L with average removal efficiencies of (99.1 +/- 0.5)% and (86.0 +/- 2.6)%. During the twice NH4+-N shock loadings [0.03 kg/(m3 x d) and 0.06 kg/(m3 x d)], ZMBS showed a strong resisting ability with average removal efficiencies of 99.0% and 92.9% higher than those of a compared system's 96.8% and 89.3%. By monitoring the change of water quality along the length of the ZMBS's cells, two function zones for different pollutant removal were found to exist, named as decarbonization/nitrification (C/N) zone and nitrification (N) zone, and the NH4+-N removal rate in N zone was 2-8 times as that in C/N zone. TOC concentrations of organic matters with relative molecular weight < 1 x 10(3), 1 x 10(3) to 1 x 10(4), and > 1 x 10(4), were 227.6, 104.8 and 35.0 mg/L in raw wastewater, and 31.2, 22.9 and 31.5 mg/L in the effluent, respectively. Organic matters with relative molecular weight < 1 x 10(3) and 1 x 10(3) to 1 x 10(4) in raw wastewater were removed effectively by ZMBS, but those with relative molecular weight > 1x 10(3) were the main remained substances in the effluent.

Chitin and Cellulose Processing in Low-Temperature Electron Beam Plasma.

PubMed

Vasilieva, Tatiana; Chuhchin, Dmitry; Lopatin, Sergey; Varlamov, Valery; Sigarev, Andrey; Vasiliev, Michael

2017-11-06

Polysaccharide processing by means of low-temperature Electron Beam Plasma (EBP) is a promising alternative to the time-consuming and environmentally hazardous chemical hydrolysis in oligosaccharide production. The present paper considers mechanisms of the EBP-stimulated destruction of crab shell chitin, cellulose sulfate, and microcrystalline cellulose, as well as characterization of the produced oligosaccharides. The polysaccharide powders were treated in oxygen EBP for 1-20 min at 40 °C in a mixing reactor placed in the zone of the EBP generation. The chemical structure and molecular mass of the oligosaccharides were analyzed by size exclusion and the reversed phase chromatography, FTIR-spectroscopy, XRD-, and NMR-techniques. The EBP action on original polysaccharides reduces their crystallinity index and polymerization degree. Water-soluble products with lower molecular weight chitooligosaccharides (weight-average molecular mass, M w = 1000-2000 Da and polydispersity index 2.2) and cellulose oligosaccharides with polymerization degrees 3-10 were obtained. The ¹H-NMR analysis revealed 25-40% deacetylation of the EBP-treated chitin and FTIR-spectroscopy detected an increase of carbonyl- and carboxyl-groups in the oligosaccharides produced. Possible reactions of β-1,4-glycosidic bonds' destruction due to active oxygen species and high-energy electrons are given.

Changes in molecular characteristics of cereal carbohydrates after processing and digestion.

PubMed

Kasprzak, Mirosław Marek; Lærke, Helle Nygaard; Knudsen, Knud Erik Bach

2012-12-10

Different extraction, purification and digestion methods were used to investigate the molecular properties of carbohydrates in arabinoxylan and β-glucan concentrates, dietary fiber (DF) rich breads and ileum content of bread fed pigs. The breads studied were: a low DF wheat bread (WF), whole meal rye bread (GR), rye bread with kernels (RK), wheat bread supplemented with wheat arabinoxylan concentrate (AX) and wheat bread supplemented with oat β-glucan concentrate (BG). The weight average molecular weight (M(w)) of extractable carbohydrates in β-glucan concentrate decreased eight-fold after inclusion in the BG bread when exposed to in vitro digestion, while the M(w) of purified extractable carbohydrates in AX bread was reduced two-fold, and remained almost unaffected until reaching the terminal ileum of pigs. Similarly, the M(w) of purified extractable carbohydrates in GR and RK bread was not significantly changed in the ileum. The AX bread resulted in the highest concentration of dissolved arabinoxylan in the ileum among all the breads that caused a substantial increased in ileal AX viscosity. Nevertheless, for none of the breads, the M(w) of extractable carbohydrates was related neither to the bread extract nor ileal viscosity.

Changes in Molecular Characteristics of Cereal Carbohydrates after Processing and Digestion

PubMed Central

Kasprzak, Mirosław Marek; Lærke, Helle Nygaard; Knudsen, Knud Erik Bach

2012-01-01

Different extraction, purification and digestion methods were used to investigate the molecular properties of carbohydrates in arabinoxylan and β-glucan concentrates, dietary fiber (DF) rich breads and ileum content of bread fed pigs. The breads studied were: a low DF wheat bread (WF), whole meal rye bread (GR), rye bread with kernels (RK), wheat bread supplemented with wheat arabinoxylan concentrate (AX) and wheat bread supplemented with oat β-glucan concentrate (BG). The weight average molecular weight (Mw) of extractable carbohydrates in β-glucan concentrate decreased eight-fold after inclusion in the BG bread when exposed to in vitro digestion, while the Mw of purified extractable carbohydrates in AX bread was reduced two-fold, and remained almost unaffected until reaching the terminal ileum of pigs. Similarly, the Mw of purified extractable carbohydrates in GR and RK bread was not significantly changed in the ileum. The AX bread resulted in the highest concentration of dissolved arabinoxylan in the ileum among all the breads that caused a substantial increased in ileal AX viscosity. Nevertheless, for none of the breads, the Mw of extractable carbohydrates was related neither to the bread extract nor ileal viscosity. PMID:23222731

High performance lignin-acrylonitrile polymer blend materials

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

Naskar, Amit K.; Tran, Chau D.

A polymer blend material comprising: (i) a lignin component having a weight-average molecular weight of up to 1,000,000 g/mol; and (ii) an acrylonitrile-containing copolymer rubber component comprising acrylonitrile units in combination with diene monomer units, and having an acrylonitrile content of at least 20 mol %; wherein said lignin component is present in an amount of at least 5 wt % and up to about 95 wt % by total weight of components (i) and (ii); and said polymer blend material possesses a tensile yield stress of at least 5 MPa, or a tensile stress of at least 5 MPamore » at 10% elongation, or a tensile stress of at least 5 MPa at 100% elongation. Methods for producing the polymer blend, molded forms thereof, and articles thereof, are also described.« less

INFLUENCE OF MASS ON DISPLACEMENT THRESHOLD

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

Setyawan, Wahyu; Selby, A.; Nandipati, Giridhar

2014-12-30

Molecular dynamics simulations are performed to investigate the effect of mass on displacement threshold energy in Cr, Mo, Fe and W. For each interatomic potential, the mass of the atoms is varied among those metals for a total of 16 combinations. The average threshold energy over all crystal directions is calculated within the irreducible crystal directions using appropriate weighting factors. The weighting factors account for the different number of equivalent directions among the grid points and the different solid angle coverage of each grid point. The grid points are constructed with a Miller index increment of 1/24 for a totalmore » of 325 points. For each direction, 10 simulations each with a different primary-knock-on atom are performed. The results show that for each interatomic potential, the average threshold energy is insensitive to the mass; i.e., the values are the same within the standard error. In the future, the effect of mass on high-energy cascades for a given interatomic potential will be investigated.« less

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.

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.

Combining forecast weights: Why and how?

NASA Astrophysics Data System (ADS)

Yin, Yip Chee; Kok-Haur, Ng; Hock-Eam, Lim

2012-09-01

This paper proposes a procedure called forecast weight averaging which is a specific combination of forecast weights obtained from different methods of constructing forecast weights for the purpose of improving the accuracy of pseudo out of sample forecasting. It is found that under certain specified conditions, forecast weight averaging can lower the mean squared forecast error obtained from model averaging. In addition, we show that in a linear and homoskedastic environment, this superior predictive ability of forecast weight averaging holds true irrespective whether the coefficients are tested by t statistic or z statistic provided the significant level is within the 10% range. By theoretical proofs and simulation study, we have shown that model averaging like, variance model averaging, simple model averaging and standard error model averaging, each produces mean squared forecast error larger than that of forecast weight averaging. Finally, this result also holds true marginally when applied to business and economic empirical data sets, Gross Domestic Product (GDP growth rate), Consumer Price Index (CPI) and Average Lending Rate (ALR) of Malaysia.

Use of the fluorescence quantum yield for the determination of the number-average molecular weight of polymers of epicatechin with 4β→8 interflavin bonds

Treesearch

D. Cho; W.L. Mattice; L.J. Porter; Richard W. Hemingway

1989-01-01

Excitation at 280 nm produces a structureless emission band with a maximum at 321-324 nm for dilute solutions of catechin, epicatechin, and their oligomers in l,4-dioxane or water. The fluorescence quantum yield, Q, has been measured in these two solvents for five dimers, a trimer, a tetramer, a pentamer, a hexamer, and a polymer in which the monomer...

Toughening elastomers with sacrificial bonds and watching them break

NASA Astrophysics Data System (ADS)

Creton, Costantino

2014-03-01

Most unfilled elastomers are relatively brittle, in particular when the average molecular weight between crosslinks is lower than the average molecular weight between entanglements. We created a new class of tough elastomers by introducing isotropically prestretched chains inside ordinary acrylic elastomers by successive swelling and polymerization steps. These new materials combine a high entanglement density with a densely crosslinked structure reaching elastic moduli of 4 MPa and fracture strength of 25 MPa. The highly prestretched chains are the minority in the material and can break in the bulk of the material before catastrophic failure occurs, increasing the toughness of the material by two orders of magnitude up to 5 kJ/m2. To investigate the details of the toughening mechanism we introduced specific sacrificial dioxetane bonds in the prestretched chains that emit light when they break. In uniaxial extension cyclic experiments, we checked that the light emission corresponded exactly and quantitatively to the energy dissipation in each cycle demonstrating that short chains break first and long chains later. We then watched crack propagation in notched samples and mapped spatially the location of bond breakage ahead of the crack tip before and during propagation. This new toughening mechanism for elastomers creates superentangled rubbers and is ideally suited to overcome the trade-off between toughness and stiffness of ordinary elastomers. We gratefully acknowledge funding from DSM Ahead

Protein-protein conjugate nanoparticles for malaria antigen delivery and enhanced immunogenicity

PubMed Central

Scaria, Puthupparampil V.; Jones, David S.; Barnafo, Emma; Fischer, Elizabeth R.; Anderson, Charles; MacDonald, Nicholas J.; Lambert, Lynn; Rausch, Kelly M.; Narum, David L.

2017-01-01

Chemical conjugation of polysaccharide to carrier proteins has been a successful strategy to generate potent vaccines against bacterial pathogens. We developed a similar approach for poorly immunogenic malaria protein antigens. Our lead candidates in clinical trials are the malaria transmission blocking vaccine antigens, Pfs25 and Pfs230D1, individually conjugated to the carrier protein Exoprotein A (EPA) through thioether chemistry. These conjugates form nanoparticles that show enhanced immunogenicity compared to unconjugated antigens. In this study, we examined the broad applicability of this technology as a vaccine development platform, by comparing the immunogenicity of conjugates prepared by four different chemistries using different malaria antigens (PfCSP, Pfs25 and Pfs230D1), and carriers such as EPA, TT and CRM197. Several conjugates were synthesized using thioether, amide, ADH and glutaraldehyde chemistries, characterized for average molecular weight and molecular weight distribution, and evaluated in mice for humoral immunogenicity. Conjugates made with the different chemistries, or with different carriers, showed no significant difference in immunogenicity towards the conjugated antigens. Since particle size can influence immunogenicity, we tested conjugates with different average size in the range of 16–73 nm diameter, and observed greater immunogenicity of smaller particles, with significant differences between 16 and 73 nm particles. These results demonstrate the multiple options with respect to carriers and chemistries that are available for protein-protein conjugate vaccine development. PMID:29281708

Inhibitors of protein-protein interactions (PPIs): an analysis of scaffold choices and buried surface area.

PubMed

Ran, Xu; Gestwicki, Jason E

2018-06-13

Protein-protein interactions (PPI) were once considered 'undruggable', but clinical successes, driven by advanced methods in drug discovery, have challenged that notion. Here, we review the last three years of literature on PPI inhibitors to understand what is working and why. From the 66 recently reported PPI inhibitors, we found that the average molecular weight was significantly greater than 500Da, but that this trend was driven, in large part, by the contribution of peptide-based compounds. Despite differences in average molecular weight, we found that compounds based on small molecules or peptides were almost equally likely to be potent inhibitors (K D <1μM). Finally, we found PPIs with buried surface area (BSA) less than 2000Å 2 were more likely to be inhibited by small molecules, while PPIs with larger BSA values were typically inhibited by peptides. PPIs with BSA values over 4000Å 2 seemed to create a particular challenge, especially for orthosteric small molecules. Thus, it seems important to choose the inhibitor scaffold based on the properties of the target interaction. Moreover, this survey suggests a (more nuanced) conclusion to the question of whether PPIs are good drug targets; namely, that some PPIs are readily 'druggable' given the right choice of scaffold, while others still seem to deserve the 'undruggable' moniker. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

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.

The effect of liquid hot water pretreatment on the chemical-structural alteration and the reduced recalcitrance in poplar.

PubMed

Li, Mi; Cao, Shilin; Meng, Xianzhi; Studer, Michael; Wyman, Charles E; Ragauskas, Arthur J; Pu, Yunqiao

2017-01-01

Hydrothermal pretreatment using liquid hot water (LHW) is capable of substantially reducing the cell wall recalcitrance of lignocellulosic biomass. It enhances the saccharification of polysaccharides, particularly cellulose, into glucose with relatively low capital required. Due to the close association with biomass recalcitrance, the structural change of the components of lignocellulosic materials during the pretreatment is crucial to understand pretreatment chemistry and advance the bio-economy. Although the LHW pretreatment has been extensively applied and studied, the molecular structural alteration during pretreatment and its significance to reduced recalcitrance have not been well understood. We investigated the effects of LHW pretreatment with different severity factors (log R 0 ) on the structural changes of fast-grown poplar ( Populus trichocarpa ). With the severity factor ranging from 3.6 to 4.2, LHW pretreatment resulted in a substantial xylan solubilization by 50-77% ( w/w , dry matter). The molecular weights of the remained hemicellulose in pretreated solids also have been significantly reduced by 63-75% corresponding to LHW severity factor from 3.6 to 4.2. In addition, LHW had a considerable impact on the cellulose structure. The cellulose crystallinity increased 6-9%, whereas its degree of polymerization decreased 35-65% after pretreatment. We found that the pretreatment severity had an empirical linear correlation with the xylan solubilization ( R 2  = 0.98, r  = + 0.99), hemicellulose molecular weight reduction ( R 2  = 0.97, r  = - 0.96 and R 2  = 0.93, r  = - 0.98 for number-average and weight-average degree of polymerization, respectively), and cellulose crystallinity index increase ( R 2  = 0.98, r  = + 0.99). The LHW pretreatment also resulted in small changes in lignin structure such as decrease of β- O -4' ether linkages and removal of cinnamyl alcohol end group and acetyl group, while the S/G ratio of lignin in LHW pretreated poplar residue remained no significant change compared with the untreated poplar. This study revealed that the solubilization of xylan, the reduction of hemicellulose molecular weights and cellulose degree of polymerization, and the cleavage of alkyl-aryl ether bonds in lignin resulted from LHW pretreatment are critical factors associated with reduced cell wall recalcitrance. The chemical-structural changes of the three major components, cellulose, lignin, and hemicellulose, during LHW pretreatment provide useful and fundamental information of factors governing feedstock recalcitrance during hydrothermal pretreatment.

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.

Characterization of aquatic dissolved organic matter by asymmetrical flow field-flow fractionation coupled to UV-Visible diode array and excitation emission matrix fluorescence.

PubMed

Guéguen, Céline; Cuss, Chad W

2011-07-08

Flow field-flow fractionation (FlFFF) with on-line UV/Visible diode array detector (DAD) and excitation emission matrix (EEM) fluorescence detector has been developed for the characterization of optical properties of aquatic dissolved organic matter (DOM) collected in the Otonabee River (Ontario, Canada) and Athabasca River (Alberta, Canada). The molecular weight (MW) distribution of DOM was estimated using a series of organic macromolecules ranging from 479 to 66,000 Da. Both the number-average (M(n)) and weight-average (M(w)) molecular weights of Suwannee River fulvic acid (SRFA) and Suwannee River humic acid (SRHA) determined using these macromolecular standards were comparable to those obtained using polystyrenesulfonate (PSS) standards, suggesting that organic macromolecules can be used to estimate MW of natural organic colloids. The MW of eight river DOM samples determined by this method was found to have an M(n) range of 0.8-1.1 kDa, which agrees with available literature estimates. The FlFFF-DAD-EEM system provided insight into the MW components of river DOM including the optical properties by on-line absorbance and fluorescence measurement. A red-shift in emission and excitation wavelength maxima associated with lower spectral slope ratios (S(R)=S₂₇₅₋₂₉₅:S₃₅₀₋₄₀₀) was related to higher MW DOM. However, DOM of different origins at similar MW also showed significant difference in optical properties. A difference of 47 and 40 nm in excitation and emission peak C maxima was found. This supports the hypothesis that river DOM is not uniform in size and optical composition. Copyright © 2010 Elsevier B.V. All rights reserved.

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.

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

Laccase-Catalyzed Synthesis of Low-Molecular-Weight Lignin-Like Oligomers and their Application as UV-Blocking Materials.

PubMed

Lim, Jieyan; Sana, Barindra; Krishnan, Ranganathan; Seayad, Jayasree; Ghadessy, Farid J; Jana, Satyasankar; Ramalingam, Balamurugan

2018-02-02

The laccase-catalyzed oxidative polymerization of monomeric and dimeric lignin model compounds was carried out with oxygen as the oxidant in aqueous medium. The oligomers were characterized by using gel permeation chromatography (GPC) and matrix-assisted laser desorption ionization time-of-flight mass spectroscopy (MALDI-TOF MS) analysis. Oxidative polymerization led to the formation of oligomeric species with a number-average molecular weight (M n ) that ranged from 700 to 2300 Da with a low polydispersity index. Spectroscopic analysis provided insight into the possible modes of linkages present in the oligomers, and the oligomerization is likely to proceed through the formation of C-C linkages between phenolic aromatic rings. The oligomers were found to show good UV light absorption characteristics with high molar extinction coefficient (5000-38 000 m -1  cm -1 ) in the UV spectral region. The oligomers were blended independently with polyvinyl chloride (PVC) by using solution blending to evaluate the compatibility and UV protection ability of the oligomers. The UV/Vis transmittance spectra of the oligomer-embedded PVC films indicated that these lignin-like oligomers possessed a notable ability to block UV light. In particular, oligomers obtained from vanillyl alcohol and the dimeric lignin model were found to show good photostability in accelerated UV weathering experiments. The UV-blocking characteristics and photostability were finally compared with the commercial low-molecular-weight UV stabilizer 2,4-dihydroxybenzophenone. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 .

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.

A structured understanding of cellobiohydrolase I binding to poplar lignin fractions after dilute acid pretreatment.

PubMed

Yao, Lan; Yoo, Chang Geun; Meng, Xianzhi; Li, Mi; Pu, Yunqiao; Ragauskas, Arthur J; Yang, Haitao

2018-01-01

Cellulase adsorption to lignin is considered a cost barrier for bioethanol production; however, its detailed association mechanism is still not fully understood. In this study, two natural poplar variants with high and low sugar release performance were selected as the low and high recalcitrant raw materials (named L and H , respectively). Three different lignin fractions were extracted using ethanol, followed by p -dioxane and then cellulase treatment from the dilute acid pretreated poplar solids (fraction 1, 2, and 3, respectively). Each lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weights for the other two lignin fractions were similar. 31 P NMR analysis revealed that lignin fraction with higher molecular weight contained more aliphatic hydroxyl groups and less phenolic hydroxyl groups. Semi-quantitative analysis by 2D HSQC NMR indicated that the lignin fractions isolated from the natural variants had different contents of syringyl (S), guaiacyl (G) and interunit linkages. Lignin extracted by ethanol contained the largest amount of S units, the smallest amounts of G and p -hydroxybenzoate (PB) subunits, while the contents of these lignin subunits in the other two lignin fractions were similar. The lignin fraction obtained after cellulase treatment was primarily comprised of β- O -4 linkages with small amounts of β-5 and β-β linkages. The binding strength of these three lignin fractions obtained by Langmuir equations were in the order of L 1  >  L 3  >  L 2 for the low recalcitrance poplar and H 1  >  H 2  >  H 3 for the high recalcitrance poplar. Overall, adsorption ability of lignin was correlated with the sugar release of poplar. Structural features of lignin were associated with its binding to CBH. For natural poplar variants, lignin fractions with lower molecular weight and polydispersity index (PDI) exhibited more CBH adsorption ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.

