Combined effects of low-molecular-weight organic acids on mobilization of arsenic and lead from multi-contaminated soils.

PubMed

Onireti, Olaronke O; Lin, Chuxia; Qin, Junhao

2017-03-01

A batch experiment was conducted to examine the combined effects of three common low-molecular-weight organic acids (LMWOAs) on the mobilization of arsenic and lead in different types of multi-contaminated soils. The capacity of individual LMWOAs (at a same molar concentration) to mobilize soil-borne As and Pb varied significantly. The combination of the organic acids did not make a marked "additive" effect on the mobilization of the investigated three elements. An "antagonistic" effect on element mobilization was clear in the treatments involving oxalic acid for some soils. The acid strength of a LMWOA did not play an important role in controlling the mobilization of elements. While the mobilization of As and Pb was closely associated with the dissolution of soil-borne Fe, soil properties such as original soil pH, organic matter contents and the total amount of the element relative to the total Fe markedly complicated the mobility of that element. Aging led to continual consumption of proton introduced from addition of LMWOAs and consequently caused dramatic changes in solution-borne Fe, which in turn resulted in change in As and Pb in the soil solution though different elements behaved differently. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of low-molecular-weight organic acids on kinetics release and fractionation of phosphorus in some calcareous soils of western Iran.

PubMed

Taghipour, M; Jalali, M

2013-07-01

Organic acid has been related to nutrient mobilization, mainly in phosphorus (P) insoluble utilization, and therefore enhances P bioavailability. In this study, we examined the effect of low-molecular-weight organic acids (malic, citric, and oxalic acids) on P release of some calcareous soils from western Iran. Fractionation and speciation of P in the soil solution were studied at the initial and final P release. Significantly different quantities of P were extracted by the organic acids. On average the maximum (1,554.9 mg kg(-1)) and the minimum (1,260.5 mg kg(-1)) P were extracted by 10 mM oxalic and malic acid, respectively. Power equation described well P release. In the initial stage of P release, the solution samples in soils were supersaturated with respect to hydroxyapatite and β-TCP. At the end of P release, all solutions were undersaturated with phosphate minerals. The percentage of Fe-Al oxide fraction generally increased after P release, while carbonate and residual P fractions were decreased in all organic acids. Compared with the native soils, adding malic and citric acids had no effect on Fe-Al oxide fraction, but oxalic acid significantly reduced this fraction.

Ancient low-molecular-weight organic acids in permafrost fuel rapid carbon dioxide production upon thaw.

PubMed

Drake, Travis W; Wickland, Kimberly P; Spencer, Robert G M; McKnight, Diane M; Striegl, Robert G

2015-11-10

Northern permafrost soils store a vast reservoir of carbon, nearly twice that of the present atmosphere. Current and projected climate warming threatens widespread thaw of these frozen, organic carbon (OC)-rich soils. Upon thaw, mobilized permafrost OC in dissolved and particulate forms can enter streams and rivers, which are important processors of OC and conduits for carbon dioxide (CO2) to the atmosphere. Here, we demonstrate that ancient dissolved organic carbon (DOC) leached from 35,800 y B.P. permafrost soils is rapidly mineralized to CO2. During 200-h experiments in a novel high-temporal-resolution bioreactor, DOC concentration decreased by an average of 53%, fueling a more than sevenfold increase in dissolved inorganic carbon (DIC) concentration. Eighty-seven percent of the DOC loss to microbial uptake was derived from the low-molecular-weight (LMW) organic acids acetate and butyrate. To our knowledge, our study is the first to directly quantify high CO2 production rates from permafrost-derived LMW DOC mineralization. The observed DOC loss rates are among the highest reported for permafrost carbon and demonstrate the potential importance of LMW DOC in driving the rapid metabolism of Pleistocene-age permafrost carbon upon thaw and the outgassing of CO2 to the atmosphere by soils and nearby inland waters.

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

PubMed

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

2007-05-01

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

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil.

PubMed

Wu, L H; Luo, Y M; Christie, P; Wong, M H

2003-02-01

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.

Biochar immobilizes soil-borne arsenic but not cationic metals in the presence of low-molecular-weight organic acids.

PubMed

Alozie, Nneka; Heaney, Natalie; Lin, Chuxia

2018-07-15

A batch experiment was conducted to examine the effects of biochar on the behaviour of soil-borne arsenic and metals that were mobilized by three low-molecular-weight organic acids. In the presence of citric acid, oxalic acid and malic acid at a molar concentration of 0.01M, the surface of biochar was protonated, which disfavours adsorption of the cationic metals released from the soil by organic acid-driven mobilization. In contrast, the oxyanionic As species were re-immobilized by the protonated biochar effectively. Biochar could also immobilize oxyanionic Cr species but not cationic Cr species. The addition of biochar increased the level of metals in the solution due to the release of the biochar-borne metals under attack by LMWOAs via cation exchange. Biochar could also have the potential to enhance reductive dissolution of iron and manganese oxides in the soil, leading to enhanced release of trace elements bound to these oxides. The findings obtained from this study have implications for evaluating the role of biochar in immobilizing trace elements in rhizosphere. Adsorption of cationic heavy metals on biochar in the presence of LMWOAs is unlikely to be a mechanism responsible for the impeded uptake of heavy metals by plants growing in heavy metal-contaminated soils. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Mercury photolytic transformation affected by low-molecular-weight natural organics in water.

PubMed

He, Feng; Zheng, Wang; Liang, Liyuan; Gu, Baohua

2012-02-01

Mechanisms by which dissolved organic matter (DOM) mediates the photochemical reduction of Hg(II) in aquatic ecosystems are not fully understood, owing to the heterogeneous nature and complex structural properties of DOM. In this work, naturally occurring aromatic compounds including salicylic, 4-hydrobenzoic, anthranilic, 4-aminobenzoic, and phthalic acid were systematically studied as surrogates for DOM in order to gain an improved mechanistic understanding of these compounds in the photoreduction of Hg(II) in water. We show that the photoreduction rates of Hg(II) are influenced not only by the substituent functional groups such as -OH, -NH(2) and -COOH on the benzene ring, but also the positioning of these functional groups on the ring structure. The Hg(II) photoreduction rate decreases in the order anthranilic acid>salicylic acid>phthalic acid according to the presence of the -NH(2), -OH, -COOH functional groups on benzoic acid. The substitution position of the functional groups affects reduction rates in the order anthranilic acid>4-aminobenzoic acid and salicylic acid>4-hydroxybenzoic acid. Reduction rates correlate strongly with ultraviolet (UV) absorption of these compounds and their concentrations, suggesting that the formation of organic free radicals during photolysis of these compounds is responsible for Hg(II) photoreduction. These results provide insight into the role of low-molecular-weight organic compounds and possibly DOM in Hg photoredox transformation and may thus have important implications for understanding Hg geochemical cycling in the environment. Copyright © 2011 Elsevier B.V. All rights reserved.

Impact of low molecular weight organic acids and dissolved organic matter on sorption and mobility of isoproturon in two soils.

PubMed

Ding, Qing; Wu, Hai Lang; Xu, Yun; Guo, Li Juan; Liu, Kai; Gao, Hui Min; Yang, Hong

2011-06-15

Isoproturon is a selective herbicide belonging to the phenylurea family and widely used for pre- and post-emergence control of annual weeds. Soil amendments (e.g. organic compounds or dissolved organic matter) may affect environmental behavior and bioavailability of pesticides. However, whether the physiochemical process of isoproturon in soils is affected by organic amendments and how it is affected in different soil types are unknown. To evaluate the impact of low molecular weight organic acids (LMWOA) and dissolved organic matter (DOM) on sorption/desorption and mobility of isoproturon in soils, comprehensive analyses were performed using two distinct soil types (Eutric gleysols and Hap udic cambisols). Our analysis revealed that adsorption of isoproturon in Eutric gleysols was depressed, and desorption and mobility of isoproturon were promoted in the presence of DOM and LMWOA. However, the opposite result was observed with Hap udic cambisols, suggesting that the soil type affected predominantly the physiochemical process. We also characterized differential components of the soils using three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy and Fourier transform infrared (FT-IR) spectroscopy and show that the two soils displayed different intensity of absorption bands for several functional groups. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of low-molecular-weight organic acids on photo-degradation of phenanthrene catalyzed by Fe(III)-smectite under visible light.

PubMed

Jia, Hanzhong; Chen, Hongxia; Nulaji, Gulimire; Li, Xiyou; Wang, Chuanyi

2015-11-01

The photolysis of polycyclic aromatic hydrocarbons (PAHs) is potentially an important process for its transformation and fate on contaminated soil surfaces. In this study, phenanthrene is employed as a model to explore PAH photodegradation with the assistance of Fe(III)-smectite under visible-light while focusing on roles played by five low-molecular-weight organic acids (LMWOAs), i.e., malic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), and nitrilotriacetic acid. Our results show that oxalic acid is most effective in promoting the photodegradation of phenanthrene, while only a slight increase in the rate of phenanthrene photodegradation is observed in the presence of malic acid. Electron paramagnetic resonance experiments confirm the formation of CO2(-) radicals in the presence of malic and oxalic acid, which provides strong evidence for generating OH and subsequent photoreaction pathways. The presence of EDTA or nitrilotriacetic acid significantly inhibits both Fe(II) formation and phenanthrene photodegradation because these organic anions tend to chelate with Fe(III), leading to decreases in the electron-accepting potential of Fe(III)-smectite and a weakened interaction between phenanthrene and Fe(III)-smectite. These observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and demonstrate the potential for using some LMWOAs as additives for the remediation of contaminated soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

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

2011-05-15

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

Marsh plant response to metals: Exudation of aliphatic low molecular weight organic acids (ALMWOAs)

NASA Astrophysics Data System (ADS)

Rocha, A. Cristina S.; Almeida, C. Marisa R.; Basto, M. Clara P.; Vasconcelos, M. Teresa S. D.

2016-03-01

Metal exposure is known to induce the production and secretion of substances, such as aliphatic low molecular weight organic acids (ALMWOAs), into the rhizosphere by plant roots. Knowledge on this matter is extensive for soil plants but still considerably scarce regarding marsh plants roots adapted to high salinity media. Phragmites australis and Halimione portulacoides, two marsh plants commonly distributed in European estuarine salt marshes, were used to assess the response of roots of both species, in terms of ALMWOAs exudation, to Cu, Ni and Cd exposure (isolated and in mixture since in natural environment, they are exposed to mixture of metals). As previous studies were carried out in unrealistic and synthetic media, here a more natural medium was selected. Therefore, in vitro experiments were carried out, with specimens of both marsh plants, and in freshwater contaminated with two different Cu, Ni and Cd concentrations (individual metal and in mixture). Both marsh plants were capable of liberating ALMWOAs into the surrounding medium. Oxalic, citric and maleic acids were found in P. australis root exudate solutions and oxalic and maleic acids in H. portulacoides root exudate solutions. ALMWOA liberation by both plants was plant species and metal-dependent. For instance, Cu affected the exudation of oxalic acid by H. portulacoides and of oxalic and citric acids by P. australis roots. In contrast, Ni and Cd did not stimulate any specific response. Regarding the combination of all metals, H. portulacoides showed a similar response to that observed for Cu individually. However, in the P. australis case, at high metal concentration mixture, a synergetic effect led to the increase of oxalic acid levels in root exudate solution and to a decrease of citric acid liberation. A correlation between ALMWOAs exudation and metal accumulation could not be established. P. australis and H. portulacoides are considered suitable metal phytoremediators of estuarine impacted areas

[Adsorption of aflatoxin on montmorillonite modified by low-molecular-weight humic acids].

PubMed

Yao, Jia-Jia; Kang, Fu-Xing; Gao, Yan-Zheng

2012-03-01

The adsorption of a typical biogenic toxin aflatoxin B1 on montmorillonite modified by low-molecular-weight humic acids (M(r) < 3 500) was investigated. The montmorillonite rapidly adsorbed the aflatoxin B1 until amounting to the maximal capacity, and then the adsorbed aflatoxin B1 slowly released into solution and reached the sorption equilibrium state after 12 h. The sorption isotherm of aflatoxin B1 by montmorillonite could be well described by Langmiur model, while the sorption isotherm by humic acid-modified montmorillonite was well fitted by using the Freundlich model. The modification of the montmorillonite with humic acids obviously enhanced its adsorption capacity for aflatoxin B1, and the amounts of aflatoxin adsorbed by modified montmorillonite were obviously higher than those by montmorillonite. The sorption enhancement by humic acid modification was attributed to (1) the enlarged adsorption sites which owed to the surface collapse of crystal layers induced by organic acids, and (2) the binding of aflatoxin with the humic acid sorbed on mineral surface. In addition, the adsorption amounts of aflatoxin by montmorillonite and modified montmorillonite increased with the increase of pH values in solution, and more significant enhancement was observed for the latter than the former, which attributed to the release of humic acids from the modified montmorillonite with the high pH values in solution. This indicates that increasing the pH values resulted in the enhanced hydrophilic property and the release of the organic acids presented in modified montmorillonite, and more sorption sites were available for aflatoxin on the modified montmorillonite. Results of this work would strengthen our understanding of the behavior and fate of biological contaminants in the environment.

Determination of low-molecular-weight organic acids in non-small cell lung cancer with a new liquid chromatography-tandem mass spectrometry method.

PubMed

Klupczynska, Agnieszka; Plewa, Szymon; Dyszkiewicz, Wojciech; Kasprzyk, Mariusz; Sytek, Natalia; Kokot, Zenon J

2016-09-10

As compared to other classes of metabolites, determination of organic acids is an underrepresented field in cancer research and till now there has been a lack of appropriate analytical procedure for determination of serum levels of organic acids potentially associated with cancer development. The aim of the study was to develop a new rapid liquid chromatography-tandem mass spectrometry method for the quantification of six low-molecular-weight organic acids in human serum and to apply this method in an analysis of samples collected from non-small cell lung cancer (NSCLC) patients and a matched control group. The samples were prepared by solid phase extraction (Clean-up CUQAX, UCT). Chromatography was conducted on a Synergi Hydro-RP column (Phenomenex) and a gradient run of 15min. Detection was performed using a negative multiple reaction monitoring mode. The calibration ranges were as follows: 0.24-38.42μmol/L for 2-hydroxybutyric acid, 0.09-17.23μmol/L for fumaric acid, 0.08-15.13μmol/L for glutaric acid, 0.11-2.22mmol/L for lactic acid, 0.39-30.98μmol/L for pyroglutamic acid, and 0.08-16.93μmol/L for succinic acid. Mean relative recovery range was 85.99-114.42% and the determined intra- and inter day coefficients of variation were ≤14%. Among the studied acids, pyroglutamic acid showed the best discriminating potential and enabled to identify accurately NSCLC patients and control subjects regardless of the cancer stage. Further investigations of serum organic acids may allow us to better understand the underlying mechanisms involved in NSCLC and develop novel means of its detection and treatment. The developed method may be also a valuable tool to study metabolic changes associated with other types of cancer. Copyright © 2016 Elsevier B.V. All rights reserved.

[Effects of several low-molecular-weight organic acids on the release kinetic of endosulfan from red soil].

PubMed

Zhao, Zhen-hua; Wu, Yu; Jiang, Xin; Xia, Li-ling; Ni, Li-xiao

2009-10-15

The kinetic release behaviors of a-endosulfan from red soil with three kinds of low-molecular-weight organic acids (LMWOA: oxalate, tartrate and citrate) solution and water leaching were investigated by kinetic device designed by ourselves and batch method. The results show that: the release percentage of endosulfan from red soil by tartrate and citrate solution (10 mmol/L) can increase by 7%-18% more than that by distilled water and oxalate solution, especially for tartrate solution. There is no significant difference between distilled water and oxalate solution for the release percentage of endosulfan (p > 0.05). There are two stages of quick and slow for the release of endosulfan from red soil, and the leaching speed is quicker especially for the initial 200 mL leaching solution. When using distilled water or oxalate solution as leaching solution, the best equations that described the kinetic release behavior of endosulfan from red soil were parabola diffuse equation and double constant equation, and weren't the apparent first dynamics equation that represented the simple surface diffusion mechanism. The kinetic release behavior of endosulfan in tartrate or citrate leaching system can be described by Elovich equation (R2 > 0.99, p < 0.0001), it implied that the simple surface diffusion mechanism is not the primary factor that effected the release of endosulfan, which three-dimensional molecule structure is complex, from red soil in aqueous phase leaching systems, and it maybe related to the outward diffuse mechanism from soil particle, activation and deactivation function of soil particles surface, the dissolution of soil mineral surface and structure change of inherent organic matter that coating onto the soil mineral surface induced by LMW organic acid. It suggested that the tartrate and citrate induced the complication of the release mechanisms of the pesticides from red soil.

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.

Effects of low-molecular-weight organic acids on the acute lethality, accumulation, and enzyme activity of cadmium in Eisenia fetida in a simulated soil solution.

PubMed

Liu, Hai-Long; Wang, Yu-Jun; Xuan, Liang; Dang, Fei; Zhou, Dong-Mei

2017-04-01

In the present study, the effects of low-molecular-weight organic acids (LMWOAs) on the toxicity of cadmium (Cd) to Eisenia fetida were investigated in a simulated soil solution. The LMWOAs protected E. fetida from Cd toxicity, as indicated by the increased median lethal concentration (LC50) values and the increased activity of superoxide dismutase. In addition, Cd concentrations in E. fetida decreased dramatically in the presence of LMWOAs. These results were likely because of the complexation between Cd and LMWOAs, which decreased the bioavailability and consequential toxicity of Cd to E. fetida. Notably, LMWOAs reduced Cd toxicity in decreasing order (ethylenediamine tetraacetic acid [EDTA] > citric acid > oxalic acid > malic acid > acetic acid), which was consistent with the decreasing complexation constants between LMWOAs and Cd. These results advance our understanding of the interactions between Cd and LMWOAs in soil. Environ Toxicol Chem 2017;36:1005-1011. © 2016 SETAC. © 2016 SETAC.

High and Low Molecular Weight Hyaluronic Acid Differentially Regulate Human Fibrocyte Differentiation

PubMed Central

Maharjan, Anu S.; Pilling, Darrell; Gomer, Richard H.

2011-01-01

Background Following tissue injury, monocytes can enter the tissue and differentiate into fibroblast-like cells called fibrocytes, but little is known about what regulates this differentiation. Extracellular matrix contains high molecular weight hyaluronic acid (HMWHA; ∼2×106 Da). During injury, HMWHA breaks down to low molecular weight hyaluronic acid (LMWHA; ∼0.8–8×105 Da). Methods and Findings In this report, we show that HMWHA potentiates the differentiation of human monocytes into fibrocytes, while LMWHA inhibits fibrocyte differentiation. Digestion of HMWHA with hyaluronidase produces small hyaluronic acid fragments, and these fragments inhibit fibrocyte differentiation. Monocytes internalize HMWHA and LMWHA equally well, suggesting that the opposing effects on fibrocyte differentiation are not due to differential internalization of HMWHA or LMWHA. Adding HMWHA to PBMC does not appear to affect the levels of the hyaluronic acid receptor CD44, whereas adding LMWHA decreases CD44 levels. The addition of anti-CD44 antibodies potentiates fibrocyte differentiation, suggesting that CD44 mediates at least some of the effect of hyaluronic acid on fibrocyte differentiation. The fibrocyte differentiation-inhibiting factor serum amyloid P (SAP) inhibits HMWHA-induced fibrocyte differentiation and potentiates LMWHA-induced inhibition. Conversely, LMWHA inhibits the ability of HMWHA, interleukin-4 (IL-4), or interleukin-13 (IL-13) to promote fibrocyte differentiation. Conclusions We hypothesize that hyaluronic acid signals at least in part through CD44 to regulate fibrocyte differentiation, with a dominance hierarchy of SAP>LMWHA≥HMWHA>IL-4 or IL-13. PMID:22022512

LMWOA (low molecular weight organic acid) exudation by salt marsh plants: Natural variation and response to Cu contamination

NASA Astrophysics Data System (ADS)

Mucha, Ana P.; Almeida, C. Marisa R.; Bordalo, Adriano A.; Vasconcelos, M. Teresa S. D.

2010-06-01

This work aimed to evaluate, in vitro, the capability of roots of two salt marsh plants to release low molecular weight organic acids (LMWOAs) and to ascertain whether Cu contamination would stimulate or not organic acids exudation. The sea rush Juncus maritimus and the sea-club rush Scirpus maritimus, both from the lower Douro river estuary (NW Portugal), were used. Plants were collected seasonally, four times a year in 2004, during low tide. After sampling, plant roots were washed for removal of adherent particles and immersed for 2 h in a solution that matched salinity (3) and pH (7.5) of the pore water from the same location to obtain plant exudates. In one of the seasons, similar experiments were carried out but spiking the solution with different amounts of Cu in order to embrace the range between 0 and 1600 nM. In the final solutions as well as in sediment pore water LMWOAs were determined by high performance liquid chromatography. Plants were able to release, in a short period of time, relatively high amounts of LMWOAs (oxalate, citrate, malate, malonate, and succinate). In the sediment pore water oxalate, succinate and acetate were also detected. Therefore, plant roots probably contributed to the presence of some of these organic compounds in pore water. Exudation differed between the plant species and also showed some seasonally variation, particularly for S. maritimus. The release of oxalate by J. maritimus increased with Cu increase in the media. However, exudation of the other LMWOAs did not seem to be stimulated by Cu contamination in the media. This fact is compatible with the existence of alternative internal mechanisms for Cu detoxification, as denoted by the fact that in media contaminated with Cu both plant species accumulated relatively high amounts (29-83%) of the initially dissolved Cu. This study expands our knowledge on the contribution of globally dominant salt marsh plants to the release of LMWOAs into the environment.

Impacts of low-molecular-weight organic acids on aquatic behavior of graphene nanoplatelets and their induced algal toxicity and antioxidant capacity.

PubMed

Wang, Zhuang; Gao, Yucheng; Wang, Se; Fang, Hao; Xu, Defu; Zhang, Fan

2016-06-01

Knowledge of the interaction between graphene-based materials and low-molecular-weight organic acids (LOAs) is essential to understand fate and effects of graphene-based materials in the aquatic environment, but this interaction remains poorly elucidated. In this study, the effects of LOAs on the physicochemical properties of graphene nanoplatelets (GNPs) in an aqueous medium and on the GNP toxicity to algae were studied. The unicellular green alga Scenedesmus obliquus was exposed to GNP suspensions in the presence of benzoic acid or gallic acid at various concentrations. The GNPs had smaller hydrodynamic sizes and the GNP suspensions were more stable and had higher or lower surface zeta potentials in the presence of LOAs than when LOAs were not present. The toxic effects in S. obliquus cultures incubated with GNP suspensions containing LOAs were related to the LOA concentration, and the presence of LOAs caused three effects: stimulation, alleviation, and synergistic inhibition. The intensities of the effects mainly correlated with the LOA concentration, the extent of agglomeration, and particle-induced oxidative stress. The results indicate that the environmental fates and toxicities of GNPs are strongly affected by the binding of GNPs to LOAs.

Impact of Low Molecular Weight Poly(3-hexylthiophene)s as Additives in Organic Photovoltaic Devices.

PubMed

Seibers, Zach D; Le, Thinh P; Lee, Youngmin; Gomez, Enrique D; Kilbey, S Michael

2018-01-24

Despite tremendous progress in using additives to enhance the power conversion efficiency of organic photovoltaic devices, significant challenges remain in controlling the microstructure of the active layer, such as at internal donor-acceptor interfaces. Here, we demonstrate that the addition of low molecular weight poly(3-hexylthiophene)s (low-MW P3HT) to the P3HT/fullerene active layer increases device performance up to 36% over an unmodified control device. Low MW P3HT chains ranging in size from 1.6 to 8.0 kg/mol are blended with 77.5 kg/mol P3HT chains and [6,6]-phenyl C 61 butyric acid methyl ester (PCBM) fullerenes while keeping P3HT/PCBM ratio constant. Optimal photovoltaic device performance increases are obtained for each additive when incorporated into the bulk heterojunction blend at loading levels that are dependent upon additive MW. Small-angle X-ray scattering and energy-filtered transmission electron microscopy imaging reveal that domain sizes are approximately invariant at low loading levels of the low-MW P3HT additive, and wide-angle X-ray scattering suggests that P3HT crystallinity is unaffected by these additives. These results suggest that oligomeric P3HTs compatibilize donor-acceptor interfaces at low loading levels but coarsen domain structures at higher loading levels and they are consistent with recent simulations results. Although results are specific to the P3HT/PCBM system, the notion that low molecular weight additives can enhance photovoltaic device performance generally provides a new opportunity for improving device performance and operating lifetimes.

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

USGS Publications Warehouse

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

2007-01-01

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

Content of selected elements and low-molecular-weight organic acids in fruiting bodies of edible mushroom Boletus badius (Fr.) Fr. from unpolluted and polluted areas.

PubMed

Mleczek, Mirosław; Magdziak, Zuzanna; Gąsecka, Monika; Niedzielski, Przemysław; Kalač, Pavel; Siwulski, Marek; Rzymski, Piotr; Zalicka, Sylwia; Sobieralski, Krzysztof

2016-10-01

The aim of the study was to (i) investigate the potential of edible mushroom Boletus badius (Fr.) Fr. to accumulate 53 elements from unpolluted acidic sandy soil and polluted alkaline flotation tailing sites in Poland, (ii) to estimate the low-molecular-weight organic acid (LMWOA) profile and contents in fruit bodies, and finally (iii) to explore the possible relationship between elements and LMWOA content in mushrooms. The content of most elements in fruiting bodies collected from the flotation tailings was significantly higher than in mushrooms from the unpolluted soils. The occurrence of elements determined in fruiting bodies of B. badius has been varied (from 0.01 mg kg -1 for Eu, Lu, and Te up to 18,932 mg kg -1 for K). The results established the high importance of element contents in substrate. Among ten organic acids, nine have been found in wide range: from below 0.01 mg kg -1 for fumaric acid to 14.8 mg g -1 for lactic acid. Lactic and succinic acids were dominant in both areas, and citric acid was also in high content in polluted area. The correlation between element contents and the individual and total content of LMWOAs was confirmed.

Effects of low molecular weight organic acids on the immobilization of aqueous Pb(II) using phosphate rock and different crystallized hydroxyapatite.