Reversible addition-fragmentation chain transfer polymerization of N-isopropylacrylamide: a comparison between a conventional and a fast initiator.

PubMed

Bouchékif, Hassen; Narain, Ravin

2007-09-27

The reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) was studied to determine the reasons for deviation of experimental molecular weights to lower molecular weight at high monomer conversion when S-1-dodecyl-S-(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAm) and S,S-bis(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAd) were used as RAFT agents at 65 degrees C. For this purpose, experiments were performed in N,N'-dimethylformamide (DMF) at the NIPAM/CTA ratio of 200 with initiators capable of yielding fast and slow initiation, respectively by photochemical and thermal process, either at ambient temperature or at 65 degrees C. When the polymerization of NIPAM was conducted under these conditions with Irgacure-2959 (IRGC) as photoinitiator, a continuing supply of primary radicals by incremental initiator addition was required to achieve reasonably high conversion. This effect was also apparent by the loss of linearity of the first-order kinetic plot with a conventional initiator (4,4-azobis(4-cyanovaleric acid) (ACVA) as azo-initiator, 10h (t1/2) decomposition at 65 degrees C) indicating that steady-state concentration of the macroradical decreases significantly with the initiator consumption. Nevertheless, polymers with predictable number-average molecular weight Mn (i.e., based on [monomer]/([CTA] + [initiator]) ratio) and narrow polydispersities were obtained (PDIs < 1.2) with CTAm indicating that the process of chain growth was controlled. When CTAd was used, instead of CTAm, the polymers obtained were characterized by a larger polydispersity (1.2 < PDIs < 1.3). The so-called "living steady-state concentration" in chain equilibration together with the linear dependence of Mn vs conversion was observed only when the 200/1 NIPAM/CTA mixture in DMF was subjected to a permanent photoirradiation at 65 degrees C. With ACVA, the deviation of the experimentally measured molecular weights at high conversion was accounted for by the simultaneous self-initiated polymerization of NIPAM with the controlled process in the presence of CTA at 65 degrees C. Similar drift from the linear dependence Mn vs conversion was also observed at 65 degrees C when a significant number of low molecular weight polymer chains were generated intentionally by photodecomposition of IRGC.

Mechanism of Lysergic Acid Diethylamide Interference with Rabbit Antibody Biosynthesis

PubMed Central

Voss, Edward W.; Winkelhake, Jeffrey L.

1974-01-01

Lymphoid cells from hyperimmune rabbits producing antibodies to a hapten, incubated in the presence of d-lysergic acid diethylamide, continued to synthesize protein at a normal rate. Isoelectric focusing analysis of the low-molecular-weight protein secreted by the cells incubated with lysergic acid diethylamide indicated two components, with pI's of 4.9 and 5.2. Immune cells not exposed to lysergic acid diethylamide secreted only 7S IgG molecules with an average pI of approximately 7.0. PMID:4524614

A general diagram for estimating pore size of ultrafiltration and reverse osmosis membranes

NASA Technical Reports Server (NTRS)

Sarbolouki, M. N.

1982-01-01

A slit sieve model has been used to develop a general correlation between the average pore size of the upstream surface of a membrane and the molecular weight of the solute which it retains by better than 80%. The pore size is determined by means of the correlation using the high retention data from an ultrafiltration (UF) or a reverse osmosis (RO) experiment. The pore population density can also be calculated from the flux data via appropriate equations.

Liquid Viscosity and Density Measurement with Flexural-Plate-Wave Sensors

DTIC Science & Technology

1996-04-01

capillary-viscometer-measured viscosity in Fig. 4. "The data from solutions of poly(ethylene glycol), having average molecular weights 3350 and 15,000...have seen similar results for the FPW-measured viscosity of salmon-sperm DNA solutions. 25 glycerol WA " PEG 3,350 H-4 . e! 2 PEG 15,000 IK- ,,,," HEC...number of aqueous solutions of the polymers poly(ethylene glycol) ( PEG ) and hydroxyethyl cellulose (HEC). The response of the FPW sensor (vertical axis

Trans-hemispheric contribution of C2-C10 α, ω-dicarboxylic acids, and related polar compounds to water-soluble organic carbon in the western Pacific aerosols in relation to photochemical oxidation reactions

NASA Astrophysics Data System (ADS)

SempéRé, Richard; Kawamura, Kimitaka

2003-06-01

Marine aerosol samples were collected during a western Pacific cruise covering the latitude range between 35°N and 40°S (140°E-180°E). They were analyzed for total carbon (TC), total nitrogen (TN), water-soluble organic carbon (WSOC) along with the molecular distributions of C2-C10 α, ω-dicarboxylic acids, and related polar compounds, mainly, ω-oxocarboxylic acids (C2-C9) and α-dicarbonyls (C2-C3). Oxalic acid (C2) was the most abundant followed by malonic (C3) and succinic (C4) acids. The total diacid concentration range was 7-605 ng m-3 (av. 85 ng m-3) and the diacid-carbon accounted for 2-15% (average 8%) of WSOC which comprised 29-55% (average 40%) of TC. Dry depositions of total diacids over the northern and southern Pacific Ocean were estimated to be 256-1907 μg m-2 yr-1 (average 735; n = 4) and 22-396 μg m-2 yr-1 (average 134; n = 14), respectively, whereas the air-to-sea flux of oxalic acid was 18-1351 μg m-2 yr-1 (average 466 μg m-2 yr-1) and 7.5-275 μg m-2 yr-1 (average 75 μg m-2 yr-1) in the Northern and Southern Hemispheres. We observed that the concentration ratios of diacid-C/WSOC, azelaic acid (C9)/ω-oxononanoic acid, maleic acid (iC4cis)/fumaric (iC4trans) acid and succinic acid (C4)/total diacids were correlated with air temperature. These findings showed that the intensity of photochemical oxidation reactions and thus the variation in sunlight intensity characterized here by air temperature, significantly control the molecular distribution of water-soluble organic compounds during the long-range transport of anthropogenic and/or biogenic higher molecular weight organic compounds.

12 CFR 702.105 - Weighted-average life of investments.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 12 Banks and Banking 6 2011-01-01 2011-01-01 false Weighted-average life of investments. 702.105... PROMPT CORRECTIVE ACTION Net Worth Classification § 702.105 Weighted-average life of investments. Except as provided below (Table 3), the weighted-average life of an investment for purposes of §§ 702.106(c...

12 CFR 702.105 - Weighted-average life of investments.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 12 Banks and Banking 6 2010-01-01 2010-01-01 false Weighted-average life of investments. 702.105... PROMPT CORRECTIVE ACTION Net Worth Classification § 702.105 Weighted-average life of investments. Except as provided below (Table 3), the weighted-average life of an investment for purposes of §§ 702.106(c...

12 CFR 702.105 - Weighted-average life of investments.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 12 Banks and Banking 7 2014-01-01 2014-01-01 false Weighted-average life of investments. 702.105... PROMPT CORRECTIVE ACTION Net Worth Classification § 702.105 Weighted-average life of investments. Except as provided below (Table 3), the weighted-average life of an investment for purposes of §§ 702.106(c...

12 CFR 702.105 - Weighted-average life of investments.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 12 Banks and Banking 7 2013-01-01 2013-01-01 false Weighted-average life of investments. 702.105... PROMPT CORRECTIVE ACTION Net Worth Classification § 702.105 Weighted-average life of investments. Except as provided below (Table 3), the weighted-average life of an investment for purposes of §§ 702.106(c...

12 CFR 702.105 - Weighted-average life of investments.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 12 Banks and Banking 7 2012-01-01 2012-01-01 false Weighted-average life of investments. 702.105... PROMPT CORRECTIVE ACTION Net Worth Classification § 702.105 Weighted-average life of investments. Except as provided below (Table 3), the weighted-average life of an investment for purposes of §§ 702.106(c...

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.

Megasupramolecules for safer, cleaner fuel by end association of long telechelic polymers

NASA Astrophysics Data System (ADS)

Wei, Ming-Hsin; Li, Boyu; David, R. L. Ameri; Jones, Simon C.; Sarohia, Virendra; Schmitigal, Joel A.; Kornfield, Julia A.

2015-10-01

We used statistical mechanics to design polymers that defy conventional wisdom by self-assembling into “megasupramolecules” (≥5000 kg/mol) at low concentration (≤0.3 weight percent). Theoretical treatment of the distribution of individual subunits—end-functional polymers—among cyclic and linear supramolecules (ring-chain equilibrium) predicts that megasupramolecules can form at low total polymer concentration if, and only if, the backbones are long (>400 kg/mol) and end-association strength is optimal. Viscometry and scattering measurements of long telechelic polymers having polycyclooctadiene backbones and acid or amine end groups verify the formation of megasupramolecules. They control misting and reduce drag in the same manner as ultralong covalent polymers. With individual building blocks short enough to avoid hydrodynamic chain scission (weight-average molecular weights of 400 to 1000 kg/mol) and reversible linkages that protect covalent bonds, these megasupramolecules overcome the obstacles of shear degradation and engine incompatibility.

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

26 CFR 1.989(b)-1 - Definition of weighted average exchange rate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 26 Internal Revenue 10 2010-04-01 2010-04-01 false Definition of weighted average exchange rate. 1... (CONTINUED) INCOME TAX (CONTINUED) INCOME TAXES Export Trade Corporations § 1.989(b)-1 Definition of weighted average exchange rate. For purposes of section 989(b)(3) and (4), the term “weighted average exchange rate...

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 analysis of the market success of FDA approvals by probing top 100 bestselling drugs.

PubMed

Polanski, Jaroslaw; Bogocz, Jacek; Tkocz, Aleksandra

2016-05-01

Target-oriented drug discovery is the main research paradigm of contemporary drug discovery. In target-oriented approaches, we attempt to maximize in vitro drug potency by finding the optimal fit to the target. This can result in a higher molecular complexity, in particular, the higher molecular weight (MW) of the drugs. However, a comparison of the successful developments of pharmaceuticals with the general trends that can be observed in medicinal chemistry resulted in the conclusion that the so-called molecular obesity is an important reason for the attrition rate of drugs. When analyzing the list of top 100 drug bestsellers versus all of the FDA approvals, we discovered that on average lower-complexity (MW, ADMET score) drugs are winners of the top 100 list in terms of numbers but that, especially, up to some optimal MW value, a higher molecular complexity can pay off with higher incomes. This indicates that slim drugs are doing better but that fat drugs are bigger fishes to catch.

The analysis of the market success of FDA approvals by probing top 100 bestselling drugs

NASA Astrophysics Data System (ADS)

Polanski, Jaroslaw; Bogocz, Jacek; Tkocz, Aleksandra

2016-05-01

Target-oriented drug discovery is the main research paradigm of contemporary drug discovery. In target-oriented approaches, we attempt to maximize in vitro drug potency by finding the optimal fit to the target. This can result in a higher molecular complexity, in particular, the higher molecular weight (MW) of the drugs. However, a comparison of the successful developments of pharmaceuticals with the general trends that can be observed in medicinal chemistry resulted in the conclusion that the so-called molecular obesity is an important reason for the attrition rate of drugs. When analyzing the list of top 100 drug bestsellers versus all of the FDA approvals, we discovered that on average lower-complexity (MW, ADMET score) drugs are winners of the top 100 list in terms of numbers but that, especially, up to some optimal MW value, a higher molecular complexity can pay off with higher incomes. This indicates that slim drugs are doing better but that fat drugs are bigger fishes to catch.

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

PubMed

Mulloy, Barbara; Hogwood, John

2015-01-01

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

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.

Synergism and foaming properties in binary mixtures of a biosurfactant derived from Camellia oleifera Abel and synthetic surfactants.

PubMed

Jian, Hong-lei; Liao, Xiao-xia; Zhu, Li-wei; Zhang, Wei-ming; Jiang, Jian-xin

2011-07-15

A biosurfactant, named tea saponin (TS), was isolated and purified from the defatted seed of Camellia oleifera Abel. The characterization of TS including molecular weight, glycosyl composition, and thermal behavior as well as the surface and foaming properties was conducted. The synergistic interactions of binary systems of CTAB-TS, SDS-TS, and Brij35-TS were investigated. The results show that TS had a weight-average molecular weight of 809.12 g mol(-1) and contained four aglycones of L-rhamnose, D-galactose, D-glucose, and D-glucuronic acid. The critical micelle concentration (cmc) of 2.242 mmol L(-1) and the minimum surface tension (γ(cmc)) of 43.5 mN m(-1) were determined for TS. Synergisms in surface tension reduction efficiency, in mixed micelle formation, and in surface tension reduction effectiveness were observed in CTAB-TS and SDS-TS systems, whereas that was not shown in Brij35-TS mixtures. The mixtures of TS with CTAB and SDS showed synergism in foaming efficiency, but this synergism did not exist in Brij35-TS system with respect to the surface properties. Nevertheless, there appears to be no significant correlation between foam stability and the surface properties. Copyright © 2011 Elsevier Inc. All rights reserved.

Nanoparticles modified with multiple organic acids

NASA Technical Reports Server (NTRS)

Luebben, Silvia DeVito (Inventor); Cook, Ronald Lee (Inventor); Wilson, Carolina (Inventor); Meiser, Manfred (Inventor); Myers, Andrew William (Inventor); Smith, Bryan Matthew (Inventor); Elliott, Brian John (Inventor); Kreutzer, Cory (Inventor)

2007-01-01

Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.

Nanoparticles modified with multiple organic acids

DOEpatents

Cook, Ronald Lee [Lakewood, CO; Luebben, Silvia DeVito [Golden, CO; Myers, Andrew William [Arvada, CO; Smith, Bryan Matthew [Boulder, CO; Elliott, Brian John [Superior, CO; Kreutzer, Cory [Brighton, CO; Wilson, Carolina [Arvada, CO; Meiser, Manfred [Aurora, CO

2007-07-17

Surface-modified nanoparticles of boehmite, and methods for preparing the same. Aluminum oxyhydroxide nanoparticles are surface modified by reaction with selected amounts of organic acids. In particular, the nanoparticle surface is modified by reactions with two or more different carboxylic acids, at least one of which is an organic carboxylic acid. The product is a surface modified boehmite nanoparticle that has an inorganic aluminum oxyhydroxide core, or part aluminum oxyhydroxide core and a surface-bonded organic shell. Organic carboxylic acids of this invention contain at least one carboxylic acid group and one carbon-hydrogen bond. One embodiment of this invention provides boehmite nanoparticles that have been surface modified with two or more acids one of which additional carries at least one reactive functional group. Another embodiment of this invention provides boehmite nanoparticles that have been surface modified with multiple acids one of which has molecular weight or average molecular weight greater than or equal to 500 Daltons. Yet, another embodiment of this invention provides boehmite nanoparticles that are surface modified with two or more acids one of which is hydrophobic in nature and has solubility in water of less than 15 by weight. The products of the methods of this invention have specific useful properties when used in mixture with liquids, as filler in solids, or as stand-alone entities.

Average Weighted Receiving Time of Weighted Tetrahedron Koch Networks

NASA Astrophysics Data System (ADS)

Dai, Meifeng; Zhang, Danping; Ye, Dandan; Zhang, Cheng; Li, Lei

2015-07-01

We introduce weighted tetrahedron Koch networks with infinite weight factors, which are generalization of finite ones. The term of weighted time is firstly defined in this literature. The mean weighted first-passing time (MWFPT) and the average weighted receiving time (AWRT) are defined by weighted time accordingly. We study the AWRT with weight-dependent walk. Results show that the AWRT for a nontrivial weight factor sequence grows sublinearly with the network order. To investigate the reason of sublinearity, the average receiving time (ART) for four cases 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...

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.

Waterborne carboxyl-terminated hyperbranched oligomer polyester ligand: Synthesis, characterization and chelation with chromium(III)

NASA Astrophysics Data System (ADS)

Yao, Qi; Li, Chenying; Huang, Henghui; Chen, Hualin; Liu, Bailing

2017-09-01

A series of carboxyl-terminated hyperbranched oligomer polyester (HBP) with different degree of branching (DB) and number average molar mass (Mbarn) have been prepared. The molecular structure, degree of branching, molecular mass and its distribution of HBP were investigated by FTIR, 1H NMR, and GPC, respectively. And the coordination number, stability constant and degree of dissociation (α) between HBP and chromium(Ⅲ) were measured via continuous variation method (Job's plot). Experimental results show that the coordination capability between HBP and chromium(Ⅲ) affected by both DB and molecular mass, and the latter plays a decisive role. Moreover HBP outperforms low molecular weight of organic acids (citric acid, acetic acid) and linear polyacrylic acid with similar molecular mass. The coordination number and stability constants of HBP-3 (Mbarn = 1713 Da, Mbarw /Mbarn (PDI) = 1.11 and DB = 0.72) can reach 4 and 6.55e+008, which demonstrated it can be selected as a good ligand to coordination with chromium(Ⅲ). Therefore HBP can be used as chrome auxiliary in chrome tanning to improve the absorption of chromium.

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

Synthesis of Transesterified Palm Olein-Based Polyol and Rigid Polyurethanes from this Polyol.

PubMed

Arniza, Mohd Zan; Hoong, Seng Soi; Idris, Zainab; Yeong, Shoot Kian; Hassan, Hazimah Abu; Din, Ahmad Kushairi; Choo, Yuen May

Transesterification of palm olein with glycerol can increase the functionality by introducing additional hydroxyl groups to the triglyceride structure, an advantage compared to using palm olein directly as feedstock for producing palm-based polyol. The objective of this study was to synthesize transesterified palm olein-based polyol via a three-step reaction: (1) transesterification of palm olein, (2) epoxidation and (3) epoxide ring opening. Transesterification of palm olein yielded approximately 78 % monoglyceride and has an hydroxyl value of approximately 164 mg KOH g -1 . The effect of formic acid and hydrogen peroxide concentrations on the epoxidation reaction was studied. The relationships between epoxide ring-opening reaction time and residual oxirane oxygen content and hydroxyl value were monitored. The synthesized transesterified palm olein-based polyol has hydroxyl value between 300 and 330 mg KOH g -1 and average molecular weight between 1,000 and 1,100 Da. On the basis of the hydroxyl value and average molecular weight of the polyol, the transesterified palm olein-based polyol is suitable for producing rigid polyurethane foam, which can be designed to exhibit desirable properties. Rigid polyurethane foams were synthesized by substituting a portion of petroleum-based polyol with the transesterified palm olein-based polyol. It was observed that by increasing the amount of transesterified palm olein-based polyol, the core density and compressive strength were reduced but at the same time the insulation properties of the rigid polyurethane foam were improved.

Effect of varying molecular weight of dextran on acrylic-derivatized dextran and concanavalin A glucose-responsive materials for closed-loop insulin delivery.

PubMed

Sahota, Tarsem; Sawicka, Kirsty; Taylor, Joan; Tanna, Sangeeta

2011-03-01

Dextran methacrylate (dex-MA) and concanavalin A (con A)-methacrylamide were photopolymerized to produce covalently cross-linked glucose-sensitive gels for the basis of an implantable closed-loop insulin delivery device. The viscoelastic properties of these polymerized gels were tested rheologically in the non-destructive oscillatory mode within the linear viscoelastic range at glucose concentrations between 0 and 5% (w/w). For each cross-linked gel, as the glucose concentration was raised, a decrease in storage modulus, loss modulus and complex viscosity (compared at 1 Hz) was observed, indicating that these materials were glucose responsive. The higher molecular weight acrylic-derivatized dextrans [degree of substitution (DS) 3 and 8%] produced higher complex viscosities across the glucose concentration range. These studies coupled with in vitro diffusion experiments show that dex-MA of 70 kDa and DS (3%) was the optimum mass average molar mass to produce gels that show reduced component leach, glucose responsiveness, and insulin transport useful as part of a self-regulating insulin delivery device.

Validation of a high-performance size-exclusion chromatography method to determine and characterize β-glucans in beer wort using a triple-detector array.