PubMed

Wei, Wei; Cui, Jing; Wei, Zhenggui

2014-06-01

Understanding the effects of low molecular weight organic acids (LMWOAs) on the transformation of Pb(II) to geochemically stable pyromorphite (PY) by apatite materials (AMs), has considerable benefits for risk assessment and remediation strategies for contaminated water and soil. In this study, we systematically investigated the immobilization of Pb(II) from aqueous solution by natural phosphate rock (PR) and different crystallized hydroxyapatite (HAp) in the absence and presence of LMWOAs (oxalic, malic and citric acids). The results indicated that the effectiveness of PR and HAp in immobilizing Pb(II) followed in descending order by HAp2 (the poorly crystallized HAp), HAp1 (the well crystallized HAp) and PR, regardlessof the presence of LMWOAs. The presence of malic and citric acids significantly decreased the immobilizationefficiency of Pb(II) by HAp1 and PR, clarifying the lower adsorption affinities of Pb(II)-organic acid complexes on HAp1 and PR rather than Pb(II) ion. On thecontrary, oxalic acid could markedly enhance the removal of Pb(II) from aqueous solution by HAp1 and PR through the formation of lead oxalate, which was confirmed by FT-IR and XRDanalysis. Results also showed that LMWOAs had little promoting or inhibiting effect on the immobilization of Pb(II) by HAp2. This study suggested that the ubiquity of LMWOAs in natural environments could retard the transformation efficiency of Pb(II) to PY by AMs, especiallyin thepresenceof oxalic acid, and the poorly crystallized HAp2 had great potential to remediate Pb(II)-contaminated water and soil due to its insusceptibility to LMWOAs. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of the biota diversity on the composition of low-molecular-weight water-soluble organic compounds in southern tundra soils

NASA Astrophysics Data System (ADS)

Shamrikova, E. V.; Kubik, O. S.; Punegov, V. V.; Gruzdev, I. V.

2014-03-01

Water extracts from the organic horizons of southern-tundra loamy permafrost-affected soils (a surface-gleyed tundra soil, a surface-gleyed soddy tundra soil (Haplic Stagnosols (Gelic)), and a peaty tundra soil (Histic Cryosol (Reductaquic)) and their undecomposed moss layers have been analyzed. The total weight concentration of the cations (Ca2+, Mg2+, K+, and Na+) determined by the atomic absorption method reaches 20 mg/dm3 in the organic horizons and 40-90 mg/dm3 in the undecomposed moss layers. Potassium and calcium ions dominate in all the organic horizons (80-90% of the total weight); potassium ions prevail in the mosses (about 70%). The weight concentration of carbon in the water-soluble organic compounds is 0.04-0.07 g/dm3 in the organic horizons and 0.20-0.40 g/dm3 in the undecomposed moss layers. The content of low-molecular-weight organic compounds (alcohols, carbohydrates, and acids) identified by gas chromatography and chromatomass spectrometry is 1-30 mg/dm3 in the organic horizons of the soils and 80-180 mg/dm3 in the mosses, which does not exceed 26% of the total organic carbon in the extracts.

Low molecular weight carboxylic acids in oxidizing porphyry copper tailings.

PubMed

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

2005-04-15

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

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

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

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

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

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

DOE PAGES

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

2015-11-16

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

Low molecular weight hyaluronic acid effects on murine macrophage nitric oxide production.

PubMed

Lyle, Daniel B; Breger, Joyce C; Baeva, Larissa F; Shallcross, Jonathan C; Durfor, Charles N; Wang, Nam Sun; Langone, John J

2010-09-01

Hyaluronic acid (HA) is increasingly used for a number of medical device applications. Since the chemical structure of HA is identical no matter its bacterial or animal origin, it should be the ideal biomaterial. However, short term transient inflammatory reactions are common, while rare long-term adverse events may correlate with subclinical chronic inflammation. Concern has been raised that low molecular weight components or degradation fragments from implanted HA may directly stimulate inflammatory reactions. This study examined a panel of HA molecular weights from the unitary disaccharide up to 1.7 x 10(6) Dalton lengths, in which endotoxin was assayed at a very low level (less than 0.03 EU/mg). The murine cell line RAW 264.7, rat splenocytes, and rat adherent differentiated primary macrophages were assayed for nitric oxide production under a variety of inflammatory conditions plus or minus HA. Under the highest inflammatory states, nitric oxide production was mildly suppressed by HMW-HA while slightly augmented by LMW-HA at mg/mL concentrations. However, at micromolar concentrations fragments below 5000 Daltons, thought to have drug-like qualities, were without effect. These data support the hypothesis that if endotoxin is reduced to an extremely low level, LMW-HA may not directly provoke normal tissue macrophage-mediated inflammatory reactions. (c) 2010 Wiley Periodicals, Inc.

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.

Effect of heavy metals and organic matter on root exudates (low molecular weight organic acids) of herbaceous species: An assessment in sand and soil conditions under different levels of contamination.

PubMed

Montiel-Rozas, M M; Madejón, E; Madejón, P

2016-09-01

Bioavailability of heavy metals can be modified by different root exudates. Among them, low molecular weight organic acids (LMWOAs) play an important role in this process. Three plant species (Poa annua, Medicago polymorpha and Malva sylvestris), potentially used for phytoremediation, have been assessed for both metal uptake and LMWOAs excretion in contaminated environments with different concentrations of Cd, Cu and Zn. The experiments have been carried out in washed sand and in three contaminated soils where two organic amendments were added (biosolid compost and alperujo compost). The most abundant LMWOAs excreted by all studied plants were oxalic and malic acids, although citric and fumaric acids were also detected. The general tendency was that plants responded to an increase of heavy metal stress releasing higher amounts of LMWOAs. This is an efficient exclusion mechanism reducing the metal uptake and allowing the plant growth at high levels of contamination. In the experiment using wash sand as substrate, the organic acids composition and quantity depended mainly on plant species and metal contamination. M. polymorpha was the species that released the highest concentrations of LMWOAs, both in sand and in soils with no amendment addition, whereas a decrease of these acids was observed with the addition of amendments. Our results established a clear effect of organic matter on the composition and total amount of LMWOAs released. The increase of organic matter and nutrients, through amendments, improved the soil quality reducing phytotoxicity. As a result, organic acids exudates decreased and were solely composed of oxalic acid (except for M. polymorpha). The release of LMWOAs has proved to be an important mechanism against heavy metal stress, unique to each species and modifiable by means of organic amendment addition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of cadmium amendments on low-molecular-weight organic acid exudates in rhizosphere soils of tobacco and sunflower.

PubMed

Chiang, Po-Neng; Wang, Ming Kuang; Chiu, Chih Yu; Chou, Shu-Yen

2006-10-01

To recognize physiological response of plants to cadmium (Cd) toxicity in rhizosphere of plants, the pot experiments were employed to investigate how low-molecular-weight organic acids (LMWOAs) were exudated from tobacco and sunflower roots of Cd-amended soils. The aims of this study were to assess the effect of LMWOAs on uptake of Cd by tobacco and sunflower under pot experiments, thus comparing the ability of tobacco and sunflower for phytoremediation. Surface soils (0-20 cm) were collected from Taichung Experiment Station (TC) (silty loam). Cadmium chloride (CdCl(2)) was amended into TC soil, giving Cd concentrations of 1, 5, 10 mg kg(-1) soil. Soils with different concentrations of Cd were put into 12 cm (i.d.) pots for incubation, and then 2-week-old tobacco and sunflower seedlings were transplanted into the pots. Tobacco and sunflower were grown in greenhouse for 50 days, respectively. The rhizosphere and bulk soils, and fresh plant tissues were collected after harvest. The Cd concentrations in the plant and transfer factor values in the sunflower were higher than that in the tobacco. No LMWOAs were detected by gas chromatograph in bulk soils, and low amounts of LMWOAs were found in uncontaminated rhizosphere soils. Acetic, lactic, glycolic, malic, maleic, and succinic acids were found in the tobacco and sunflower rhizosphere soils. Concentrations of LMWOAs increased with increasing amendment of Cd concentrations in tobacco and sunflower rhizosphere soils. Correlation coefficient (r) of concentrations of Cd amendment versus LMWOAs exudates of tobacco and sunflower were 0.85 and 0.98, respectively. These results suggest that the different levels of LMWOAs present in the rhizosphere soil play an important role in the solubilization of Cd that bound with soil particle into soil solution and then uptake by plants.

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.

Effects of three low-molecular-weight organic acids (LMWOAs) and pH on the mobilization of arsenic and heavy metals (Cu, Pb, and Zn) from mine tailings.

PubMed

Wang, Suiling; Mulligan, Catherine N

2013-02-01

Natural organic acids may play an important role in influencing the mobility of toxic contaminants in the environment. The mobilization of arsenic (As) and heavy metals from an oxidized Pb-Zn mine tailings sample in the presence of three low-molecular-weight organic acids, aspartic acid, cysteine, and succinic acid, was investigated at a mass ratio of 10 mg organic additive/g mine tailings in this study. The effect of pH was also evaluated. The mine tailings sample, containing elevated levels of As (2,180 mg/kg), copper (Cu, 1,100 mg/kg), lead (Pb, 12,860 mg/kg), and zinc (Zn, 5,075 mg/kg), was collected from Bathurst, New Brunswick, Canada. It was found that the organic additives inhibited As and heavy metal mobilization under acidic conditions (at pH 3 or 5), but enhanced it under neutral to alkaline conditions (at pH above 7) through forming aqueous organic complexes. At pH 11, As, Cu, Pb, and Zn were mobilized mostly by the organic additives, 45, 46, 1,660, and 128 mg/kg by aspartic acid, 31, 28, 1,040, and 112 mg/kg by succinic acid, and 53, 38, 2,020, and 150 mg/kg by cysteine, respectively, whereas those by distilled water were 6, 16, 260, and 52 mg/kg, respectively. It was also found that the mobilization of As and the heavy metals was closely correlated, and both were closely correlated to Fe mobilization. Arsenic mobilization by the three LMWOAs was found to be consistent with the order of the stability of Fe-, Cu-, Pb-, and Zn-organic ligand complexes. The organic acids might be used potentially in the natural attenuation and remediation of As and heavy metal-contaminated sites.

[Effects of Low-Molecular-Weight Organic Acids on the Speciation of Pb in Purple Soil and Soil Solution].

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Zhang, Jin-zhong; Chen, Hong

2016-04-15

Lead (Pb) in purple soil was selected as the research target, using one-step extraction method with 0.01 mol · L⁻¹ sodium nitrate as the background electrolyte to study the release effect of citric acid (CA), tartaric acid (TA) and acetic acid (AC) with different concentrations. Sequential extraction and geochemical model (Visual Minteq v3.0) were applied to analyze and predict the speciation of Pb in soil solid phase and soil solution phase. Then the ebvironmental implications and risks of low-molecule weight organic acid (LMWOA) on soil Pb were analyzed. The results indicated that all three types of LMWOA increased the desorption capacity of Pb in purple soil, and the effect followed the descending order of CA > TA > AC. After the action of LMWOAs, the exchangeable Pb increased; the carbonate-bound Pb and Fe-Mn oxide bound Pb dropped in soil solid phase. Organic bound Pb was the main speciation in soil solution phase, accounting for 45.16%-75.05%. The following speciation of Pb in soil solution was free Pb, accounting for 22.71%-50.25%. For CA and TA treatments, free Pb ions and inorganic bound Pb in soil solution increased with increasing LMWOAs concentration, while organic bound Pb suffered a decrease in this process. An opposite trend for AC treatment was observed compared with CA and TA treatments. Overall, LMWOAs boosted the bioavailability of Pb in purple soil and had a potential risk to contaminate underground water. Among the three LMWOAs in this study, CA had the largest potential to activate soil Pb.

Use of Low Molecular Weight Heparin and Aminocaproic Acid in Chronic DIC Associated with Prostate Cancer- A Case Report

PubMed Central

Shirai, Keisuke; Chaudhary, Uzair B.

2007-01-01

Disseminated Intravascular Coagulopathy (DIC) is the most common coagulopathy in patients with prostate cancer. Though rare, it could be fatal without treatment. Literature suggests that there is significant activation of fibrinolytic pathway. Pathophysiology of DIC in patients with prostate cancer is not completely understood. We present here a case of chronic DIC in a patient with metastatic androgen independent prostate cancer. His DIC was managed successfully with a combination of aminocaproic acid and low weight molecular heparin. The use of low molecular weight heparin may make management of chronic DIC in prostate cancer more feasible in an out patient setting. PMID:17619757

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

PubMed

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

2014-09-01

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

Reducing Capacities and Distribution of Redox-Active Functional Groups in Low Molecular Weight Fractions of Humic Acids.

PubMed

Yang, Zhen; Kappler, Andreas; Jiang, Jie

2016-11-15

Humic substances (HS) are redox-active organic compounds with a broad spectrum of molecular sizes and reducing capacities, that is, number of electrons donated or accepted. However, it is unknown which role the distribution of redox-active functional groups in different molecule sizes plays for HS redox reactions in varying pore sizes microenvironments. We used dialysis experiments to separate bulk humic acids (HA) into low molecular weight fractions (LMWF) and retentate, for example, the remaining HA in the dialysis bag. LMWF accounted for only 2% of the total organic carbon content of the HA. However, their reducing capacities per gram of carbon were up to 33 times greater than either those of the bulk HA or the retentate. For a structural/mechanistic understanding of the high reducing capacity of the LMWF, we used fluorescence spectroscopy. We found that the LWMF showed significant fluorescence intensities for quinone-like functional groups, as indicated by the quinoid π-π* transition, that are probably responsible for the high reducing capacities. Therefore, the small-sized HS fraction can play a major role for redox transformation of metals or pollutants trapped in soil micropores (<2.5 nm diameter).

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.

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.

Low molecular weight components in an aquatic humic substance as characterized by membrane dialysis and orbitrap mass spectrometry.

PubMed

Remucal, Christina K; Cory, Rose M; Sander, Michael; McNeill, Kristopher

2012-09-04

Suwannee River fulvic acid (SRFA) was dialyzed through a 100-500 molecular weight cutoff dialysis membrane, and the dialysate and retentate were analyzed by UV-visible absorption and high-resolution Orbitrap mass spectrometry (MS). A significant fraction (36% based on dissolved organic carbon) of SRFA passed through the dialysis membrane. The fraction of SRFA in the dialysate had a different UV-visible absorption spectrum and was enriched in low molecular weight molecules with a more aliphatic composition relative to the initial SRFA solution. Comparison of the SRFA spectra collected by Orbitrap MS and Fourier transform ion cyclotron resonance MS (FT-ICR MS) demonstrated that the mass accuracy of the Orbitrap MS is sufficient for determination of unique molecular formulas of compounds with masses <600 Da in a complex mixture, such as SRFA. The most intense masses detected by Orbitrap MS were found in the 100-200 Da mass range. Many of these low molecular masses corresponded to molecular formulas of previously identified compounds in organic matter, lignin, and plants, and the use of the standard addition method provided an upper concentration estimate of selected target compounds in SRFA. Collectively, these results provide evidence that SRFA contains low molecular weight components that are present individually or in loosely bound assemblies.

Aging impacts of low molecular weight organic acids (LMWOAs) on furfural production residue-derived biochars: Porosity, functional properties, and inorganic minerals.

PubMed

Liu, Guocheng; Chen, Lei; Jiang, Zhixiang; Zheng, Hao; Dai, Yanhui; Luo, Xianxiang; Wang, Zhenyu

2017-12-31

The aging of biochar by low molecular weight organic acids (LMWOAs), which are typical root-derived exudates, is not well understood. Three LMWOAs (ethanoic, malic, and citric acids) were employed to investigate their aging impacts on the biochars from furfural production residues at 300-600°C (BC300-600). The LMWOAs created abundant macropores in BC300, whereas they significantly increased the mesoporosity and surface area of BC600 by 13.5-27.0% and 44.6-61.5%, respectively. After LMWOA aging, the content of C and H of the biochars increased from 51.3-60.2% and 1.87-3.45% to 56.8-69.9% and 2.06-4.45%, respectively, but the O content decreased from 13.8-24.8% to 7.82-19.4% (except BC300). For carbon fraction in the biochars, the LMWOAs barely altered the bulk and surface functional properties during short-term aging. The LMWOAs facilitated the dissolution of minerals (e.g., K 2 Mg(PO 3 ) 4 , AlPO 4 , and Pb 2 P 2 O 7 ) and correspondingly promoted the release of not only plant nutrients (K + , Ca 2+ , Mg 2+ , Fe 3+ , PO 4 3- , and SO 4 2- ) but also toxic metals (Al 3+ and Pb 2+ ). This research provided systematic insights on the responses of biochar properties to LMWOAs and presented direct evidence for acid activation of inorganic minerals in the biochars by LMWOAs, which could enhance the understanding of environmental behaviors of biochars in rhizosphere soils. Copyright © 2017 Elsevier B.V. All rights reserved.

Low-molecular-weight heparin for thromboprophylaxis.

PubMed

Camporese, Giuseppe; Bernardi, Enrico

2009-09-01

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

On the use of hydroxyl radical kinetics to assess the number-average molecular weight of dissolved organic matter.

PubMed

Appiani, Elena; Page, Sarah E; McNeill, Kristopher

2014-10-21

Dissolved organic matter (DOM) is involved in numerous environmental processes, and its molecular size is important in many of these processes, such as DOM bioavailability, DOM sorptive capacity, and the formation of disinfection byproducts during water treatment. The size and size distribution of the molecules composing DOM remains an open question. In this contribution, an indirect method to assess the average size of DOM is described, which is based on the reaction of hydroxyl radical (HO(•)) quenching by DOM. HO(•) is often assumed to be relatively unselective, reacting with nearly all organic molecules with similar rate constants. Literature values for HO(•) reaction with organic molecules were surveyed to assess the unselectivity of DOM and to determine a representative quenching rate constant (k(rep) = 5.6 × 10(9) M(-1) s(-1)). This value was used to assess the average molecular weight of various humic and fulvic acid isolates as model DOM, using literature HO(•) quenching constants, kC,DOM. The results obtained by this method were compared with previous estimates of average molecular weight. The average molecular weight (Mn) values obtained with this approach are lower than the Mn measured by other techniques such as size exclusion chromatography (SEC), vapor pressure osmometry (VPO), and flow field fractionation (FFF). This suggests that DOM is an especially good quencher for HO(•), reacting at rates close to the diffusion-control limit. It was further observed that humic acids generally react faster than fulvic acids. The high reactivity of humic acids toward HO(•) is in line with the antioxidant properties of DOM. The benefit of this method is that it provides a firm upper bound on the average molecular weight of DOM, based on the kinetic limits of the HO(•) reaction. The results indicate low average molecular weight values, which is most consistent with the recent understanding of DOM. A possible DOM size distribution is discussed to

Effect of soil sieving on respiration induced by low-molecular-weight substrates

NASA Astrophysics Data System (ADS)

Datta, Rahul; Vranová, Valerie; Pavelka, Marian; Rejšek, Klement; Formánek, Pavel

2014-03-01

The mesh size of sieves has a significant impact upon soil disturbance, affecting pore structure, fungal hyphae, proportion of fungi to bacteria, and organic matter fractions. The effects are dependent upon soil type and plant coverage. Sieving through a 2 mm mesh increases mineralization of exogenously supplied carbohydrates and phenolics compared to a 5 mm mesh and the effect is significant (p<0.05), especially in organic horizons, due to increased microbial metabolism and alteration of other soil properties. Finer mesh size particularly increases arabinose, mannose, galactose, ferulic and pthalic acid metabolism, whereas maltose mineralization is less affected. Sieving through a 5 mm mesh size is suggested for all type of experiments where enhanced mineralization of low-molecular-weight organic compounds needs to be minimalized.

[Effects of low molecular weight organic acids on speciation of exogenous Cu in an acid soil].

PubMed

Huang, Guo-Yong; Fu, Qing-Ling; Zhu, Jun; Wan, Tian-Ying; Hu, Hong-Qing

2014-08-01

In order to ascertain the effect of LMWOA (citric acid, tartaric acid, oxalic acid) on Cu-contaminated soils and to investigate the change of Cu species, a red soil derived from quartz sandstone deposit was added by Cu (copper) in the form of CuSO4 x 5H2O so as to simulate soil Cu pollution, keeping the additional Cu concentrations were 0, 100, 200, 400 mg x kg(-1) respectively. After 9 months, different LMWOA was also added into the simulated soil, keeping the additional LMWOAs in soil were 0, 5, 10, 20 mmol x kg(-1) respectively. After 2 weeks incubation, the modified sequential extraction method on BCR (European Communities Bureau of Reference) was used to evaluate the effects of these LMWOAs on the changes of copper forms in soil. The result showed that the percentage of weak acid dissolved Cu, the most effective form in the soil increased with three organic acids increase in quantity in the simulated polluted soil. And there was a good activation effect on Cu in the soil when organic acid added. Activation effects on Cu increased with concentration of citric acid increasing, but it showed a rise trend before they are basically remained unchanged in the case of tartaric acid and oxalic acid added in the soil. On the contrary, the state of the reduction of copper which was regarded as a complement for effective state decreased with the increased concentration of organic acid in the soil, especially with citric acid. When 20 mmol x kg(-1) oxalic acid and citric acid were added into the soil, the activation effect was the best; whereas for tartaric, the concentration was 10 mmol x kg(-1). In general, the effect on the changes of Cu forms in the soil is citric acid > tartaric acid > oxalic acid.

Comparative investigation of low-molecular-weight fulvic acids of different origin by SEC-Q-TOF-ms: new insights into structure and formation.

PubMed

Reemtsma, Thorsten; These, Anja

2005-05-15

Size exclusion chromatography (SEC) coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Q-TOF-MS) was used to analyze the elemental composition and structure of low-molecular-weight fulvic acid molecules. It is shown that the set of hundreds of individual molecules form a homogeneous and structurally unique class of compounds that can be clearly differentiated from any other class of biogenic matter investigated to date. The molecular composition of low-molecular-weight fulvic acids in isolates of very different origin (surface water, groundwater, peat) is virtually indistinguishable. Significant and characteristic differences are, however, recognized when qualitative information and quantitative information provided by ESI-Q-TOF-MS are linked to each other. The relative frequency of the various molecules in each mixture can differ significantly, with the peat showing higher intensity of the aromatic and less carboxylated molecules of this set, whereas the aquatic fulvic acids show a strong contribution of the molecules with less aromaticity and a higher carboxylate content. The identity of fulvic acid molecules in isolates of different origin implies that no specific source material is required forfulvic acid formation but that they may be formed from different sources by different oxidative processes.

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

Comparison of synthetic chelators and low molecular weight organic acids in enhancing phytoextraction of heavy metals by two ecotypes of Sedum alfredii Hance.

PubMed

Liu, Dan; Islam, Ejazul; Li, Tingqiang; Yang, Xiaoe; Jin, Xiaofen; Mahmood, Qaisar

2008-05-01

Lab scale and pot experiments were conducted to compare the effects of synthetic chelators and low molecular weight organic acids (LMWOA) on the phytoextraction of multi-contaminated soils by two ecotypes of Sedum alfredii Hance. Through lab scale experiments, the treatment dosage of 5 and 10 mM for synthetic chelators and LMWOA, respectively, and the treatment time of 10 days were selected for pot experiment. In pot experiment, the hyperaccumulating ecotype (HE) was found more tolerant to the metal toxicity compared with the non-hyperaccumulating ecotype (NHE). EDTA for Pb, EDDS for Cu, and DTPA for Cu and Cd were found more effective to enhance heavy metal accumulation in the shoots of S. alfredii Hance. Compared with synthetic chelators, the phytoextraction ability of LMWOA was lesser. Considering the strong post-harvest effects of synthetic chelators, it is suggested that higher dosage of LMWOA could be practiced during phytoextraction, and some additional measures could also be taken to lower the potential environmental risks of synthetic chelators in the future studies.

Improving the mining soil quality for a vegetation cover after addition of sewage sludges: inorganic ions and low-molecular-weight organic acids in the soil solution.

PubMed

Peña, Aránzazu; Mingorance, Mª Dolores; Guzmán-Carrizosa, Ignacio; Fernández-Espinosa, Antonio J

2015-03-01

We assessed the effects of applying stabilized sewage sludge (SSL) and composted sewage sludge (CLV), at 5 and 10% to an acid mining soil. Limed soil (NCL) amended or not with SSL and CLV was incubated for 47 days. We studied the cations and organic and inorganic anions in the soil solution by means of ion chromatography. Liming led to big increases in Ca(2+) and SO4(2-) and to significant decreases in K(+), Mg(2+), NH4(+) and NO3(-). Addition of both organic amendments increased some cations (NH4(+), K(+), Mg(2+), Na(+)) and anions (Cl(-), NO3(-) only with CLV and PO4(3-) only with SSL) and provided a greater amount of low-molecular-weight organic acids (LMWOAs) (SSL more than CLV). Incubation led to decreases in all cations, particularly remarkable for Ca(2+) and Mg(2+) in SSL-10. A decrease in NH4(+) was associated with variations in NO2(-) and NO3(-) resulting from nitrification reactions. During incubation the LMWOAs content tended to decrease similarly to the cations, especially in SSL-10. Chemometric tools revealed a clear discrimination between SSL, CLV and NCL. Furthermore, treatment effects depended upon dose, mainly in SSL. Amendment nature and dose affect the quality of a mining soil and improve conditions for plant establishment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Identification and analysis of low molecular weight dissolved organic carbon in subglacial basal ice ecosystems by ion chromatography

NASA Astrophysics Data System (ADS)

Lawson, E. C.; Wadham, J. L.; Lis, G. P.; Tranter, M.; Pickard, A. E.; Stibal, M.; Dewsbury, P.; Fitzsimons, S.

2015-08-01

Glacial runoff is an important source of dissolved organic carbon (DOC) for downstream heterotrophic activity, despite the low overall DOC concentrations. This is because of the abundance of bioavailable, low molecular weight (LMW) DOC species. However, the provenance and character of LMW-DOC is not fully understood. We investigated the abundance and composition of DOC in subglacial environments via a molecular level DOC analysis of basal ice, which forms by water/sediment freeze-on to the glacier sole. Spectrofluorometry and a novel ion chromatographic method, which has been little utilised in glacial science for LMW-DOC determinations, were employed to identify and quantify the major LMW fractions (free amino acids, carbohydrates and carboxylic acids) in basal ice from four glaciers, each with a different basal debris type. Basal ice from Joyce Glacier (Antarctica) was unique in that 98 % of the LMW-DOC was derived from the extremely diverse FAA pool, comprising 14 FAAs. LMW-DOC concentrations in basal ice were dependent on the bioavailability of the overridden organic carbon (OC), which in turn, was influenced by the type of overridden material. Mean LMW-DOC concentrations in basal ice from Russell Glacier (Greenland), Finsterwalderbreen (Svalbard) and Engabreen (Norway) were low (0-417 nM C), attributed to the relatively refractory nature of the OC in the overridden paleosols and bedrock. In contrast, mean LMW-DOC concentrations were an order of magnitude higher (4430 nM C) in basal ice from Joyce Glacier, a reflection of the high bioavailability of the overridden lacustrine material (>17 % of the sediment OC comprised extractable carbohydrates, a proxy for bioavailable OC). We find that the overridden material may act as a direct (via abiotic leaching) and indirect (via microbial cycling) source of DOC to the subglacial environment and provides a range of LMW-DOC compounds that may stimulate microbial activity in wet sediments in current subglacial

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

USGS Publications Warehouse

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

1979-01-01

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

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.

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

PubMed

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

2018-04-01

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

Size distributions of low molecular weight dicarboxylic acids, ketocarboxylic acids, glyoxal and methylglyoxal in the marine aerosols from Okinawa Island, Japan

NASA Astrophysics Data System (ADS)

Kawamura, K.; Lazaar, M.

2008-12-01

Size-segregated marine aerosol samples (5 sets) were collected in 2008 spring at Cape Hedo Station of National Institute of Environmental Studies, Okinawa (128.25° E, 26.87° N), an outflow region of Chinese aerosols and their precursors, using an Andersen middle volume impactor at a flow rate of 100 lpm and pre-combusted quartz fiber filters. The samples were analyzed for low molecular weight diacids and related compounds, using a capillary gas chromatography and GC/MS after BF3/n-butanol derivatization. Particle size cuts (8 stages + BUF) are 0.43, 0.65, 1.1, 2.1, 3.3, 4.7, 7 and 11.3 µm in diameter. Homologous series of aliphatic (C2-C12) and aromatic (phthalic, iso- and tere-phthalic) diacids were detected as well as w-oxoacids (C2-C9), glyoxal and methylglyoxal. Oxalic acid (C2) was found as the dominant diacid in all the size ranges, followed by malonic (C3) and succinic (C4) acids. Glyoxylic (wC2) acid was the most abundant ketoacid followed by wC4 acid. Most of the organic species maximized in fine mode of 0.65-1.1 or 1.1-2.1µm. Oxalic acid (C2, 4.4-70.6 ngm-3, av. 23.9 ngm-3) comprised 54-80% (av. 67%) of total diacid concentrations. The small diacids showed concentration peaks on fine mode, suggesting that they are produced by photochemical oxidation of volatile organic precursors during long-range atmospheric transport from Asian Continent. They may also be produced by heterogeneous reactions in the atmospheric particles (dusts and cloud droplets).

Analysis of low molecular weight acids by monolithic immobilized pH gradient-based capillary isoelectric focusing coupled with mass spectrometry.

PubMed

Wang, Tingting; Fekete, Agnes; Gaspar, Andras; Ma, Junfeng; Liang, Zhen; Yuan, Huiming; Zhang, Lihua; Schmitt-Kopplin, Philippe; Zhang, Yukui

2011-02-01

A novel method for the separation and detection of low molecular weight (LMW) acids was developed using monolithic immobilized pH gradient-based capillary isoelectric focusing coupled with mass spectrometry. Two main parameters, focusing conditions and delivery buffer conditions, which might affect separation efficiency, were optimized with the focusing time of 7 min at 350 V/cm and the delivery buffer of 50% (v/v) acetonitrile in 10 mmol/L ammonium formate (pH 3.0). Under these conditions, the linear correlation between the volume of delivery solvent and the pK(a) of the model components was observed. In addition, the separation mechanism of LMW acids was proposed as well. We suppose that this method may provide a useful tool for the characterization of LMW components (e.g. natural organic matter of different origins). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of molecular weight of hyaluronic acid on its viscosity and enzymatic activities of lysozyme and peroxidase.

PubMed

Kim, Jihoon; Chang, Ji-Youn; Kim, Yoon-Young; Kim, Moon-Jong; Kho, Hong-Seop

2018-05-01

To investigate the effects of the molecular weight of hyaluronic acid on its viscosity and enzymatic activities of lysozyme and peroxidase in solution and on the hydroxyapatite surface. Hyaluronic acids of four different molecular weights (10 kDa, 100 kDa, 1 MDa, and 2 MDa), hen egg-white lysozyme, bovine lactoperoxidase, and human whole saliva were used. Viscosity values of hyaluronic acids were measured using a cone-and-plate viscometer at six different concentrations (0.1-5.0 mg/mL). Enzymatic activities of lysozyme and peroxidase were examined by hydrolysis of fluorescein-labeled Micrococcus lysodeikticus and oxidation of fluorogenic 2',7'-dichlorofluorescein to fluorescing 2',7'-dichlorofluorescein, respectively. In solution assays, only 2 MDa-hyaluronic acid significantly inhibited lysozyme activities in saliva. In surface assays, hyaluronic acids inhibited lysozyme and peroxidase activities; the inhibitory activities were more apparent with high-molecular-weight ones in saliva than in purified enzymes. The 100 kDa-hyaluronic acid at 5.0 mg/mL, 1 MDa-one at 0.5 mg/mL, and 2 MDa-one at 0.2 mg/mL showed viscosity values similar to those of human whole saliva at a shear rate range required for normal oral functions. The differences among the influences of the three conditions on the enzymatic activities were not statistically significant. High-molecular-weight hyaluronic acids at low concentration and low-molecular-weight ones at high concentration showed viscosity values similar to those of human whole saliva. Inhibitory effects of hyaluronic acids on lysozyme and peroxidase activities were more significant with high-molecular-weight ones on the surface and in saliva compared with in solution and on purified enzymes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Solubility of crystalline organic compounds in high and low molecular weight amorphous matrices above and below the glass transition by zero enthalpy extrapolation.

PubMed

Amharar, Youness; Curtin, Vincent; Gallagher, Kieran H; Healy, Anne Marie

2014-09-10

Pharmaceutical applications which require knowledge of the solubility of a crystalline compound in an amorphous matrix are abundant in the literature. Several methods that allow the determination of such data have been reported, but so far have only been applicable to amorphous polymers above the glass transition of the resulting composites. The current work presents, for the first time, a reliable method for the determination of the solubility of crystalline pharmaceutical compounds in high and low molecular weight amorphous matrices at the glass transition and at room temperature (i.e. below the glass transition temperature), respectively. The solubilities of mannitol and indomethacin in polyvinyl pyrrolidone (PVP) K15 and PVP K25, respectively were measured at different temperatures. Mixtures of undissolved crystalline solute and saturated amorphous phase were obtained by annealing at a given temperature. The solubility at this temperature was then obtained by measuring the melting enthalpy of the crystalline phase, plotting it as a function of composition and extrapolating to zero enthalpy. This new method yielded results in accordance with the predictions reported in the literature. The method was also adapted for the measurement of the solubility of crystalline low molecular weight excipients in amorphous active pharmaceutical ingredients (APIs). The solubility of mannitol, glutaric acid and adipic acid in both indomethacin and sulfadimidine was experimentally determined and successfully compared with the difference between their respective calculated Hildebrand solubility parameters. As expected from the calculations, the dicarboxylic acids exhibited a high solubility in both amorphous indomethacin and sulfadimidine, whereas mannitol was almost insoluble in the same amorphous phases at room temperature. This work constitutes the first report of the methodology for determining an experimentally measured solubility for a low molecular weight crystalline solute

Identification and analysis of low-molecular-weight dissolved organic carbon in subglacial basal ice ecosystems by ion chromatography

NASA Astrophysics Data System (ADS)

O'Donnell, Emily C.; Wadham, Jemma L.; Lis, Grzegorz P.; Tranter, Martyn; Pickard, Amy E.; Stibal, Marek; Dewsbury, Paul; Fitzsimons, Sean

2016-07-01

Determining the concentration and composition of dissolved organic carbon (DOC) in glacial ecosystems is important for assessments of in situ microbial activity and contributions to wider biogeochemical cycles. Nonetheless, there is limited knowledge of the abundance and character of DOC in basal ice and the subglacial environment and a lack of quantitative data on low-molecular-weight (LMW) DOC components, which are believed to be highly bioavailable to microorganisms. We investigated the abundance and composition of DOC in basal ice via a molecular-level DOC analysis. Spectrofluorometry and a novel ion chromatographic method, which has been little utilized in glacial science for LMW-DOC determinations, were employed to identify and quantify the major LMW fractions (free amino acids, carbohydrates, and carboxylic acids) in basal ice from four glaciers, each with a different type of overridden material (i.e. the pre-entrainment sedimentary type such as lacustrine material or palaeosols). Basal ice from Joyce Glacier (Antarctica) was unique in that 98 % of the LMW-DOC was derived from the extremely diverse free amino acid (FAA) pool, comprising 14 FAAs. LMW-DOC concentrations in basal ice were dependent on the bioavailability of the overridden organic carbon (OC), which in turn was influenced by the type of overridden material. Mean LMW-DOC concentrations in basal ice from Russell Glacier (Greenland), Finsterwalderbreen (Svalbard), and Engabreen (Norway) were low (0-417 nM C), attributed to the relatively refractory nature of the OC in the overridden palaeosols and bedrock. In contrast, mean LMW-DOC concentrations were an order of magnitude higher (4430 nM C) in basal ice from Joyce Glacier, a reflection of the high bioavailability of the overridden lacustrine material (> 17 % of the sediment OC comprised extractable carbohydrates, a proxy for bioavailable OC). We find that the overridden material may act as a direct (via abiotic leaching) and indirect (via

Bioavailable concentrations of germanium and rare earth elements in soil as affected by low molecular weight organic acids and root exudates

NASA Astrophysics Data System (ADS)

Wiche, Oliver; Székely, Balázs; Kummer, Nicolai-Alexeji; Heinemann, Ute; Tesch, Silke; Heilmeier, Hermann

2014-05-01

Availability of elements in soil to plant is generally dependent on the solubility and mobility of elements in soil solution which is controlled by soil, elemental properties and plant-soil interactions. Low molecular organic acids or other root exudates may increase mobility and availability of certain elements for plants as an effect of lowering pH in the rhizosphere and complexation. However, these processes take place in a larger volume in soil, therefore to understand their nature, it is also important to know in which layers of the soil what factors modify these processes. In this work the influence of citric acid and root exudates of white lupin (Lupinus albus L.) on bioavailable concentrations of germanium, lanthan, neodymium, gadolinium and erbium in soil solution and uptake in root and shoot of rape (Brassica napus L.), comfrey (Symphytum officinale L.), common millet (Panicum milliaceum L.) and oat (Avena sativa L.) was investigated. Two different pot experiments were conducted: (1) the mentioned plant species were treated with nutrient solutions containing various amount of citric acid; (2) white lupin was cultivated in mixed culture (0 % lupin, 33 % lupin) with oat (Avena sativa L.) and soil solution was obtained by plastic suction cups placed at various depths. As a result, addition of citric acid significantly increased germanium concentrations in plant tissue of comfrey and rape and increased translocation of germanium, lanthan, neodymium, gadolinium and erbium from root to shoot. The cultivation of white lupin in mixed culture with oat led to significantly higher concentrations of germanium and increasing concentrations of lanthan, neodymium, gadolinium and erbium in soil solution and aboveground plant tissue. In these pots concentrations of citric acid in soil solution were significantly higher than in the control. The results show, that low molecular organic acids exuded by plant roots are of great importance for the mobilization of germanium

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.

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

PubMed

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

2008-05-01

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

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.

Enhanced levels of atmospheric low-molecular weight monocarboxylic acids in gas and particulates over Mt. Tai, North China, during field burning of agricultural wastes

NASA Astrophysics Data System (ADS)

Mochizuki, Tomoki; Kawamura, Kimitaka; Nakamura, Shinnosuke; Kanaya, Yugo; Wang, Zifa

2017-12-01

To understand the source and atmospheric behaviour of low molecular weight monocarboxylic acids (monoacids), gaseous (G) and particulate (P) organic acids were collected at the summit of Mt. Tai in the North China Plain (NCP) during field burning of agricultural waste (wheat straw). Particulate organic acids were collected with neutral quartz filter whereas gaseous organic acids were collected with KOH-impregnated quartz filter. Normal (C1-C10), branched (iC4-iC6), hydroxy (lactic and glycolic), and aromatic (benzoic) monoacids were determined with a capillary gas chromatography employing p-bromophenacyl esters. We found acetic acid as the most abundant gas-phase species whereas formic acid is the dominant particle-phase species. Concentrations of formic (G/P 1 570/1 410 ng m-3) and acetic (3 960/1 120 ng m-3) acids significantly increased during the enhanced field burning of agricultural wastes. Concentrations of formic and acetic acids in daytime were found to increase in both G and P phases with those of K+, a field-burning tracer (r = 0.32-0.64). Primary emission and secondary formation of acetic acid is linked with field burning of agricultural wastes. In addition, we found that particle-phase fractions (Fp = P/(G + P)) of formic (0.50) and acetic (0.31) acids are significantly high, indicating that semi-volatile organic acids largely exist as particles. Field burning of agricultural wastes may play an important role in the formation of particulate monoacids in the NCP. High levels (917 ng m-3) of particle-phase lactic acid, which is characteristic of microorganisms, suggest that microbial activity associated with terrestrial ecosystem significantly contributes to the formation of organic aerosols.

Effects of Low-Molecular-Weight Organic Acids on the Dissolution of Hydroxyapatite Nanoparticles in Batch and Column Experiments: A Perspective from Phosphate Oxygen Isotope Fractionation

NASA Astrophysics Data System (ADS)

Wang, D.; Jaisi, D. P.; Jin, Y.

2015-12-01

Hydroxyapatite nanoparticles (HANPs) are increasingly being advocated as an efficient and environment-friendly "green" phosphorus nanofertilizer attributed to their nanoscale dimension, large reactive surface area, and low leaching potential. However, knowledge of how naturally occurring low-molecular-weight organic acids (LMWOAs) that are secreted by plant roots mediate the dissolution of HANPs (releasing PO43- ion for plant growth) is nonexistent. Here three most commonly encountered LMWOAs (acetic acid, oxalic acid, and citric acid) at environmentally relevant concentration (1 mM) were evaluated for their effects on HANPs' dissolution in static batch and dynamic column systems. Particularly, phosphate oxygen isotope fractionation of HANPs during dissolution was examined to disentangle mechanisms controlling the evolution of O-isotopic composition of dissolved PO43- ion. Our results reveal that in batch experiments the dissolution of HANPs was fast but the overall dissolution efficiency of HANPs was limited (≤30%). In contrast, ~100% HANPs were dissolved in columns where LMWOAs were continuously injected. The limited dissolution of HANPs in static batch systems was due primarily to pH buffer effect (pH increased sharply when LMWOA was added in HANPs suspension), whereas in dynamic column systems the HANPs were continuously dissolved by low pH LMWOAs and leached away. Regardless of LMWOA type and experimental system, the isotopically light phosphate (P16O4) was preferentially released during dissolution and the O-isotopic composition of dissolved PO43- ion increased gradually with increasing dissolution due to equilibrium isotope effect between dissolved PO43- ion and HANPs. However, the overall magnitude of O-isotopic fractionation of dissolved PO43- ion was less in batch than in column systems, due to less mass transfer between dissolved PO43- ions and HANPs in batch relative to column experiments. Our findings provide new insights into bioavailability

Methylmercury production in soil in the water-level-fluctuating zone of the Three Gorges Reservoir, China: The key role of low-molecular-weight organic acids.

PubMed

Yin, Deliang; Wang, Yongmin; Jiang, Tao; Qin, Caiqing; Xiang, Yuping; Chen, Qiuyu; Xue, Jinping; Wang, Dingyong

2018-04-01

As important parts of dissolved organic matter, low-molecular-weight organic acids (LMWOAs) typically play important roles in desorbing Hg(II) from the soil solid-phase, which may directly or indirectly impact methylmercury (MeHg) production. However, the mechanism of these processes remains unclear. To better understand the effects of LMWOAs on Hg methylation in the soil, a field study was conducted to investigate the distribution of LMWOAs and their relationship with soil MeHg in a seasonally inundated area in the Three Gorges Reservoir (TGR), China. Meanwhile, laboratory simulation experiments were performed to determine the potential mechanism of LMWOAs in Hg methylation. The field investigation detected considerable amounts of LMWOAs in soil, among which tartaric acid and oxalic acid were dominant components. Among which, tartaric acid and oxalic acid were dominant components. Also, a seasonally and spatially heterogeneous distribution of LMWOAs in soil was observed. Notably, a significant positive relationship was found between MeHg concentrations and LMWOA pools in soil (r = 0.969, p < .01), implying that LMWOAs could promote soil MeHg production. The simulation experiments confirmed that the MeHg levels in soil were largely elevated with the addition of LMWOAs, which occurred mainly in oxygen-deficient environment and was mediated by biotic factors. The soluble Hg-LMWOA complexes, which were formed by the enhanced desorption of Hg(II) from solid-phase, were mostly responsible for the elevated MeHg production in soil. Moreover, those LMWOAs with more carboxylic groups were believed to enhance the net production of MeHg. The generated MeHg in sediment could diffuse into the overlying water, which thus poses a potential threat to the aquatic food web. Therefore, the enhanced Hg methylation caused by LMWOAs should be given more attention, especially in a seasonally inundated ecosystem, where the MeHg exposure is usually related to fishery activities

[Inhibition of Low Molecular Organic Acids on the Activity of Acidithiobacillus Species and Its Effect on the Removal of Heavy Metals from Contaminated Soil].

PubMed

Song, Yong-wei; Wang, He-rul; Cao, Yan-xiao; Li, Fei; Cui, Chun-hong; Zhou, Li

2016-05-15

Application of organic fertilizer can reduce the solubility and bioavailability of heavy metals in contaminated soil, but in the flooded anaerobic environment, organic fertilizer will be decomposed to produce a large number of low molecular organic acids, which can inhibit the biological activity of Acidithiobacillus species. Batch cultures studies showed that the monocarboxylic organic acids including formic acid, acetic acid, propionic acid, and butyric acid exhibited a marked toxicity to Acidithiobacillus species, as indicated by that 90% of inhibitory rate for Fe2 and So oxidation in 72 h were achieved at extremely low concentrations of 41.2 mg · L⁻¹, 78.3 mg · L⁻¹, 43.2 mg · L⁻¹, 123.4 mg · L⁻¹ and 81.9 mg 230. 4 mg · L⁻¹, 170.1 mg · L⁻¹, 123.4 mg · L⁻¹ respectively. Of these organic acids, formic acid was the most toxic one as indicated by that Fe2 and So oxidation was almost entirely inhibited at a low concentration. In addition, it was found that Acidithiobacillus ferrooxidans was more sensitive to low molecular organic acids than Acidithiobacillus thiooxidans. What's more, there was little effect on biological acidification process of heavy metal contaminated soil when organic acids were added at initial stage (Oh), but it was completely inhibited when these acids were added after 12 h of conventional biological acidification, thus decreasing the efficiency of heavy metals dissolution from soil.

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

The potential of flow-through microdialysis for probing low-molecular weight organic anions in rhizosphere soil solution.

PubMed

Sulyok, Michael; Miró, Manuel; Stingeder, Gerhard; Koellensperger, Gunda

2005-08-01

In this paper, flow-through microdialysis is presented as a novel analytical tool for automatic sampling of low molecular weight organic anions (LMWOA), such as oxalate and citrate, in solid samples of environmental concern. The microsampling methodology involves the implantation of dedicated capillary-type probes offering unrivalled spatial resolution (ca. 200μm) in definite soil sites. These passive samplers are aimed at monitoring local processes, such as the release of organic acids occurring in the rhizosphere environment, in nearly real-time. The influence of chemical and physical variables (composition and flow rate of the perfusion liquid, ionic strength and pH of the outer medium and presence of metal ions therein) was assessed in vitro using liquid-phase assays. On the other hand, the resistance of the external solid medium to mass transfer, and the actual applicability of in vivo calibration methods were investigated using quartz sand as an inert model soil. Microdialysers furnished with 3cm long semipermeable tubular membranes were perfused with 0.01M NaNO 3 at a flow rate of 2.0μl/min, yielding dialysis recoveries ≥45% for both assayed LMWOAs in simulated background soil electrolyte solutions, and ≥24% in the interstitial liquid of complex solid samples. Full knowledge of the fate of LMWOAs in soils was obtained through the application of stimulus-response approaches that mimic the discrete exudation pulses of roots. Highly time-resolved microdialysates were used to discern readily available species such as free carboxylic anions and LMW metal-organic acid complexes from adsorbed, precipitated or mineralised analyte species in a variety of soil samples containing variable amounts of organic matter, exchangeable cations and different levels of metal pollution.

Effect of CMC Molecular Weight on Acid-Induced Gelation of Heated WPI-CMC Soluble Complex.

PubMed

Huan, Yan; Zhang, Sha; Vardhanabhuti, Bongkosh

2016-02-01

Acid-induced gelation properties of heated whey protein isolate (WPI) and carboxymethylcellulose (CMC) soluble complex were investigated as a function of CMC molecular weight (270, 680, and 750 kDa) and concentrations (0% to 0.125%). Heated WPI-CMC soluble complex with 6% protein was made by heating biopolymers together at pH 7.0 and 85 °C for 30 min and diluted to 5% protein before acid-induced gelation. Acid-induced gel formed from heated WPI-CMC complexes exhibited increased hardness and decreased water holding capacity with increasing CMC concentrations but gel strength decreased at higher CMC content. The highest gel strength was observed with CMC 750 k at 0.05%. Gels with low CMC concentration showed homogenous microstructure which was independent of CMC molecular weight, while increasing CMC concentration led to microphase separation with higher CMC molecular weight showing more extensive phase separation. When heated WPI-CMC complexes were prepared at 9% protein the acid gels showed improved gel hardness and water holding capacity, which was supported by the more interconnected protein network with less porosity when compared to complexes heated at 6% protein. It is concluded that protein concentration and biopolymer ratio during complex formation are the major factors affecting gel properties while the effect of CMC molecular weight was less significant. © 2016 Institute of Food Technologists®

Uptake of Alkylamines on Dicarboxylic Acids Relevant to Secondary Organic Aerosol Formation

NASA Astrophysics Data System (ADS)

Marrero-Ortiz, W.; Secrest, J.; Zhang, R.

2017-12-01

Aerosols play a critical role in climate directly by scattering and absorbing solar radiation, and indirectly by functioning as cloud condensation nuclei (CCN); both represent the largest uncertainties in climate predictions. New particle formation contributes significantly to CCN production; however, the mechanisms related to particle nucleation and growth processes are not well understood. Organic acids are atmospherically abundant, and their neutralization by low molecular weight amines may result in the formation of stable low volatility aminium salt products contributing to the growth of secondary organic aerosols and even the alteration of the aerosol properties. The acid-base neutralization of particle phase succinic acid and tartaric acid by low molecular weight aliphatic amines, i.e. methylamine, dimethylamine, and trimethylamine, has been investigated by employing a low-pressure fast flow reactor at 298K with an ion drift - chemical ionization mass spectrometer (ID-CIMS). The heterogeneous uptake is time dependent and influenced by organic acids functionality, alkylamines basicity, and steric effect. The implications of our results to atmospheric nanoparticle growth will be discussed.

Microbial utilization of low molecular weight organics in soil depends on the substances properties

NASA Astrophysics Data System (ADS)

Gunina, Anna

2016-04-01

Utilization of low molecular weight organic substances (LMWOS) in soil is regulated by microbial uptake from solution and following incorporation of into specific cell cycles. Various chemical properties of LMWOS, namely oxidation state, number of carbon (C) atoms, number of carboxylic (-COOH) groups, can affect their uptake from soil solution and further microbial utilization. The aim of the study was to trace the initial fate (including the uptake from soil solution and utilization by microorganisms) of three main classes of LMWOS, having contrast properties - sugars, carboxylic and amino acids. Top 10 cm of mineral soil were collected under Silver birch stands within the Bangor DIVERSE experiment, UK. Soil solution was extracted by centrifugation at 4000 rpm during 15 min. Soil was spiked with 14C glucose or fructose; malic, succinic or formic acids; alanine or glycine. No additional non-labeled LMWOS were added. 14C was traced in the dissolved organic matter (DOM), CO2, cytosol and soil organic matter (SOM) during one day. To estimate half-life times (T1 /2)of LMWOS in soil solution and in SOM pools, the single and double first order kinetic equations were fitted to the uptake and mineralization dynamics, respectively. The LMWOS T1 /2in DOM pool varied between 0.6-5 min, with the highest T1 /2for sugars (3.7 min) and the lowest for carboxylic acids (0.6-1.4 min). Thus, initial uptake of LMWOS is not a limiting step of microbial utilization. The T1 /2 of carboxylic and amino acids in DOM were closely related with oxidation state, showing that reduced substances remain in soil solution longer, than oxidized. The initial T1 /2 of LMWOS in SOM ranged between 30-80 min, with the longest T1 /2 for amino acids (50-80 min) and the shortest for carboxylic acids (30-48 min). These T1 /2values were in one-two orders of magnitude higher than LMWOS T1 /2 in soil solution, pointing that LMWOS mineralization occur with a delay after the uptake. Absence of correlations between

Effect of warming on the degradation and production of low-molecular-weight labile organic carbon in an Arctic tundra soil

DOE PAGES

Yang, Ziming; Wullschleger, Stan D.; Liang, Liyuan; ...