PubMed

Tomasi, Ivan; Marconi, Ombretta; Sileoni, Valeria; Perretti, Giuseppe

2017-01-01

Beer wort β-glucans are high-molecular-weight non-starch polysaccharides of that are great interest to the brewing industries. Because glucans can increase the viscosity of the solutions and form gels, hazes, and precipitates, they are often related to poor lautering performance and beer filtration problems. In this work, a simple and suitable method was developed to determine and characterize β-glucans in beer wort using size exclusion chromatography coupled with a triple-detector array, which is composed of a light scatterer, a viscometer, and a refractive-index detector. The method performances are comparable to the commercial reference method as result from the statistical validation and enable one to obtain interesting parameters of β-glucan in beer wort, such as the molecular weight averages, fraction description, hydrodynamic radius, intrinsic viscosity, polydispersity and Mark-Houwink parameters. This characterization can be useful in brewing science to understand filtration problems, which are not always explained through conventional analysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis and characterization of low-molecular-weight π-conjugated polymers covered by persilylated β-cyclodextrin

PubMed Central

Resmerita, Ana-Maria; Stefanache, Andreea; Balan, Mihaela; Harabagiu, Valeria

2012-01-01

Summary The paper reports the preparation of a poly[2,7-(9,9-dioctylfluorene)-alt-5,5'-bithiophene/PS-βCD] (PDOF-BTc) polyrotaxane copolymer, through a Suzuki coupling reaction between the 5,5'-dibromo-2,2'-bithiophene (BT) inclusion complex with persilylated β-cyclodextrin (PS-βCD), and 9,9-dioctylfluorene-2,7-bis(trimethylene borate) (DOF) as the blocking group. The chemical structure and the thermal and morphological properties of the resulting polyrotaxane were investigated by using NMR and FT-IR spectroscopy, TGA, DSC and AFM analysis. The encapsulation of BT inside the PS-βCD cavity results in improvements in the solubility, as well as in different surface morphology and thermal properties of the PDOF-BTc rotaxane copolymer compared to its noncomplexed PDOF-BT homologue. In contrast, the number-average molecular weight (M n) of PDOF-BTc rotaxane copolymer indicated lower values suggesting that the condensation reaction is subjected to steric effects of the bulkier silylated groups, affecting the ability of the diborate groups from the DOF molecule to partially penetrate the PS-βCD cavity. PMID:23019485

Extraction, chemical composition, rheological behavior, antioxidant activity and functional properties of Cordia myxa mucilage.

PubMed

Dokht, Shaghayegh Keshani; Djomeh, Zahra Emam; Yarmand, Mohammad Saeid; Fathi, Morteza

2018-06-14

This paper aims to investigate chemical composition, rheological behavior, antioxidant activity and functional properties of Cordia myxa mucilage (CMM). Response surface methodology (RSM) demonstrated that optimum conditions for CMM extraction were as follow: ultrasound power of 99.37 W, extraction temperature of 88.05 °C and solid to water ratio of 16.25 w/w. CMM had, on average, 77.51% carbohydrate, 5.86% total ash, 8.90% protein, 6.90% moisture, and 1.00% fat. Due to a high level of nutrients, CMM can be suggested as a value added by-product in food and pharmaceutical systems. CMM is a low molecular weight polysaccharide containing three fractions with various molecular weights. FT-IR spectrum illustrated that this polymer had all typical bands and peaks characteristics of polysaccharides. Based on steady shear measurements, CMM can be introduced as a new source of hydrocolloid with high-temperature stability. CMM had the desirable antiradical capacity, water solubility and water/oil holding capacity. Copyright © 2017. Published by Elsevier B.V.

Biodegradable thermoplastic polyurethanes incorporating polyhedral oligosilsesquioxane.

PubMed

Knight, Pamela T; Lee, Kyung Min; Qin, Haihu; Mather, Patrick T

2008-09-01

A new hybrid thermoplastic polyurethane (TPU) system that incorporates an organic, biodegradable poly(D, L-lactide) soft block with a hard block bearing the inorganic polyhedral oligosilsesquioxane (POSS) moiety is introduced and studied. Changes in the polyol composition made through variation of the hydrophilic initiator molecular weight show direct control of the final transition temperatures. Incorporating POSS into the hard segments allows for excellent elasticity above T(g), as evidenced with dynamic mechanical analysis, not seen in most other biodegradable materials. This elasticity is attributed to physical cross-links formed in the hard block through POSS crystallization, as revealed with wide-angle X-ray diffraction. Increasing the POSS incorporation level in the TPU hard block was observed to increase crystallinity and also the rigidity of the material. The highest incorporation, using a statistical average of three POSS units per hard block, demonstrated one-way shape memory with excellent shape fixing capabilities. In vitro degradation of this sample was also investigated during a two month period. Moderate water uptake and dramatic molecular weight decrease were immediately observed although large mass loss (approximately 20 wt %) was not observed until the two month time point.

Effect of γ-irradiation on structure and nutraceutical potential of β-D-glucan from barley (Hordeum vulgare).

PubMed

Shah, Asima; Ahmad, Mudasir; Ashwar, Bilal Ahmad; Gani, Adil; Masoodi, Farooq Ahmad; Wani, Idrees Ahmed; Wani, Sajad Mohd; Gani, Asir

2015-01-01

This paper reports the characterization and potential antioxidant activity of β-D-glucan isolated from barley treated with γ-rays. The β-D-glucan was irradiated with 0, 2, 4 and 8 kGy by gamma ray. The samples were characterized by Fourier transform-infrared spectroscopy, gel permeation chromatography (GPC) and quantitative estimation by Megazyme β-D-glucan assay kit. The average molecular weight of non-irradiated β-D-glucan was 177 kDa that decreased to 79 kDa at 8 kGy. Antioxidant activity was evaluated by five complementary assays including DPPH, lipid peroxidation, reducing power, metal chelating ability and oxidative DNA damage assays. Further, the antiproliferative potential of irradiated β-D-glucan was tested against three human cancer cell lines including Colo-205, T47D and MCF7 using MTT assay. Irradiated β-D-glucan exhibited dose dependent cancer cell growth inhibition. In conclusion, the present study demonstrates that irradiation leads to the formation of low molecular weight β-D-glucan with enhanced antioxidant and antiproliferative activities. Copyright © 2014 Elsevier B.V. All rights reserved.

Molecular weight between entanglements for κ- and ι-carrageenans in an ionic liquid.

PubMed

Horinaka, Jun-ichi; Urabayashi, Yuhei; Wang, Xiaochen; Takigawa, Toshikazu

2014-08-01

The molecular weight between entanglements (Me) for κ- and ι-carrageenans, sulfated galactans, was examined in concentrated solutions using an ionic liquid 1-butyl-3-methylimidazolium acetate as a solvent. The dynamic viscoelasticity data for the solutions measured at different temperatures were overlapped according to the time-temperature superposition principle, and the obtained master curves exhibited the flow and rubbery plateau zones, being typical of concentrated polymer solutions having entanglement coupling. The values of Me for κ- and ι-carrageenans in the solutions were determined from the plateau moduli. Then the values of Me in the molten state (Me,melt) estimated as a material constant to be 6.6×10(3) and 7.2×10(3), respectively. The close values of Me,melt for κ- and ι-carrageenans indicate that 4-sulfate group of ι-carrageenan are not so influential for the entanglement network. Compared with agarose, a non-sulfate galactan, carrageenans have larger values of average spacing between entanglements. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Chemical composition and molecular structure of polysaccharide-protein biopolymer from Durio zibethinus seed: extraction and purification process

PubMed Central

2012-01-01

Background The biological functions of natural biopolymers from plant sources depend on their chemical composition and molecular structure. In addition, the extraction and further processing conditions significantly influence the chemical and molecular structure of the plant biopolymer. The main objective of the present study was to characterize the chemical and molecular structure of a natural biopolymer from Durio zibethinus seed. A size-exclusion chromatography coupled to multi angle laser light-scattering (SEC-MALS) was applied to analyze the molecular weight (Mw), number average molecular weight (Mn), and polydispersity index (Mw/Mn). Results The most abundant monosaccharide in the carbohydrate composition of durian seed gum were galactose (48.6-59.9%), glucose (37.1-45.1%), arabinose (0.58-3.41%), and xylose (0.3-3.21%). The predominant fatty acid of the lipid fraction from the durian seed gum were palmitic acid (C16:0), palmitoleic acid (C16:1), stearic acid (C18:0), oleic acid (C18:1), linoleic acid (C18:2), and linolenic acid (C18:2). The most abundant amino acids of durian seed gum were: leucine (30.9-37.3%), lysine (6.04-8.36%), aspartic acid (6.10-7.19%), glycine (6.07-7.42%), alanine (5.24-6.14%), glutamic acid (5.57-7.09%), valine (4.5-5.50%), proline (3.87-4.81%), serine (4.39-5.18%), threonine (3.44-6.50%), isoleucine (3.30-4.07%), and phenylalanine (3.11-9.04%). Conclusion The presence of essential amino acids in the chemical structure of durian seed gum reinforces its nutritional value. PMID:23062269

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.

Impact of autoclave sterilization on the activity and structure of formulated heparin.

PubMed

Beaudet, Julie M; Weyers, Amanda; Solakyildirim, Kemal; Yang, Bo; Takieddin, Majde; Mousa, Shaker; Zhang, Fuming; Linhardt, Robert J

2011-08-01

The stability of a formulated heparin was examined during its sterilization by autoclaving. A new method to follow loss in heparin binding to the serine protease inhibitor, antithrombin III, and the serine protease, thrombin, was developed using a surface plasmon resonance competitive binding assay. This loss in binding affinity correlated well with loss in antifactor IIa (thrombin) activity as well as antifactor Xa activity as measured using conventional amidolytic assays. Autoclaving also resulted in a modest breakdown of the heparin backbone as confirmed by a slight reduction in number-averaged and weight-averaged molecular weight and an increase in polydispersity. Although no clear changes were observed by nuclear magnetic resonance spectroscopy, disaccharide composition analysis using high-performance liquid chromatography-electrospray ionization-mass spectrometry suggested that loss of selected sulfo groups had taken place. It is this sulfo group loss that probably accounts for a decrease in the binding of autoclaved heparin to antithrombin III and thrombin as well as the observed decrease in its amidolytic activity. Copyright © 2011 Wiley-Liss, Inc.

Optimization of high molecular weight pullulan production by Aureobasidium pullulans in batch fermentations.

PubMed

Gibson, Larry H; Coughlin, Robert W

2002-01-01

Of five strains of Aureobasidium pullulans studied, NRRL Y-2311-1 yielded the highest titer (26.2 g/L) of pullulan and formed the lowest amount of melanin-like pigment. Sucrose was superior to glucose as the carbon and energy source on the basis of yield and titer of pullulan produced. Pullulan titer was higher (26.2 vs 5.1 g/L), biomass concentration was lower (6.9 vs 12.7 g/L), and DO was lower (0 vs 60% of saturation) when the fermenter was agitated by a marine propeller compared to Rushton impellers. Pullulan produced by strain NRRL Y-2311-1 ranged in weight-average molar mass (M(w)) from 486 KDa and number-average molar mass (M(n)) from 220 Da on day 1 of growth to 390 KDa and 690 Da on day 6; M(w) declined by about 35% from day 1 to day 3, the day of maximum pullulan titer. For the other strains, the ranges of molar mass on the day of maximum pullulan titer were 338-614 KDa (M(w)) and 100-6820 Da (M(n)).

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.

Viscosupplementation for treatment of osteoarthritis: from initial discovery to current status and results.

PubMed

Balazs, Endre A

2004-01-01

Viscosupplementation is a therapeutic modality based on the replacement of synovial fluid or exudates with an elastoviscous hyaluronan solution. The first clinical trials were carried out on race horses with painful osteoarthritis of traumatic origin. In the early 1970s, the clinical trials were extended to painful osteoarthritis in humans. Analgesic effects lasting longer than the residence time of the injected hyaluronan in joints were reported both in horses and humans. The hyaluronan used was a noninflammatory fraction of the molecule with an average molecular weight of 2-3 million at a 1% concentration. The analgesic effect of this elastoviscous hyaluronan solution was demonstrated in behavioral animal pain models. Later it was shown that the elastoviscous properties of hyaluronan solutions are the determining factors in reducing pain-elicited nerve activity in both normal and inflamed cat and rat joints. It also was demonstrated in animal arthritis models that elastoviscous hyaluronan solutions promote the healing of traumatic intra-articular wounds. From the mid-1980s, several hyaluronan preparations of greatly varying average molecular weight but with the same concentration were introduced as viscosupplementation-based therapeutic agents. The elastoviscous properties of these solutions varied also, because of the greatly varying average molecular weights (0.5-6.0 million), imitating the rheological properties of either healthy or pathological synovial fluid. Currently, viscosupplementation products available worldwide vary greatly in their elastoviscous properties, and their dosage is not standardized in terms of frequency of injections required or in regard to the removal of exudates before injection. The question of which patient at what stage of the disease responds best with long-lasting pain relief to the many therapeutic products marketed with greatly varying elastoviscous properties has not yet been answered. At the same time, viscosupplementation was introduced, the same highly elastoviscous hyaluronan solutions also were applied in ophthalmic surgery as viscosurgical tools to protect sensitive tissues in the eye during surgery and to be used as soft instruments for tissue manipulation. Modified hyaluronan products (gels) also were introduced for augmentation of the intercellular matrix in tissues (viscoaugmentation) and for separating tissues to prevent adhesions and excessive scar formation (viscoseparation). Hyaluronan and its derivatives (gels) also have been used for drug delivery. The therapeutic use of highly elastoviscous solutions and gels of hyaluronan and its derivatives to build intercellular matrices for supplementation, regeneration, and developing new tissues introduced the concept of matrix engineering into medical practice.

Determination of the molecular weight of poly(ethylene glycol) in biological samples by reversed-phase LC-MS with in-source fragmentation.

PubMed

Warrack, Bethanne M; Redding, Brian P; Chen, Guodong; Bolgar, Mark S

2013-05-01

PEGylation has been widely used to improve the biopharmaceutical properties of therapeutic proteins and peptides. Previous studies have used multiple analytical techniques to determine the fate of both the therapeutic molecule and unconjugated poly(ethylene glycol) (PEG) after drug administration. A straightforward strategy utilizing liquid chromatography-mass spectrometry (LC-MS) to characterize high-molecular weight PEG in biologic matrices without a need for complex sample preparation is presented. The method is capable of determining whether high-MW PEG is cleaved in vivo to lower-molecular weight PEG species. Reversed-phase chromatographic separation is used to take advantage of the retention principles of polymeric materials whereby elution order correlates with PEG molecular weight. In-source collision-induced dissociation (CID) combined with selected reaction monitoring (SRM) or selected ion monitoring (SIM) mass spectrometry (MS) is then used to monitor characteristic PEG fragment ions in biological samples. MS provides high sensitivity and specificity for PEG and the observed retention times in reversed-phase LC enable estimation of molecular weight. This method was successfully used to characterize PEG molecular weight in mouse serum samples. No change in molecular weight was observed for 48 h after dosing.

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.

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

PubMed

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

2017-08-15

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

Anti-proliferative effects of O-acyl-low-molecular-weight heparin derivatives on bovine pulmonary artery smooth muscle cells.

PubMed

Garg, Hari G; Mrabat, Hicham; Yu, Lunyin; Hales, Charles A; Li, Boyangzi; Moore, Casey N; Zhang, Fuming; Linhardt, Robert J

2011-08-01

Heparin (HP) inhibits the growth of several cell types in vitro including bovine pulmonary artery (BPA) smooth muscle cells (SMCs). In initial studies we discovered that an O-hexanoylated low-molecular-weight (LMW) HP derivative having acyl groups with 6-carbon chain length was more potent inhibitor of BPA-SMCs than the starting HP. We prepared several O-acylated LMWHP derivatives having 4-, 6-, 8-, 10-, 12-, and 18- carbon acyl chain lengths to determine the optimal acyl chain length for maximum anti-proliferative properties of BPA-SMCs. The starting LMWHP was prepared from unfractionated HP by sodium periodate treatment followed by sodium borohydride reduction. The tri-n-butylammonium salt of this LMWHP was O-acylated with butanoic, hexanoic, octanoic, decanoic, dodecanoic, and stearyl anhydrides separately to give respective O-acylated LMWHP derivatives. Gradient polyacrylamide gel electrophoresis (PAGE) was used to examine the average molecular weights of those O-acylated LMWHP derivatives. NMR analysis indicated the presence of one O-acyl group per disaccharide residue. Measurement of the inhibition of BPA-SMCS as a function of O-acyl chain length shows two optima, at a carbon chain length of 6 (O-hexanoylated LMWHP) and at a carbon chain length 12-18 (O-dodecanoyl and O-stearyl LMWHPs). A solution competition SPR study was performed to test the ability of different O-acylated LMWHP derivatives to inhibit fibroblast growth factor (FGF) 1 and FGF2 binding to surface-immobilized heparin. All the LMWHP derivatives bound to FGF1 and FGF2 but each exhibited slightly different binding affinity.

Primitive-path statistics of entangled polymers: mapping multi-chain simulations onto single-chain mean-field models

NASA Astrophysics Data System (ADS)

Steenbakkers, Rudi J. A.; Tzoumanekas, Christos; Li, Ying; Liu, Wing Kam; Kröger, Martin; Schieber, Jay D.

2014-01-01

We present a method to map the full equilibrium distribution of the primitive-path (PP) length, obtained from multi-chain simulations of polymer melts, onto a single-chain mean-field ‘target’ model. Most previous works used the Doi-Edwards tube model as a target. However, the average number of monomers per PP segment, obtained from multi-chain PP networks, has consistently shown a discrepancy of a factor of two with respect to tube-model estimates. Part of the problem is that the tube model neglects fluctuations in the lengths of PP segments, the number of entanglements per chain and the distribution of monomers among PP segments, while all these fluctuations are observed in multi-chain simulations. Here we use a recently proposed slip-link model, which includes fluctuations in all these variables as well as in the spatial positions of the entanglements. This turns out to be essential to obtain qualitative and quantitative agreement with the equilibrium PP-length distribution obtained from multi-chain simulations. By fitting this distribution, we are able to determine two of the three parameters of the model, which govern its equilibrium properties. This mapping is executed for four different linear polymers and for different molecular weights. The two parameters are found to depend on chemistry, but not on molecular weight. The model predicts a constant plateau modulus minus a correction inversely proportional to molecular weight. The value for well-entangled chains, with the parameters determined ab initio, lies in the range of experimental data for the materials investigated.

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.

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.

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 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.

[A comparative study of biodegradation kinetics of biopolymer systems based on poly(3-hydroxybutyrate)].

PubMed

Boskhomdzhiev, A P; Banartsev, A P; Makhina, T K; Myshkina, V L; Ivanov, E A; Bagrov, D V; Filatova, E V; Iordanskiĭ, A L; Bonartseva, G A

2009-01-01

The aim of this study was to evaluate and to compare of long-term kinetics curves of biodegradation of poly(3-hydroxybutyrate) (PHB), its copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and PHB/polylactic acid blend. The total weight loss and the change of average viscosity molecular weight were used as an index of biodegradation degree. The rate of biodegradation was analyzed in vitro in presence oflipase and in vivo when the films were implanted in animal tissues. The morphology of PHB films surface was studied by atomic force microscopy technique. It was shown that biodegradation of PHB is occurred by means of as polymer hydrolysis, and as its enzymatic biodegradation. The obtained data can be used for development of medical devices on the base of PHB.

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 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

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.

Gas sorption and barrier properties of polymeric membranes from molecular dynamics and Monte Carlo simulations.