2016-01-16

The fate of soil organic carbon (SOC) stored in the Arctic permafrost is a key concern as temperatures continue to rise in the northern hemisphere. Studies and conceptual models suggest that SOC degradation is affected by the composition of SOC, but it is unclear exactly what portions of SOC are vulnerable to rapid breakdown and what mechanisms may be controlling SOC degradation upon permafrost thaw. Here, we examine the dynamic consumption and production of labile SOC in an anoxic incubation experiment using soil samples from the active layer at the Barrow Environmental Observatory, Barrow, Alaska, USA. Free-reducing sugars, alcohols, andmore » low-molecular-weight (LMW) organic acids were analyzed during incubation at either –2 or 8 °C for up to 240 days. Results show that simple sugar and alcohol SOC largely account for the initial rapid release of CO 2 and CH 4 through anaerobic fermentation, whereas the fermentation products, acetate and formate, are subsequently utilized as primary substrates for methanogenesis. Iron(III) reduction is correlated to acetate production and methanogenesis, suggesting its important role as an electron acceptor in tundra SOC respiration. These observations are further supported in a glucose addition experiment, in which rapid CO 2 and CH 4 production occurred concurrently with rapid production and consumption of labile organics such as acetate. However, addition of tannic acid, as a more complex organic substrate, showed little influence on the overall production of CO 2 and CH 4 and organic acids. Together our study shows that LMW labile organics in SOC control the initial rapid release of green-house gases upon warming. We thus present a conceptual framework for the labile SOC transformations and their relations to fermentation, iron reduction and methanogenesis, thereby providing the basis for improved model prediction of climate feedbacks in the Arctic.« less

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

USGS Publications Warehouse

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

1994-01-01

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

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

PubMed

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

2014-09-23

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

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

PubMed Central

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

2014-01-01

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

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

PubMed

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

2018-04-23

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

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.

Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight

NASA Astrophysics Data System (ADS)

Burek, Katja; Eidner, Sascha; Kuke, Stefanie; Kumke, Michael U.

2018-02-01

The luminescence of Lanthanide(III) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(III) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K ≤ T ≤ 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M ≤ I ≤ 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites.

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.

Ancient low–molecular-weight organic acids in permafrost fuel rapid carbon dioxide production upon thaw

USGS Publications Warehouse

Drake, Travis W.; Wickland, Kimberly P.; Spencer, Robert G. M.; McKnight, Diane M.; Striegl, Robert G.

2015-01-01

Northern permafrost soils store a vast reservoir of carbon, nearly twice that of the present atmosphere. Current and projected climate warming threatens widespread thaw of these frozen, organic carbon (OC)-rich soils. Upon thaw, mobilized permafrost OC in dissolved and particulate forms can enter streams and rivers, which are important processors of OC and conduits for carbon dioxide (CO2) to the atmosphere. Here, we demonstrate that ancient dissolved organic carbon (DOC) leached from 35,800 y B.P. permafrost soils is rapidly mineralized to CO2. During 200-h experiments in a novel high–temporal-resolution bioreactor, DOC concentration decreased by an average of 53%, fueling a more than sevenfold increase in dissolved inorganic carbon (DIC) concentration. Eighty-seven percent of the DOC loss to microbial uptake was derived from the low–molecular-weight (LMW) organic acids acetate and butyrate. To our knowledge, our study is the first to directly quantify high CO2 production rates from permafrost-derived LMW DOC mineralization. The observed DOC loss rates are among the highest reported for permafrost carbon and demonstrate the potential importance of LMW DOC in driving the rapid metabolism of Pleistocene-age permafrost carbon upon thaw and the outgassing of CO2 to the atmosphere by soils and nearby inland waters.

Ancient low–molecular-weight organic acids in permafrost fuel rapid carbon dioxide production upon thaw

PubMed Central

Drake, Travis W.; Wickland, Kimberly P.; Spencer, Robert G. M.; McKnight, Diane M.; Striegl, Robert G.

2015-01-01

Northern permafrost soils store a vast reservoir of carbon, nearly twice that of the present atmosphere. Current and projected climate warming threatens widespread thaw of these frozen, organic carbon (OC)-rich soils. Upon thaw, mobilized permafrost OC in dissolved and particulate forms can enter streams and rivers, which are important processors of OC and conduits for carbon dioxide (CO2) to the atmosphere. Here, we demonstrate that ancient dissolved organic carbon (DOC) leached from 35,800 y B.P. permafrost soils is rapidly mineralized to CO2. During 200-h experiments in a novel high–temporal-resolution bioreactor, DOC concentration decreased by an average of 53%, fueling a more than sevenfold increase in dissolved inorganic carbon (DIC) concentration. Eighty-seven percent of the DOC loss to microbial uptake was derived from the low–molecular-weight (LMW) organic acids acetate and butyrate. To our knowledge, our study is the first to directly quantify high CO2 production rates from permafrost-derived LMW DOC mineralization. The observed DOC loss rates are among the highest reported for permafrost carbon and demonstrate the potential importance of LMW DOC in driving the rapid metabolism of Pleistocene-age permafrost carbon upon thaw and the outgassing of CO2 to the atmosphere by soils and nearby inland waters. PMID:26504243

Removal of low-molecular weight DBPs and inorganic ions for characterization of high-molecular weight DBPs in drinking water.

PubMed

Zhang, Xiangru; Minear, Roger A

2006-03-01

High-molecular weight (MW) halogenated disinfection byproducts (DBPs) may cause adverse health effects. In this work several issues related to the better separation and characterization of the high MW halogenated DBPs (MW>500Da) were studied. Ultra-filtration (UF) coupled with a nominal 500-Da membrane was employed to flush out low MW DBPs and inorganic ions. Two procedures, intermittent UF and continuous UF, were used and compared. The results demonstrate that haloacetic acids, chloride and sodium ions could be effectively flushed out, and most of phosphate ions could be flushed out for a given dilution number or sufficient Milli-Q water. The size exclusion chromatograms indicate that haloacetic acids and trihalomethanes were not bound to Suwannee River fulvic acid (SRFA); 2,4,6-trichlorophenol might form some binding with SRFA, but it appeared to be very weak and readily broken up when passing along the size exclusion column. The octanol-water partition coefficients of low MW DBPs and the properties of humic substances seem to play key roles in determining the formation of possible bindings between low MW DBPs and humic substances.

Low molecular weight polylactic acid as a matrix for the delayed release of pesticides.

PubMed

Zhao, Jing; Wilkins, Richard M

2005-05-18

Low molecular weight polylactic acid (LMW PLA) was used as a matrix to formulate biodegradable matrix granules and films with bromacil using a melt process. The compatibility of the PLA with bromacil was evaluated. The release characteristics of the formulations were investigated in vitro. The degradation and erosion of the formulations were monitored by pH and gravimetric analysis during the course of release. Various granules and films had similar biphasic release patterns, a delayed release followed by an explosive release. The release rates were independent of bromacil content in the matrix, but varied with the geometry of matrices. The mechanisms of diffusion and erosion were involved in the release. The delayed release of the formulations was dominantly governed by the degradation and erosion of PLA. LMW PLA underwent bulk erosion. LMW PLA-based matrix formulations could thus be useful for the application of pesticides to sensitive targets such as seed treatment.

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.

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

PubMed

Jeon, Hyun Jeong; Kim, Mal Nam

2013-02-01

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

Inkjet-printed gold nanoparticle surfaces for the detection of low molecular weight biomolecules by laser desorption/ionization mass spectrometry.

PubMed

Marsico, Alyssa L M; Creran, Brian; Duncan, Bradley; Elci, S Gokhan; Jiang, Ying; Onasch, Timothy B; Wormhoudt, Joda; Rotello, Vincent M; Vachet, Richard W

2015-11-01

Effective detection of low molecular weight compounds in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is often hindered by matrix interferences in the low m/z region of the mass spectrum. Here, we show that monolayer-protected gold nanoparticles (AuNPs) can serve as alternate matrices for the very sensitive detection of low molecular weight compounds such as amino acids. Amino acids can be detected at low fmol levels with minimal interferences by properly choosing the AuNP deposition method, density, size, and monolayer surface chemistry. By inkjet-printing AuNPs at various densities, we find that AuNP clusters are essential for obtaining the greatest sensitivity. Graphical Abstract ᅟ.

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.

Method for characterization of low molecular weight organic acids in atmospheric aerosols using ion chromatography mass spectrometry.

PubMed

Brent, Lacey C; Reiner, Jessica L; Dickerson, Russell R; Sander, Lane C

2014-08-05

The structural composition of PM2.5 monitored in the atmosphere is usually divided by the analysis of organic carbon, black (also called elemental) carbon, and inorganic salts. The characterization of the chemical composition of aerosols represents a significant challenge to analysts, and studies are frequently limited to determination of aerosol bulk properties. To better understand the potential health effects and combined interactions of components in aerosols, a variety of measurement techniques for individual analytes in PM2.5 need to be implemented. The method developed here for the measurement of organic acids achieves class separation of aliphatic monoacids, aliphatic diacids, aromatic acids, and polyacids. The selective ion monitoring capability of a triple quadropole mass analyzer was frequently capable of overcoming instances of incomplete separations. Standard Reference Material (SRM) 1649b Urban Dust was characterized; 34 organic acids were qualitatively identified, and 6 organic acids were quantified.

Different low-molecular-mass organic acids specifically control leaching of arsenic and lead from contaminated soil

NASA Astrophysics Data System (ADS)

Ash, Christopher; Tejnecký, Václav; Borůvka, Luboš; Drábek, Ondřej

2016-04-01

Low-molecular-mass organic acids (LMMOA) are of key importance for mobilisation and fate of metals in soil, by functioning as ligands that increase the amount of dissolved metal in solution or by dissociation of metal binding minerals. Column leaching experiments were performed on soil polluted with As and Pb, in order to determine the specificity of LMMOA related release for individual elements, at varying organic acid concentrations. Acetic, citric and oxalic acids were applied in 12 h leaching experiments over a concentration range (0.5-25 mM) to soil samples that represent organic and mineral horizons. The leaching of As followed the order: oxalic > citric > acetic acid in both soils. Arsenic leaching was attributed primarily to ligand-enhanced dissolution of mineral oxides followed by As released into solution, as shown by significant correlation between oxalic and citric acids and content of Al and Fe in leaching solutions. Results suggest that subsurface mineral soil layers are more vulnerable to As toxicity. Leaching of Pb from both soils followed the order: citric > oxalic > acetic acid. Mineral soil samples were shown to be more susceptible to leaching of Pb than samples characterised by a high content of organic matter. The leaching efficiency of citric acid was attributed to formation of stable complexes with Pb ions, which other acids are not capable of. Results obtained in the study are evidence that the extent of As and Pb leaching in contaminated surface and subsurface soil depends significantly on the types of carboxylic acid involved. The implications of the type of acid and the specific element that can be mobilised become increasingly significant where LMMOA concentrations are highest, such as in rhizosphere soil.

Relationship between chemical structure and the occupational asthma hazard of low molecular weight organic compounds

PubMed Central

Jarvis, J; Seed, M; Elton, R; Sawyer, L; Agius, R

2005-01-01

Aims: To investigate quantitatively, relationships between chemical structure and reported occupational asthma hazard for low molecular weight (LMW) organic compounds; to develop and validate a model linking asthma hazard with chemical substructure; and to generate mechanistic hypotheses that might explain the relationships. Methods: A learning dataset used 78 LMW chemical asthmagens reported in the literature before 1995, and 301 control compounds with recognised occupational exposures and hazards other than respiratory sensitisation. The chemical structures of the asthmagens and control compounds were characterised by the presence of chemical substructure fragments. Odds ratios were calculated for these fragments to determine which were associated with a likelihood of being reported as an occupational asthmagen. Logistic regression modelling was used to identify the independent contribution of these substructures. A post-1995 set of 21 asthmagens and 77 controls were selected to externally validate the model. Results: Nitrogen or oxygen containing functional groups such as isocyanate, amine, acid anhydride, and carbonyl were associated with an occupational asthma hazard, particularly when the functional group was present twice or more in the same molecule. A logistic regression model using only statistically significant independent variables for occupational asthma hazard correctly assigned 90% of the model development set. The external validation showed a sensitivity of 86% and specificity of 99%. Conclusions: Although a wide variety of chemical structures are associated with occupational asthma, bifunctional reactivity is strongly associated with occupational asthma hazard across a range of chemical substructures. This suggests that chemical cross-linking is an important molecular mechanism leading to the development of occupational asthma. The logistic regression model is freely available on the internet and may offer a useful but inexpensive adjunct to the

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

Topochemical approach to efficiently produce main-chain poly(bile acid)s with high molecular weights.

PubMed

Li, Weina; Li, Xuesong; Zhu, Wei; Li, Changxu; Xu, Dan; Ju, Yong; Li, Guangtao

2011-07-21

Based on a topochemical approach, a strategy for efficiently producing main-chain poly(bile acid)s in the solid state was developed. This strategy allows for facile and scalable synthesis of main-chain poly(bile acid)s not only with high molecular weights, but also with quantitative conversions and yields.

Microbial utilization of low molecular weight organic substrates in soil depends on their carbon oxidation state

NASA Astrophysics Data System (ADS)

Gunina, Anna; Smith, Andrew; Jones, Davey; Kuzyakov, Yakov

2017-04-01

Removal of low molecular weight organic substances (LMWOS), originating from plants and microorganisms, from soil solution is regulated by microbial uptake. In addition to the concentration of LMWOS in soil solution, the chemical properties of each substance (e.g. C oxidation state, number of C atoms, number of -COOH groups) can affect their uptake and subsequent partitioning of C within the soil microbial community. The aim of this study was to trace the initial fate of three dominant classes of LMWOS in soil (sugars, carboxylic and amino acids), including their removal from solution and utilization by microorganisms, and to reveal the effect of substance chemical properties on these processes. Soil solution, spiked at natural abundance levels with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the dissolved organic carbon (DOC), CO2, cytosol and soil organic carbon (SOC) over 24 hours. The half-life time of all LMWOS in the DOC (T1 /2-solution) varied between 0.6-5.0 min showing extremely fast initial uptake of LMWOS. The T1 /2-solution of substances was dependent on C oxidation state, indicating that less oxidized organic substances (with C oxidation state "0") were retained longer in soil solution than oxidized substances. The LMWOS-C T1 /2-fast, characterizing the half-life time of 14C in the fast mineralization pool, ranged between 30 and 80 min, with the T1 /2-fast of carboxylic acids (malic acid) being the fastest and the T1 /2-fast of amino acids (glycine) being the slowest. An absence of correlation between T1 /2-fast and either C oxidation state, number of C atoms, or number of -COOH groups suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The CO2 release during LMWOS mineralization accounted for 20-90% of 14C applied. Mineralization of LMWOS was the least for sugars and the greatest for

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.

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

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.

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.

Different low-molecular-mass organic acids specifically control leaching of arsenic and lead from contaminated soil.

PubMed

Ash, Christopher; Tejnecký, Václav; Borůvka, Luboš; Drábek, Ondřej

2016-04-01

Low-molecular-mass organic acids (LMMOA) are of key importance for mobilisation and fate of metals in soil, by functioning as ligands that increase the amount of dissolved metal in solution or by dissociation of metal binding minerals. Column leaching experiments were performed on soil polluted with As and Pb, in order to determine the specificity of LMMOA related release for individual elements, at varying organic acid concentrations. Acetic, citric and oxalic acids were applied in 12h leaching experiments over a concentration range (0.5-25 mM) to soil samples that represent organic and mineral horizons. The leaching of As followed the order: oxalic>citric>acetic acid in both soils. Arsenic leaching was attributed primarily to ligand-enhanced dissolution of mineral oxides followed by As released into solution, as shown by significant correlation between oxalic and citric acids and content of Al and Fe in leaching solutions. Results suggest that subsurface mineral soil layers are more vulnerable to As toxicity. Leaching of Pb from both soils followed the order: citric>oxalic>acetic acid. Mineral soil samples were shown to be more susceptible to leaching of Pb than samples characterised by a high content of organic matter. The leaching efficiency of citric acid was attributed to formation of stable complexes with Pb ions, which other acids are not capable of. Results obtained in the study are evidence that the extent of As and Pb leaching in contaminated surface and subsurface soil depends significantly on the types of carboxylic acid involved. The implications of the type of acid and the specific element that can be mobilised become increasingly significant where LMMOA concentrations are highest, such as in rhizosphere soil. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Contribution of low molecular weight phenols to bitter taste and mouthfeel properties in red wines.

PubMed

Gonzalo-Diago, Ana; Dizy, Marta; Fernández-Zurbano, Purificación

2014-07-01

The aim of this study was to explore the relationship between low molecular weight compounds present in wines and their sensory contribution. Six young red wines were fractionated by gel permeation chromatography and subsequently each fraction obtained was separated from sugars and acids by solid phase extraction. Wines and both fractions were in-mouth evaluated by a trained sensory panel and UPLC-MS analyses were performed. The lack of ethanol and proanthocyanidins greatly increased the acidity perceived. The elimination of organic acids enabled the description of the samples, which were evaluated as bitter, persistent and slightly astringent. Coutaric acid and quercetin-3-O-rutinoside appear to be relevant astringent compounds in the absence of proanthocyanidins. Bitter taste was highly correlated with the in-mouth persistence. A significant predictive model for bitter taste was built by means of PLSR. Further research must be carried out to validate the sensory contribution of the compounds involved in bitterness and astringency and to verify the sensory interactions observed. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Mass Spectrometry Imaging of low Molecular Weight Compounds in Garlic (Allium sativum L.) with Gold Nanoparticle Enhanced Target.

PubMed

Misiorek, Maria; Sekuła, Justyna; Ruman, Tomasz

2017-11-01

Garlic (Allium sativum) is the subject of many studies due to its numerous beneficial properties. Although compounds of garlic have been studied by various analytical methods, their tissue distributions are still unclear. Mass spectrometry imaging (MSI) appears to be a very powerful tool for the identification of the localisation of compounds within a garlic clove. Visualisation of the spatial distribution of garlic low-molecular weight compounds with nanoparticle-based MSI. Compounds occurring on the cross-section of sprouted garlic has been transferred to gold-nanoparticle enhanced target (AuNPET) by imprinting. The imprint was then subjected to MSI analysis. The results suggest that low molecular weight compounds, such as amino acids, dipeptides, fatty acids, organosulphur and organoselenium compounds are distributed within the garlic clove in a characteristic manner. It can be connected with their biological functions and metabolic properties in the plant. New methodology for the visualisation of low molecular weight compounds allowed a correlation to be made between their spatial distribution within a sprouted garlic clove and their biological function. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

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.

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.

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.

Blends of low molecular weight of poly lactic acid (PLA) with gondorukem (gum rosin)

NASA Astrophysics Data System (ADS)

Kaavessina, Mujtahid; Distantina, Sperisa; Chafidz, Achmad; Utama, Aditya; Anggraeni, Venisa Mega Puteri

2018-02-01

The utilization of plastic was increasing as well as the increasing its demand in wide range application. Consequently, the number of plastic litter will increase and make more serious environmental problems. This research concerns to minimize waste problems by designing biodegradable plastic. In this research, biodegradable plastic was made of poly lactic acid (PLA) and gondorukem (Gum rosin, Resina colophonium) as the plasticizer. The effect of gondorukem towards PLA properties such as rheology and degradability was investigated. The research divided into two steps: (i) the polycondensation of lactic acid (LA) and (ii) modification of obtained poly lactic acid. In the first step, polycondensation was done in N2 atmosphere (138°C) for 30 hours and added 0.1 %w of SnCl2 as catalyst. Bulk modification was conducted by blending of gondurukem in varied weight (0.5, 1, and 2 g in 10 g of PLA). Furthermore, the modified PLA was analyzed its molecular structure, biodegradability and rheological property. The presence of gondorukem enhanced the biodegradability of poly lactic acid. Gondorukem could act as the plasticizer. It is confirmed that the complex viscosity of PLA melt decreased upon the addition of gondorukem

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

PubMed

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

2002-01-01

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

Characterization of the Organic Component of Low-Molecular-Weight Chromium-Binding Substance and Its Binding of Chromium123

PubMed Central

Chen, Yuan; Watson, Heather M.; Gao, Junjie; Sinha, Sarmistha Halder; Cassady, Carolyn J.; Vincent, John B.

2011-01-01

Chromium was proposed to be an essential element over 50 y ago and was shown to have therapeutic potential in treating the symptoms of type 2 diabetes; however, its mechanism of action at a molecular level is unknown. One chromium-binding biomolecule, low-molecular weight chromium-binding substance (LMWCr or chromodulin), has been found to be biologically active in in vitro assays and proposed as a potential candidate for the in vivo biologically active form of chromium. Characterization of the organic component of LMWCr has proven difficult. Treating bovine LMWCr with trifluoroacetic acid followed by purification on a graphite powder micro-column generates a heptapeptide fragment of LMWCr. The peptide sequence of the fragment was analyzed by MS and tandem MS (MS/MS and MS/MS/MS) using collision-induced dissociation and post-source decay. Two candidate sequences, pEEEEGDD and pEEEGEDD (where pE is pyroglutamate), were identified from the MS/MS experiments; additional tandem MS suggests the sequence is pEEEEGDD. The N-terminal glutamate residues explain the inability to sequence LMWCr by the Edman method. Langmuir isotherms and Hill plots were used to analyze the binding constants of chromic ions to synthetic peptides similar in composition to apoLMWCr. The sequence pEEEEGDD was found to bind 4 chromic ions per peptide with nearly identical cooperativity and binding constants to those of apoLMWCr. This work should lead to further studies elucidating or eliminating a potential role for LMWCr in treating the symptoms of type 2 diabetes and other conditions resulting from improper carbohydrate and lipid metabolism. PMID:21593351

Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions.

PubMed

Gilchrist, Elizabeth S; Nesterenko, Pavel N; Smith, Norman W; Barron, Leon P

2015-03-20

There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5-50 mM hydroxide with 0-80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20-45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30-40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks. Copyright © 2015 Elsevier B.V. All rights reserved.

Hylan G-F 20 Versus Low Molecular Weight Hyaluronic Acids for Knee Osteoarthritis: A Meta-Analysis.

PubMed

Zhao, Hongmou; Liu, Hongliang; Liang, Xiaojun; Li, Yi; Wang, Junhu; Liu, Cheng

2016-10-01

Hyaluronic acid injection has been reported to decrease pain compared with baseline levels in knee joint osteoarthritis. Hylan G-F 20 is distinguished from the other products by its chemical structure and relatively higher molecular weight. Many trials have compared hylan G-F 20 and low molecular weight hyaluronic acids (LMWHAs); however, their relative efficacy and safety are still debated. The aim was to compare the effectiveness and safety of intra-articular injection of hylan G-F 20 and LMWHA in the treatment of knee joint osteoarthritis. A comprehensive search of the literature up to February 2016 was performed; multiple databases were searched with 'Synvisc' or 'hylan' or 'hyaluronan' as free word terms. The pain-related outcomes and treatment-related adverse events from intent-to-treat analyzed studies were pooled for meta-analysis; other functional outcomes were included in the qualitative analysis. Twenty trials with a total of 3034 patients and 3153 knees were included, with a pooled dropout rate of 7.2 %. The pooled pain-related outcomes at 2 to 3 months reached a statistically significant difference in favor of hylan G-F 20 (I 2  = 88 %; random effects; P = 0.02), and the significance still existed with exclusion (in order to eliminate heterogeneity) of the three studies that most favored hylan G-F 20 (I 2  = 51 %; fixed effect; P = 0.03). No significant difference was reached for other group and subgroup analyses. No significant difference was reached in comparing the patients with treatment-related adverse events (seven trials; 2025 patients; P = 0.13) or the treatment-related adverse events (six trials; 1633 patients; P = 0.14). According to the current results, limited evidence showed a superior effect favoring hylan G-F 20 over LMWHA in the period from 2 to 3 months post-injection for pain-related outcomes. There was no evidence of increased risk of treatment-related adverse events for hylan G-F 20 injections.

Synthesis of the low molecular weight heat shock proteins in plants

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

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

1987-08-01

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

Low-Molecular-Weight Plasma Proteome Analysis Using Top-Down Mass Spectrometry.

PubMed

Cheon, Dong Huey; Yang, Eun Gyeong; Lee, Cheolju; Lee, Ji Eun

2017-01-01

While human plasma has a wealth of diagnostic information regarding the state of the human body in heath and disease, low molecular weight (LMW) proteome (<30 kDa) has been shown to contain a rich source of diagnostic biomarkers. Here we describe a protocol for top-down proteomic analysis to identify and characterize the LMW proteoforms present in four types of human plasma samples without immunoaffinity depletion and with depletion of the top two, six, and seven high-abundance proteins. Each type of plasma sample was first fractionated based on molecular weight using gel-eluted liquid fraction entrapment electrophoresis (GELFrEE). Then, the GELFrEE fractions containing up to 30 kDa were subjected to nanocapillary-LC-MS/MS, and the high-resolution MS and MS/MS data were processed using ProSightPC software. As a result, a total of 442 LMW proteins and cleaved products, including those with posttranslational modifications (PTMs) and single amino acid variations (SAAVs), were identified with a threshold E-value of 1 × 10 -4 from the four types of plasma samples.

Different types of degradable vectors from low-molecular-weight polycation-functionalized poly(aspartic acid) for efficient gene delivery.

PubMed

Dou, X B; Hu, Y; Zhao, N N; Xu, F J

2014-03-01

Poly(aspartic acid) (PAsp) has been employed as the potential backbone for the preparation of efficient gene carriers, due to its low cytotoxicity, good biodegradability and excellent biocompatibility. In this work, the degradable linear or star-shaped PBLA was first prepared via ring-opining polymerization of β-benzyl-L-aspartate N-carboxy anhydride (BLA-NCA) initiated by ethylenediamine (ED) or ED-functionalized cyclodextrin cores. Then, PBLA was functionalized via aminolysis reaction with low-molecular-weight poly(2-(dimethylamino)ethyl methacrylate) with one terminal primary amine group (PDMAEMA-NH2), followed by addition of excess ED or ethanolamine (EA) to complete the aminolysis process. The obtained different types of cationic PAsp-based vectors including linear or star PAsp-PDM-NH2 and PAsp-PDM-OH exhibited good condensation capability and degradability, benefiting gene delivery process. In comparison with gold standard polyethylenimine (PEI, ∼ 25 kDa), the cationic PAsp-based vectors, particularly star-shaped ones, exhibited much better transfection performances. Copyright © 2013 Elsevier Ltd. All rights reserved.

Efficient aquatic bacterial metabolism of dissolved low-molecular-weight compounds from terrestrial sources.