PubMed

Cozmuta, Ioana; Blanco, Mario; Goddard, William A

2007-03-29

It is important for many industrial processes to design new materials with improved selective permeability properties. Besides diffusion, the molecule's solubility contributes largely to the overall permeation process. This study presents a method to calculate solubility coefficients of gases such as O2, H2O (vapor), N2, and CO2 in polymeric matrices from simulation methods (Molecular Dynamics and Monte Carlo) using first principle predictions. The generation and equilibration (annealing) of five polymer models (polypropylene, polyvinyl alcohol, polyvinyl dichloride, polyvinyl chloride-trifluoroethylene, and polyethylene terephtalate) are extensively described. For each polymer, the average density and Hansen solubilities over a set of ten samples compare well with experimental data. For polyethylene terephtalate, the average properties between a small (n = 10) and a large (n = 100) set are compared. Boltzmann averages and probability density distributions of binding and strain energies indicate that the smaller set is biased in sampling configurations with higher energies. However, the sample with the lowest cohesive energy density from the smaller set is representative of the average of the larger set. Density-wise, low molecular weight polymers tend to have on average lower densities. Infinite molecular weight samples do however provide a very good representation of the experimental density. Solubility constants calculated with two ensembles (grand canonical and Henry's constant) are equivalent within 20%. For each polymer sample, the solubility constant is then calculated using the faster (10x) Henry's constant ensemble (HCE) from 150 ps of NPT dynamics of the polymer matrix. The influence of various factors (bad contact fraction, number of iterations) on the accuracy of Henry's constant is discussed. To validate the calculations against experimental results, the solubilities of nitrogen and carbon dioxide in polypropylene are examined over a range of temperatures between 250 and 650 K. The magnitudes of the calculated solubilities agree well with experimental results, and the trends with temperature are predicted correctly. The HCE method is used to predict the solubility constants at 298 K of water vapor and oxygen. The water vapor solubilities follow more closely the experimental trend of permeabilities, both ranging over 4 orders of magnitude. For oxygen, the calculated values do not follow entirely the experimental trend of permeabilities, most probably because at this temperature some of the polymers are in the glassy regime and thus are diffusion dominated. Our study also concludes large confidence limits are associated with the calculated Henry's constants. By investigating several factors (terminal ends of the polymer chains, void distribution, etc.), we conclude that the large confidence limits are intimately related to the polymer's conformational changes caused by thermal fluctuations and have to be regarded--at least at microscale--as a characteristic of each polymer and the nature of its interaction with the solute. Reducing the mobility of the polymer matrix as well as controlling the distribution of the free (occupiable) volume would act as mechanisms toward lowering both the gas solubility and the diffusion coefficients.

Entanglement in miscible blends

NASA Astrophysics Data System (ADS)

Watanabe, Hiroshi

2010-03-01

The entanglement length Le of polymer chains (corresponding to the entanglement molecular weight Me) is not an intrinsic material parameter but changes with the interaction with surrounding chains. For miscible blends of cis-polyisoprene (PI) and poly(tert-butyl styrene) (PtBS), changes of Le on blending was examined. It turned out that the Le averaged over the number fractions of the Kuhn segments of the components (PI and PtBS) satisfactorily describes the viscoelastic behavior of pseudo-monodisperse blends in which the terminal relaxation time is the same for PI and PtBS.

In vitro and in vivo antioxidant activity of a water-soluble polysaccharide from dendrobium denneanum

USGS Publications Warehouse

Luo, A.; Ge, Z.; Fan, Y.; Chun, Z.; Jin, He X.

2011-01-01

The water-soluble crude polysaccharide (DDP) obtained from the aqueous extracts of the stem of Dendrobium denneanum through hot water extraction followed by ethanol precipitation, was found to have an average molecular weight (Mw) of about 484.7 kDa. Monosaccharide analysis revealed that DDP was composed of arabinose, xylose, mannose, glucose and galactose in a molar ratio of 1.00:2.66:8.92:34.20:10.16. The investigation of antioxidant activity both in vitro and in vivo showed that DDP is a potential antioxidant. ?? 2011.

Spin-echo small-angle neutron scattering (SESANS) measurements of needle-like crystallites of gelator compounds

NASA Astrophysics Data System (ADS)

Coumou, Pieter-Jan C. J. J.; Brizard, Aurelie M. A.; van Esch, Jan H.; de Schepper, Ignatz M.; Bouwman, Wim G.

2010-11-01

From dibenzoyl cystine, a low molecular weight gelator, we have prepared needle shaped crystals at relatively high concentrations. For the first time SESANS measurements are performed on objects with this geometry. From the measurements the average diameter can be seen directly. From a more careful analysis the width distribution is determined. The gel phase itself prepared at lower concentrations did not show any signal, in contrast to what one observes with conventional SANS. This shows the complementarity of SESANS and SANS.

In vitro Antioxidant of a Water-Soluble Polysaccharide from Dendrobium fimhriatum Hook.var.oculatum Hook

PubMed Central

Luo, Aoxue; Fan, Yijun

2011-01-01

A water-soluble crude polysaccharide (DFHP) obtained from the aqueous extracts of the stem of Dendrobium fimhriatum Hook.var.oculatum Hook through hot water extraction followed by ethanol precipitation, was found to have an average molecular weight (Mw) of about 209.3 kDa. Monosaccharide analysis revealed that DFHP was composed of mannose, glucose and galactose in a content ratio of 37.52%; 43.16%; 19.32%. The investigation of antioxidant activity in vitro showed that DFHP is a potential antioxidant. PMID:21747725

LASER APPLICATIONS AND OTHER ASPECTS OF QUANTUM ELECTRONICS Nonlinearity, optoelectronic properties, and their correlations for some mixed ternary defect chalcopyrites

NASA Astrophysics Data System (ADS)

Dutta Roy, S.

2010-12-01

The refractive index, optical nonlinearity, lowest energy band gap, and other related parameters of some mixed defect ternary chalcopyrites are calculated using Levine's bond charge model and its modification developed by Samanta et al. for multinary and mixed compounds. The dependence of the band gap energy on the average quantum number, molecular weight, and anion displacement parameter is shown for the first time, which will be very useful for designing various optoelectronic and nonlinear laser devices.

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)

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.

26 CFR 1.989(b)-1 - Definition of weighted average exchange rate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 26 Internal Revenue 10 2011-04-01 2011-04-01 false Definition of weighted average exchange rate. 1... (CONTINUED) INCOME TAX (CONTINUED) INCOME TAXES (CONTINUED) Export Trade Corporations § 1.989(b)-1 Definition of weighted average exchange rate. For purposes of section 989(b)(3) and (4), the term “weighted...

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.

WDL-RF: Predicting Bioactivities of Ligand Molecules Acting with G Protein-coupled Receptors by Combining Weighted Deep Learning and Random Forest.

PubMed

Wu, Jiansheng; Zhang, Qiuming; Wu, Weijian; Pang, Tao; Hu, Haifeng; Chan, Wallace K B; Ke, Xiaoyan; Zhang, Yang; Wren, Jonathan

2018-02-08

Precise assessment of ligand bioactivities (including IC50, EC50, Ki, Kd, etc.) is essential for virtual screening and lead compound identification. However, not all ligands have experimentally-determined activities. In particular, many G protein-coupled receptors (GPCRs), which are the largest integral membrane protein family and represent targets of nearly 40% drugs on the market, lack published experimental data about ligand interactions. Computational methods with the ability to accurately predict the bioactivity of ligands can help efficiently address this problem. We proposed a new method, WDL-RF, using weighted deep learning and random forest, to model the bioactivity of GPCR-associated ligand molecules. The pipeline of our algorithm consists of two consecutive stages: 1) molecular fingerprint generation through a new weighted deep learning method, and 2) bioactivity calculations with a random forest model; where one uniqueness of the approach is that the model allows end-to-end learning of prediction pipelines with input ligands being of arbitrary size. The method was tested on a set of twenty-six non-redundant GPCRs that have a high number of active ligands, each with 200∼4000 ligand associations. The results from our benchmark show that WDL-RF can generate bioactivity predictions with an average root-mean square error 1.33 and correlation coefficient (r2) 0.80 compared to the experimental measurements, which are significantly more accurate than the control predictors with different molecular fingerprints and descriptors. In particular, data-driven molecular fingerprint features, as extracted from the weighted deep learning models, can help solve deficiencies stemming from the use of traditional hand-crafted features and significantly increase the efficiency of short molecular fingerprints in virtual screening. The WDL-RF web server, as well as source codes and datasets of WDL-RF, is freely available at https://zhanglab.ccmb.med.umich.edu/WDL-RF/ for academic purposes. Xiaoyan Ke (kexynj@hotmail.com); Yang Zhang (zhng@umich.edu). Supplementary data are available at Bioinformatics online. © The Author (2018). Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com

A structured understanding of cellobiohydrolase I binding to poplar lignin fractions after dilute acid pretreatment

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

Yao, Lan; Yoo, Chang Geun; Meng, Xianzhi

Background: Cellulase adsorption to lignin is considered a cost barrier for bioethanol production; however, its detailed association mechanism is still not fully understood. In this study, two natural poplar variants with high and low sugar release performance were selected as the low and high recalcitrant raw materials (named L and H, respectively). Three different lignin fractions were extracted using ethanol, followed by p-dioxane and then cellulase treatment from the dilute acid pretreated poplar solids (fraction 1, 2, and 3, respectively).Results: Each lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weightsmore » for the other two lignin fractions were similar. 31P NMR analysis revealed that lignin fraction with higher molecular weight contained more aliphatic hydroxyl groups and less phenolic hydroxyl groups. Semi-quantitative analysis by 2D HSQC NMR indicated that the lignin fractions isolated from the natural variants had different contents of syringyl (S), guaiacyl (G) and interunit linkages. Lignin extracted by ethanol contained the largest amount of S units, the smallest amounts of G and p-hydroxybenzoate (PB) subunits, while the contents of these lignin subunits in the other two lignin fractions were similar. The lignin fraction obtained after cellulase treatment was primarily comprised of β-O-4 linkages with small amounts of β-5 and β–β linkages. The binding strength of these three lignin fractions obtained by Langmuir equations were in the order of L1 > L3 > L2 for the low recalcitrance poplar and H1 > H2 > H3 for the high recalcitrance poplar.Conclusions: Overall, adsorption ability of lignin was correlated with the sugar release of poplar. Structural features of lignin were associated with its binding to CBH. For natural poplar variants, lignin fractions with lower molecular weight and polydispersity index (PDI) exhibited more CBH adsorption ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.« less

Chemical modification of protein A chromatography ligands with polyethylene glycol. I: Effects on IgG adsorption equilibrium, kinetics, and transport.

PubMed

Weinberg, Justin; Zhang, Shaojie; Crews, Gillian; Carta, Giorgio; Przybycien, Todd

2018-04-20

Chemical modification of Protein A (ProA) chromatography ligands with polyethylene glycol (PEGylation) has been proposed as a strategy to increase the process selectivity and resin robustness by providing the ligand with a steric repulsion barrier against non-specific binding. This article comprises a comprehensive study of IgG adsorption and transport in Repligen CaptivA PriMAB resin with PEGylated ProA ligands that are modified using 5.2 and 21.5 kDa PEG chains. We studied the impact of the molecular weight of the PEG as well as the extent of PEGylation for the 5.2 kDa PEG modification. In all cases, PEGylation of ProA ligands decreases the resin average pore size, particle porosity, and static binding capacity for IgG proportional to the volume of conjugated PEG in the resin. Resin batch uptake experiments conducted in bulk via a stirred-tank system and with individual resin particles under confocal laser scanning microscopy suggests that PEGylation introduces heterogeneity into IgG binding kinetics: a fraction of the IgG binding sites are transformed from typical fast association kinetic behavior to slow kinetic behavior. pH gradient elution experiments of an IgG molecule on the modified resins show an increase in IgG elution pH for all modified resins, implying a decrease in IgG-ProA binding affinity on modification. Despite losses in static binding capacity for all resins with PEGylated ligands, the loss of dynamic binding capacity at 10% breakthrough (DBC 10% ) ranged more broadly from almost 0-47% depending on the PEG molecular weight and the extent of PEGylation. Minimal losses in DBC 10% were observed with a low extent of PEGylation with a smaller molecular weight PEG, while higher losses were observed at higher extents of PEGylation and with higher molecular weight PEG due to decreased static binding capacity and increased mass transfer resistance. This work provides insight into the practical implications for resin performance if PEGylation is considered as a strategy for selectivity enhancement in affinity chromatography with macromolecular ligands. Copyright © 2018 Elsevier B.V. All rights reserved.

A structured understanding of cellobiohydrolase I binding to poplar lignin fractions after dilute acid pretreatment

DOE PAGES

Yao, Lan; Yoo, Chang Geun; Meng, Xianzhi; ...

2018-04-04

Background: Cellulase adsorption to lignin is considered a cost barrier for bioethanol production; however, its detailed association mechanism is still not fully understood. In this study, two natural poplar variants with high and low sugar release performance were selected as the low and high recalcitrant raw materials (named L and H, respectively). Three different lignin fractions were extracted using ethanol, followed by p-dioxane and then cellulase treatment from the dilute acid pretreated poplar solids (fraction 1, 2, and 3, respectively).Results: Each lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weightsmore » for the other two lignin fractions were similar. 31P NMR analysis revealed that lignin fraction with higher molecular weight contained more aliphatic hydroxyl groups and less phenolic hydroxyl groups. Semi-quantitative analysis by 2D HSQC NMR indicated that the lignin fractions isolated from the natural variants had different contents of syringyl (S), guaiacyl (G) and interunit linkages. Lignin extracted by ethanol contained the largest amount of S units, the smallest amounts of G and p-hydroxybenzoate (PB) subunits, while the contents of these lignin subunits in the other two lignin fractions were similar. The lignin fraction obtained after cellulase treatment was primarily comprised of β-O-4 linkages with small amounts of β-5 and β–β linkages. The binding strength of these three lignin fractions obtained by Langmuir equations were in the order of L1 > L3 > L2 for the low recalcitrance poplar and H1 > H2 > H3 for the high recalcitrance poplar.Conclusions: Overall, adsorption ability of lignin was correlated with the sugar release of poplar. Structural features of lignin were associated with its binding to CBH. For natural poplar variants, lignin fractions with lower molecular weight and polydispersity index (PDI) exhibited more CBH adsorption ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.« less

Ultrafiltration characteristics of glucose polymers with low polydispersity.

PubMed

Leypoldt, John K; Hoff, Catherine M; Piscopo, Dean; Carr, Seraya N; Svatek, Jessica M; Holmes, Clifford J

2013-01-01

Icodextrin, a glucose polymer with a polydispersity [ratio of weight-average molecular weight (Mw) to number-average molecular weight] of approximately 2.6, has been shown, compared with glucose, to provide superior ultrafiltration (UF) efficiency [ratio of UF to carbohydrate (CHO) absorbed] when used as an osmotic agent during a long-dwell peritoneal dialysis exchange. In an experimental rabbit model, we evaluated the effect of Mw on the UF and UF efficiency of glucose polymers with low polydispersity. A crossover trial in female New Zealand White rabbits (2.20 - 2.65 kg) with surgically implanted peritoneal catheters evaluated two glucose polymers at nominal concentrations of 7.5 g/dL: a 6K polymer (Mw: 6.4 kDa; polydispersity: 2.3) and a 19K polymer (Mw: 18.8 kDa; polydispersity: 2.0). Rabbits were randomized to receive either the 6K (n = 11) or the 19K (n = 12) solution during the first exchange (40 mL/kg body weight). The alternative solution was evaluated in a second exchange 3 days later. During each 4-hour dwell, the UF and total glucose polymer CHO absorbed were determined. The UF was higher for the 6K (p < 0.0001) than for the 19K polymer (mean ± standard deviation: 73.6 ± 30.8 mL vs. 43.0 ± 20.2 mL), as was the amount of CHO absorbed (42.5% ± 9.8% vs. 35.7% ± 11.0%, p = 0.021). In spite of higher CHO absorption, an approximately 50% higher (p = 0.029) UF efficiency was achieved with the 6K polymer (28.3 ± 18.8 mL/g) than with the 19K polymer (19.0 ± 11.3 mL/g). The results were independent of the order of the experimental exchanges. Glucose polymers with low polydispersity are effective osmotic agents in a rabbit model. The low-Mw polymer was more effective at generating UF and had a higher UF efficiency, but those results came at the expense of the polymer being more readily absorbed from the peritoneal cavity.

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.

STUDIES ON THE PURIFICATION OF BACTERIOPHAGE

PubMed Central

Kalmanson, G.; Bronfenbrenner, J.

1939-01-01

A simple method of concentrating and purifying bacteriophage has been described. The procedure consisted essentially in collecting the active agent on a reinforced collodion membrane of a porosity that would just retain all the active agent and permit extraneous material to pass through. Advantage was taken of the fact that B. coli will proliferate and regenerate bacteriophage in a completely diffusible synthetic medium with ammonia as the only source of nitrogen, which permitted the purification of the bacteriophage by copious washing. The material thus obtained was concentrated by suction and after thorough washing possessed all the activity of the original filtrate. It was labile, losing its activity in a few days on standing, and was quickly and completely inactivated upon drying. This material contained approximately 15 per cent of nitrogen and with 2 or 3 mg. samples of inactive dry residue it was possible to obtain positive protein color tests. The concentrated and purified bacteriophage has about 10–14 mg. of nitrogen, or 6 x 10–17 gm. of protein per unit of lytic activity. Assuming that each unit of activity represents a molecule, the calculated maximum average molecular weight would be approximately 36,000,000, and on the assumption of a spherical shape of particles and a density of 1.3, the calculated radius would be about 22 millimicra. By measurement of the diffusion rate, the average radius of particle of the fraction of the purified bacteriophage which diffuses most readily through a porous plate was found to be of the order of magnitude of 9 millimicra, or of a calculated molecular weight of 2,250,000. Furthermore, when this purified bacteriophage was fractionated by forcing it through a thin collodion membrane, which permits the passage of only the smaller particles, it was possible to demonstrate in the ultrafiltrate active particles of about 2 millimicra in radius, and of a calculated molecular weight of 25,000. It was of interest to apply this method of purification to a staphylococcus bacteriophage. Since this organism does not readily grow in synthetic medium, a diffusate of yeast extract medium was employed. The better of two preparations contained about 10–12 mg. of nitrogen per unit of lytic activity. Although this is about one hundred times the amount of nitrogen found in an active unit of B. coli bacteriophage, nevertheless, the diffusion rate experiments gave results which paralleled those obtained with the coliphage. The diffusible particles of the crude staphylococcus bacteriophage had a radius of about 7 millimicra, and a calculated molecular weight of about 1,000,000, while the particles of the same phage which appeared in the ultrafiltrate through a thin collodion membrane had a radius of about 2.4 millimicra and a calculated molecular weight of about 45,000. It appears, therefore, that the active principle is distributed as particles of widely different sizes. However, since the smaller particles have all the properties of bacteriophage, the larger particles probably do not represent free molecules, but either are aggregates, or more likely, inactive colloids to which the active agent is adsorbed. The protein isolated, which bears the phage activity, is capable of stimulating the production of antilytic antibodies on parenteral injection into rabbits or guinea pigs. It retains its specific antigenicity when inactivated by formalin, but not when inactivated by drying. PMID:19873149

12 CFR Appendix B to Subpart A of... - Conversion of Scorecard Measures into Score

Code of Federal Regulations, 2014 CFR

2014-01-01

... 327—Conversion of Scorecard Measures into Score 1. Weighted Average CAMELS Rating Weighted average CAMELS ratings between 1 and 3.5 are assigned a score between 25 and 100 according to the following equation: S = 25 + [(20/3) * (C 2 −1)], where: S = the weighted average CAMELS score; and C = the weighted...

12 CFR Appendix B to Subpart A of... - Conversion of Scorecard Measures into Score

Code of Federal Regulations, 2013 CFR

2013-01-01

... 327—Conversion of Scorecard Measures into Score 1. Weighted Average CAMELS Rating Weighted average CAMELS ratings between 1 and 3.5 are assigned a score between 25 and 100 according to the following equation: S = 25 + [(20/3) * (C 2 −1)], where: S = the weighted average CAMELS score; and C = the weighted...

12 CFR Appendix B to Subpart A of... - Conversion of Scorecard Measures into Score

Code of Federal Regulations, 2012 CFR

2012-01-01

... 327—Conversion of Scorecard Measures into Score 1. Weighted Average CAMELS Rating Weighted average CAMELS ratings between 1 and 3.5 are assigned a score between 25 and 100 according to the following equation: S = 25 + [(20/3) * (C 2 −1)], where: S = the weighted average CAMELS score; and C = the weighted...

Mild acetosolv process to fractionate bamboo for the biorefinery: structural and antioxidant properties of the dissolved lignin.

PubMed

Li, Ming-Fei; Sun, Shao-Ni; Xu, Feng; Sun, Run-Cang

2012-02-22

Fractionation of lignocellulosic material into its constitutive components is of vital importance for the production of biofuels as well as other value-added chemicals. The conventional acetosolv processes are mainly focused on the production of pulp from woody lignocelluloses. In this study, a mild acetosolv process was developed to fractionate bamboo under atmospheric pressure to obtain cellulosic pulp, water-soluble fraction, and acetic acid lignin. The structural features of the lignins obtained under various conditions were characterized with elemental analysis, sugar analysis, alkaline nitrobenzene oxidation, gel permeation chromatography (GPC), (1)H nuclear magnetic resonance ((1)H NMR), and heteronuclear single-quantum coherence (HSQC) spectroscopy. As compared to milled wood lignin (MWL) of bamboo, acetic acid lignins had low impurities (carbohydrates 2.48-4.56%) mainly due to the cleavage of linkages between lignin and carbohydrates. In addition, acetic acid lignins showed a low proportion of syringyl (S) units. Due to the cleavage of linkages between lignin units, acetic acid lignins had weight-average molecular weights ranging from 4870 to 5210 g/mol, less than half that of MWL (13000 g/mol). In addition, acetic acid lignins showed stronger antioxidant activity mainly due to the significant increase of free phenolic hydroxyls. The lignins obtained with such low impurities, high free phenolic hydroxyls, and medium molecular weights are promising feedstocks to replace petroleum chemicals.

Megasupramolecules for safer, cleaner fuel by end association of long telechelic polymers.

PubMed

Wei, Ming-Hsin; Li, Boyu; David, R L Ameri; Jones, Simon C; Sarohia, Virendra; Schmitigal, Joel A; Kornfield, Julia A

2015-10-02

We used statistical mechanics to design polymers that defy conventional wisdom by self-assembling into "megasupramolecules" (≥5000 kg/mol) at low concentration (≤0.3 weight percent). Theoretical treatment of the distribution of individual subunits—end-functional polymers—among cyclic and linear supramolecules (ring-chain equilibrium) predicts that megasupramolecules can form at low total polymer concentration if, and only if, the backbones are long (>400 kg/mol) and end-association strength is optimal. Viscometry and scattering measurements of long telechelic polymers having polycyclooctadiene backbones and acid or amine end groups verify the formation of megasupramolecules. They control misting and reduce drag in the same manner as ultralong covalent polymers. With individual building blocks short enough to avoid hydrodynamic chain scission (weight-average molecular weights of 400 to 1000 kg/mol) and reversible linkages that protect covalent bonds, these megasupramolecules overcome the obstacles of shear degradation and engine incompatibility. Copyright © 2015, American Association for the Advancement of Science.

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

ERIC Educational Resources Information Center

Mathias, Lon J.; Moore, D. Roger

1985-01-01

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

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.

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.

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

PubMed

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

2014-11-01

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

Effects of gene carrier polyethyleneimines on the structure and binding capability of bovine serum albumin

NASA Astrophysics Data System (ADS)

Guo, Zhiyong; Kong, Zhijie; Wei, Yanshan; Li, Hua; Wang, Yajing; Huang, Aimin; Ma, Lin

2017-02-01

Polyethyleneimine (PEI), one of the most effective non-viral gene carriers, is also cytotoxic, however the molecular basis is poorly understood. Little is known about the effects of PEI on the structure and functions of the biomacromolecules. In this work, fluorescence, UV-vis absorption, circular dichroism (CD) spectroscopy and zeta-potential measurement were conducted to reveal the interaction between PEIs (average molecular weight 25, 10 and 1.8 kDa) and bovine serum albumin (BSA), and to evaluate the effects on the conformation of BSA as long as its binding capability to the model compounds, 8-anilino-1-naphthalenesulfonic acid (ANS) and quercetin. PEIs were found to complex with BSA and induced a conformational change of the protein by a major reduction of α-helix at PEI concentration < 0.2 mg·mL- 1 and an increase at higher PEI concentration. The binding efficacy of ANS and quercetin to BSA was greatly reduced by the competitive binding by PEI and influenced by the conformational change of BSA, which was found to display a similar trend to the change of the α-helix content of the protein. The polymer size played an important role in PEI-BSA interaction. PEI of higher molecular weight was more favorable to interact with BSA and more efficient to perturb the conformation and binding capability of the protein.

Biological and molecular characterization of silkworm strains from the Brazilian germplasm bank of Bombyx mori.

PubMed

Pereira, N C; Munhoz, R E F; Bignotto, T S; Bespalhuk, R; Garay, L B; Saez, C R N; Fassina, V A; Nembri, A; Fernandez, M A

2013-06-28

Brazil has only one public genetic pool of Bombyx mori strains, which was established in 2005 at Universidade Estadual de Maringá, Maringá, Paraná State. This genetic bank has been maintained, and the strains have been characterized using genetic and morphological tools. The quantitative and qualitative traits, directly or indirectly related to productivity, were evaluated in 14 silkworm strains. In addition to biological and productivity analyses, DNA markers related to susceptibility to the B. mori nucleopolyhedrovirus (BmNPV) were analyzed. BmNPV is a major cause of production loss and is a serious problem for Paraná sericulture. The silkworm strains from diverse geographic origins were found to have different characteristics, including body weight, larval stage duration, cocoon weight, and other biological traits. In terms of productivity, the raw silk percentages were almost uniform, with an overall average of 16.28%. Overall, the Chinese strain C37 gave the best performance in many of the quantitative traits, and it surpassed the other strains in productivity traits. Therefore, it can be used as one of the strains that compose the elite germplasm for silkworm breeding programs. Additionally, genetic molecular markers were efficient in discriminating between B. mori strains that had been identified based on their geographical origin. We found that all Japanese strains produced a 400-bp molecular marker that has been associated with susceptibility to BmNPV.

[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.

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

Biodegradation of Degradable Plastic Polyethylene by Phanerochaete and Streptomyces Species †

PubMed Central

Lee, Byungtae; Pometto, Anthony L.; Fratzke, Alfred; Bailey, Theodore B.

1991-01-01

The ability of lignin-degrading microorganisms to attack degradable plastics was investigated in pure shake flask culture studies. The degradable plastic used in this study was produced commercially by using the Archer-Daniels-Midland POLYCLEAN masterbatch and contained pro-oxidant and 6% starch. The known lignin-degrading bacteria Streptomyces viridosporus T7A, S. badius 252, and S. setonii 75Vi2 and fungus Phanerochaete chrysosporium were used. Pro-oxidant activity was accelerated by placing a sheet of plastic into a drying oven at 70°C under atmospheric pressure and air for 0, 4, 8, 12, 16, or 20 days. The effect of 2-, 4-, and 8-week longwave UV irradiation at 365 nm on plastic biodegradability was also investigated. For shake flask cultures, plastics were chemically disinfected and incubated-shaken at 125 rpm at 37°C in 0.6% yeast extract medium (pH 7.1) for Streptomyces spp. and at 30°C for the fungus in 3% malt extract medium (pH 4.5) for 4 weeks along with an uninoculated control for each treatment. Weight loss data were inconclusive because of cell mass accumulation. For almost every 70°C heat-treated film, the Streptomyces spp. demonstrated a further reduction in percent elongation and polyethylene molecular weight average when compared with the corresponding uninoculated control. Significant (P < 0.05) reductions were demonstrated for the 4- and 8-day heat-treated films by all three bacteria. Heat-treated films incubated with P. chrysosporium consistently demonstrated higher percent elongation and molecular weight average than the corresponding uninoculated controls, but were lower than the corresponding zero controls (heat-treated films without 4-week incubation). The 2- and 4-week UV-treated films showed the greatest biodegradation by all three bacteria. Virtually no degradation by the fungus was observed. To our knowledge, this is the first report demonstrating bacterial degradation of these oxidized polyethylenes in pure culture. PMID:16348434

Influence of therapeutic radiation on polycaprolactone and polyurethane biomaterials.

PubMed

Cooke, Shelley L; Whittington, Abby R

2016-03-01

Biomedical polymers are exposed in vivo to ionizing radiation as implants, coatings and bystander materials. High levels of ionizing radiation (e.g. X-ray and gamma) have been reported to cause degradation and/or cross-linking in many polymers. This pilot study sought to determine causes of failure, by investigating how therapeutic radiation affects two different porous polymeric scaffolds: polycaprolactone (PCL) and polyurethane (PU). PCL is a bioresorbable material used in biomedical devices (e.g., dentistry, internal fixation devices and targeted drug delivery capsules). PU is commonly used in medical applications (e.g., coatings for pacemakers, tissue expanders, catheter tubing and wound dressings). PU was specifically fabricated to be a non-degradable polymer in this study. Porous scaffolds, fabricated using solvent casting and/or salt leeching techniques, were placed in phosphate buffered saline (PBS, pH=7.4) and exposed to typical cancer radiotherapy. A total dose of 50 Gy was broken into 25 doses over an eleven-week period. Collected PBS was tested for polymer leachants and degradation products using Gas Chromatography Mass Spectroscopy (GC-MS), results revealed no analyzable leachants from either polymer. Scaffolds were characterized using Environmental Scanning Electron Microscopy, Size-exclusion chromatography (SEC), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR). No gross visual changes were observed in either polymer, however PU exhibited microstructure changes after irradiation. Increased number average molecular weight and weight average molecular weight in PCL and PU were observed after irradiation, indicating crosslinking. PU displayed an increase in intrinsic viscosity that further confirms increased crosslinking. PCL and PU showed decreases in crystallinity after irradiation, and PU crystallinity shifted from long-range-order hard segments to short-range-order hard segments after irradiation. Results from both PCL and PU suggest changes in polymer backbones. This preliminary study suggests that therapeutic radiation doses cause both degradation and crosslinking in PCL and PU. Copyright © 2015 Elsevier B.V. All rights reserved.

Biodegradation of degradable plastic polyethylene by phanerochaete and streptomyces species.

PubMed

Lee, B; Pometto, A L; Fratzke, A; Bailey, T B

1991-03-01

The ability of lignin-degrading microorganisms to attack degradable plastics was investigated in pure shake flask culture studies. The degradable plastic used in this study was produced commercially by using the Archer-Daniels-Midland POLYCLEAN masterbatch and contained pro-oxidant and 6% starch. The known lignin-degrading bacteria Streptomyces viridosporus T7A, S. badius 252, and S. setonii 75Vi2 and fungus Phanerochaete chrysosporium were used. Pro-oxidant activity was accelerated by placing a sheet of plastic into a drying oven at 70 degrees C under atmospheric pressure and air for 0, 4, 8, 12, 16, or 20 days. The effect of 2-, 4-, and 8-week longwave UV irradiation at 365 nm on plastic biodegradability was also investigated. For shake flask cultures, plastics were chemically disinfected and incubated-shaken at 125 rpm at 37 degrees C in 0.6% yeast extract medium (pH 7.1) for Streptomyces spp. and at 30 degrees C for the fungus in 3% malt extract medium (pH 4.5) for 4 weeks along with an uninoculated control for each treatment. Weight loss data were inconclusive because of cell mass accumulation. For almost every 70 degrees C heat-treated film, the Streptomyces spp. demonstrated a further reduction in percent elongation and polyethylene molecular weight average when compared with the corresponding uninoculated control. Significant (P < 0.05) reductions were demonstrated for the 4- and 8-day heat-treated films by all three bacteria. Heat-treated films incubated with P. chrysosporium consistently demonstrated higher percent elongation and molecular weight average than the corresponding uninoculated controls, but were lower than the corresponding zero controls (heat-treated films without 4-week incubation). The 2- and 4-week UV-treated films showed the greatest biodegradation by all three bacteria. Virtually no degradation by the fungus was observed. To our knowledge, this is the first report demonstrating bacterial degradation of these oxidized polyethylenes in pure culture.

Light controls phospholipase A2α and β gene expression in Citrus sinensis

PubMed Central

Liao, Hui-Ling; Burns, Jacqueline K.

2010-01-01

The low-molecular weight secretory phospholipase A2α (CssPLA2α) and β (CsPLA2β) cloned in this study exhibited diurnal rhythmicity in leaf tissue of Citrus sinensis. Only CssPLA2α displayed distinct diurnal patterns in fruit tissues. CssPLA2α and CsPLA2β diurnal expression exhibited periods of approximately 24 h; CssPLA2α amplitude averaged 990-fold in the leaf blades from field-grown trees, whereas CsPLA2β amplitude averaged 6.4-fold. Diurnal oscillation of CssPLA2α and CsPLA2β gene expression in the growth chamber experiments was markedly dampened 24 h after transfer to continuous light or dark conditions. CssPLA2α and CsPLA2β expressions were redundantly mediated by blue, green, red and red/far-red light, but blue light was a major factor affecting CssPLA2α and CsPLA2β expression. Total and low molecular weight CsPLA2 enzyme activity closely followed diurnal changes in CssPLA2α transcript expression in leaf blades of seedlings treated with low intensity blue light (24 μmol m−2 s−1). Compared with CssPLA2α basal expression, CsPLA2β expression was at least 10-fold higher. Diurnal fluctuation and light regulation of PLA2 gene expression and enzyme activity in citrus leaf and fruit tissues suggests that accompanying diurnal changes in lipophilic second messengers participate in the regulation of physiological processes associated with phospholipase A2 action. PMID:20388744

The effects of dietary kefir and low molecular weight sodium alginate on serum immune parameters, resistance against Streptococcus agalactiae and growth performance in Nile tilapia (Oreochromis niloticus).

PubMed

Van Doan, Hien; Hoseinifar, Seyed Hossein; Tapingkae, Wanaporn; Khamtavee, Pimporn

2017-03-01

The present study evaluates the effects of dietary kefir and low molecular weight sodium alginate (LWMSA) (singular or combined) on non-specific immune response, disease resistance and growth performance of Nile tilapia (Oreochromis niloticus). Fish with average weight of 18.60 ± 0.04 g were supplied and randomly stocked in sixteen glass tanks (150 L) at density of 20 fish per tank. Fish were fed experimental diets as follows: 0 g kg -1 LMWSA (Control, Diet 1), 10 g kg -1 LMWSA (Diet 2), 40 g kg -1 kefir (Diet 3), and 10 g kg -1 LMWSA + 40 g kg -1 kefir (Diet 4) for 50 days. At the end of the feeding trial, serum lysozyme (SL), phagocytosis (PI), respiratory burst (RB), and alternative complement (ACH50) activities as well as growth performance were measured. Singular and combined administration of kefir and low molecular weight sodium alginate (LMWSA) significantly increased serum SL, PI, RB, and ACH50 activities compared control group (P < 0.05); the highest innate immune responses were observed in fish fed combinational diet (kefir + LMWSA) (P < 0.05). The results of experimental challenge revealed significantly higher resistance against Streptococcus agalactiae in fish fed supplemented diets and the highest post challenge survival rate was observed in synbiotic diet (P < 0.05). Similar results obtained in case of growth parameters. Feeding on supplemented diet significantly improved SGR and FCR and the highest growth parameters was observed in fish fed synbiotic diet (P < 0.05). These finding revealed that combined administration of dietary kefir and LMWSA can be considered for improving immune response, disease resistance and growth performance of Nile tilapia. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

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.

Immunomodulatory activity of polysaccharides isolated from Alchornea cordifolia

PubMed Central

Kouakou, Koffi; Schepetkin, Igor A.; Yapi, Ahoua; Kirpotina, Liliya N.; Jutila, Mark A.; Quinn, Mark T.

2013-01-01

Ethnopharmacological relevance Extracts of leaves from different species of the genus Alchornea have been used for centuries to treat a variety of medicinal problems in tropical Africa. However, little is known about the high-molecular weight active components conferring therapeutic properties to these extracts. Objective The aim of this study was to evaluate the immunomodulatory activity of polysaccharides isolated from the leaves of Alchornea cordifolia. Materials and methods Water-soluble polysaccharides from leaves of A. cordifolia were extracted and fractionated by DEAE-cellulose, Diaion HP-20, and size-exclusion chromatography. Molecular weight, sugar analysis, and other physical and chemical characterization of the fractions were performed. Immunomodulatory activity of the polysaccharide fractions was evaluated by determining their ability to induce monocyte/macrophage nitric oxide (NO) and cytokine production. Activation of mitogen activated protein kinases (MAPK) was also assessed using a phospho-MAPK array. Activation of nuclear factor κB (NF-κB) was measured using an alkaline phosphatase reporter gene assay in THP1-Blue monocytic cells. Results Six polysaccharide fractions from A. cordifolia were isolated. Fractions containing type II arabinogalactan had potent immunomodulatory activity. Particularly, the parent fraction AP-AU and its high-molecular weight sub-fraction AP-AU1 (average Mr was estimated to be 39.5 kDa) induced production of NO and cytokines [interleukin (IL)-1β, -6, -10, tumor necrosis factor (TNF)-α, and granulocyte macrophage-colony stimulating factor (GM-CSF)] in human peripheral blood mononuclear cells and human and murine monocyte/macrophages cell lines in vitro. Furthermore, treatment with AP-AU1 induced phosphorylation of Akt2, p38δ/p38γ, p70S6K1, RSK2, and mTOR, as well as stimulation of NF-κB transcriptional activity. Conclusion Our results provide a molecular basis to explain a portion of the beneficial therapeutic properties of water extracts from A. cordifolia leaves in traditional folk medicine of Africa. PMID:23291534

Immunomodulatory activity of polysaccharides isolated from Alchornea cordifolia.

PubMed

Kouakou, Koffi; Schepetkin, Igor A; Yapi, Ahoua; Kirpotina, Liliya N; Jutila, Mark A; Quinn, Mark T

2013-03-07

Extracts of leaves from different species of the genus Alchornea have been used for centuries to treat a variety of medicinal problems in tropical Africa. However, little is known about the high-molecular weight active components conferring therapeutic properties to these extracts. The aim of this study was to evaluate the immunomodulatory activity of polysaccharides isolated from the leaves of Alchornea cordifolia. Water-soluble polysaccharides from leaves of Alchornea cordifolia were extracted and fractionated by DEAE-cellulose, Diaion HP-20, and size-exclusion chromatography. Molecular weight, sugar analysis, and other physical and chemical characterization of the fractions were performed. Immunomodulatory activity of the polysaccharide fractions was evaluated by determining their ability to induce monocyte/macrophage nitric oxide (NO) and cytokine production. Activation of mitogen activated protein kinases (MAPK) was also assessed using a phospho-MAPK array. Activation of nuclear factor κB (NF-κB) was measured using an alkaline phosphatase reporter gene assay in THP1-Blue monocytic cells. Six polysaccharide fractions from Alchornea cordifolia were isolated. Fractions containing type II arabinogalactan had potent immunomodulatory activity. Particularly, the parent fraction AP-AU and its high-molecular weight sub-fraction AP-AU1 (average M(r) was estimated to be 39.5kDa) induced production of NO and cytokines [interleukin (IL)-1β, -6, -10, tumor necrosis factor (TNF)-α, and granulocyte-macrophage-colony stimulating factor (GM-CSF)] in human peripheral blood mononuclear cells and human and murine monocyte/macrophages cell lines in vitro. Furthermore, treatment with AP-AU1 induced phosphorylation of Akt2, p38δ/p38γ, p70S6K1, RSK2, and mTOR, as well as stimulation of NF-κB transcriptional activity. Our results provide a molecular basis to explain a portion of the beneficial therapeutic properties of water extracts from Alchornea cordifolia leaves in traditional folk medicine of Africa. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Liquid-State NMR Analysis of Nanocelluloses.

PubMed

King, Alistair W T; Mäkelä, Valtteri; Kedzior, Stephanie A; Laaksonen, Tiina; Partl, Gabriel J; Heikkinen, Sami; Koskela, Harri; Heikkinen, Harri A; Holding, Ashley J; Cranston, Emily D; Kilpeläinen, Ilkka

2018-04-11

Recent developments in ionic liquid electrolytes for cellulose or biomass dissolution has also allowed for high-resolution 1 H and 13 C NMR on very high molecular weight cellulose. This permits the development of advanced liquid-state quantitative NMR methods for characterization of unsubstituted and low degree of substitution celluloses, for example, surface-modified nanocelluloses, which are insoluble in all molecular solvents. As such, we present the use of the tetrabutylphosphonium acetate ([P 4444 ][OAc]):DMSO- d 6 electrolyte in the 1D and 2D NMR characterization of poly(methyl methacrylate) (PMMA)-grafted cellulose nanocrystals (CNCs). PMMA- g-CNCs was chosen as a difficult model to study, to illustrate the potential of the technique. The chemical shift range of [P 4444 ][OAc] is completely upfield of the cellulose backbone signals, avoiding signal overlap. In addition, application of diffusion-editing for 1 H and HSQC was shown to be effective in the discrimination between PMMA polymer graft resonances and those from low molecular weight components arising from the solvent system. The bulk ratio of methyl methacrylate monomer to anhydroglucose unit was determined using a combination of HSQC and quantitative 13 C NMR. After detachment and recovery of the PMMA grafts, through methanolysis, DOSY NMR was used to determine the average self-diffusion coefficient and, hence, molecular weight of the grafts compared to self-diffusion coefficients for PMMA GPC standards. This finally led to a calculation of both graft length and graft density using liquid-state NMR techniques. In addition, it was possible to discriminate between triads and tetrads, associated with PMMA tacticity, of the PMMA still attached to the CNCs (before methanolysis). CNC reducing end and sulfate half ester resonances, from sulfuric acid hydrolysis, were also assignable. Furthermore, other biopolymers, such as hemicelluloses and proteins (silk and wool), were found to be soluble in the electrolyte media, allowing for wider application of this method beyond just cellulose analytics.