PubMed

Berggren, Martin; Laudon, Hjalmar; Haei, Mahsa; Ström, Lena; Jansson, Mats

2010-03-01

Carboxylic acids (CAs), amino acids (AAs) and carbohydrates (CHs) in dissolved free forms can be readily assimilated by aquatic bacteria and metabolized at high growth efficiencies. Previous studies have shown that these low-molecular-weight (LMW) substrates are released by phytoplankton but also that unidentified LMW compounds of terrestrial origin is a subsidy for bacterial metabolism in unproductive freshwater systems. We tested the hypothesis that different terrestrially derived CA, AA and CH compounds can offer substantial support for aquatic bacterial metabolism in fresh waters that are dominated by allochthonous dissolved organic matter (DOM). Drainage water from three catchments of different characters in the Krycklan experimental area in Northern Sweden were studied at the rising and falling limb of the spring flood, using a 2-week bioassay approach. A variety of CA, AA and CH compounds were significantly assimilated by bacteria, meeting 15-100% of the bacterial carbon demand and explaining most of the observed variation in bacterial growth efficiency (BGE; R(2)=0.66). Of the 29 chemical species that was detected, acetate was the most important, representing 45% of the total bacterial consumption of all LMW compounds. We suggest that LMW organic compounds in boreal spring flood drainage could potentially support all in situ bacterial production in receiving lake waters during periods of weeks to months after the spring flood.

Low-molecular-weight poly(alpha-methyl beta,L-malate) of microbial origin: synthesis and crystallization.

PubMed

Fernández, Carlos E; Mancera, Manuel; Holler, Eggehard; Bou, Jordi J; Galbis, Juan A; Muñoz-Guerra, Sebastián

2005-02-23

Low-molecular-weight poly(alpha-methyl beta,L-malate) made of approximately 25-30 units was prepared from microbial poly(beta,L-malic acid) by treatment with diazomethane. The thermal characterization of the polymalate methyl ester was carried out and its crystalline structure was preliminary examined. Its ability to crystallize both from solution and from the melt was comparatively evaluated.

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

PubMed

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

2006-02-01

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

Investigation of colloidal graphite as a matrix for matrix-assisted laser desorption/ionisation mass spectrometry of low molecular weight analytes.

PubMed

Warren, Alexander D; Conway, Ulric; Arthur, Christopher J; Gates, Paul J

2016-07-01

The analysis of low molecular weight compounds by matrix-assisted laser desorption/ionisation mass spectrometry is problematic due to the interference and suppression of analyte ionisation by the matrices typically employed - which are themselves low molecular weight compounds. The application of colloidal graphite is demonstrated here as an easy to use matrix that can promote the ionisation of a wide range of analytes including low molecular weight organic compounds, complex natural products and inorganic complexes. Analyte ionisation with colloidal graphite is compared with traditional organic matrices along with various other sources of graphite (e.g. graphite rods and charcoal pencils). Factors such as ease of application, spectra reproducibility, spot longevity, spot-to-spot reproducibility and spot homogeneity (through single spot imaging) are explored. For some analytes, considerable matrix suppression effects are observed resulting in spectra completely devoid of matrix ions. We also report the observation of radical molecular ions [M(-●) ] in the negative ion mode, particularly with some aromatic analytes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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

PubMed

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

2012-10-15

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

Factors that affect molecular weight distribution of Suwannee river fulvic acid as determined by electrospray ionization/mass spectrometry

USGS Publications Warehouse

Rostad, Colleen E.; Leenheer, Jerry A.

2004-01-01

Effects of methylation, molar response, multiple charging, solvents, and positive and negative ionization on molecular weight distributions of aquatic fulvic acid were investigated by electrospray ionization/mass spectrometry. After preliminary analysis by positive and negative modes, samples and mixtures of standards were derivatized by methylation to minimize ionization sites and reanalyzed.Positive ionization was less effective and produced more complex spectra than negative ionization. Ionization in methanol/water produced greater response than in acetonitrile/water. Molar response varied widely for the selected free acid standards when analyzed individually and in a mixture, but after methylation this range decreased. After methylation, the number average molecular weight of the Suwannee River fulvic acid remained the same while the weight average molecular weight decreased. These differences are probably indicative of disaggregation of large aggregated ions during methylation. Since the weight average molecular weight decreased, it is likely that aggregate formation in the fulvic acid was present prior to derivatization, rather than multiple charging in the mass spectra.

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.

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

NASA Astrophysics Data System (ADS)

Tian, Ran; Chen, Jin; Niu, Runfang

2014-03-01

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

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

PubMed

Ged, Evan C; Boyer, Treavor H

2013-05-01

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

Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

NASA Astrophysics Data System (ADS)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

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

PubMed

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

2017-05-01

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

Rapid screening of low-molecular-weight phenols from persimmon (Diospyros kaki) pulp using liquid chromatography/UV-visible/electrospray mass spectrometry analysis.

PubMed

Sentandreu, Enrique; Cerdán-Calero, Manuela; Halket, John M; Navarro, José L

2015-06-01

Persimmon fruits have been widely used in traditional medicine owing to their phenolic composition. This research aims to perform a rapid, detailed and affordable study of the profile of low-molecular-weight phenols from persimmon pulp. Two different HPLC-DAD/ESI-MS(n) analyses were performed using a routine three-dimensional ion trap mass spectrometer to analyze the ethanolic extract of persimmon pulp: (1) an untargeted data-dependent analysis to identify the majority of small phenols that included full MS and MS(2) scan events; (2) a targeted data-dependent analysis to identify polymerized phenols (dimers and formic acid adducts) through a source-induced dissociation analysis that included full MS and MS(2) scan events. Thirty-two low-molecular-weight phenols were detected, comprising gallic acid and its glycoside and acyl derivatives, glycosides of p-coumaric, vanillic and cinnamic acids and different flavone di-C-hexosides, most of them reported for the first time in persimmon. The use of a straightforward and affordable methodology of analysis led to obtain an up-to-date profiling of low-molecular-weight phenols in persimmon. The results can help future actions aimed to expand the understanding of the phenolic metabolome of persimmon cultivars. © 2014 Society of Chemical Industry.

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.

Factors that affect molecular weight distribution of Suwannee river fulvic acid as determined by electrospray ionization/mass spectrometry

USGS Publications Warehouse

Rostad, C.E.; Leenheer, J.A.

2004-01-01

Effects of methylation, molar response, multiple charging, solvents, and positive and negative ionization on molecular weight distributions of aquatic fulvic acid were investigated by electrospray ionization/mass spectrometry. After preliminary analysis by positive and negative modes, samples and mixtures of standards were derivatized by methylation to minimize ionization sites and reanalyzed.Positive ionization was less effective and produced more complex spectra than negative ionization. Ionization in methanol/water produced greater response than in acetonitrile/water. Molar response varied widely for the selected free acid standards when analyzed individually and in a mixture, but after methylation this range decreased. After methylation, the number average molecular weight of the Suwannee River fulvic acid remained the same while the weight average molecular weight decreased. These differences are probably indicative of disaggregation of large aggregated ions during methylation. Since the weight average molecular weight decreased, it is likely that aggregate formation in the fulvic acid was present prior to derivatization, rather than multiple charging in the mass spectra. ?? 2004 Elsevier B.V. All rights reserved.

Direct 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.

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

PubMed

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

2016-06-01

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

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.

Vapor-pressure osmometric study of the molecular weight and aggregation tendency of a reference-soil fulvic acid

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.

1990-01-01

The molecular weight and aggregation tendency of a reference-soil fulvic acid in Armadale horizon Bh were determined by vapor-pressure osmometry using tetrahydrofuran and water as solvents. With tetrahydrofuran, number-average molecular weight values of 767 ?? 34 and 699 ?? 8 daltons were obtained from two separate sets of measurements. Two sets of measurements with water also yielded values within this range (754 ?? 70 daltons) provided that the fulvic acid concentration in water did not exceed 7 mg ml-1; at higher concentrations (9.1-13.7 mg ml-1) a number-average molecular weight of 956 ?? 25 daltons was resolved, providing evidence of molecular aggregation. Extension of these studies to 80% neutralized fulvic acid showed that a sizeable fraction of the sodium counter ion is not osmotically active.

Effects of surfactants on low-molecular-weight organic acids to wash soil zinc.

PubMed

Chen, Yue; Zhang, Shirong; Xu, Xiaoxun; Yao, Ping; Li, Ting; Wang, Guiyin; Gong, Guoshu; Li, Yun; Deng, Ouping

2016-03-01

Soil washing is an effective approach to the removal of heavy metals from contaminated soil. In this study, the effects of the surfactants sodium dodecyl sulfate, Triton X-100, and non-ionic polyacrylamide (NPAM) on oxalic acid, tartaric acid, and citric acid used to remove zinc from contaminated soils were investigated. The Zn removal efficiencies of all washing solutions showed a logarithmic increase with acid concentrations from 0.5 to 10.0 g/L, while they decreased as pH increased from 4 to 9. Increasing the reaction time enhanced the effects of surfactants on Zn removal efficiencies by the acids during washing and significantly (P < 0.05) improved the removal under some mixed cases. Oxalic acid suffered antagonistic effects from the three surfactants and seriously damaged soil nutrients during the removal of soil Zn. Notably, the three surfactants caused synergistic effects on tartaric and citric acid during washing, with NPAM leading to an increase in Zn removal by 5.0 g/L citric acid of 10.60 % (P < 0.05) within 2 h. NPAM also alleviated the loss of cation exchange capacity of washed soils and obviously improved soil nitrogen concentrations. Overall, combining citric acid with NPAM offers a promising approach to the removal of zinc from contaminated soil.

Changes of synovial fluid protein concentrations in supra-patellar bursitis patients after the injection of different molecular weights of hyaluronic acid.

PubMed

Chen, Carl P C; Hsu, Chih Chin; Pei, Yu-Cheng; Chen, Ruo Li; Zhou, Shaobo; Shen, Hsuan-Chen; Lin, Shih-Cherng; Tsai, Wen Chung

2014-04-01

Knee pain is commonly seen in orthopedic and rehabilitation outpatient clinical settings, and in the aging population. Bursitis of the knee joint, especially when the volume of the synovial fluid is large enough, can compress and distend the nearby soft tissues, causing pain in the knee joint. Out of all the bursae surrounding the knee joint, supra-patellar bursitis is most often associated with knee pain. Treatment strategies in managing supra-patellar bursitis include the aspiration of joint synovial fluid and then followed by steroid injection into the bursa. When supra-patellar bursitis is caused by degenerative disorders, the concept of viscosupplementation treatment may be effective by injecting hyaluronic acid into the bursa. However, the rheology or the changes in the concentrations of proteins (biomarkers) that are related to the development of bursitis in the synovial fluid is virtually unexplored. Therefore, this study aimed to identify the concentration changes in the synovial fluid total protein amount and individual proteins associated with supra-patellar bursitis using the Bradford protein assay and western immunoglobulin methods. A total of 20 patients were divided into two groups with 10 patients in each group. One group received the high molecular weight hyaluronic acid product of Synvisc Hylan G-F 20 and the other group received the low molecular weight hyaluronic acid product of Hya-Joint Synovial Fluid Supplement once per week injection into the bursa for a total of 3 weeks. Significant decreases in the synovial fluid total protein concentrations were observed after the second dosage of high molecular weight hyaluronic acid injections. Apolipoprotein A-I, interleukin 1 beta, alpha 1 antitrypsin, and matrix metalloproteinase 1 proteins revealed a trend of decreasing western immunoblotting band densities after hyaluronic acid injections. The decreases in apolipoprotein A-I and interleukin 1 beta protein band densities were significant in the high

Characterizing Low Molecular Weight Organic Matter in Arctic Polygonal Tundra Soils to Identify Biogeochemical Hotspots Using a Dual-Separation, High-Resolution Mass Spectrometry Approach

NASA Astrophysics Data System (ADS)

Ladd, M.; Wullschleger, S. D.; Iversen, C. M.; Hettich, R.

2016-12-01

Reliably modeling biogeochemical processes (e.g. decomposition, plant-microbial competition for nutrients) across spatial or temporal scales requires elucidating the chemical composition of low molecular weight (LMW) dissolved soil organic matter (DOM). Our understanding is limited, however, by the wide-ranging physicochemical properties and high fluxes of these compounds, posing major challenges in detection, isolation, and quantification. Here, we developed and evaluated a sensitive, non-targeted approach to characterize LMW DOM in the Arctic, a unique system that is warming at a rate twice that of the global average and may have significant feedbacks to global C and N cycles. Soil cores were collected from a continuous permafrost, polygonal tundra landscape near Barrow, Alaska (71° 16' N) and sectioned into 5 cm increments. Water and salt extracts from each section were filtered and injected onto C18 reversed-phase or zwitterionic-type hydrophilic interaction chromatography (ZIC-pHILIC) columns for separation. LMW DOM profiles were obtained using high-resolution mass spectrometry (HRMS), and unique features, known and unknown, were characterized by LC retention time, accurate mass (m/z), and molecular fragmentation pattern. Coupling two orthogonal chromatographic separations with HRMS enabled the characterization of hundreds of analytes in a single measurement providing enhanced, high-throughput coverage of LMW DOM from soil extracts. The complexity and relative/absolute intensities of LMW DOM features (e.g. organic acids, amino sugars, peptides) varied across polygon type (high- or low-centered), extract condition, and with depth, providing an information-rich, molecular signal of LMW DOM availability across scales. Comprehensively profiling this complex mixture of small molecules of both biotic and abiotic origin provides a chemical signature of biological function, allowing for more reliable predictions of how discrete, molecular-scale processes may control

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions

NASA Astrophysics Data System (ADS)

D'Ambro, Emma L.; Lee, Ben H.; Liu, Jiumeng; Shilling, John E.; Gaston, Cassandra J.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Zaveri, Rahul A.; Mohr, Claudia; Lutz, Anna; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Rivera-Rios, Jean C.; Keutsch, Frank N.; Thornton, Joel A.

2017-01-01

We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C5 compounds were major components (˜ 50 %) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, > 30 % of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.

Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments

NASA Astrophysics Data System (ADS)

Seewald, Jeffrey S.

2001-05-01

Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low

High Molecular Weight Dimer Esters in α-Pinene Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Kristensen, Kasper; Cui, Tianqu; Zhang, Haofei; Gold, Avram; Glasius, Marianne; Surratt, Jason D.

2014-05-01

Monoterpenes, such as α-pinene, constitute an important group of biogenic volatile organic compounds (BVOC). Once emitted into the atmosphere α-pinene is removed by oxidization by the hydroxyl radical (OH), reactions with ozone (O3), and with nitrate radicals (NO3) resulting in the formation of first-generation oxidation products, such as semi-volatile carboxylic acids. In addition, higher molecular weight dimer esters originating from the oxidation of α-pinene have been observed in both laboratory-generated and ambient secondary organic aerosols (SOA). While recent studies suggest that the dimers are formed through esterification between carboxylic acids in the particle phase, the formation mechanism of the dimer esters is still ambiguous. In this work, we present the results of a series of smog chamber experiments to assess the formation of dimer esters formed from the oxidation of α-pinene. Experiments were conducted in the University of North Carolina (UNC) dual outdoor smog chamber facility to investigate the effect of oxidant species (OH versus O3), relative humidity (RH), and seed aerosol acidity in order to obtain a better understanding of the conditions leading to the formation of the dimer esters and how these parameters may affect the formation and chemical composition of SOA. The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), and a total of eight carboxylic acids and four dimer esters were identified, constituting between 8 and 12 % of the total α-pinene SOA mass.

Aluminium Uptake and Translocation in Al Hyperaccumulator Rumex obtusifolius Is Affected by Low-Molecular-Weight Organic Acids Content and Soil pH

PubMed Central

Vondráčková, Stanislava; Száková, Jiřina; Drábek, Ondřej; Tejnecký, Václav; Hejcman, Michal; Müllerová, Vladimíra; Tlustoš, Pavel

2015-01-01

Background and Aims High Al resistance of Rumex obtusifolius together with its ability to accumulate Al has never been studied in weakly acidic conditions (pH > 5.8) and is not sufficiently described in real soil conditions. The potential elucidation of the role of organic acids in plant can explain the Al tolerance mechanism. Methods We established a pot experiment with R. obtusifolius planted in slightly acidic and alkaline soils. For the manipulation of Al availability, both soils were untreated and treated by lime and superphosphate. We determined mobile Al concentrations in soils and concentrations of Al and organic acids in organs. Results Al availability correlated positively to the extraction of organic acids (citric acid < oxalic acid) in soils. Monovalent Al cations were the most abundant mobile Al forms with positive charge in soils. Liming and superphosphate application were ambiguous measures for changing Al mobility in soils. Elevated transport of total Al from belowground organs into leaves was recorded in both lime-treated soils and in superphosphate-treated alkaline soil as a result of sufficient amount of Ca available from soil solution as well as from superphosphate that can probably modify distribution of total Al in R. obtusifolius as a representative of “oxalate plants.” The highest concentrations of Al and organic acids were recorded in the leaves, followed by the stem and belowground organ infusions. Conclusions In alkaline soil, R. obtusifolius is an Al-hyperaccumulator with the highest concentrations of oxalate in leaves, of malate in stems, and of citrate in belowground organs. These organic acids form strong complexes with Al that can play a key role in internal Al tolerance but the used methods did not allow us to distinguish the proportion of total Al-organic complexes to the free organic acids. PMID:25880431

Aluminium uptake and translocation in Al hyperaccumulator Rumex obtusifolius is affected by low-molecular-weight organic acids content and soil pH.

PubMed

Vondráčková, Stanislava; Száková, Jiřina; Drábek, Ondřej; Tejnecký, Václav; Hejcman, Michal; Müllerová, Vladimíra; Tlustoš, Pavel

2015-01-01

High Al resistance of Rumex obtusifolius together with its ability to accumulate Al has never been studied in weakly acidic conditions (pH > 5.8) and is not sufficiently described in real soil conditions. The potential elucidation of the role of organic acids in plant can explain the Al tolerance mechanism. We established a pot experiment with R. obtusifolius planted in slightly acidic and alkaline soils. For the manipulation of Al availability, both soils were untreated and treated by lime and superphosphate. We determined mobile Al concentrations in soils and concentrations of Al and organic acids in organs. Al availability correlated positively to the extraction of organic acids (citric acid < oxalic acid) in soils. Monovalent Al cations were the most abundant mobile Al forms with positive charge in soils. Liming and superphosphate application were ambiguous measures for changing Al mobility in soils. Elevated transport of total Al from belowground organs into leaves was recorded in both lime-treated soils and in superphosphate-treated alkaline soil as a result of sufficient amount of Ca available from soil solution as well as from superphosphate that can probably modify distribution of total Al in R. obtusifolius as a representative of "oxalate plants." The highest concentrations of Al and organic acids were recorded in the leaves, followed by the stem and belowground organ infusions. In alkaline soil, R. obtusifolius is an Al-hyperaccumulator with the highest concentrations of oxalate in leaves, of malate in stems, and of citrate in belowground organs. These organic acids form strong complexes with Al that can play a key role in internal Al tolerance but the used methods did not allow us to distinguish the proportion of total Al-organic complexes to the free organic acids.

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

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

Distributions of low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls in the marine aerosols collected over the Arctic Ocean during late summer

NASA Astrophysics Data System (ADS)

Kawamura, K.; Ono, K.; Tachibana, E.; Charriére, B.; Sempéré, R.

2012-11-01

Oxalic and other small dicarboxylic acids have been reported as important water-soluble organic constituents of atmospheric aerosols from different environments. Their molecular distributions are generally characterized by the predominance of oxalic acid (C2) followed by malonic (C3) and/or succinic (C4) acids. In this study, we collected marine aerosols from the Arctic Ocean during late summer in 2009 when sea ice was retreating. The marine aerosols were analyzed for the molecular distributions of dicarboxylic acids as well as ketocarboxylic acids and α-dicarbonyls to better understand the source of water-soluble organics and their photochemical processes in the high Arctic marine atmosphere. We found that diacids are more abundant than ketoacids and α-dicarbonyls, but their concentrations are generally low (< 30 ng m-3), except for one sample (up to 70 ng m-3) that was collected near the mouth of Mackenzie River during clear sky condition. Although the molecular compositions of diacids are in general characterized by the predominance of oxalic acid, a depletion of C2 was found in two samples in which C4 became the most abundant. Similar depletion of oxalic acid has previously been reported in the Arctic aerosols collected at Alert after polar sunrise and in the summer aerosols from the coast of Antarctica. Because the marine aerosols that showed a depletion of C2 were collected under the overcast and/or foggy conditions, we suggest that a photochemical decomposition of oxalic acid may have occurred in aqueous phase of aerosols over the Arctic Ocean via the photo dissociation of oxalate-Fe (III) complex. We also determined stable carbon isotopic compositions (δ13C) of bulk aerosol carbon and individual diacids. The δ13C of bulk aerosols showed -26.5‰ (range: -29.7 to -24.7‰, suggesting that marine aerosol carbon is derived from both terrestrial and marine organic materials. In contrast, oxalic acid showed much larger δ13C values (average: -20.9‰, range

Distributions of low molecular weight dicarboxylic acids, ketoacids and α-dicarbonyls in the marine aerosols collected over the Arctic Ocean during late summer

NASA Astrophysics Data System (ADS)

Kawamura, K.; Ono, K.; Tachibana, E.; Charriére, B.; Sempéré, R.

2012-08-01

Oxalic and other small dicarboxylic acids have been reported as important water-soluble organic constituents of atmospheric aerosols from different environments. Their molecular distributions are generally characterized by the predominance of oxalic acid (C2) followed by malonic (C3) and/or succinic (C4) acids. In this study, we collected marine aerosols from the Arctic Ocean during late summer in 2009 when sea ice is retreated. The marine aerosols were analyzed for the molecular distributions of dicarboxylic acids as well as ketocarboxylic acids and α-dicarbonyls to better understand the source of water-soluble organics and their photochemical processes in the high Arctic marine atmosphere. We found that diacids are more abundant than ketoacids and α-dicarbonyls, but their concentrations are generally low (< 30 ng m-3), except for one sample (up to 70 ng m-3) that was collected near the mouth of Mackenzie River during clear sky condition. Although the molecular compositions of diacids are in general characterized by the predominance of oxalic acid, a depletion of C2 was found in two samples in which C4 became the most abundant. Similar depletion of oxalic acid has previously been reported in the Arctic aerosols collected at Alert after polar sunrise and in the summer aerosols from the coastal Antarctica. Because the marine aerosols that showed a depletion of C2 were observed under the overcast and/or foggy conditions, we suggest that a photochemical decomposition of oxalic acid may have occurred in aqueous phase of aerosols over the Arctic Ocean via the photo dissociation of oxalate-Fe (III) complex. We also determined stable carbon isotopic compositions (δ13C) of bulk aerosol carbon and individual diacids. The δ13C of bulk aerosols showed -26.5‰ (range: -29.7‰ to -24.7‰), suggesting that marine aerosol carbon is derived from both terrestrial and marine organic materials. In contrast, oxalic acid showed much larger δ13C values (average: -20.9‰, range

Determination of low-molecular-weight dicarboxylic acids in atmospheric aerosols by injection-port derivatization and gas chromatography-mass spectrometry.

PubMed

Hsu, Ching-Lin; Ding, Wang-Hsien

2009-12-15

A rapid and environmental-friendly injection-port derivatization with gas chromatography-mass spectrometry (GC-MS) method was developed to determine selected low-molecular weight (LMW) dicarboxylic acids (from C2 to C10) in atmospheric aerosol samples. The parameters related to the derivatization process (i.e., type of ion-pair reagent, injection-port temperature and concentration of ion-pair reagent) were optimized. Tetrabutylammonium hydroxide (TBA-OH) 20 mM in methanol gave excellent yield for di-butyl ester dicarboxylate derivatives at injection-port temperature at 300 degrees C. Solid-phase extraction (SPE) method instead of rotary evaporation was used to concentrate analytes from filter extracts. The recovery from filter extracts ranged from 78 to 95% with relative standard deviation (RSD) less than 12%. Limits of quantitation (LOQs) ranged from 25 to 250 pg/m(3). The concentrations of di-carboxylated C2-C5 and total C6-C10 in particles of atmospheric aerosols ranged from 91.9 to 240, 11.3 to 56.7, 9.2 to 49.2, 8.7 to 35.3 and n.d. to 37.8 ng/m(3), respectively. Oxalic acid (C2) was the dominant LMW-dicarboxylic acids detected in aerosol samples. The quantitative results were comparable to the results obtained by the off-line derivatization.

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

PubMed

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

2009-09-03

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

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

PubMed

Silina, Yuliya E; Volmer, Dietrich A

2013-12-07

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

Influence of low-molecular-weight glutenin subunit haplotypes on dough rheology and baking quality in elite common wheat varieties

USDA-ARS?s Scientific Manuscript database

The low molecular weight glutenin subunits (LMW-GSs) are a class of wheat seed storage proteins directly involved in the formation of gluten. Depending on the first amino acid residue of the mature proteins, the LMW-GSs are divided into methionine, serine or isoleucine type. These proteins are encod...

Nanowires formed by the co-assembly of a negatively charged low-molecular weight gelator and a zwitterionic polythiophene.

PubMed

Li, Feng; Palaniswamy, Ganesan; de Jong, Menno R; Aslund, Andreas; Konradsson, Peter; Marcelis, Antonius T M; Sudhölter, Ernst J R; Stuart, Martien A Cohen; Leermakers, Frans A M

2010-06-21

Conjugated organic nanowires have been prepared by co-assembling a carboxylate containing low-molecular weight gelator (LMWG) and an amino acid substituted polythiophene derivative (PTT). Upon introducing the zwitterionic polyelectrolyte PTT to a basic molecular solution of the organogelator, the negative charges on the LMWG are compensated by the positive charges of the PTT. As a result, nanowires form through co-assembly. These nanowires are visualized by both transmission electron microscopy (TEM) and atomic force microscopy (AFM). Depending on the concentration and ratio of the components these nanowires can be micrometers long. These measurements further suggest that the aggregates adopt a helical conformation. The morphology of these nanowires are studied with fluorescent confocal laser scanning microscopy (CLSM). The interactions between LMWG and PTT are characterized by steady-state and time-resolved fluorescence spectroscopy studies. The steady-state spectra indicate that the backbone of the PTT adopts a more planar and more aggregated conformation when interacting with LMWG. The time- resolved fluorescence decay studies confirm this interpretation.

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.

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

Molecular Dynamic Analysis of Hyaluronic Acid and Phospholipid Interaction in Tribological Surgical Adjuvant Design for Osteoarthritis.