Effects of condensed tannin fractions of different molecular weights from a Leucaena leucocephala hybrid on in vitro methane production and rumen fermentation.

PubMed

Saminathan, Mookiah; Sieo, Chin Chin; Abdullah, Norhani; Wong, Clemente Michael Vui Ling; Ho, Yin Wan

2015-10-01

Molecular weights (MWs) and their chemical structures are the primary factors determining the influence of condensed tannins (CTs) on animal nutrition and methane (CH4 ) production in ruminants. In this study the MWs of five CT fractions from Leucaena leucocephala hybrid-Rendang (LLR) were determined and the CT fractions were investigated for their effects on CH4 production and rumen fermentation. The number-average molecular weight (Mn ) of fraction F1 (1265.8 Da), which was eluted first, was the highest, followed by those of fractions F2 (1028.6 Da), F3 (652.2 Da), F4 (562.2 Da) and F5 (469.6 Da). The total gas (mL g(-1) dry matter (DM)) and CH4 production decreased significantly (P < 0.05) with increasing MWs of the CT fractions, but there were no significant (P > 0.05) differences between the CT fractions and control on DM degradation. However, the in vitro N disappearance decreased significantly (P < 0.05) with the inclusion of CT fraction F1 (highest MW) compared with the control and other fractions (F2-F5). The inclusion of CT fraction F1 also significantly decreased (P < 0.05) total volatile fatty acid and acetic acid concentrations compared with the control. The acetic/propionic acid ratio was significantly decreased (P < 0.05) by fraction F1 but not by the control and other fractions (F2-F5). The CT fractions of different MWs from LLR could affect rumen fermentation and CH4 production, and the impact was more pronounced for the CT fraction with a higher MW. © 2014 Society of Chemical Industry.

The removal of organic precursors of DBPs during three advanced water treatment processes including ultrafiltration, biofiltration, and ozonation.

PubMed

Zha, Xiao-Song; Ma, Lu-Ming; Wu, Jin; Liu, Yan

2016-08-01

The removal efficiency of organic matter, the formation potential of trihalomethanes (THMFP), and the formation potential of haloacetic acids (HAAFP) in each unit of three advanced treatment processes were investigated in this paper. The molecular weight distribution and the components of organic matter in water samples were also determined to study the transformation of organic matter during these advanced treatments. Low-molecular-weight matter was the predominant fraction in raw water, and it could not be removed effectively by ultrafiltration and biofiltration. The dominant species of disinfection by-product formation potential (DBPFP) in raw water were chloroform and monochloroacetic acid (MCAA), with average concentrations of 107.3 and 125.9 μg/L, respectively. However, the formation potential of chloroform and MCAA decreased to 36.2 and 11.5 μg/L after ultrafiltration. Similarly, biological pretreatment obtained high removal efficiency for DBPFP. The total THMFP decreased from 173.8 to 81.8 μg/L, and the total HAAFP decreased from 211.9 to 84.2 μg/L. Separate ozonation had an adverse effect on DBPFP, especially for chlorinated HAAFP. Numerous low-molecular-weight compounds such as aldehydes, ketones, and alcohols were generated during the ozonation, which have been proven to be important precursors of HAAs. However, the ozonation/biological activated carbon (BAC) combined process had a better removal efficiency for DBPFP. The total DBPFP decreased remarkably from 338.7 to 113.3 μg/L after the O3/BAC process, far below the separated BAC of process B (189.1 μg/L).

On-the-Fly Kinetic Monte Carlo Simulation of Aqueous Phase Advanced Oxidation Processes.

PubMed

Guo, Xin; Minakata, Daisuke; Crittenden, John

2015-08-04

We have developed an on-the-fly kinetic Monte Carlo (KMC) model to predict the degradation mechanisms and fates of intermediates and byproducts that are produced during aqueous-phase advanced oxidation processes (AOPs). The on-the-fly KMC model is composed of a reaction pathway generator, a reaction rate constant estimator, a mechanistic reduction module, and a KMC solver. The novelty of this work is that we develop the pathway as we march forward in time rather than developing the pathway before we use the KMC method to solve the equations. As a result, we have fewer reactions to consider, and we have greater computational efficiency. We have verified this on-the-fly KMC model for the degradation of polyacrylamide (PAM) using UV light and titanium dioxide (i.e., UV/TiO2). Using the on-the-fly KMC model, we were able to predict the time-dependent profiles of the average molecular weight for PAM. The model provided detailed and quantitative insights into the time evolution of the molecular weight distribution and reaction mechanism. We also verified our on-the-fly KMC model for the destruction of (1) acetone, (2) trichloroethylene (TCE), and (3) polyethylene glycol (PEG) for the ultraviolet light and hydrogen peroxide AOP. We demonstrated that the on-the-fly KMC model can achieve the same accuracy as the computer-based first-principles KMC (CF-KMC) model, which has already been validated in our earlier work. The on-the-fly KMC is particularly suitable for molecules with large molecular weights (e.g., polymers) because the degradation mechanisms for large molecules can result in hundreds of thousands to even millions of reactions. The ordinary differential equations (ODEs) that describe the degradation pathways cannot be solved using traditional numerical methods, but the KMC can solve these equations.

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

Evaluation of bending modulus of lipid bilayers using undulation and orientation analysis

NASA Astrophysics Data System (ADS)

Chaurasia, Adarsh K.; Rukangu, Andrew M.; Philen, Michael K.; Seidel, Gary D.; Freeman, Eric C.

2018-03-01

In the current paper, phospholipid bilayers are modeled using coarse-grained molecular dynamics simulations with the MARTINI force field. The extracted molecular trajectories are analyzed using Fourier analysis of the undulations and orientation vectors to establish the differences between the two approaches for evaluating the bending modulus. The current work evaluates and extends the implementation of the Fourier analysis for molecular trajectories using a weighted horizon-based averaging approach. The effect of numerical parameters in the analysis of these trajectories is explored by conducting parametric studies. Computational modeling results are validated against experimentally characterized bending modulus of lipid membranes using a shape fluctuation analysis. The computational framework is then used to estimate the bending moduli for different types of lipids (phosphocholine, phosphoethanolamine, and phosphoglycerol). This work provides greater insight into the numerical aspects of evaluating the bilayer bending modulus, provides validation for the orientation analysis technique, and explores differences in bending moduli based on differences in the lipid nanostructures.

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.

Effect of the different chain transfer agents on molecular weight and optical properties of poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Çetinkaya, Onur; Demirci, Gökhan; Mergo, Paweł

2017-08-01

Investigation of molecular weight and optical properties of poly(methyl metacrylate) (PMMA) polymerized in house with different chain transfer agents was studied. Isopropyl alcohol (IPA), n-butyl mercaptan (nBMC) and pentamethyl disilane (PMDS) were used as chain transfer agents. The molecular weight (Mw) of PMMA samples were measured by Ostwald viscometer. Mw of bulk polymer samples were decreased with increase the concentration of chain transfer agents (CTA). Since reactivity of used CTAs is not same, molecular weights of samples which were produced with different type of CTA but same concentration of CTA was varied. Higher concentration of n-BMC showed higher scattering. Transmission of samples could not be correlated with different concentration of CTA. Refractive index of samples was not affected by concentration of CTA nevertheless higher molecular weight of CTA showed higher refractive index.

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.

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).

Synthesis and characterization of poly(lactic acid)/ montmorillonite nanocomposites by in situ polycondensation catalyzed by non-metal-based compound.

PubMed

Kaewprapan, Kulwadee; Phattanarudee, Siriwan

2012-01-01

Poly(lactic acid)/montmorillonite nanocomposites were prepared by using non-toxic catalysts, i.e., phthalic acid and succinimide, via in situ polycondensation in presence of silicate. Concentrations of catalysts and clay were varied in a range of 0-3% wt and 0-0.5% wt, respectively. The reaction condition was controlled at 180 degrees C for 24 hr under a reduced pressure. Viscosity average molecular weight of the synthesized polymers and nanocomposites were characterized and compared using an Ubbelohde viscometer. Pattern of silicate distribution in the composites was investigated by X-ray diffraction to correlate with thermal properties evaluated by differential scanning calorimetry and thermogravimetric analysis. The results showed that the addition of catalysts at 2% wt gave the highest product yield (55-60%). The presence of silicate affected on molecular weight reduction, and the diffracted patterns suggested an intercalated structure. With a small amount of added filler, a significant improvement in thermal property and crystallinity of the resultant composites was obtained compared to those of the catalyzed polymers, in which the composites with succinimide exhibited overall better thermal stability and higher crystallinity than the ones prepared with phthalic acid.

Characterization of polysaccharides extracted from Platycodon grandiflorus (Jacq.) A.DC. affecting activation of chicken peritoneal macrophages.

PubMed

Zheng, Pimiao; Fan, Wentao; Wang, Shenghua; Hao, Pan; Wang, Yang; Wan, Huiyu; Hao, Zhihui; Liu, Jianzhu; Zhao, Xiaona

2017-03-01

Polysaccharides were isolated from Platycodon grandiflorus (Jacq.) A.DC. (PG) and the effects of three polysaccharides (PGPS 80 , PGPS 60 , PGPS t ) on their immunological activities were studied. The structure identification of PGPSs was assessed using physicochemical and spectral methods. Results showed that PGPS t (2.67×10 5 Da) compared to PGPS 80 (1.01×10 5 Da) and PGPS 60 (1.12×10 5 Da) has relatively higher average molecular weight(Mw) at the first peak with a narrower molecular weight distribution and all consisted of glucose, mannose, arabinose, galactose, xylose and rhamnose in different mass percentages. PGPS 80 and PGPS t linked mainly by 1,3-and 1,6-β-d-Galp residues. The immunological efficacy of PGPSs was performed on chicken peritoneal macrophages. Results showed that PGPS t significantly increased phagocytic rates, proliferation and NO production, stimulated macrophages to produce cytokines, including TNF-α, IL-1β and IL-6 as well as stimulated macrophages to express the maturation markers CD80 and CD86. These findings suggest that PGPS t exerted significant immunological activity and might be associated with special characters. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica.

PubMed

Mubarekyan; Santore

2000-07-15

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.

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

Wang, Wenwen; Wang, Weiyu; Li, Hui

In this study, high molecular weight “comb-shaped” graft copolymers, poly(isoprene-g-styrene), with polyisoprene as the backbone and polystyrene as side chains, were synthesized via free radical emulsion polymerization by copolymerization of isoprene with a polystyrene macromonomer synthesized using anionic polymerization. A small amount of toluene was used in order to successfully disperse the macromonomer. Both a redox and thermal initiation system were used in the emulsion polymerization, and the latex particle size and distribution were investigated by dynamic light scattering. The structural characteristics of the macromonomer and comb graft copolymers were investigated through use of size exclusion chromatography, spectroscopy, microscopy, thermalmore » analysis, and rheology. While the macromonomer was successfully copolymerized to obtain the desired multigraft copolymers, small amounts of unreacted macromonomer remained in the products, reflecting its reduced reactivity due to steric effects. Nevertheless, the multigraft copolymers obtained were very high in molecular weight (5–12 × 10 5 g/mol) and up to 10 branches per chain, on average, could be incorporated. A material incorporating 29 wt% polystyrene exhibits a disordered microphase separated morphology and elastomeric properties. As a result, these materials show promise as new, highly tunable, and potentially low cost thermoplastic elastomers.« less

Methacrylic Zwitterionic, Thermoresponsive, and Hydrophilic (Co)Polymers via Cu(0)-Polymerization: The Importance of Halide Salt Additives.

PubMed

Simula, Alexandre; Anastasaki, Athina; Haddleton, David M

2016-02-01

The synthesis of hydrophilic, thermoresponsive, and zwitterionic polymethacrylates is reported by Cu(0)-mediated reversible deactivation radical polymerization in water and/or water/alcohol mixtures. The predisproportionation of [Cu(I) (PMDETA)Cl] in water prior to initiator and monomer addition is exploited to yield well-defined polymethacrylates with full monomer conversions in 30 min. The addition of supplementary halide salts (NaCl) enables the synthesis of various molecular weight poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA475) (DPn = 10-80, Mn ≈ 10,000-40 000 g mol(-1)) with full monomer conversion and narrow molecular weight distributions attained in all cases (Đ ≈ 1.20-1.30). A bifunctional PEG initiator (average Mn ≈ 1000 g mol(-1)) is utilized for the polymerization of a wide range of methacrylates including 2-dimethylaminoethyl methacrylate, 2-morpholinoethyl methacrylate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and 2-methacryloyloxyethyl phosphorylcholine. Despite the high water content, high end group fidelity is demonstrated by in situ chain extensions and block copolymerizations with PEGMA475 yielding well-defined functional telechelic pentablock copolymers within 2.5 h. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous-Time Random Walk Models of DNA Electrophoresis in a Post Array: II. Mobility and Sources of Band Broadening

PubMed Central

Olson, Daniel W.; Dutta, Sarit; Laachi, Nabil; Tian, Mingwei; Dorfman, Kevin D.

2011-01-01

Using the two-state, continuous-time random walk model, we develop expressions for the mobility and the plate height during DNA electrophoresis in an ordered post array that delineate the contributions due to (i) the random distance between collisions and (ii) the random duration of a collision. These contributions are expressed in terms of the means and variances of the underlying stochastic processes, which we evaluate from a large ensemble of Brownian dynamics simulations performed using different electric fields and molecular weights in a hexagonal array of 1 μm posts with a 3 μm center-to-center distance. If we fix the molecular weight, we find that the collision frequency governs the mobility. In contrast, the average collision duration is the most important factor for predicting the mobility as a function of DNA size at constant Péclet number. The plate height is reasonably well-described by a single post rope-over-pulley model, provided that the extension of the molecule is small. Our results only account for dispersion inside the post array and thus represent a theoretical lower bound on the plate height in an actual device. PMID:21290387

Air quality at night markets in Taiwan.

PubMed

Zhao, Ping; Lin, Chi-Chi

2010-03-01

In Taiwan, there are more than 300 night markets and they have attracted more and more visitors in recent years. Air quality in night markets has become a public concern. To characterize the current air quality in night markets, four major night markets in Kaohsiung were selected for this study. The results of this study showed that the mean carbon dioxide (CO2) concentrations at fixed and moving sites in night markets ranged from 326 to 427 parts per million (ppm) during non-open hours and from 433 to 916 ppm during open hours. The average carbon monoxide (CO) concentrations at fixed and moving sites in night markets ranged from 0.2 to 2.8 ppm during non-open hours and from 2.1 to 14.1 ppm during open hours. The average 1-hr levels of particulate matter with aerodynamic diameters less than 10 microm (PM10) and less than 2.5 microm (PM2.5) at fixed and moving sites in night markets were high, ranging from 186 to 451 microg/m3 and from 175 to 418 microg/m3, respectively. The levels of PM2.5 accounted for 80-97% of their respective PM10 concentrations. The average formaldehyde (HCHO) concentrations at fixed and moving sites in night markets ranged from 0 to 0.05 ppm during non-open hours and from 0.02 to 0.27 ppm during open hours. The average concentration of individual polycyclic aromatic hydrocarbons (PAHs) was found in the range of 0.09 x 10(4) to 1.8 x 10(4) ng/m3. The total identified PAHs (TIPs) ranged from 7.8 x 10(1) to 20 x 10(1) ng/m3 during non-open hours and from 1.5 x 10(4) to 4.0 x 10(4) ng/m3 during open hours. Of the total analyzed PAHs, the low-molecular-weight PAHs (two to three rings) were the dominant species, corresponding to an average of 97% during non-open hours and 88% during open hours, whereas high-molecular-weight PAHs (four to six rings) represented 3 and 12% of the total detected PAHs in the gas phase during non-open and open hours, respectively.

Application of parylene for surface (polymer) enhanced laser desorption/ionization of synthetic polymers.

PubMed

Miksa, Beata J; Sochacki, Marek; Sroka-Bartnicka, Anna; Uznański, Paweł; Nosal, Andrzej; Potrzebowski, Marek J

2013-04-15

Synthetic polymers of molecular masses up to a few kDa can be analyzed without the use of any matrix by direct laser desorption/ionization mass spectrometry (LDI-MS). In this technique, the surface of the sample plate plays a crucial role, and many attempts have been made to understand the influence of the surface on the ease of desorption. Since this technique requires no tedious sample pretreatment, it is a promising method for the rapid characterization of various synthetic polymers. Parylene (poly(p-xylylenes), PPX) was tested as a surface support for studying the molecular masses of biocompatible polymers: poly(ethylene glycol) (PEG), poly(L-lactide) (PLLA), and poly(methyl methacrylate) (PMMA). The average molecular masses of the polymers were: PEG (600.0 Da and 3.5 kDa), PMMA (2.0 kDa), and PLLA (2.8 kDa). LDI mass spectra of polymers deposited on parylene were enhanced by a factor of two over those obtained directly from the gold target plate. Modification of the surface of the target plate by the addition of a PPX layer extended the functionality of LDI-TOF MS, especially for the analysis of low-mass compounds. The LDI analysis using the PPX-coated target plate provided details of polymers including: end-group, composition, monomer unit, and molecular mass distribution. The average molecular weights of four tested polymers on the gold target plate and the PPX support were unchanged, indicating that sample degradation was not occurring despite the high energy of the laser beam. The LDI investigations showed that the PPX support boosted ion yields by a factor of two compared with the gold target plate. Copyright © 2013 John Wiley & Sons, Ltd.

Shear-stress fluctuations and relaxation in polymer glasses

NASA Astrophysics Data System (ADS)

Kriuchevskyi, I.; Wittmer, J. P.; Meyer, H.; Benzerara, O.; Baschnagel, J.

2018-01-01

We investigate by means of molecular dynamics simulation a coarse-grained polymer glass model focusing on (quasistatic and dynamical) shear-stress fluctuations as a function of temperature T and sampling time Δ t . The linear response is characterized using (ensemble-averaged) expectation values of the contributions (time averaged for each shear plane) to the stress-fluctuation relation μsf for the shear modulus and the shear-stress relaxation modulus G (t ) . Using 100 independent configurations, we pay attention to the respective standard deviations. While the ensemble-averaged modulus μsf(T ) decreases continuously with increasing T for all Δ t sampled, its standard deviation δ μsf(T ) is nonmonotonic with a striking peak at the glass transition. The question of whether the shear modulus is continuous or has a jump singularity at the glass transition is thus ill posed. Confirming the effective time-translational invariance of our systems, the Δ t dependence of μsf and related quantities can be understood using a weighted integral over G (t ) .

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.

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.

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.

9 CFR 54.6 - Amount of indemnity payments.

Code of Federal Regulations, 2011 CFR

2011-01-01

... will be used. The AMS reports from the most recent week or month prior to the date APHIS offers to pay... weighted average Choice/Prime slaughter lamb price per pound at Greeley, CO; (2) The weekly weighted average Utility slaughter ewe price per pound at San Angelo, TX; (3) The monthly weighted average...

46 CFR 164.009-15 - Test procedure.

Code of Federal Regulations, 2011 CFR

2011-10-01

... seconds. (4) The average weight loss of the specimens after heating is not more than 50 percent of their... described in paragraphs (b) through (k) of this section, except the average weight loss of the sample is... weighed while still hot. (6) The average weight loss of the specimens after heating may not be more than...

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.

Calcium-tolerant N-substituted acrylamides as thickeners for aqueous systems

DOEpatents

McCormick, Charles L.; Blackmon, Kenneth P.

1986-01-01

A water-soluble ionically-charged random copolymer of acrylamide and an alkaline or alkali metal 3-acrylamido-3-methylbutanoate having an average molecular weight of greater than about 50,000 has been found to maintain unusually stable and effective viscosities in the presence of salts such as NaCl and CaCl.sub.2 when added to water in minor amounts, thus making it a highly effective mobility control agent for secondary and tertiary oil recovery methods. Also within the scope of the invention are terpolymers which additionally contain olefinically unsaturated monomers such as acrylic acid or sodium acrylate.

Calcium-tolerant N-substituted acrylamides as thickeners for aqueous systems

DOEpatents

McCormick, C.L.; Blackmon, K.P.