PubMed

Siódmiak, Jacek; Bełdowski, Piotr; Augé, Wayne K; Ledziński, Damian; Śmigiel, Sandra; Gadomski, Adam

2017-09-04

Tribological surgical adjuvants constitute a therapeutic discipline made possible by surgical advances in the treatment of damaged articular cartilage beyond palliative care. The purpose of this study is to analyze interactions between hyaluronic acid and phospholipid molecules, and the formation of geometric forms, that play a role in the facilitated lubrication of synovial joint organ systems. The analysis includes an evaluation of the pathologic state to detail conditions that may be encountered by adjuvants during surgical convalescence. The synovial fluid changes in pH, hyaluronic acid polydispersity, and phospholipid concentration associated with osteoarthritis are presented as features that influence the lubricating properties of adjuvant candidates. Molecular dynamic simulation studies are presented, and the Rouse model is deployed, to rationalize low molecular weight hyaluronic acid behavior in an osteoarthritic environment of increased pH and phospholipid concentration. The results indicate that the hyaluronic acid radius of gyration time evolution is both pH- and phospholipid concentration-dependent. Specifically, dipalmitoylphosphatidylcholine induces hydrophobic interactions in the system, causing low molecular weight hyaluronic acid to shrink and at high concentration be absorbed into phospholipid vesicles. Low molecular weight hyaluronic acid appears to be insufficient for use as a tribological surgical adjuvant because an increased pH and phospholipid concentration induces decreased crosslinking that prevents the formation of supramolecular lubricating forms. Dipalmitoylphosphatidylcholine remains an adjuvant candidate for certain clinical situations. The need to reconcile osteoarthritic phenotypes is a prerequisite that should serve as a framework for future adjuvant design and subsequent tribological testing.

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

DOEpatents

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

1995-07-11

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

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

DOEpatents

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

1995-01-01

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

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.

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

PubMed Central

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

2016-01-01

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

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.

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

PubMed

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

2017-11-01

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

Novel Synthesis of Core-Shell Silica Nanoparticles for the Capture of Low Molecular Weight Proteins and Peptides.

PubMed

Hernandez-Leon, Sergio G; Sarabia-Sainz, Jose Andre-I; Montfort, Gabriela Ramos-Clamont; Guzman-Partida, Ana M; Robles-Burgueño, Maria Del Refugio; Vazquez-Moreno, Luz

2017-10-12

Silica nanoparticles were functionalized with immobilized molecular bait, Cibacron Blue, and a porous polymeric bis-acrylamide shell. These nanoparticles represent a new alternative to capture low molecular weight (LMW) proteins/peptides, that might be potential biomarkers. Functionalized core-shell silica nanoparticles (FCSNP) presented a size distribution of 243.9 ± 11.6 nm and an estimated surface charge of -38.1 ± 0.9 mV. The successful attachment of compounds at every stage of synthesis was evidenced by ATR-FTIR. The capture of model peptides was determined by mass spectrometry, indicating that only the peptide with a long sequence of hydrophobic amino acids (alpha zein 34-mer) interacted with the molecular bait. FCSNP excluded the high molecular weight protein (HMW), BSA, and captured LMW proteins (myoglobin and aprotinin), as evidenced by SDS-PAGE. Functionalization of nanoparticles with Cibacron Blue was crucial to capture these molecules. FCSNP were stable after twelve months of storage and maintained a capacity of 3.1-3.4 µg/mg.

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes.

PubMed

Zhang, Ying; Zhang, Ning; Zhao, Peng; Niu, Zhiguang

2018-03-01

The characteristics of dissolved organic matter (DOM) and bromide ion concentration have a significant influence on the formation of disinfection by-products (DBPs). In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight (MW), trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes (pre-chlorination, coagulation, sand filtration, disinfection) were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW <1kDa and fraction with MW 3-10kDa, and the DBP's generation ability of lower molecular weight DOM (<10kDa) was higher than that of higher molecular weight DOM. During different processes, pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes (THMs) were mainly generated in pre-chlorination and disinfection, while haloacetic acids (HAAs) were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration. Copyright © 2017. Published by Elsevier B.V.

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

PubMed

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

1998-09-10

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

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

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

PubMed

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

2016-08-23

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

Molecular characterization of low molecular weight dissolved organic matter in water reclamation processes using Orbitrap mass spectrometry.

PubMed

Phungsai, Phanwatt; Kurisu, Futoshi; Kasuga, Ikuro; Furumai, Hiroaki

2016-09-01

Reclaimed water has recently become an important water source for urban use, but the composition of dissolved organic matter (DOM) in reclaimed water has rarely been characterized at the compound level because of its complexity. In this study, the transformation and changes in composition of low molecular weight DOM in water reclamation processes, where secondary effluent of the municipal wastewater treatment plant was further treated by biofiltration, ozonation and chlorination, were investigated by "unknown" screening analysis using Orbitrap mass spectrometry (Orbitrap MS). The intense ions were detected over an m/z range from 100 to 450. In total, 2412 formulae with various heteroatoms were assigned, and formulae with carbon (C), hydrogen (H) and oxygen (O) only and C, H, O and sulfur (S) were the most abundant species. During biofiltration, CHO-only compounds with relatively high hydrogen to carbon (H/C) ratio or with saturated structure were preferentially removed, while CHOS compounds were mostly removed. Ozonation induced the greatest changes in DOM composition. CHOS compounds were mostly decreased after ozonation while ozone selectively removed CHO compounds with relatively unsaturated structure and produced compounds that were more saturated and with a higher degree of oxidation. After chlorination, 168 chlorine-containing formulae, chlorinated disinfection by-products (DBPs), were additionally detected. Candidate DBP precursors were determined by tracking chlorinated DBPs formed via electrophilic substitution, half of which were generated during the ozonation. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Galloylglucoses of low molecular weight as mordant in electron microscopy. I. Procedure, and evidence for mordanting effect

PubMed Central

1976-01-01

Gallotannin, consisting mainly of low molecular weight esters such as penta- and hexagalloylglucoses (commercially available as tannic acid produced from Turkish nutgall), can be used for increasing and diversifying tissue contrast in electron microscopy. When applied on tissue specimens previously fixed by conventional methods (aldehydes and OsO4), the low molecular weight galloylglucoses (LMGG) penetrate satisfactorily the cells and induce general high contrast with fine delineation of extra- and intracellular structures, especially membranes. In some features, additional details of their intimate configuration are revealed. Various experimental conditions tested indicate that the LMGG display a complex effect on fixed tissues: they act primarily as a mordant between osmium-treated structures and lead, and concomitantly stabilize some tissue components against extraction incurred during dehydration and subsequent processing. Experiments with aldehyde blocking reagents (sodium borohydride and glycine) suggested that the LMGG mordanting effect is not dependent on residual aldehydes groups in tissues. PMID:783172

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

PubMed

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

2016-11-01

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

Lability of High Molecular Weight Dissolved Organic Matter Polysaccharides Increases with Mild Acid or Base Treatment.

NASA Astrophysics Data System (ADS)

Pedler Sherwood, B.; Sosa, O.; Nelson, C. E.; Repeta, D.; DeLong, E.

2016-02-01

Approximately 662 Pg of dissolved organic carbon (DOC) has accumulated in the global ocean, yet the biological and chemical constraints on DOC turnover remain poorly understood. High molecular weight dissolved organic matter (HMWDOM) is largely comprised of semi-labile polysaccharides. These polysaccharides resist degradation even in the presence of nutrient amendments, suggesting unknown factors of polysaccharide composition affect microbial degradation. In a series of microcosm incubations conducted at station ALOHA in the North Pacific Subtropical Gyre, we tested the affect of mild base (KOH-DOM) and acid (HCl-DOM) treatments on polysaccharide lability. KOH-DOM, HCl-DOM, and untreated HMWDOM was added to seawater from the deep chlorophyll maximum and 200m. Microcosms amended with KOH-DOM and HCl-DOM yielded higher bacterial abundance and greater carbon drawdown relative to untreated HMWDOM and unamended controls. Microcosms amended with KOH-DOM and HCl-DOM also showed significant production of fluorescent DOM (fDOM), whereas untreated HMWDOM and unamended controls showed a net decrease in fDOM as measured by parallel factor analysis of DOM excitation-emission spectra. Metagenomic analyses revealed that microcosms amended with untreated HMWDOM and controls became dominated by Alteromonas genera ( 60% total sequence reads). In contrast, KOH-DOM and HCl-DOM amended microcosms yielded greater bacterial diversity; Alteromonas genera comprised 25% of sequence reads, with differences primarily accounted for by proportional increases in vibrio, roseobacter, rugeria and marinomonas clades. Transcriptomic analyses identified differential gene expression during growth on each DOM fraction. This study provides new insight into specific chemical moieties that may limit the bacterial degradation rate of semi-labile HMWDOM in the ocean.

Molecular resolution and fragmentation of fulvic acid by electrospray ionization/multistage tandem mass spectrometry

USGS Publications Warehouse

Leenheer, J.A.; Rostad, C.E.; Gates, Paul M.; Furlong, E.T.; Ferrer, I.

2001-01-01

Molecular weight distributions of fulvic acid from the Suwannee River, Georgia, were investigated by electrospray ionization/quadrupole mass spectrometry (ESI/QMS), and fragmentation pathways of specific fulvic acid masses were investigated by electrospray ionization/ion trap multistage tandem mass spectrometry (ESI/MST/MS). ESI/QMS studies of the free acid form of low molecular weight poly(carboxylic acid) standards in 75% methanol/25% water mobile phase found that negative ion detection gave the optimum generation of parent ions that can be used for molecular weight determinations. However, experiments with poly(acrylic acid) mixtures and specific high molecular weight standards found multiply charged negative ions that gave a low bias to molecular mass distributions. The number of negative charges on a molecule is dependent on the distance between charges. ESI/MST/MS of model compounds found characteristic water loss from alcohol dehydration and anhydride formation, as well as CO2 loss from decarboxylation, and CO loss from ester structures. Application of these fragmentation pathways to specific masses of fulvic acid isolated and fragmented by ESI/MST/MS is indicative of specific structures that can serve as a basis for future structural confirmation after these hypothesized structures are synthesized.

Physical Properties of Low-Molecular Weight Polydimethylsiloxane Fluids

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

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

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

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

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

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

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

USDA-ARS?s Scientific Manuscript database

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

The association of low-molecular-weight hydrophobic compounds with native casein micelles in bovine milk

PubMed Central

Cheema, M.; Mohan, M. S.; Campagna, S. R.; Jurat-Fuentes, J. L.; Harte, F. M.

2015-01-01

The agreed biological function of the casein micelles in milk is to carry minerals (calcium, magnesium, and phosphorus) from mother to young along with amino acids for growth and development. Recently, native and modified casein micelles were used as encapsulating and delivery agents for various hydrophobic low-molecular-weight probes. The ability of modified casein micelles to bind certain probes may derive from the binding affinity of native casein micelles. Hence, a study with milk from single cows was conducted to further elucidate the association of hydrophobic molecules into native casein micelles and further understand their biological function. Hydrophobic and hydrophilic extraction followed by ultraperformance liquid chromatography-high resolution mass spectrometry analysis were performed over protein fractions obtained from size exclusion fractionation of raw skim milk. Hydrophobic compounds, including phosphatidylcholine, lyso-phosphatidylcholine, phosphatidylethanolamine, and sphingomyelin, showed strong association exclusively to casein micelles as compared with whey proteins, whereas hydrophilic compounds did not display any preference for their association among milk proteins. Further analysis using liquid chromatography-tandem mass spectrometry detected 42 compounds associated solely with the casein-micelles fraction. Mass fragments in tandem mass spectrometry identified 4 of these compounds as phosphatidylcholine with fatty acid composition of 16:0/18:1, 14:0/16:0, 16:0/16:0, and 18:1/18:0. These results support that transporting low-molecular-weight hydrophobic molecules is also a biological function of the casein micelles in milk. PMID:26074238

Acidity in organic horizons of arctic soils on the Barents Sea coast

NASA Astrophysics Data System (ADS)

Shamrikova, E. V.; Deneva, S. V.; Kubik, O. S.; Punegov, V. V.; Kyz”yurova, E. V.; Bobrova, Yu. I.; Zueva, O. M.

2017-11-01

Parameters of water and KCl extracts from organic horizons of arctic soils on the coast of Khaipudyr Bay of the Barents Sea, in which the values of pH are 3.8-4.3 and 2.7-3.5, respectively, have been compared. It has been found that the content of water-extractable organic carbon is 0.2-0.5 g/dm3; the contents of low-molecular-weight carbohydrates and acids are 1-24 and 6 mg/dm3, respectively, and the content of Fe3+ ions is 1-4 mmol/dm3. The increase in the ionic strength of solution reduces the extraction efficiency of total organic carbon in 1.2 times and that of acids and carbohydrates in 3 times on the average at the simultaneous increase in the content of iron ions in the liquid phase in 7-15 times. It has been shown that organic acids and iron compounds are the main sources of acidity in salt extracts from organic soil horizons. The low contents of Ca2+ and Mg2+, which participate in the neutralization of acids, favor the high acidity of the studied horizons.

Synthesis and characterization of sugar based low molecular weight gelators and the preparation of chiral sulfinamides

NASA Astrophysics Data System (ADS)

Mangunuru, Hari Prasad Reddy

Low molecular weight gelators (LMWGs) have received considerable attention in the field of chemistry from last few decades. These compounds form self-assembled fibrous networks like micelles, cylindrical, sheets, fibers, layers and so on. The fibrous network entraps the solvent and forms gel, because of the self-assembly phenomenon and their demonstrated potential uses in a variety of areas, ranging from environmental to medicinal applications. Sugars are good starting materials to synthesize the new class of LMWG's, because these are different from some expensive materials, these are natural products. We have synthesized and characterized the LMGS's based on D-glucose and D-glucosamine. D-glucosamine is the versatile starting material to make different peptoids and triazoles. Several series of compounds were synthesized using compounds 1-3 as starting material and studied the gelation behavior all the compounds. We have studied the self-assembling properties of a new class of tripeptoids, synthesized by one-pot Ugi reaction from simple starting materials. Among the focused library of tripeptoids synthesized, we found that several efficient low molecular weight organogelators were obtained for aqueous DMSO and ethanol mixtures. We have also synthesized and characterized a series of monosaccharide triazole derivatives. These compounds were synthesized from N-acetyl glucosamine and D-glucose via a Cu(I) catalyzed azide/alkyne cycloaddition reaction (CuAAc). The compounds have been screened for their gelation properties and several efficient low molecular weight organo/hydro gelators were obtained, among these compounds, five per-acetyl glucosamine derivatives and one peracetyl glucose derivative were able to form gels in water. These new molecules are expected to be useful in drug delivery and tissue engineering.*. Asymmetric synthesis of chiral amines is a challenging in synthetic organic chemistry. The development of new catalysts for asymmetric organic

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

PubMed

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

2016-09-05

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

High molecular weight hyaluronic acid increases the differentiation potential of the murine chondrocytic ATDC5 cell line.

PubMed

Sato, Eiichi; Ando, Takashi; Ichikawa, Jiro; Okita, Genki; Sato, Nobutaka; Wako, Masanori; Ohba, Tetsuro; Ochiai, Satoshi; Hagino, Tetsuo; Jacobson, Richard; Haro, Hirotaka

2014-12-01

Osteoarthritis (OA) is a group of common, chronic, and painful inflammatory joint diseases. One important finding in OA patients is a remarkable decrease in the molecular weight of hyaluronic acid (HA) in the synovial fluid of affected joints. Therapeutic HA is available to patients in most parts of the world as a viscosupplementation product for the treatment of OA. Previous clinical reports show that high molecular weight HA (HMWHA) more effectively relieves pain than low molecular weight HA (LMWHA). However, the mechanism behind this finding remains unclear. In this study, we investigated whether a LMWHA (Low-0.9 MDa) and two types of HMWHA (High-1.9 MDa and 6 MDa) differentially affected chondroregulatory action. We tested this using ATDC5 cell, a murine chondrocytic cell line widely used in culture systems to study chondrogenic differentiation. We found that HMWHA, especially hylan G-F 20 (High-6 MDa), significantly induced aggrecan and proteoglycan accumulation, nodule formation, and mRNA expression of chondrogenic differentiation markers in a time- and dose-dependent manner. In addition, we showed that HMWHA prevented TNF-α induced inhibition of chondrogenic differentiation, with no effect on cell proliferation or viability. These results reveal that HMWHA significantly promotes chondrogenic differentiation of ATDC5 cells in vitro, and suggest that HMWHA plays a significant chondroregulatory role in vivo. © 2014 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

Feline urine metabolomic signature: characterization of low-molecular-weight substances in urine from domestic cats.

PubMed

Rivera-Vélez, Sol-Maiam; Villarino, Nicolas F

2018-02-01

Objectives This aim of this study was to characterize the composition and content of the feline urine metabolome. Methods Eight healthy domestic cats were acclimated at least 10 days before starting the study. Urine samples (~2 ml) were collected by ultrasound-guided cystocentesis. Samples were centrifuged at 1000 × g for 8 mins, and the supernatant was analyzed by gas chromatography/time-of-flight mass spectrometery. The urine metabolome was characterized using an untargeted metabolomics approach. Results Three hundred and eighteen metabolites were detected in the urine of the eight cats. These molecules are key components of at least 100 metabolic pathways. Feline urine appears to be dominated by carbohydrates, carbohydrate conjugates, organic acid and derivatives, and amino acids and analogs. The five most abundant molecules were phenaceturic acid, hippuric acid, pseudouridine phosphate and 3-(4-hydroxyphenyl) propionic acid. Conclusions and relevance This study is the first to characterize the feline urine metabolome. The results of this study revealed the presence of multiple low-molecular-weight substances that were not known to be present in feline urine. As expected, the origin of the metabolites detected in urine was diverse, including endogenous compounds and molecules biosynthesized by microbes. Also, the diet seemed to have had a relevant role on the urine metabolome. Further exploration of the urine metabolic phenotype will open a window for discovering unknown, or poorly understood, metabolic pathways. In turn, this will advance our understanding of feline biology and lead to new insights in feline physiology, nutrition and medicine.

Enhancing the intestinal absorption of low molecular weight chondroitin sulfate by conjugation with α-linolenic acid and the transport mechanism of the conjugates.

PubMed

Xiao, Yuliang; Li, Pingli; Cheng, Yanna; Zhang, Xinke; Sheng, Juzheng; Wang, Decai; Li, Juan; Zhang, Qian; Zhong, Chuanqing; Cao, Rui; Wang, Fengshan

2014-04-25

The purpose of this report was to demonstrate the effect of amphiphilic polysaccharides-based self-assembling micelles on enhancing the oral absorption of low molecular weight chondroitin sulfate (LMCS) in vitro and in vivo, and identify the transepithelial transport mechanism of LMCS micelles across the intestinal barrier. α-Linolenic acid-low molecular weight chondroitin sulfate polymers(α-LNA-LMCS) were successfully synthesized, and characterized by FTIR, (1)HNMR, TGA/DSC, TEM, laser light scattering and zeta potential. The significant oral absorption enhancement and elimination half-life (t₁/₂) extension of LNA-LMCS2 in rats were evidenced by intragastric administration in comparison with CS and LMCS. Caco-2 transport studies demonstrated that the apparent permeability coefficient (Papp) of LNA-LMCS2 was significantly higher than that of CS and LMCS (p<0.001), and no significant effects on the overall integrity of the monolayer were observed during the transport process. In addition, α-LNA-LMCS micelles accumulated around the cell membrane and intercellular space observed by confocal laser scanning microscope (CLSM). Furthermore, evident alterations in the F-actin cytoskeleton were detected by CLSM observation following the treatment of the cell monolayers with α-LNA-LMCS micelles, which further certified the capacity of α-LNA-LMCS micelles to open the intercellular tight junctions rather than disrupt the overall integrity of the monolayer. Therefore, LNA-LMCS2 with low cytotoxicity and high bioavailability might be a promising substitute for CS in clinical use, such as treating osteoarthritis, atherosclerosis, etc. Copyright © 2014 Elsevier B.V. All rights reserved.

A global survey of low-molecular weight carbohydrates in lentils

USDA-ARS?s Scientific Manuscript database

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

A global survey of low-molecular weight carbohydrates in lentils

USDA-ARS?s Scientific Manuscript database

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

Drying Affects the Fiber Network in Low Molecular Weight Hydrogels

PubMed Central

2017-01-01

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

Temporal variations of low molecular mass organic acids during vegetation period in temperate forest soil affected by acidification

NASA Astrophysics Data System (ADS)

Tejnecky, V.; Drabek, O.; Bradová, M.; Němeček, K.; Šebek, O.; Zenáhlíková, J.; Boruvka, L.

2011-12-01

The Low Molecular Mass Organic Acids (LMMOA) are essential in processes affecting the soils and represent reactive fraction of dissolved organic carbon (DOC). LMMOA influence soil-chemistry behaviour, participate in transport of mineral nutrition and reduce potential toxicity of selected elements like Al. The aim of this research was to assess behaviour, amount and composition of LMMOA in forest soil under different vegetation cover. The researched area is located in the naturally acid Jizera Mountains (Czech Republic), which was further affected by acid deposition and improper forest management. Soil samples from organic F and H horizons, organo-mineral A horizon and spodic or cambic mineral B horizons were taken under beech and spruce stands monthly (from April to October). Both stands were located immediately next to each other. The collected soil samples were analyzed immediately in a "fresh" state. Contents of LMMOA in deionised water extract were determined by means of ion-exchange chromatography (ICS-1600, Dionex, USA) with suppressed conductivity and gradient elution of KOH mobile phase. The contents of LMMOAS were also determined in precipitation samples. In addition, other selected elements (Al, Fe, Ca, Na, Mg and K), Al speciation and main inorganic anions were determined in water extract and precipitation samples. The highest amounts of LMMOA (mainly lactic, acetic, formic, malic and oxalic acid) were observed in organic F and H horizons and measured amounts decreased with increasing soil profile depth. Higher contents were determined in soil under spruce forest than under beech forest. External inputs of LMMOA in a form of precipitation were assessed as less significant in comparison with the soil processes (e.g. soil biological activity, soil organic matter decomposition processes). LMMOA amounts were higher in spring and summer (from April to August), caused by increased biological activity, while lower amounts were observed during the autumn period

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

PubMed

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

2013-07-16

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

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

PubMed

Spichtig, Véronique; Austin, Sean

2008-01-01

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

Acidic organic compounds in beverage, food, and feed production.

PubMed

Quitmann, Hendrich; Fan, Rong; Czermak, Peter

2014-01-01

Organic acids and their derivatives are frequently used in beverage, food, and feed production. Acidic additives may act as buffers to regulate acidity, antioxidants, preservatives, flavor enhancers, and sequestrants. Beneficial effects on animal health and growth performance have been observed when using acidic substances as feed additives. Organic acids could be classified in groups according to their chemical structure. Each group of organic acids has its own specific properties and is used for different applications. Organic acids with low molecular weight (e.g. acetic acid, lactic acid, and citric acid), which are part of the primary metabolism, are often produced by fermentation. Others are produced more economically by chemical synthesis based on petrochemical raw materials on an industrial scale (e.g. formic acid, propionic and benzoic acid). Biotechnology-based production is of interest due to legislation, consumer demand for natural ingredients, and increasing environmental awareness. In the United States, for example, biocatalytically produced esters for food applications can be labeled as "natural," whereas identical conventional acid catalyst-based molecules cannot. Natural esters command a price several times that of non-natural esters. Biotechnological routes need to be optimized regarding raw materials and yield, microorganisms, and recovery methods. New bioprocesses are being developed for organic acids, which are at this time commercially produced by chemical synthesis. Moreover, new organic acids that could be produced with biotechnological methods are under investigation for food applications.

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

PubMed

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

2017-08-01

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

Body weight reducing effect of oral boric acid intake.

PubMed

Aysan, Erhan; Sahin, Fikrettin; Telci, Dilek; Yalvac, Mehmet Emir; Emre, Sinem Hocaoglu; Karaca, Cetin; Muslumanoglu, Mahmut

2011-01-01

Boric acid is widely used in biology, but its body weight reducing effect is not researched. Twenty mice were divided into two equal groups. Control group mice drank standard tap water, but study group mice drank 0.28mg/250ml boric acid added tap water over five days. Total body weight changes, major organ histopathology, blood biochemistry, urine and feces analyses were compared. Study group mice lost body weight mean 28.1% but in control group no weight loss and also weight gained mean 0.09% (p<0.001). Total drinking water and urine outputs were not statistically different. Cholesterol, LDL, AST, ALT, LDH, amylase and urobilinogen levels were statistically significantly high in the study group. Other variables were not statistically different. No histopathologic differences were detected in evaluations of all resected major organs. Low dose oral boric acid intake cause serious body weight reduction. Blood and urine analyses support high glucose, lipid and middle protein catabolisms, but the mechanism is unclear.

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.

Isolation, purification, and immunological activities of a low-molecular-weight polysaccharide from the Lingzhi or Reishi medicinal mushroom Ganoderma lucidum (higher Basidiomycetes).

PubMed

Zhu, Lina; Luo, Xi; Tang, Qingjiu; Liu, Yanfang; Zhou, Shuai; Yang, Yan; Zhang, Jingsong

2013-01-01

To obtain a low-molecular-weight polysaccharide with immuno-enhancing activity, hot water extract of Ganoderma lucidum fruit bodies was separated by membrane ultrafiltration, anion exchange, and gel filtration chromatography, and the immunological activities of fractions were assessed on the basis of nitric oxide production by RAW 264.7 macrophages. A novel polysaccharide (TB3-2-2) was successfully isolated and purified. TB3-2-2 is a homogeneous polysaccharide, with a relative molecular weight of 5.11 × 103 Da, identified by high-performance liquid chromatography and was composed of galactose and glucose in a molar ratio of 2:3 determined by high-performance anion exchange chromatography. TB3-2-2 had a carbohydrate content of 99%, as measured using the phenol-sulfuric acid method. Proliferation of mouse spleen lymphocytes and the expression level of interleukin-6 was significantly increased by TB3-2-2. Results indicate that the low-molecular-weight polysaccharide with immunological activity in G. lucidum is worthy of further research and development.

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

PubMed

Guerrini, Marco; Bisio, Antonella

2012-01-01

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

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

PubMed

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

2012-06-15

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

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

PubMed

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

2014-09-01

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

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).

The association of low-molecular-weight hydrophobic compounds with native casein micelles in bovine milk.