1986-04-22

A water-soluble ionically-charged random copolymer of acrylamide and an alkaline or alkali metal 3-acrylamido-3-methylbutanoate having an average molecular weight of greater than about 50,000 has been found to maintain unusually stable and effective viscosities in the presence of salts such as NaCl and CaCl[sub 2] when added to water in minor amounts, thus making it a highly effective mobility control agent for secondary and tertiary oil recovery methods. Also within the scope of the invention are terpolymers which additionally contain olefinically unsaturated monomers such as acrylic acid or sodium acrylate.

Recent progress in cell-free solubilization of coal

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

Cohen, M.S.; Aronson, H.; Feldman, K.

1988-01-01

Low rank coal has been solubilized using cell-free filtrates separated from cultures of Polyporus versicolor. Solubilization has been obtained with neat filtrates and with fractions collected from the neat filtrates after gel permeation chromatography. The coal solubilizing enzymes have been collected in enriched fractions with gpc. This increased relative purity has allowed the determination of the average molecular weight of this enzyme by gel permeation chromatography and by polyacrylamide gel electrophoresis. Rates of coal solubilization are dependent on the size of coal particles, mass of coal, temperature, pH, concentration of the cell-free filtrate, and the concentration of several inorganic ions.

Lignin-derived thermoplastic co-polymers and methods of preparation

DOEpatents

Naskar, Amit K.; Saito, Tomonori; Pickel, Joseph M.; Baker, Frederick S.; Eberle, Claude Clifford; Norris, Robert E.; Mielenz, Jonathan Richard

2014-06-10

The present invention relates to a crosslinked lignin comprising a lignin structure having methylene or ethylene linking groups therein crosslinking between phenyl ring carbon atoms, wherein said crosslinked lignin is crosslinked to an extent that it has a number-average molecular weight of at least 10,000 g/mol, is melt-processible, and has either a glass transition temperature of at least 100.degree. C., or is substantially soluble in a polar organic solvent or aqueous alkaline solution. Thermoplastic copolymers containing the crosslinked lignin are also described. Methods for producing the crosslinked lignin and thermoplastic copolymers are also described.

Deconstructing Free Energies in the Law of Matching Water Affinities.

PubMed

Shi, Yu; Beck, Thomas

2017-03-09

The law of matching water affinities (LMWA) is explored in classical molecular dynamics simulations of several alkali halide ion pairs, spanning the size range from small kosmotropes to large chaotropes. The ion-ion potentials of mean force (PMFs) are computed using three methods: the local molecular field theory (LMFT), the weighted histogram analysis method (WHAM), and integration of the average force. All three methods produce the same total PMF for a given ion pair. In addition, LMFT-based partitioning into van der Waals and local and far-field electrostatic free energies and assessment of the enthalpic, entropic, and ion-water components yield insights into the origins of the observed free energy profiles in water. The results highlight the importance of local electrostatic interactions in determining the shape of the PMFs, while longer-ranged interactions enhance the overall ion-ion attraction, as expected in a dielectric continuum model. The association equilibrium constants are estimated from the smooth WHAM curves and compared to available experimental conductance data. By examining the variations in the average hydration numbers of ions with ion-ion distance, a correlation of the water structure in the hydration shells with the free energy features is found.

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.

24 CFR Appendix B to Part 1000 - IHBG Block Grant Formula Mechanisms

Code of Federal Regulations, 2011 CFR

2011-04-01

... weighted average for AEL (NAEL). The FMR factor is also defined in § 1000.302 as the relative difference between a local area Fair Market Rent (FMR) and the national weighted average for FMR. OPSUB = [LR * LRSUB... FMR Factor weighted by national average of AEL Factor and FRM Factor. AEL FACTOR = AEL/NAEL. AEL...

[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.

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

The use of computed tomography for the estimation of DIEP flap weights in breast reconstruction: a simple mathematical formula.

PubMed

Nanidis, Theodore G; Ridha, Hyder; Jallali, Navid

2014-10-01

Estimation of the volume of abdominal tissue is desirable when planning autologous abdominal based breast reconstruction. However, this can be difficult clinically. The aim of this study was to develop a simple, yet reliable method of calculating the deep inferior epigastric artery perforator flap weight using the routine preoperative computed tomography angiogram (CTA) scan. Our mathematical formula is based on the shape of a DIEP flap resembling that of an isosceles triangular prism. Thus its volume can be calculated with a standard mathematical formula. Using bony landmarks three measurements were acquired from the CTA scan to calculate the flap weight. This was then compared to the actual flap weight harvested in both a retrospective feasibility and prospective study. In the retrospective group 17 DIEP flaps in 17 patients were analyzed. Average predicted flap weight was 667 g (range 293-1254). The average actual flap weight was 657 g (range 300-1290) giving an average percentage error of 6.8% (p-value for weight difference 0.53). In the prospective group 15 DIEP flaps in 15 patients were analyzed. Average predicted flap weight was 618 g (range 320-925). The average actual flap weight was 624 g (range 356-970) giving an average percentage error of 6.38% (p-value for weight difference 0.57). This formula is a quick, reliable and accurate way of estimating the volume of abdominal tissue using the preoperative CTA scan. Copyright © 2014 British Association of Plastic, Reconstructive and Aesthetic Surgeons. Published by Elsevier Ltd. All rights reserved.

SU-F-BRD-01: A Logistic Regression Model to Predict Objective Function Weights in Prostate Cancer IMRT

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

Boutilier, J; Chan, T; Lee, T

2014-06-15

Purpose: To develop a statistical model that predicts optimization objective function weights from patient geometry for intensity-modulation radiotherapy (IMRT) of prostate cancer. Methods: A previously developed inverse optimization method (IOM) is applied retrospectively to determine optimal weights for 51 treated patients. We use an overlap volume ratio (OVR) of bladder and rectum for different PTV expansions in order to quantify patient geometry in explanatory variables. Using the optimal weights as ground truth, we develop and train a logistic regression (LR) model to predict the rectum weight and thus the bladder weight. Post hoc, we fix the weights of the leftmore » femoral head, right femoral head, and an artificial structure that encourages conformity to the population average while normalizing the bladder and rectum weights accordingly. The population average of objective function weights is used for comparison. Results: The OVR at 0.7cm was found to be the most predictive of the rectum weights. The LR model performance is statistically significant when compared to the population average over a range of clinical metrics including bladder/rectum V53Gy, bladder/rectum V70Gy, and mean voxel dose to the bladder, rectum, CTV, and PTV. On average, the LR model predicted bladder and rectum weights that are both 63% closer to the optimal weights compared to the population average. The treatment plans resulting from the LR weights have, on average, a rectum V70Gy that is 35% closer to the clinical plan and a bladder V70Gy that is 43% closer. Similar results are seen for bladder V54Gy and rectum V54Gy. Conclusion: Statistical modelling from patient anatomy can be used to determine objective function weights in IMRT for prostate cancer. Our method allows the treatment planners to begin the personalization process from an informed starting point, which may lead to more consistent clinical plans and reduce overall planning time.« less

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.

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

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.

Molecular distributions of water soluble dicarboxylic acids in marine aerosols over the Pacific Ocean including tropics

NASA Astrophysics Data System (ADS)

Kawamura, Kimitaka; Sakaguchi, Futoshi

1999-02-01

Remote marine aerosols collected over the western North to equatorial Pacific (34°N-14°S, 140°E-150°W) were studied for low molecular weight dicarboxylic acids using a capillary gas chromatography (GC) and GC/mass spectrometer, and for total carbon and nitrogen contents. Homologous series of dicarboxylic acids (C2-C10) including keto- and hydroxy-dicarboxylic acids were detected in the samples with a concentration range of 10-250 ng m-3 (average 63 ng m-3 and median 44 ng m-3). Their molecular distributions showed a predominance of oxalic acid (C2), followed by malonic acid (C3). The smallest diacid (C2, 6.5-161 ng m-3 with average 40 ng m-3 and median 17 ng m-3) composed 45-75% (average 65%) of the total diacids. The diacids showed higher concentrations in the western Pacific rim near Japanese islands and showed lower concentrations in the central and tropical Pacific. However, relative abundances of the diacid-carbon in the total aerosol carbon (1.1-15.8%) were found to be higher in the equatorial central Pacific. These diacids are probably in situ produced in the Pacific atmosphere by photochemical oxidation of gaseous and particulate precursors. Results of principal component analysis of individual diacid, coupled with an information on photochemical reactions, further support that C2 and C3 diacids are likely produced by the oxidation of C4 and longer-chain diacids, whereas longer-chain (C5-C10) diacids are produced through the oxidation of semivolatile fatty acids which are also oxidation products of unsaturated fatty acids. Concentrations of total C (0.069-5.27 μg m-3 with average 0.39 μg m-3 and median 0.15 μg m-3) and total N (0.026-1.44 μg m-3 with average 0.12 μg m-3 and median 0.077 μg m-3) were generally higher over the western Pacific.

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.

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.

Radiation-induced synthesis of poly(acrylic acid) nanogels

NASA Astrophysics Data System (ADS)

Matusiak, Malgorzata; Kadlubowski, Slawomir; Ulanski, Piotr

2018-01-01

Nanogel is a two-component system of a diameter in the range of tens of nanometers, consisting of an intramolecularly crosslinked polymer chain and solvent, typically water, filling the space between segments of the macromolecule. Microgels are bigger than nanogels and their size range is between 100 nm to 100 μm. One of the methods used for synthesizing nanogels is linking the segments of a single macromolecule with the use of ionizing radiation, by intramolecular recombination of radiation-generated polymer radicals. The main advantage of this technique is absence of monomers, catalysts, surfactants or crosslinking agents. This method is an interesting alternative way of synthesizing polymeric carriers for biomedical applications. The aim of the study was radiation synthesis and characterization of poly(acrylic acid) - PAA - nanogels and microgels. The physico-chemical properties were described by determination of weight-average molecular weight and dimensions (radius of gyration, hydrodynamic radius) of the nanogels and microgels. Influence of polymer concentration and dose on these parameters was analyzed. Adjusting the PAA concentration and absorbed dose, one can control the molecular weight and dimensions of nanogels. The solutions of PAA were irradiated with two sources of ionizing radiation: γ-source and electron accelerator. The former method yields mainly microgels due to prevailing intermolecular crosslinking, while the latter promotes intramolecular recombination of PAA-derived radicals and in consequence formation of nanogels. In the future radiation-synthesized PAA nanogels, after functionalization, will be tested as carriers for delivering radionuclides to the tumor cells.

Lectin from embryos and oocytes of Xenopus laevis. Purification and properties.

PubMed

Roberson, M M; Barondes, S H

1982-07-10

Soluble extracts of Xenopus laevis blastula stage embryos, oocytes, and adult liver contain lectin activities detected by agglutination of trypsinized, glutaraldehyde-fixed rabbit erythrocytes. Lectin from the embryos and oocytes was purified by affinity chromatography on a column derivatized with melibiose. Trace contaminants were removed either by preparative isoelectric focusing or by gel filtration. Based on its behavior on Sepharose 6B the purified oocyte lectin has an apparent molecular weight of approximately 480,000. On sodium dodecyl sulfate polyacrylamide gel electrophoresis under reducing conditions there were two major bands with molecular weight ranges of about 43,000 and 45,000, with diffuse trails. Since the purified lectin contains about 20% saccharides by weight and since both bands are glycosylated, diffuseness might be due to variable glycosylation. Heterogeneity was indicated by isoelectric focusing in polyacrylamide gels, which showed four protein bands with isoelectric points ranging from 4.4 to 4.9. Lectins from both embryos and oocytes comprised about 1 to 2% of the total soluble protein and could not be distinguished by sodium dodecyl sulfate polyacrylamide gel electrophoresis. However, the specific hemagglutination activity of the purified oocyte lectin was, on the average, 7-fold higher. Levels in crude extracts of liver were 3 orders of magnitude lower than those from oocytes. The hemagglutination activities of the lectins from embryos, oocytes, and adult liver required Ca2+ and were blocked by similar concentrations of both alpha- and beta-galactosides.

Design and physicochemical characterisation of novel dissolving polymeric microneedle arrays for transdermal delivery of high dose, low molecular weight drugs

PubMed Central

McCrudden, Maelíosa T.C.; Alkilani, Ahlam Zaid; McCrudden, Cian M.; McAlister, Emma; McCarthy, Helen O.; Woolfson, A. David; Donnelly, Ryan F.

2014-01-01

We describe formulation and evaluation of novel dissolving polymeric microneedle (MN) arrays for the facilitated delivery of low molecular weight, high dose drugs. Ibuprofen sodium was used as the model here and was successfully formulated at approximately 50% w/w in the dry state using the copolymer poly(methylvinylether/maleic acid). These MNs were robust and effectively penetrated skin in vitro, dissolving rapidly to deliver the incorporated drug. The delivery of 1.5 mg ibuprofen sodium, the theoretical mass of ibuprofen sodium contained within the dry MN alone, was vastly exceeded, indicating extensive delivery of the drug loaded into the baseplates. Indeed in in vitro transdermal delivery studies, approximately 33 mg (90%) of the drug initially loaded into the arrays was delivered over 24 h. Iontophoresis produced no meaningful increase in delivery. Biocompatibility studies and in vivo rat skin tolerance experiments raised no concerns. The blood plasma ibuprofen sodium concentrations achieved in rats (263 μg ml− 1 at the 24 h time point) were approximately 20 times greater than the human therapeutic plasma level. By simplistic extrapolation of average weights from rats to humans, a MN patch design of no greater than 10 cm2 could cautiously be estimated to deliver therapeutically-relevant concentrations of ibuprofen sodium in humans. This work, therefore, represents a significant progression in exploitation of MN for successful transdermal delivery of a much wider range of drugs. PMID:24556420

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.

Epoxy resin

DOEpatents

Wilson, Glenn R.; Salyer, Ival O.; Ball, III, George L.

1976-07-13

By mixing one part of a prepolymer containing a polyamine partially polymerized with an organic epoxide and subsequently reacted with a fatty acid containing from 8 to 32 carbon atoms, and then reacting this prepolymer mixture with 3 parts of an organic epoxide, a composition was obtained which made a gas frothable, shear-stable, room temperature curing, low density foam. A particularly advantageous prepolymer was prepared using a polyamine selected from the group consisting of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, partially polymerized with an organic epoxide having an average molecular weight of about 350 and having an epoxide equivalent of 185 to 192, and reacted with 2-10 weight percent linoleic acid. When one part of this prepolymer was reacted with about three parts of epoxy, and frothed by whipping in air or nitrogen an epoxy foam was produced which could be troweled onto surfaces and into corners or crevices, and subsequently cured, at near ambient temperature, to a strong dimensionally stable foam product.

Studies on cellulose nanocrystals isolated from groundnut shells.

PubMed

Bano, Saleheen; Negi, Yuvraj Singh

2017-02-10

Today, various renewable biomass resources are accepted as waste material and are mostly burnt or used as cattle feed. The commercial value of these wastes can be increased by utilising them in production of nanomaterials. So, the present work was conducted for isolation of cellulose nanocrystals (CNCs) from groundnut shells which are produced annually as waste in large quantity (∼7 million tons). The structural, thermal, morphological & elemental analyses were assessed through corresponding techniques. Light Scattering studies were performed to analyse more likely weight average molecular weight (M w ) & radius of radius (R g ). The high M w ∼10 5 g/mol obtained for CNCs in lithium chloride (LiCl)/N,N-dimethylacetamide (DMAc) system, was an interesting feature which gets affected by LiCl and polymer concentrations. Solution with high polymer and low LiCl concentration was found to show higher values of M w & R g . Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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

Boutilier, Justin J., E-mail: j.boutilier@mail.utoronto.ca; Lee, Taewoo; Craig, Tim

Purpose: To develop and evaluate the clinical applicability of advanced machine learning models that simultaneously predict multiple optimization objective function weights from patient geometry for intensity-modulated radiation therapy of prostate cancer. Methods: A previously developed inverse optimization method was applied retrospectively to determine optimal objective function weights for 315 treated patients. The authors used an overlap volume ratio (OV) of bladder and rectum for different PTV expansions and overlap volume histogram slopes (OVSR and OVSB for the rectum and bladder, respectively) as explanatory variables that quantify patient geometry. Using the optimal weights as ground truth, the authors trained and appliedmore » three prediction models: logistic regression (LR), multinomial logistic regression (MLR), and weighted K-nearest neighbor (KNN). The population average of the optimal objective function weights was also calculated. Results: The OV at 0.4 cm and OVSR at 0.1 cm features were found to be the most predictive of the weights. The authors observed comparable performance (i.e., no statistically significant difference) between LR, MLR, and KNN methodologies, with LR appearing to perform the best. All three machine learning models outperformed the population average by a statistically significant amount over a range of clinical metrics including bladder/rectum V53Gy, bladder/rectum V70Gy, and dose to the bladder, rectum, CTV, and PTV. When comparing the weights directly, the LR model predicted bladder and rectum weights that had, on average, a 73% and 74% relative improvement over the population average weights, respectively. The treatment plans resulting from the LR weights had, on average, a rectum V70Gy that was 35% closer to the clinical plan and a bladder V70Gy that was 29% closer, compared to the population average weights. Similar results were observed for all other clinical metrics. Conclusions: The authors demonstrated that the KNN and MLR weight prediction methodologies perform comparably to the LR model and can produce clinical quality treatment plans by simultaneously predicting multiple weights that capture trade-offs associated with sparing multiple OARs.« less

ESIprot: a universal tool for charge state determination and molecular weight calculation of proteins from electrospray ionization mass spectrometry data.

PubMed

Winkler, Robert

2010-02-01

Electrospray ionization (ESI) ion trap mass spectrometers with relatively low resolution are frequently used for the analysis of natural products and peptides. Although ESI spectra of multiply charged protein molecules also can be measured on this type of devices, only average spectra are produced for the majority of naturally occurring proteins. Evaluating such ESI protein spectra would provide valuable information about the native state of investigated proteins. However, no suitable and freely available software could be found which allows the charge state determination and molecular weight calculation of single proteins from average ESI-MS data. Therefore, an algorithm based on standard deviation optimization (scatter minimization) was implemented for the analysis of protein ESI-MS data. The resulting software ESIprot was tested with ESI-MS data of six intact reference proteins between 12.4 and 66.7 kDa. In all cases, the correct charge states could be determined. The obtained absolute mass errors were in a range between -0.2 and 1.2 Da, the relative errors below 30 ppm. The possible mass accuracy allows for valid conclusions about the actual condition of proteins. Moreover, the ESIprot algorithm demonstrates an extraordinary robustness and allows spectral interpretation from as little as two peaks, given sufficient quality of the provided m/z data, without the necessity for peak intensity data. ESIprot is independent from the raw data format and the computer platform, making it a versatile tool for mass spectrometrists. The program code was released under the open-source GPLv3 license to support future developments of mass spectrometry software. Copyright 2010 John Wiley & Sons, Ltd.

Characterization, treatment and releases of PBDEs and PAHs in a typical municipal sewage treatment plant situated beside an urban river, East China.

PubMed

Wang, Xiaowei; Xi, Beidou; Huo, Shouliang; Sun, Wenjun; Pan, Hongwei; Zhang, Jingtian; Ren, Yuqing; Liu, Hongliang

2013-07-01

Characterization, treatment and releases of eight polybrominated diphenyl ethers (PBDEs) congeners and sixteen polycyclic aromatic hydrocarbons (PAHs) in wastewater were evaluated along the treatment processes of a typical secondary treatment municipal sewage treatment plant (STP) (in Hefei City) situated the beside Nanfei River, East China. The findings showed that the average concentrations of the total PBDEs in raw wastewater and treated effluent were 188.578 and 36.884 ng/L respectively. Brominated diphenyl ether (BDE) 209 congener, the predominant PBDE in the STP and Nanfei River, could be related to the discharge of car-industry-derived wastes. For PAHs, the average concentrations in raw wastewater and treated effluent were 5758.8 and 2240.4 ng/L respectively, with naphthalene, benzo[a]pyrene and indeno[1,2,3-c,d]pyrene being detected at the highest concentrations. PAHs mainly originate from the combustion of biomass/coal and petroleum. The STP reduced about 80% of the PBDEs and 61% of the PAHs, which were eliminated mainly by sedimentation processes. The removal rates of PBDEs/PAHs increased with the increase of their solid-water partitioning coefficients. Accordingly, the STP's effluent, containing some PBDE congeners (e.g., BDE 47, 99 and 209, etc.) and low-molecular-weight PAHs, could be an important contributor of these contaminants' input to Nanfei River. It resulted in a significant increase of PBDE/PAH concentrations and PAH toxicological risk in the river water downstream. About 4.040 kg/yr of PBDEs and 245.324 kg/yr of PAHs could be released into the Nanfei River. The current conventional wastewater treatment processes should be improved to remove the relatively low-molecular-weight PBDEs/PAHs more effectively.

Preparation of poly(BMA-co-MMA) particles by soap-free emulsion polymerization and its optical properties as photonic crystals.

PubMed

Lee, Ki-Chang; Choo, Hun-Seung

2014-11-01

Narrowly dispersed poly(BMA-co-MMA) and PBMA latices with particle diameters ranging within 216-435 nm were synthesized successfully by surfactant-free emulsion polymerization with KPS and AIBA. The average particle diameter and particle size distribution, average molecular weight and its distribution, glass transition temperature, reflectance spectra in visible wavelength, and refractive indices for the respective poly(BMA-co-MMA) latices and their photonic crystals were systematically investigated in terms of BMA/MMA ratio, BMA content, polymerization temperature, and DVB effect. The rate of polymerization increased with increasing MMA concentration in BMA/MMA ratio. The particle diameter increased with BMA concentration in BMA/MMA ratio. The molecular weight increased with BMA concentration in BMA/MMA ratio and monomer concentration. The drying of the latices offered self-assembled shiny colloidal crystal films showing the characteristic structural colors in visible wavelength. All the poly(BMA-co-MMA) latices prepared in the study were fallen within the range of photonic grade microspheres. The reflectance measurement on the colloidal photonic crystals having different particle diameters clearly exhibited narrow stopbands. The reflection maxima (λ(max)) measured in this study were well close to the λ(max) calculated, derived from the Bragg's equation. The refractive indices of poly(BMA-co-MMA) photonic crystals were found to be almost same as the theoretical values and increased proportionally from 1.50 to 1.57 with BMA content in BMA/MMA ratios. It was, thus, found that the optical reflectance properties of the poly(BMA-co-MMA) colloidal photonic crystals can be controlled easily by adjusting the reaction conditions and BMA/MMA ratio in soap-free emulsion copolymerization of BMA and MMA.

Identification of early indicators of altered metabolism in normal development using a rodent model system.

PubMed

Prabakaran, Ashok Daniel; Karakkat, Jimsheena Valiyakath; Vijayan, Ranjit; Chalissery, Jisha; Ibrahim, Marwa F; Kaimala, Suneesh; Adeghate, Ernest A; Al-Marzouqi, Ahmed Hassan; Ansari, Suraiya Anjum; Mensah-Brown, Eric; Emerald, Bright Starling

2018-03-01

Although the existence of a close relationship between the early maternal developmental environment, fetal size at birth and the risk of developing disease in adulthood has been suggested, most studies, however, employed experimentally induced intrauterine growth restriction as a model to link this with later adult disease. Because embryonic size variation also occurs under normal growth and differentiation, elucidating the molecular mechanisms underlying these changes and their relevance to later adult disease risk becomes important. The birth weight of rat pups vary according to the uterine horn positions. Using birth weight as a marker, we compared two groups of rat pups - lower birth weight (LBW, 5th to 25th percentile) and average birth weight (ABW, 50th to 75th percentile) - using morphological, biochemical and molecular biology, and genetic techniques. Our results show that insulin metabolism, Pi3k/Akt and Pparγ signaling and the genes regulating growth and metabolism are significantly different in these groups. Methylation at the promoter of the InsII ( Ins2 ) gene and DNA methyltransferase 1 in LBW pups are both increased. Additionally, the Dnmt1 repressor complex, which includes Hdac1, Rb (Rb1) and E2f1, was also upregulated in LBW pups. We conclude that the Dnmt1 repressor complex, which regulates the restriction point of the cell cycle, retards the rate at which cells traverse the G1 or G0 phase of the cell cycle in LBW pups, thereby slowing down growth. This regulatory mechanism mediated by Dnmt1 might contribute to the production of small-size pups and altered physiology and pathology in adult life. © 2018. Published by The Company of Biologists Ltd.

Identification of early indicators of altered metabolism in normal development using a rodent model system

PubMed Central

Prabakaran, Ashok Daniel; Karakkat, Jimsheena Valiyakath; Chalissery, Jisha; Ibrahim, Marwa F.; Kaimala, Suneesh; Adeghate, Ernest A.; Al-Marzouqi, Ahmed Hassan; Ansari, Suraiya Anjum

2018-01-01

ABSTRACT Although the existence of a close relationship between the early maternal developmental environment, fetal size at birth and the risk of developing disease in adulthood has been suggested, most studies, however, employed experimentally induced intrauterine growth restriction as a model to link this with later adult disease. Because embryonic size variation also occurs under normal growth and differentiation, elucidating the molecular mechanisms underlying these changes and their relevance to later adult disease risk becomes important. The birth weight of rat pups vary according to the uterine horn positions. Using birth weight as a marker, we compared two groups of rat pups – lower birth weight (LBW, 5th to 25th percentile) and average birth weight (ABW, 50th to 75th percentile) – using morphological, biochemical and molecular biology, and genetic techniques. Our results show that insulin metabolism, Pi3k/Akt and Pparγ signaling and the genes regulating growth and metabolism are significantly different in these groups. Methylation at the promoter of the InsII (Ins2) gene and DNA methyltransferase 1 in LBW pups are both increased. Additionally, the Dnmt1 repressor complex, which includes Hdac1, Rb (Rb1) and E2f1, was also upregulated in LBW pups. We conclude that the Dnmt1 repressor complex, which regulates the restriction point of the cell cycle, retards the rate at which cells traverse the G1 or G0 phase of the cell cycle in LBW pups, thereby slowing down growth. This regulatory mechanism mediated by Dnmt1 might contribute to the production of small-size pups and altered physiology and pathology in adult life. PMID:29434026

Production of high levels of poly-3-hydroxybutyrate in plastids of Camelina sativa seeds.

PubMed

Malik, Meghna R; Yang, Wenyu; Patterson, Nii; Tang, Jihong; Wellinghoff, Rachel L; Preuss, Mary L; Burkitt, Claire; Sharma, Nirmala; Ji, Yuanyuan; Jez, Joseph M; Peoples, Oliver P; Jaworski, Jan G; Cahoon, Edgar B; Snell, Kristi D

2015-06-01

Poly-3-hydroxybutyrate (PHB) production in plastids of Camelina sativa seeds was investigated by comparing levels of polymer produced upon transformation of plants with five different binary vectors containing combinations of five seed-specific promoters for expression of transgenes. Genes encoding PHB biosynthetic enzymes were modified at the N-terminus to encode a plastid targeting signal. PHB levels of up to 15% of the mature seed weight were measured in single sacrificed T1 seeds with a genetic construct containing the oleosin and glycinin promoters. A more detailed analysis of the PHB production potential of two of the best performing binary vectors in a Camelina line bred for larger seed size yielded lines containing up to 15% polymer in mature T2 seeds. Transmission electron microscopy showed the presence of distinct granules of PHB in the seeds. PHB production had varying effects on germination, emergence and survival of seedlings. Once true leaves formed, plants grew normally and were able to set seeds. PHB synthesis lowered the total oil but not the protein content of engineered seeds. A change in the oil fatty acid profile was also observed. High molecular weight polymer was produced with weight-averaged molecular weights varying between 600 000 and 1 500 000, depending on the line. Select lines were advanced to later generations yielding a line with 13.7% PHB in T4 seeds. The levels of polymer produced in this study are the highest reported to date in a seed and are an important step forward for commercializing an oilseed-based platform for PHB production. © 2014 Society for Experimental Biology, Association of Applied Biologists and John Wiley & Sons Ltd.

Thermal properties of tannin extracted from Anacardium occidentale L. using TGA and FT-IR spectroscopy.

PubMed

Viswanath, Vinod; Leo, Vincent Vineeth; Prabha, S Sabna; Prabhakumari, C; Potty, V P; Jisha, M S

2016-01-01

The chemical nature of the polyphenols of cashew kernel testa has been determined. Testa contains tannins, which present large molecular complexity and has an ancient use as tanning agents. The use of tannins extracted from cashew testa, considered in many places as a waste, grants an extra value to the cashew. In this work we have analysed through high performance liquid chromatography, infrared spectroscopy (FT-IR) and thermo gravimetric analysis the average molecular weight, main functional groups and thermal properties of tannins extracted from Anacardium occidentale L. The results of these analyses are compared with the commercial grade tannic acid. The FT-IR spectra showed bands characteristic of C = C, C-C and OH bonds. This important bioactive compound present in the cashew nut kernel testa was suggested as an interesting economical source of antioxidants for use in the food and nutraceutical industry.

Molecular properties and prebiotic effect of inulin obtained from artichoke (Cynara scolymus L.).

PubMed

López-Molina, Dorotea; Navarro-Martínez, María Dolores; Rojas Melgarejo, Francisco; Hiner, Alexander N P; Chazarra, Soledad; Rodríguez-López, José Neptuno

2005-06-01

A high molecular weight inulin has been prepared from artichoke (Cynara scolymus L.) agroindustrial wastes using environmentally benign aqueous extraction procedures. Physico-chemical analysis of the properties of artichoke inulin was carried out. Its average degree of polymerization was 46, which is higher than for Jerusalem artichoke, chicory, and dahlia inulins. GC-MS confirmed that the main constituent monosaccharide in artichoke inulin was fructose and its degradation by inulinase indicated that it contained the expected beta-2,1-fructan bonds. The FT-IR spectrum was identical to that of chicory inulin. These data indicate that artichoke inulin will be suitable for use in a wide range of food applications. The health-promoting prebiotic effects of artichoke inulin were demonstrated in an extensive microbiological study showing a long lasting bifidogenic effect on Bifidobacterium bifidum ATCC 29521 cultures and also in mixed cultures of colonic bacteria.

Kinetic and molecular analyses reveal isoprene degradation potential of Methylobacterium sp.

PubMed

Srivastva, Navnita; Vishwakarma, P; Bhardwaj, Y; Singh, A; Manjunath, K; Dubey, Suresh K

2017-10-01

Efforts were made to isolate and characterize bacteria capable of growing on methane and organic compounds, and to achieve the simultaneous degradation of more than one pollutant. Among the methanotrophs, species of Methylobacterium was able to catabolize a variety of hydrocarbons, including the branched-chain alkenes. Therefore, laboratory incubations experiments were carried out in batch mode to assess the potential of Methylobacterium sp. PV1 for degrading isoprene, the low-molecular-weight alkene, the most abundant non-methane volatile hydrocarbon present in the environment. Methylobacterium sp. PV1, isolated from paddy field soil, was characterized by pmoA and 16S rRNA gene sequencing and FAME analysis, and used for isoprene degradation. The kinetics of biodegradation is studied using the Michaelis-Menten model. The optimum degradation (80%) with maximum average relative degradation rate was observed at 150ppm isoprene. The degradation products were also analyzed using FTIR. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Summary of GPC/DV results for space exposed poly(arylene ether phosphine oxide)s

NASA Technical Reports Server (NTRS)

Siochi, Emilie

1995-01-01

Gel Permeation Chromatography (GPC) was used to analyze poly(arylene ether phosphine oxide)s whose backbones were identical except for the ketone content and placement. These samples were exposed to low Earth orbit environment (predominantly atomic oxygen) on space shuttle flights. The materials and their unexposed controls were then characterized by GPC to investigate the effect of atomic oxygen on the molecular weight distributions. Analysis of the soluble portion of the samples revealed that there was significant loss of high molecular weight species. The presence of insoluble material also suggested that crosslinking was induced by the atomic oxygen exposure and that this very likely occurred at the high molecular weight portion of the molecular weight distribution.

Characterization of gizzards and grits of wild cranes found dead at Izumi Plain in Japan

PubMed Central

UEGOMORI, Mima; HARAGUCHI, Yuko; OBI, Takeshi; TAKASE, Kozo

2018-01-01

We analyzed the gizzards, and grits retained in the gizzards of 41 cranes that migrated to the Izumi Plain during the winter of 2015/2016 and died there, either due to accident or disease. These included 31 Hooded Cranes (Grus monacha) and 10 White-naped Cranes (G. vipio). We determined body weight, gizzard weight, total grit weight and number per gizzard, and size, shape, and surface roundness of the grits. Average gizzard weights were 92.4 g for Hooded Cranes and 97.1 g for White-naped Cranes, and gizzard weight positively correlated with body weight in both species. Average total grit weights per gizzard were 19.7 g in Hooded Cranes and 25.7 g in White-naped Cranes, and were significantly higher in the latter. Average percentages of body weight to grit weight were 0.8% in Hooded Cranes and 0.5% in White-naped Cranes. Average grit number per gizzard was 693.5 in Hooded Cranes and 924.2 in White-naped Cranes, and were significantly higher in the latter. The average grit size was 2.8 mm in both species. No differences were found in the shape and surface roundness of grits between the two species. To the best of our knowledge, this is the first study on the grits retained in the gizzards of Hooded and White-naped Cranes. PMID:29503349

Characterization of gizzards and grits of wild cranes found dead at Izumi Plain in Japan.

PubMed

Uegomori, Mima; Haraguchi, Yuko; Obi, Takeshi; Takase, Kozo

2018-04-18

We analyzed the gizzards, and grits retained in the gizzards of 41 cranes that migrated to the Izumi Plain during the winter of 2015/2016 and died there, either due to accident or disease. These included 31 Hooded Cranes (Grus monacha) and 10 White-naped Cranes (G. vipio). We determined body weight, gizzard weight, total grit weight and number per gizzard, and size, shape, and surface roundness of the grits. Average gizzard weights were 92.4 g for Hooded Cranes and 97.1 g for White-naped Cranes, and gizzard weight positively correlated with body weight in both species. Average total grit weights per gizzard were 19.7 g in Hooded Cranes and 25.7 g in White-naped Cranes, and were significantly higher in the latter. Average percentages of body weight to grit weight were 0.8% in Hooded Cranes and 0.5% in White-naped Cranes. Average grit number per gizzard was 693.5 in Hooded Cranes and 924.2 in White-naped Cranes, and were significantly higher in the latter. The average grit size was 2.8 mm in both species. No differences were found in the shape and surface roundness of grits between the two species. To the best of our knowledge, this is the first study on the grits retained in the gizzards of Hooded and White-naped Cranes.

76 FR 28998 - Implementation of Revised Passenger Weight Standards for Existing Passenger Vessels

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-19

... Inspection prior to a change in the assumed average weight per person standard that will become effective in... several factors, including the total weight of people carried based on an Assumed Average Weight per... reason, the policy letter referred to in this notice provides supplemental guidance to the implementation...

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.

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

PubMed Central

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

2015-01-01

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

Some structural features of the teichuronic acid of Bacillus licheniformis N.C.T.C. 6346 cell walls

PubMed Central

Hughes, R. C.; Thurman, P. F.

1970-01-01

A teichuronic acid, containing glucuronic acid and N-acetylgalactosamine, was purified from acid extracts of Bacillus licheniformis 6346 cell walls as described by Janczura, Perkins & Rogers (1961). After reduction of the carboxyl function of glucuronic acid residues in the polysaccharide the reduced polymer contains equimolar amounts of N-acetylgalactosamine and glucose. Methylation of the reduced polysaccharide by the Hakamori (1964) technique showed the glucose residues to be substituted on C-4. A disaccharide, 3-O-glucuronosylgalactosamine, was isolated from partial acid hydrolysates of teichuronic acid. After N-acetylation the disaccharide produces chromogen readily on heating at pH7, in agreement with C-3 substitution of the reducing N-acetylamino sugar. Teichuronic acid also produces chromogen under the same conditions, with concurrent elimination of a modified polysaccharide from C-3 of reducing terminal N-acetylgalactosamine residues of the teichuronic acid chains. The number-average chain lengths of several preparations of teichuronic acid were estimated from the amounts of chromogen produced in comparison with the N-acetylated disaccharide. The values obtained are in good agreement with the weight-average molecular weight determined by ultracentrifugal analysis. The reducing terminals of teichuronic acid are shown to be exclusively N-acetylgalactosamine by reduction with sodium boro[3H]hydride. The number-average chain lengths of the teichuronic acid preparations were estimated by the extent of in corporation of tritium and are in agreement with values obtained by the other methods. PMID:5419741

Flagellated bacterial motility in polymer solutions

PubMed Central

Martinez, Vincent A.; Schwarz-Linek, Jana; Reufer, Mathias; Wilson, Laurence G.; Morozov, Alexander N.; Poon, Wilson C. K.

2014-01-01

It is widely believed that the swimming speed, v, of many flagellated bacteria is a nonmonotonic function of the concentration, c, of high-molecular-weight linear polymers in aqueous solution, showing peaked v(c) curves. Pores in the polymer solution were suggested as the explanation. Quantifying this picture led to a theory that predicted peaked v(c) curves. Using high-throughput methods for characterizing motility, we measured v and the angular frequency of cell body rotation, Ω, of motile Escherichia coli as a function of polymer concentration in polyvinylpyrrolidone (PVP) and Ficoll solutions of different molecular weights. We find that nonmonotonic v(c) curves are typically due to low-molecular-weight impurities. After purification by dialysis, the measured v(c) and Ω(c) relations for all but the highest-molecular-weight PVP can be described in detail by Newtonian hydrodynamics. There is clear evidence for non-Newtonian effects in the highest-molecular-weight PVP solution. Calculations suggest that this is due to the fast-rotating flagella seeing a lower viscosity than the cell body, so that flagella can be seen as nano-rheometers for probing the non-Newtonian behavior of high polymer solutions on a molecular scale. PMID:25468981

Seasonal variations of low molecular weight hydroxy-dicarboxylic acids and oxaloacetic acid in remote marine aerosols from Chichijima Island in the western North Pacific (December 2010-November 2011)

NASA Astrophysics Data System (ADS)

Gowda, Divyavani; Kawamura, Kimitaka

2018-05-01

Concentrations of homologous hydroxy-dicarboxylic acids (diacids) (hC3-hC6) and keto-diacid (oxaloacetic acid) were measured in the atmospheric aerosols collected at Chichijima Island (27.04° N, 142.13° E) in the western North Pacific from December 2010 to November 2011. The monthly averaged concentrations of hydroxy-diacids and oxaloacetic acid were significantly higher in spring followed by winter and autumn. Molecular distributions of hydroxy-diacids demonstrated that malic acid was the most abundant species in all four seasons, followed by tartronic acid in winter and spring and 3- and 2-hydroxyglutaric acids in summer and autumn. Hydroxy-diacids and keto-diacid maximized in spring and winter when air masses originated from the Asian continent with westerly winds. The concentrations of total hydroxy-diacids and oxaloacetic acid ranged from 0.1 to 27.3 ng m-3 and <0.005 to 2 ng m-3, respectively. The enhanced concentrations of diacids and their intermediates in winter and spring are associated with a long-range atmospheric transport of pollutants from East Asia to remote Chichijima Island followed by photochemical processing of organic aerosols. Seasonal molecular distribution of hydroxy-diacids and oxaloacetic acid was found to be dependent on the source strengths and plausible photochemical processing to form smaller diacids. Moderate to strong correlations among hydroxy-diacids, oxaloacetic acid and low molecular weight (LMW) diacids suggest that hydroxy-diacids and oxaloacetic acid are the intermediates in the photochemical oxidation of LMW diacid. Hence, photochemical formation of the most abundant LMW diacids, i.e., oxalic acid, could be produced from hydroxy- and keto-diacid as intermediates.

Polycyclic aromatic hydrocarbons (PAHs) in atmospheric dustfall from the industrial corridor in Hubei Province, Central China.

PubMed

Zhang, Jiaquan; Qu, Chengkai; Qi, Shihua; Cao, Junji; Zhan, Changlin; Xing, Xinli; Xiao, Yulun; Zheng, Jingru; Xiao, Wensheng

2015-10-01

Thirty atmospheric dustfall samples collected from an industrial corridor in Hubei Province, central China, were analyzed for 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) to investigate their concentrations, spatial distributions, sources, and health risks. Total PAH concentrations (ΣPAHs) ranged from 1.72 to 13.17 µg/g and averaged 4.91 µg/g. High molecular weight (4-5 rings) PAHs averaged 59.67% of the ΣPAHs. Individual PAH concentrations were not significantly correlated with total organic carbon, possibly due to the semi-continuous inputs from anthropogenic sources. Source identification studies suggest that the PAHs were mainly from motor vehicles and biomass/coal combustion. The incremental lifetime cancer risks associated with exposure to PAHs in the dustfall ranged from 10(-4) to 10(-6); these indicate potentially serious carcinogenic risks for exposed populations in the industrial corridor.