PubMed

Cheema, M; Mohan, M S; Campagna, S R; Jurat-Fuentes, J L; Harte, F M

2015-08-01

The agreed biological function of the casein micelles in milk is to carry minerals (calcium, magnesium, and phosphorus) from mother to young along with amino acids for growth and development. Recently, native and modified casein micelles were used as encapsulating and delivery agents for various hydrophobic low-molecular-weight probes. The ability of modified casein micelles to bind certain probes may derive from the binding affinity of native casein micelles. Hence, a study with milk from single cows was conducted to further elucidate the association of hydrophobic molecules into native casein micelles and further understand their biological function. Hydrophobic and hydrophilic extraction followed by ultraperformance liquid chromatography-high resolution mass spectrometry analysis were performed over protein fractions obtained from size exclusion fractionation of raw skim milk. Hydrophobic compounds, including phosphatidylcholine, lyso-phosphatidylcholine, phosphatidylethanolamine, and sphingomyelin, showed strong association exclusively to casein micelles as compared with whey proteins, whereas hydrophilic compounds did not display any preference for their association among milk proteins. Further analysis using liquid chromatography-tandem mass spectrometry detected 42 compounds associated solely with the casein-micelles fraction. Mass fragments in tandem mass spectrometry identified 4 of these compounds as phosphatidylcholine with fatty acid composition of 16:0/18:1, 14:0/16:0, 16:0/16:0, and 18:1/18:0. These results support that transporting low-molecular-weight hydrophobic molecules is also a biological function of the casein micelles in milk. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Capillary Electrophoresis-Mass Spectrometry for the Analysis of Heparin Oligosaccharides and Low Molecular Weight Heparin.

PubMed

Sun, Xiaojun; Lin, Lei; Liu, Xinyue; Zhang, Fuming; Chi, Lianli; Xia, Qiangwei; Linhardt, Robert J

2016-02-02

Heparins, highly sulfated, linear polysaccharides also known as glycosaminoglycans, are among the most challenging biopolymers to analyze. Hyphenated techniques in conjunction with mass spectrometry (MS) offer rapid analysis of complex glycosaminoglycan mixtures, providing detailed structural and quantitative data. Previous analytical approaches have often relied on liquid chromatography (LC)-MS, and some have limitations including long separation times, low resolution of oligosaccharide mixtures, incompatibility of eluents, and often require oligosaccharide derivatization. This study examines the analysis of glycosaminoglycan oligosaccharides using a novel electrokinetic pump-based capillary electrophoresis (CE)-MS interface. CE separation and electrospray were optimized using a volatile ammonium bicarbonate electrolyte and a methanol-formic acid sheath fluid. The online analyses of highly sulfated heparin oligosaccharides, ranging from disaccharides to low molecular weight heparins, were performed within a 10 min time frame, offering an opportunity for higher-throughput analysis. Disaccharide compositional analysis as well as top-down analysis of low molecular weight heparin was demonstrated. Using normal polarity CE separation and positive-ion electrospray ionization MS, excellent run-to-run reproducibility (relative standard deviation of 3.6-5.1% for peak area and 0.2-0.4% for peak migration time) and sensitivity (limit of quantification of 2.0-5.9 ng/mL and limit of detection of 0.6-1.8 ng/mL) could be achieved.

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

PubMed

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

2008-01-01

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

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.

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

NASA Astrophysics Data System (ADS)

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

2013-06-01

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

Effect of molecular weight of chitosan on the shelf life and other quality parameters of three different cultivars of Actinidia kolomikta (kiwifruit).

PubMed

Drevinskas, Tomas; Naujokaitytė, Gintarė; Maruška, Audrius; Kaya, Murat; Sargin, Idris; Daubaras, Remigijus; Česonienė, Laima

2017-10-01

The kiwi fruit, Actinidia kolomikta, has valuable properties such as high antioxidant activity, high vitamin C, polyphenols, chlorophylls and organic acids content, but the species are hardly commercialized due to their short shelf life (less than two days). In this study three different cultivars of A. kolomikta (Anykšta, Sentiabrskaya and VIR2) were coated with low, medium and high molecular weight chitosan bio-polymer with the aim to extend the shelf life. The changes in fruit firmness, mass, phenolic compound content, vitamin C content and subjective criteria (withering level, decoloration level and aesthetic appearance) were monitored. It was observed that high molecular weight chitosan had higher positive effect on the shelf life of Sentiabrskaya and Anykšta cultivars than VIR2. Low molecular weight chitosan was found effective on VIR2. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molecular marker characterization and source appointment of particulate matter and its organic aerosols.

PubMed

Choi, Jong-Kyu; Ban, Soo-Jin; Kim, Yong-Pyo; Kim, Yong-Hee; Yi, Seung-Muk; Zoh, Kyung-Duk

2015-09-01

This study was carried out to identify possible sources and to estimate their contribution to total suspended particle (TSP) organic aerosol (OA) contents. A total of 120 TSP and PM2.5 samples were collected simultaneously every third day over a one-year period in urban area of Incheon, Korea. High concentration in particulate matters (PM) and its components (NO3(-), water soluble organic compounds (WSOCs), and n-alkanoic acids) were observed during the winter season. Among the organics, n-alkanes, n-alkanoic acids, levoglucosan, and phthalates were major components. Positive matrix factorization (PMF) analysis identified seven sources of organic aerosols including combustion 1 (low molecular weight (LMW)-polycyclic aromatic hydrocarbons (PAHs)), combustion 2 (high molecular weight (HMW)-PAHs), biomass burning, vegetative detritus (n-alkane), secondary organic aerosol 1 (SOA1), secondary organic aerosol 2 (SOA2), and motor vehicles. Vegetative detritus increased during the summer season through an increase in biogenic/photochemical activity, while most of the organic sources were prominent in the winter season due to the increases in air pollutant emissions and atmospheric stability. The correlation factors were high among the main components of the organic carbon (OC) in the TSP and PM2.5. The results showed that TSP OAs had very similar characteristics to the PM2.5 OAs. SOA, combustion (PAHs), and motor vehicle were found to be important sources of carbonaceous PM in this region. Our results imply that molecular markers (MMs)-PMF model can provide useful information on the source and characteristics of PM. Copyright © 2015 Elsevier Ltd. All rights reserved.

Low Molecular Weight Polymethacrylates as Multi-Functional Lubricant Additives

DOE PAGES

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

2018-04-24

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

Low Molecular Weight Polymethacrylates as Multi-Functional Lubricant Additives

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

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

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

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.

Physicochemical and immunologic characterization of low-molecular-weight allergoids of Dactylis glomerata pollen proteins.

PubMed

Cirković, T D; Bukilica, M N; Gavrović, M D; Vujcić, Z M; Petrović, S; Jankov, R M

1999-02-01

Orchard grass (Dactylis glomerata) pollen proteins were chemically modified by means of acid anhydrides (maleic and succinic anhydride) to obtain low-molecular-weight allergoids. Chemical modification in both cases led to the replacement of one positive charge (epsilon amino group of Lys) by one negative charge, yielding proteins with changed physicochemical properties in comparison to the native orchard grass-pollen proteins. Physicochemical characterization of derivatives was done by gel chromatography, SDS-PAGE, and isoelectric focusing. To examine the IgE-binding properties of these derivatives, we carried out immunoblotting. To examine the ability of derivatives to induce IgG production, we immunized rabbits. Skin prick testing with the allergoids was performed on 15 individuals allergic to orchard grass pollens and on two healthy subjects. It was shown that the modified proteins retain their original molecular weights, but change pI to more acidic values. In the case of allergoids, a strong reduction in IgE binding was found. Immunization of rabbits with allergoids showed that the derivatives retain the ability to induce IgG production, and that the antisera obtained in such a way react to native (unmodified) extract. The ability of derivatives to induce allergic reaction was significantly reduced. The patients (86.6%) included in our study exhibited less than 50% of native extract response. Among them, 53.3% had no response to one or both allergoids. These modification procedures yield allergoids with a reduced allergenic activity and preserved immunogenic potential suitable for use in immunotherapy.

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

New Insights into the Organization, Recombination, Expression and Functional Mechanism of Low Molecular Weight Glutenin Subunit Genes in Bread Wheat

PubMed Central

Fan, Huajie; Sun, Jiazhu; Zhang, Zhongjuan; Qin, Huanju; Li, Bin; Hao, Shanting; Li, Zhensheng; Wang, Daowen; Zhang, Aimin; Ling, Hong-Qing

2010-01-01

The bread-making quality of wheat is strongly influenced by multiple low molecular weight glutenin subunit (LMW-GS) proteins expressed in the seeds. However, the organization, recombination and expression of LMW-GS genes and their functional mechanism in bread-making are not well understood. Here we report a systematic molecular analysis of LMW-GS genes located at the orthologous Glu-3 loci (Glu-A3, B3 and D3) of bread wheat using complementary approaches (genome wide characterization of gene members, expression profiling, proteomic analysis). Fourteen unique LMW-GS genes were identified for Xiaoyan 54 (with superior bread-making quality). Molecular mapping and recombination analyses revealed that the three Glu-3 loci of Xiaoyan 54 harbored dissimilar numbers of LMW-GS genes and covered different genetic distances. The number of expressed LMW-GS in the seeds was higher in Xiaoyan 54 than in Jing 411 (with relatively poor bread-making quality). This correlated with the finding of higher numbers of active LMW-GS genes at the A3 and D3 loci in Xiaoyan 54. Association analysis using recombinant inbred lines suggested that positive interactions, conferred by genetic combinations of the Glu-3 locus alleles with more numerous active LMW-GS genes, were generally important for the recombinant progenies to attain high Zeleny sedimentation value (ZSV), an important indicator of bread-making quality. A higher number of active LMW-GS genes tended to lead to a more elevated ZSV, although this tendency was influenced by genetic background. This work provides substantial new insights into the genomic organization and expression of LMW-GS genes, and molecular genetic evidence suggesting that these genes contribute quantitatively to bread-making quality in hexaploid wheat. Our analysis also indicates that selection for high numbers of active LMW-GS genes can be used for improvement of bread-making quality in wheat breeding. PMID:20975830

Partial Hydrothermal Oxidation of High Molecular Weight Unsaturated Carboxylic Acids for Upgrading of Biodiesel Fuel

NASA Astrophysics Data System (ADS)

Kawasaki, K.; Jin, F.; Kishita, A.; Tohji, K.; Enomoto, H.

2007-03-01

With increasing environmental awareness and crude oil price, biodiesel fuel (BDF) is gaining recognition as a renewable fuel which may be used as an alternative diesel fuel without any modification to the engine. The cold flow and viscosity of BDF, however, is a major drawback that limited its use in cold area. In this study, therefore, we investigated that partial oxidation of high molecular weight unsaturated carboxylic acids in subcritical water, which major compositions in BDF, to upgrade biodiesel fuel. Oleic acid, (HOOC(CH2)7CH=CH(CH2)7CH3), was selected as a model compound of high molecular weight unsaturated carboxylic acids. All experiments were performed with a batch reactor made of SUS 316 with an internal volume of 5.7 cm3. Oleic acid was oxidized at 300 °C with oxygen supply varying from 1-10 %. Results showed that a large amount of carboxylic acids and aldehydes having 8-9 carbon atoms were formed. These experimental results suggest that the hydrothermal oxidative cleavage may mainly occur at double bonds and the cleavage of double bonds could improve the cold flow and viscosity of BDF.

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

PubMed

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

2004-01-01

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

Ferric reductase activity of low molecular weight human milk fraction is associated with enhanced iron solubility and uptake in Caco-2 cells.

PubMed

Pullakhandam, Raghu; Nair, Madhavan Krishnapillai; Kasula, Sunanda; Kilari, Sreenivasulu; Thippande, Tippeswamy Gowda

2008-09-19

It is known that the fractional absorption of extrinsic iron from human milk is higher in infants and adults. A low molecular weight milk fraction has been proposed to increase the bioavailability of iron from human milk. Nevertheless, the mechanisms remained elusive. Here in we demonstrate ferric reductase activity (Km7.73x10(-6)M) in low molecular weight human milk fraction (10kF, filtrate derived from ultra filtration of milk whey through 10kDa cutoff membrane), which increased ferric iron solubility and iron uptake in Caco-2 cells. The 10kF fraction was as effective as ascorbic acid (1:20 iron to ascorbic acid) in increasing the ferric iron solubility and uptake in Caco-2 cells. Further, gel filtration chromatography on peptide column led to co-elution of ferric reductase and iron solubilization activities at an apparent molecular mass of <1500Da. Interestingly, only these fractions containing ferric reductase activity also stimulated the uptake of iron in Caco-2 cells. Thus, it is concluded that human milk possesses ferric reductase activity and is associated with ferric iron solubilization and enhanced absorption.

Body Weight Reducing Effect of Oral Boric Acid Intake

PubMed Central

Aysan, Erhan; Sahin, Fikrettin; Telci, Dilek; Yalvac, Mehmet Emir; Emre, Sinem Hocaoglu; Karaca, Cetin; Muslumanoglu, Mahmut

2011-01-01

Background: Boric acid is widely used in biology, but its body weight reducing effect is not researched. Methods: Twenty mice were divided into two equal groups. Control group mice drank standard tap water, but study group mice drank 0.28mg/250ml boric acid added tap water over five days. Total body weight changes, major organ histopathology, blood biochemistry, urine and feces analyses were compared. Results: Study group mice lost body weight mean 28.1% but in control group no weight loss and also weight gained mean 0.09% (p<0.001). Total drinking water and urine outputs were not statistically different. Cholesterol, LDL, AST, ALT, LDH, amylase and urobilinogen levels were statistically significantly high in the study group. Other variables were not statistically different. No histopathologic differences were detected in evaluations of all resected major organs. Conclusion: Low dose oral boric acid intake cause serious body weight reduction. Blood and urine analyses support high glucose, lipid and middle protein catabolisms, but the mechanism is unclear. PMID:22135611

Isoleucine epimerization in the high-molecular-weight fraction of pleistocene Arctica

NASA Astrophysics Data System (ADS)

Kaufman, Darrell S.; Sejrup, Hans-Petter

The extent of amino acid racemization, as traditionally determined in the entire (total acid hydrolysate) pool of amino acids comprising the organic remains of fossils, is a function of the integrated effects of a complex diagenetic reaction network. We investigated the possibility that some of the complications involved in protein diagenesis might be circumvented by isolating one component of the reaction network and studying the extent of racemization in that fraction alone. We used gel-filtration to extract the high-molecular-weight (HMW) fraction of proteinaceous matter from fossil and modem molluscan shells. This fraction contains the largest (ca. > 15,000 MW), most-pristine macromolecules and has been less affected by diagenesis than the more-degraded, lower molecular-weight fractions. Variations in the extent of racemization (isoleucine epimerization; alle/Ile) measured in the HMW fraction of subsamples taken along cross sections of Arctica shells from two interglacial sites, Bø and Fjøsanger, southwestern Norway, are within the range of analytical uncertainty [coefficient of variation (cv) = 5-8%], despite the strong gradient (cv = 20-24%) in alle/Ile of the total amino acid population. Because there is no age difference across a shell, this finding supports the idea that the HMW fraction contains more geochronologically reliable proteinaceous matter than the total amino acid pool. Weighted mean alle/Ile ratios in the HMW fraction of aliquots of powdered sample from the two shells overlap at ± 1σ, despite significantly different alle/Ile ratios in the total amino acid population of some shells from the two sites. The difference in alle/Ile ratios in the total population is attributed to a greater proportion of low-molecular-weight (ca. 300 MW), and hence, extensively epimerized molecules measured in gel-filtered samples from the Fjøsanger shell. Because the rate of epimerization in the HMW fraction is much lower than in the total population, the

Modeling the influence of organic acids on soil weathering

NASA Astrophysics Data System (ADS)

Lawrence, Corey; Harden, Jennifer; Maher, Kate

2014-08-01

Biological inputs and organic matter cycling have long been regarded as important factors in the physical and chemical development of soils. In particular, the extent to which low molecular weight organic acids, such as oxalate, influence geochemical reactions has been widely studied. Although the effects of organic acids are diverse, there is strong evidence that organic acids accelerate the dissolution of some minerals. However, the influence of organic acids at the field-scale and over the timescales of soil development has not been evaluated in detail. In this study, a reactive-transport model of soil chemical weathering and pedogenic development was used to quantify the extent to which organic acid cycling controls mineral dissolution rates and long-term patterns of chemical weathering. Specifically, oxalic acid was added to simulations of soil development to investigate a well-studied chronosequence of soils near Santa Cruz, CA. The model formulation includes organic acid input, transport, decomposition, organic-metal aqueous complexation and mineral surface complexation in various combinations. Results suggest that although organic acid reactions accelerate mineral dissolution rates near the soil surface, the net response is an overall decrease in chemical weathering. Model results demonstrate the importance of organic acid input concentrations, fluid flow, decomposition and secondary mineral precipitation rates on the evolution of mineral weathering fronts. In particular, model soil profile evolution is sensitive to kaolinite precipitation and oxalate decomposition rates. The soil profile-scale modeling presented here provides insights into the influence of organic carbon cycling on soil weathering and pedogenesis and supports the need for further field-scale measurements of the flux and speciation of reactive organic compounds.

Modeling the influence of organic acids on soil weathering

USGS Publications Warehouse

Lawrence, Corey R.; Harden, Jennifer W.; Maher, Kate

2014-01-01

Biological inputs and organic matter cycling have long been regarded as important factors in the physical and chemical development of soils. In particular, the extent to which low molecular weight organic acids, such as oxalate, influence geochemical reactions has been widely studied. Although the effects of organic acids are diverse, there is strong evidence that organic acids accelerate the dissolution of some minerals. However, the influence of organic acids at the field-scale and over the timescales of soil development has not been evaluated in detail. In this study, a reactive-transport model of soil chemical weathering and pedogenic development was used to quantify the extent to which organic acid cycling controls mineral dissolution rates and long-term patterns of chemical weathering. Specifically, oxalic acid was added to simulations of soil development to investigate a well-studied chronosequence of soils near Santa Cruz, CA. The model formulation includes organic acid input, transport, decomposition, organic-metal aqueous complexation and mineral surface complexation in various combinations. Results suggest that although organic acid reactions accelerate mineral dissolution rates near the soil surface, the net response is an overall decrease in chemical weathering. Model results demonstrate the importance of organic acid input concentrations, fluid flow, decomposition and secondary mineral precipitation rates on the evolution of mineral weathering fronts. In particular, model soil profile evolution is sensitive to kaolinite precipitation and oxalate decomposition rates. The soil profile-scale modeling presented here provides insights into the influence of organic carbon cycling on soil weathering and pedogenesis and supports the need for further field-scale measurements of the flux and speciation of reactive organic compounds.

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

NASA Astrophysics Data System (ADS)

Yang, Z.; Jiang, J.

2015-12-01

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

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).

Effects of root exudates on gel-beads/reeds combination remediation of high molecular weight polycyclic aromatic hydrocarbons.

PubMed

Tian, Weijun; Zhao, Jing; Zhou, Yuhang; Qiao, Kaili; Jin, Xin; Liu, Qing

2017-01-01

Changes in root exudates, including low molecular weight organic acids (LMWOAs), amino acids and sugars, in rhizosphere soils during the gel-beads/reeds combination remediation for high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) and the degree of the effects on HMW-PAH biodegradation were evaluated in this study. The results showed that the gel-beads/reeds combination remediation notably increased the removal rates of pyrene, benzo(a)pyrene and indeno(1,2,3-cd)pyrene (65.0-68.9%, 60.0-68.5% and 85.2-85.9%, respectively). During the removal of HMW-PAHs, the LMWOAs, particularly maleic acid, enhanced the biodegradation of HMW-PAHs. Arginine and trehalose monitored in reed root exudates promoted the growth of plants and microorganisms and then improved the removal of HMW-PAHs, especially pyrene. However, the contribution of reed root exudates on degradation of 5- and 6-ring PAHs was minor. These results indicated that the utilization of root exudates was certainly not the only important trait for the removal of HMW-PAHs. Copyright © 2016 Elsevier Inc. All rights reserved.

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 method for measuring low-weight carboxylic acids from biosolid compost.

PubMed

Himanen, Marina; Latva-Kala, Kyösti; Itävaara, Merja; Hänninen, Kari

2006-01-01

Concentration of low-weight carboxylic acids (LWCA) is one of the important parameters that should be taken into consideration when compost is applied as soil improver for plant cultivation, because high amounts of LWCA can be toxic to plants. The present work describes a method for analysis of LWCA in compost as a useful tool for monitoring compost quality and safety. The method was tested on compost samples of two different ages: 3 (immature) and 6 (mature) months old. Acids from compost samples were extracted at high pH, filtered, and freeze-dried. The dried sodium salts were derivatized with a sulfuric acid-methanol mixture and concentrations of 11 low-weight fatty acids (C1-C10) were analyzed using headspace gas chromatography. The material was analyzed with two analytical techniques: the external calibration method (tested on 11 LWCA) and the standard addition method (tested only on formic, acetic, propionic, butyric, and iso-butyric acids). The two techniques were compared for efficiency of acids quantification. The method allowed good separation and quantification of a wide range of individual acids with high sensitivity at low concentrations. Detection limit for propionic, butyric, caproic, caprylic, and capric acids was 1 mg kg(-1) compost; for formic, acetic, valeric, enanthoic and pelargonic acids it was 5 mg kg(-1) compost; and for iso-butyric acid it was 10 mg kg(-1) compost. Recovery rates of LWCA were higher in 3-mo-old compost (57-99%) than in 6-mo-old compost (29-45%). In comparison with the external calibration technique the standard addition technique proved to be three to four times more precise for older compost and two times for younger compost. Disadvantages of the standard addition technique are that it is more time demanding and laborious.

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

PubMed

Huang, Steve S; Heston, Warren D W

2017-01-01

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

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

PubMed

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

2013-01-01

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

Photoelectron resonance capture ionization-aerosol mass spectrometry of the ozonolysis products of oleic acid particles: Direct measure of higher molecular weight oxygenates

NASA Astrophysics Data System (ADS)

Zahardis, James; Lafranchi, Brian W.; Petrucci, Giuseppe A.

2005-04-01

The heterogeneous reaction of particle-phase 9-octadecenoic acid (oleic acid) and gas-phase ozone in a flow reactor was studied by photoelectron resonance capture ionization (PERCI) mass spectrometry. This soft ionization technique facilitated one of the first simultaneous, direct observations of all four of the major products predicted for this reaction: nonanal, nonanoic acid, 9-oxononanoic acid, and azelaic acid. In addition, a series of higher molecular weight oxygenated compounds were observed directly for the first time. The proposed structures are all cyclic oxygenates and contain the oxygen-oxygen moiety, including secondary ozonides and cyclic geminal diperoxides. Mechanisms for the formation of these products are proposed. The mechanisms are generally 1,3-dipolar cycloadditions that lead to five- and six-member oxygen-containing rings. The mechanisms are shown to involve short-lived Criegee intermediates reacting with aldehydes and other Criegee intermediates. Atmospheric implications of these higher molecular weight compounds are suggested and include enhancing the fatty acid medium's capacity to act as a source of radicals due to the prominence of the peroxide moiety. The low volatility coupled with the high polarity of these compounds may alter particle phase hygroscopicity that can enhance the cloud condensation nuclei properties of these particles.

Identification of Organic Sulfate Esters in d-Limonene Ozonolysis SOA Under Acidic Condition

NASA Astrophysics Data System (ADS)

Iinuma, Y.; Mueller, C.; Boege, O.; Herrmann, H.

2006-12-01

Secondary organic aerosol (SOA) components from gas phase ozonolysis of d-limonene were investigated in a series of indoor chamber experiments. The compounds smaller than 300 Da were quantified using capillary electrophoresis coupled to electrospray ionisation ion trap mass spectrometry (CE/ESI-ITMS). HPLC coupled to an ESI-TOFMS and an ESI-ITMS was used for structural study of dimmers and oligomers. Only 10% of the produced SOA could be attributed to low molecular weight carboxylic acids (Mw<300). The oxidation products which have molecular weights over 300 were detected regardless of the seed particle acidity but the concentrations of these compounds were much higher for acidic seed particle experiments. Strong signals of the compounds with mass to charge ratios (m/z) 281, 465 and 481 were detected when sulphuric acid was used in the seed particles. These compounds showed a strong fragment of m/z 97 in MS2 or MS3 spectra indicating the presence of sulfate in the structures. HPLC/ESI-TOFMS analysis suggests the elemental compositions of C10H17O7S-, C20H33O10S- and C20H33O11S- for m/z 281, 465 and 481, respectively. Based on MS^{n} and TOFMS results, they are most likely organic sulfate esters, possibly formed by a heterogeneous acid catalyzed reaction of a limonene oxidation product and sulfuric acid in the particle phase. The concentrations of the organic sulfate ester were as high as 3.7 μgm-3 for m/z 281.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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

PubMed

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

2015-10-01

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

Vitamin K antagonists or low-molecular-weight heparin for the long term treatment of symptomatic venous thromboembolism.

PubMed

van der Heijden, J F; Hutten, B A; Büller, H R; Prins, M H

2002-01-01

People with venous thromboembolism are generally treated for five days with intravenous unfractionated heparin or subcutaneous low-molecular-weight heparin followed by three months of vitamin K antagonists treatment. Treatment with vitamin K antagonists requires regular laboratory measurements and some patients have contraindications for treatment. To evaluate the efficacy and safety of long-term treatment of venous thromboembolism with low-molecular-weight heparins compared to vitamin K antagonists. Searches of MEDLINE, EMBASE and ISI Web of Science, the Specialised Trials Register of the Cochrane Peripheral Vascular Disease Group and the Cochrane Controlled Trials Register were made and relevant journals were hand-searched. Additional trials were sought through communication with colleagues and pharmaceutical companies. Two reviewers evaluated studies independently for methodological quality. Two reviewers extracted data independently. Primary analysis concerned all trial participants during the period of randomized treatment. Separate analyses were performed for category I and category II studies; i.e. studies using similar treatments initially in both study arms, and those that did not; and the different periods of follow-up. All seven studies fulfilling our criteria combined, a statistically non-significant reduction in the risk of recurrent venous thromboembolism favoring low-molecular-weight heparin treatment (OR 0.70; 95% CI [0.42, 1.16]) was found. Analysis of pooled data for category I studies showed a non-significant reduction in the risk of recurrent venous thromboembolism favoring low-molecular-weight heparin treatment (OR 0.75; 95% CI [0.40, 1.39]). Omitting a potentially-confounded study, a statistically non-significant reduction in the risk of recurrent venous thromboembolism favoring vitamin K antagonist treatment remained (OR 1.95; 95% CI [0.74, 5.19]). All studies combined, the difference in bleeding significantly favored treatment with low-molecular-weight

Comprehensive Analysis of Low-Molecular-Weight Human Plasma Proteome Using Top-Down Mass Spectrometry.

PubMed

Cheon, Dong Huey; Nam, Eun Ji; Park, Kyu Hyung; Woo, Se Joon; Lee, Hye Jin; Kim, Hee Cheol; Yang, Eun Gyeong; Lee, Cheolju; Lee, Ji Eun

2016-01-04

While human plasma serves as a great source for disease diagnosis, low-molecular-weight (LMW) proteome (<30 kDa) has been shown to contain a rich source of diagnostic biomarkers. Here we employ top-down mass spectrometry to analyze the LMW proteoforms present in four types of human plasma samples pooled from three healthy controls (HCs) without immunoaffinity depletion and with depletion of the top two, six, and seven high-abundance proteins. The LMW proteoforms were first fractionated based on molecular weight using gel-eluted liquid fraction entrapment electrophoresis (GELFrEE). Then, the GELFrEE fractions containing up to 30 kDa were subjected to nanocapillary-LC-MS/MS, and the high-resolution MS and MS/MS data were processed using ProSightPC 3.0. As a result, a total of 442 LMW proteins and cleaved products, including those with post-translational modifications and single amino acid variations, were identified. From additional comparative analysis of plasma samples without immunoaffinity depletion between HCs and colorectal cancer (CRC) patients via top-down approach, tens of LMW proteoforms, including platelet factor 4, were found to show >1.5-fold changes between the plasma samples of HCs and CRC patients, and six of the LMW proteins were verified by Western blot analysis.

[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.

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

PubMed

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

2002-01-01

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

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

PubMed

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

2013-01-01

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

[Anaphylactic reactions to low-molecular weight chemicals].

PubMed

Nowak, Daria; Panaszek, Bernard

2015-02-06

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

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

PubMed Central

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

2012-01-01

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

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

PubMed Central

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

2010-01-01

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

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

PubMed

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

2010-02-01

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

Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids

NASA Astrophysics Data System (ADS)

Zhang, Peng; Yuan, Songhu

2017-12-01

Besides acidic environments, pyrite oxidation also occurs in circumneutral environments, such as well-buffered marine and estuarine sediments and salt marshes where low-molecular-weight organic acids (LMWOAs) (e.g., citrate and oxalate) prevail. However, the production of hydroxyl radicals (radOH) from pyrite oxidation by oxygen (O2) in these circumneutral environments is poorly understood. In this study, radOH production was measured during the abiotic oxidation of pyrite by O2 under circumneutral conditions. A pyrite suspension (50 g/L pyrite) that was buffered at pH 6-8 was exposed to air for oxygenation in the dark. Benzoate (20 mM) was added into the suspension to trap radOH. At pH 7, the cumulative radOH reached 7.5 μM within 420 min in the absence of LMWOAs, whereas it increased to 14.8, 12 and 11.2 μM in the presence of 1 mM ethylenediaminotetraacetate, citrate and oxalate, respectively. When the citrate concentration, which serves as a LMWOAs model, was increased from 0.5 to 5 mM, the cumulative radOH increased from 10.3 to 27.3 μM within 420 min at pH 7. With the decrease in pH from 8 to 6, the cumulative radOH increased from 2.1 to 23.3 μM in the absence of LMWOAs, but it increased from 8.8 to 134.9 μM in the presence of 3 mM citrate. The presence of LMWOAs enhanced the radOH production from pyrite oxidation under circumneutral conditions. In the absence of LMOWAs, radOH is produced mostly from the oxidation of adsorbed Fe(II) by O2. In the presence of citrate, radOH production is attributed mainly to the oxidation of Fe(II)-citrate- by O2 and secondarily to the oxidation of H2O on surface-sulfur defects. The acceleration of pyrite oxidation by Fe(III)-citrate increases radOH production. Fe(II)-citrate- is generated mainly from the complexation of adsorbed Fe(II) by citrate and the reduction of Fe(III)-citrate, and the generation is suppressed by the oxidation of adsorbed Fe(II). Fe(III)-citrate is generated predominantly from Fe

Lake secondary production fueled by rapid transfer of low molecular weight organic carbon from terrestrial sources to aquatic consumers.

PubMed

Berggren, M; Ström, L; Laudon, H; Karlsson, J; Jonsson, A; Giesler, R; Bergström, A-K; Jansson, M

2010-07-01

Carbon of terrestrial origin often makes up a significant share of consumer biomass in unproductive lake ecosystems. However, the mechanisms for terrestrial support of lake secondary production are largely unclear. By using a modelling approach, we show that terrestrial export of dissolved labile low molecular weight carbon (LMWC) compounds supported 80% (34-95%), 54% (19-90%) and 23% (7-45%) of the secondary production by bacteria, protozoa and metazoa, respectively, in a 7-km(2) boreal lake (conservative to liberal estimates in brackets). Bacterial growth on LMWC was of similar magnitude as that of primary production (PP), and grazing on bacteria effectively channelled the LMWC carbon to higher trophic levels. We suggest that rapid turnover of forest LMWC pools enables continuous export of fresh photosynthates and other labile metabolites to aquatic systems, and that substantial transfer of LMWC from terrestrial sources to lake consumers can occur within a few days. Sequestration of LMWC of terrestrial origin, thus, helps explain high shares of terrestrial carbon in lake organisms and implies that lake food webs can be closely dependent on recent terrestrial PP.

Molecular weight distribution of organic matter by ozonation and biofiltration.

PubMed

Lin, Yen-Hui

2012-01-01

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

Distinct high molecular weight organic compound (HMW-OC) types in aerosol particles collected at a coastal urban site

NASA Astrophysics Data System (ADS)

Dall'Osto, M.; Healy, R. M.; Wenger, J. C.; O'Dowd, C.; Ovadnevaite, J.; Ceburnis, D.; Harrison, Roy M.; Beddows, D. C. S.

2017-12-01

Organic oligomers were discovered in laboratory-generated atmospheric aerosol over a decade ago. However, evidence for the presence of oligomers in ambient aerosols is scarce and mechanisms for their formation have yet to be fully elucidated. In this work, three unique aerosol particle types internally mixed with High molecular weight organic compounds (HMW-OC) species - likely oligomers - were detected in ambient air using single particle Aerosol Time-Of-Flight Mass Spectrometry (ATOFMS) in Cork (Ireland) during winter 2009. These particle types can be described as follows: (1) HMW-OCs rich in organic nitrogen - possibly containing nitrocatechols and nitroguaiacols - originating from primary emissions of biomass burning particles during evening times; (2) HMW-OCs internally mixed with nitric acid, occurring in stagnant conditions during night time; and (3) HMW-OCs internally mixed with sea salt, likely formed via photochemical reactions during day time. The study exemplifies the power of methodologies capable of monitoring the simultaneous formation of organic and inorganic particle-phase reaction products. Primary emissions and atmospheric aging of different types of HMW-OC contributes to aerosol with a range of acidity, hygroscopic and optical properties, which can have different impacts on climate and health.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

REMOVAL BY COAGULATION OF TRACE ORGANICS FROM MISSISSIPPI RIVER WATER

EPA Science Inventory

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

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

PubMed

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

2016-01-01

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

The pPSU Plasmids for Generating DNA Molecular Weight Markers.

PubMed

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

2017-05-26

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

Low-Vacuum Deposition of Glutamic Acid and Pyroglutamic Acid: A Facile Methodology for Depositing Organic Materials beyond Amino Acids

PubMed Central

Sugimoto, Iwao; Maeda, Shunsaku; Suda, Yoriko; Makihara, Kenji; Takahashi, Kazuhiko

2014-01-01

Thin layers of pyroglutamic acid (Pygl) have been deposited by thermal evaporation of the molten L-glutamic acid (L-Glu) through intramolecular lactamization. This deposition was carried out with the versatile handmade low-vacuum coater, which was simply composed of a soldering iron placed in a vacuum degassing resin chamber evacuated by an oil-free diaphragm pump. Molecular structural analyses have revealed that thin solid film evaporated from the molten L-Glu is mainly composed of L-Pygl due to intramolecular lactamization. The major component of the L-Pygl was in β-phase and the minor component was in γ-phase, which would have been generated from partial racemization to DL-Pygl. Electron microscopy revealed that the L-Glu-evaporated film generally consisted of the 20 nm particulates of Pygl, which contained a periodic pattern spacing of 0.2 nm intervals indicating the formation of the single-molecular interval of the crystallized molecular networks. The DL-Pygl-evaporated film was composed of the original DL-Pygl preserving its crystal structures. This methodology is promising for depositing a wide range of the evaporable organic materials beyond amino acids. The quartz crystal resonator coated with the L-Glu-evaporated film exhibited the pressure-sensing capability based on the adsorption-desorption of the surrounding gas at the film surface. PMID:25254114

Low-Vacuum Deposition of Glutamic Acid and Pyroglutamic Acid: A Facile Methodology for Depositing Organic Materials beyond Amino Acids.

PubMed

Sugimoto, Iwao; Maeda, Shunsaku; Suda, Yoriko; Makihara, Kenji; Takahashi, Kazuhiko

2014-01-01

Thin layers of pyroglutamic acid (Pygl) have been deposited by thermal evaporation of the molten L-glutamic acid (L-Glu) through intramolecular lactamization. This deposition was carried out with the versatile handmade low-vacuum coater, which was simply composed of a soldering iron placed in a vacuum degassing resin chamber evacuated by an oil-free diaphragm pump. Molecular structural analyses have revealed that thin solid film evaporated from the molten L-Glu is mainly composed of L-Pygl due to intramolecular lactamization. The major component of the L-Pygl was in β-phase and the minor component was in γ-phase, which would have been generated from partial racemization to DL-Pygl. Electron microscopy revealed that the L-Glu-evaporated film generally consisted of the 20 nm particulates of Pygl, which contained a periodic pattern spacing of 0.2 nm intervals indicating the formation of the single-molecular interval of the crystallized molecular networks. The DL-Pygl-evaporated film was composed of the original DL-Pygl preserving its crystal structures. This methodology is promising for depositing a wide range of the evaporable organic materials beyond amino acids. The quartz crystal resonator coated with the L-Glu-evaporated film exhibited the pressure-sensing capability based on the adsorption-desorption of the surrounding gas at the film surface.

Effect of molecular weight of polystyrensulfonic acid sodium salt polymers on the precipitation kinetics of sodium bicarbonate

NASA Astrophysics Data System (ADS)

Martínez-Cruz, Nancy; Carrillo-Romo, Felipe; Jaramillo-Vigueras, David

2004-10-01

This paper analyzes the effect of polystyrensulfonic acid sodium salt (NaPSS), obtained by kinetic precipitation from solutions of polymers of molecular weight 245 000 and 38 000 g mol-1 in sodium bicarbonate (NaHCO3) itself precipitated from synthetic brine. Crystal size, shape and the additive adsorbed are reported. X shaped and hexagonal prisms crystals with different aspect ratios were obtained. The results show that with increasing polymer concentration the crystal size decreases, from 0.27 to 0.48 mm. Additionally, the higher molecular weight polymer shows both higher adsorption capacity and higher crystal habit modification. Crystal shape patterns were similar for both polymers; however, the higher molecular weight material induced changes at lower concentration. It was observed that the precipitation rate reached a minimum with increasing additive concentration.

Alternative CHCA-based matrices for the analysis of low molecular weight compounds by UV-MALDI-tandem mass spectrometry.

PubMed

Porta, Tiffany; Grivet, Chantal; Knochenmuss, Richard; Varesio, Emmanuel; Hopfgartner, Gérard

2011-02-01

Analysis of low molecular weight compounds (LMWC) in complex matrices by vacuum matrix-assisted laser desorption/ionization (MALDI) often suffers from matrix interferences, which can severely degrade limits of quantitation. It is, therefore, useful to have available a range of suitable matrices, which exhibit complementary regions of interference. Two newly synthesized α-cyanocinnamic acid derivatives are reported here; (E)-2-cyano-3-(naphthalen-2-yl)acrylic acid (NpCCA) and (2E)-3-(anthracen-9-yl)-2-cyanoprop-2enoic acid (AnCCA). Along with the commonly used α-cyano-4-hydroxycinnamic acid (CHCA), and the recently developed 4-chloro-α-cyanocinnamic acid (Cl-CCA) matrices, these constitute a chemically similar series of matrices covering a range of molecular weights, and with correspondingly differing ranges of spectral interference. Their performance was compared by measuring the signal-to-noise ratios (S/N) of 47 analytes, mostly pharmaceuticals, with the different matrices using the selected reaction monitoring (SRM) mode on a triple quadrupole instrument equipped with a vacuum MALDI source. AnCCA, NpCCA and Cl-CCA were found to offer better signal-to-noise ratios in SRM mode than CHCA, but Cl-CCA yielded the best results for 60% of the compounds tested. To better understand the relative performance of this matrix series, the proton affinities (PAs) were measured using the kinetic method. Their relative values were: AnCCA > CHCA > NpCCA > Cl-CCA. This ordering is consistent with the performance data. The synthesis of the new matrices is straightforward and they provide (1) tunability of matrix background interfering ions and (2) enhanced analyte response for certain classes of compounds. Copyright © 2011 John Wiley & Sons, Ltd.

Anti-angiogenic activity and antitumor efficacy of amphiphilic twin drug from ursolic acid and low molecular weight heparin

NASA Astrophysics Data System (ADS)

Cheng, Wenming; Zohra Dahmani, Fatima; Zhang, Juan; Xiong, Hui; Wu, Yuanyuan; Yin, Lifang; Zhou, Jianping; Yao, Jing

2017-02-01

Heparin, a potential blood anti-coagulant, is also known for its binding ability to several angiogenic factors through electrostatic interactions due to its polyanionic character. However, the clinical application of heparin for cancer treatment is limited by several drawbacks, such as unsatisfactory therapeutic effects and severe anticoagulant activity that could induce hemorrhaging. Herein, low molecular weight heparin (LMWH) was conjugated to ursolic acid (UA), which is also an angiogenesis inhibitor, by binding the amine group of aminoethyl-UA (UA-NH2) with the carboxylic groups of LMWH. The resulting LMWH-UA conjugate as an amphiphilic twin drug showed reduced anticoagulant activity and could also self-assemble into nanomicelles with a mean particle size ranging from 200-250 nm. An in vitro endothelial tubular formation assay and an in vivo Matrigel plug assay were performed to verify the anti-angiogenic potential of LMWH-UA. Meanwhile, the in vivo antitumor effect of LMWH-UA was also evaluated using a B16F10 mouse melanoma model. LMWH-UA nanomicelles were shown to inhibit angiogenesis both in vitro and in vivo. In addition, the i.v. administration of LMWH-UA to the B16F10 tumor-bearing mice resulted in a significant inhibition of tumor growth as compared to the free drug solutions. These findings demonstrate the therapeutic potential of LMWH-UA as a new therapeutic remedy for cancer therapy.

Gold nanoparticle-enhanced target (AuNPET) as universal solution for laser desorption/ionization mass spectrometry analysis and imaging of low molecular weight compounds.

PubMed

Sekuła, Justyna; Nizioł, Joanna; Rode, Wojciech; Ruman, Tomasz

2015-05-22

Preparation is described of a durable surface of cationic gold nanoparticles (AuNPs), covering commercial and custom-made MALDI targets, along with characterization of the nanoparticle surface properties and examples of the use in MS analyses and MS imaging (IMS) of low molecular weight (LMW) organic compounds. Tested compounds include nucleosides, saccharides, amino acids, glycosides, and nucleic bases for MS measurements, as well as over one hundred endogenous compounds in imaging experiment. The nanoparticles covering target plate were enriched in sodium in order to promote sodium-adduct formation. The new surface allows fast analysis, high sensitivity of detection and high mass determination accuracy. Example of application of new Au nanoparticle-enhanced target for fast and simple MS imaging of a fingerprint is also presented. Copyright © 2015 Elsevier B.V. All rights reserved.

Method for solubilization of low-rank coal using low molecular weight cell-free filtrates derived from cultures of Coriolus versicolor

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

Stewart, D.L.; Fredrickson, J.K.; Campbell, J.A.

1992-01-28

This patent describes a method for isolating an extracellular product derived from a broth of Coriolus versicolor. It comprises separating the cells from a broth of C. versicolor to obtain a cell-free filtrate; separating from the cell-free filtrate a fraction containing molecules of molecular weight in the range of about 500 to 1000 daltons. This patent also describes a method for degrading low-rank coal to a water-soluble material. It comprises contacting the low-rank coal with a cell-free fraction from the broth of Coriolus versicolor containing molecules in the molecular weight range of about 500 to 1000 daltons.

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

USDA-ARS?s Scientific Manuscript database

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

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

EPA Science Inventory

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

Understanding the primary emissions and secondary formation of gaseous organic acids in the oil sands region of Alberta, Canada

NASA Astrophysics Data System (ADS)

Liggio, John; Moussa, Samar G.; Wentzell, Jeremy; Darlington, Andrea; Liu, Peter; Leithead, Amy; Hayden, Katherine; O'Brien, Jason; Mittermeier, Richard L.; Staebler, Ralf; Wolde, Mengistu; Li, Shao-Meng

2017-07-01

Organic acids are known to be emitted from combustion processes and are key photochemical products of biogenic and anthropogenic precursors. Despite their multiple environmental impacts, such as on acid deposition and human-ecosystem health, little is known regarding their emission magnitudes or detailed chemical formation mechanisms. In the current work, airborne measurements of 18 gas-phase low-molecular-weight organic acids were made in the summer of 2013 over the oil sands region of Alberta, Canada, an area of intense unconventional oil extraction. The data from these measurements were used in conjunction with emission retrieval algorithms to derive the total and speciated primary organic acid emission rates, as well as secondary formation rates downwind of oil sands operations. The results of the analysis indicate that approximately 12 t day-1 of low-molecular-weight organic acids, dominated by C1-C5 acids, were emitted directly from off-road diesel vehicles within open pit mines. Although there are no specific reporting requirements for primary organic acids, the measured emissions were similar in magnitude to primary oxygenated hydrocarbon emissions, for which there are reporting thresholds, measured previously ( ≈ 20 t day-1). Conversely, photochemical production of gaseous organic acids significantly exceeded the primary sources, with formation rates of up to ≈ 184 t day-1 downwind of the oil sands facilities. The formation and evolution of organic acids from a Lagrangian flight were modelled with a box model, incorporating a detailed hydrocarbon reaction mechanism extracted from the Master Chemical Mechanism (v3.3). Despite evidence of significant secondary organic acid formation, the explicit chemical box model largely underestimated their formation in the oil sands plumes, accounting for 39, 46, 26, and 23 % of the measured formic, acetic, acrylic, and propionic acids respectively and with little contributions from biogenic VOC precursors. The model

Low-molecular-weight heparin in pediatric patients.

PubMed

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

2004-02-01

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

Influence of low molecular weight fractions of humic substances on reducing capacities and distribution of redox functional groups

NASA Astrophysics Data System (ADS)

Yang, Zhen; Jiang, Jie

2016-04-01

Humic substances (HS) are redox-active organic compounds and their reducing capacities depend on their molecule structure and distribution of redox functional groups (RFG). During dialysis experiments, bulk humic acids (HA) were separated into low molecular weight fractions (LMWF) and retentate. LMWF account for only 2% of the total organic carbon content of HA molecules, however, their reducing capacities are up to 33 times greater than either those of the bulk HA or retentate. Furthermore, the total reducing capacity of the bulk HA accounts for less than 15% of the total reducing capacity of bulk HA, retentate and LMWF combined, suggesting that releasing of LMWF cannot reduce the number of RFG. RFG are neither in fixed amounts nor in uniformly distributed in bulk HA. LWMF have great fluorescence intensities for humic-like fluorophores (quinone-like functional groups), where quinonoid π-π* transition is responsible for the great reducing capacities of LMWF, and protein-like fluorophores. The 3,500 Da molecules (1.25 nm diameter) of HS could stimulate transformation of redox-active metals or potential pollutants trapped in soil micropores (< 2 nm diameter). A development of relationship between reducing capacity and Ex/Em position provides a possibility to predicate relative reducing capacities of HS in environmental samples.

In situ reinforced polymers using low molecular weight compounds

NASA Astrophysics Data System (ADS)

Yordem, Onur Sinan

2011-12-01

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

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

PubMed

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

2012-03-01

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

Can thiolation render a low molecular weight polymer of just 20-kDa mucoadhesive?

PubMed

Mahmood, Arshad; Bonengel, Sonja; Laffleur, Flavia; Ijaz, Muhammad; Idrees, Muneeb Ahmad; Hussain, Shah; Huck, Christian W; Matuszczak, Barbara; Bernkop-Schnürch, Andreas

2016-01-01

The objective was to investigate whether even low-molecular weight polymers (LMWPs) can be rendered mucoadhesive due to thiolation. Interceded by the double catalytic system carbodiimide/N-hydroxysuccinimide, cysteamine was covalently attached to a copolymer, poly(4-styrenesulfonic acid-co-maleic acid) (PSSA-MA) exhibiting a molecular weight of just 20 kDa. Depending on the amount of added N-hydroxysuccinimide and cysteamine, the resulting PSSA-MA-cysteamine (PC) conjugates exhibited increasing degree of thiolation, highest being "PC 2300" exhibiting 2300.16 ± 149.86 μmol thiol groups per gram of polymer (mean ± SD; n = 3). This newly developed thiolated polymer was evaluated regarding mucoadhesive, rheological and drug release properties as well from the toxicological point of view. Swelling behavior in 100 mM phosphate buffer pH 6.8 was improved up to 180-fold. Furthermore, due to thiolation, the mucoadhesive properties of the polymer were 240-fold improved. Rheological measurements of polymer/mucus mixtures confirmed results obtained by mucoadhesion studies. In comparison to unmodified polymer, PC 2300 showed 2.3-, 2.3- and 2.4-fold increase in dynamic viscosity, elastic modulus and viscous modulus, respectively. Sustained release of the model drug codeine HCl out of the thiomer was provided for 2.5 h (p < 0.05), whereas the drug was immediately released from the unmodified polymer. Moreover, the thiomer was found non-toxic over Caco-2 cells for a period of 6- and 24-h exposure. Findings of the present study provide evidence that due to thiolation LMWPs can be rendered highly mucoadhesive as well as cohesive and that a controlled drug release out of such polymers can be provided.

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.

Mechanochemical Ring-Opening Polymerization of Lactide: Liquid-Assisted Grinding for the Green Synthesis of Poly(lactic acid) with High Molecular Weight.

PubMed

Ohn, Nuri; Shin, Jihoon; Kim, Sung Sik; Kim, Jeung Gon

2017-09-22

Mechanochemical polymerization of lactide is carried out by using ball milling. Mechanical energy from collisions between the balls and the vessel efficiently promotes an organic-base-mediated metal- and solvent-free solid-state polymerization. Investigation of the parameters of the ball-milling synthesis revealed that the degree of lactide ring-opening polymerization could be modulated by the ball-milling time, vibration frequency, mass of the ball media, and liquid-assisted grinding. Liquid-assisted grinding was found to be an especially important factor for achieving a high degree of mechanochemical polymerization. Although polymer-chain scission from the strong collision energy prevented mechanical-force-driven high-molecular-weight polymer synthesis, the addition of only a small amount of liquid enabled sufficient energy dissipation and poly(lactic acid) was thereby obtained with a molecular weight of over 1×10 5  g mol -1 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of comprehensive NMR-based analysis strategy in annotation, isolation and structure elucidation of low molecular weight metabolites of Ricinus communis seeds.

PubMed

Vučković, Ivan; Rapinoja, Marja-Leena; Vaismaa, Matti; Vanninen, Paula; Koskela, Harri

2016-01-01

Powder-like extract of Ricinus communis seeds contain a toxic protein, ricin, which has a history of military, criminal and terroristic use. As the detection of ricin in this "terrorist powder" is difficult and time-consuming, related low mass metabolites have been suggested to be useful for screening as biomarkers of ricin. To apply a comprehensive NMR-based analysis strategy for annotation, isolation and structure elucidation of low molecular weight plant metabolites of Ricinus communis seeds. The seed extract was prepared with a well-known acetone extraction approach. The common metabolites were annotated from seed extract dissolved in acidic solution using (1)H NMR spectroscopy with spectrum library comparison and standard addition, whereas unconfirmed metabolites were identified using multi-step off-line HPLC-DAD-NMR approach. In addition to the common plant metabolites, two previously unreported compounds, 1,3-digalactoinositol and ricinyl-alanine, were identified with support of MS analyses. The applied comprehensive NMR-based analysis strategy provided identification of the prominent low molecular weight metabolites with high confidence. Copyright © 2015 John Wiley & Sons, Ltd.

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

PubMed

Lépinay, Sandrine; Ianoul, Anatoli; Albert, Jacques

2014-10-01

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

Colonic Absorption of Low-Molecular-Weight Metabolites Influenced by the Intestinal Microbiome: A Pilot Study.

PubMed

Matsumoto, Mitsuharu; Ooga, Takushi; Kibe, Ryoko; Aiba, Yuji; Koga, Yasuhiro; Benno, Yoshimi

2017-01-01

Low-molecular-weight metabolites produced by the intestinal microbiome play a direct role in health and disease. However, little is known about the ability of the colon to absorb these metabolites. It is also unclear whether these metabolites are bioavailable. Here, metabolomics techniques (capillary electrophoresis with time-of-flight mass spectrometry, CE-TOFMS), germ-free (GF) mice, and colonized (Ex-GF) mice were used to identify the colonic luminal metabolites transported to colonic tissue and/or blood. We focused on the differences in each metabolite between GF and Ex-GF mice to determine the identities of metabolites that are transported to the colon and/or blood. CE-TOFMS identified 170, 246, 166, and 193 metabolites in the colonic feces, colonic tissue, portal plasma, and cardiac plasma, respectively. We classified the metabolites according to the following influencing factors: (i) the membrane transport system of the colonocytes, (ii) metabolism during transcellular transport, and (iii) hepatic metabolism based on the similarity in the ratio of each metabolite between GF and Ex-GF mice and found 62 and 22 metabolites that appeared to be absorbed from the colonic lumen to colonocytes and blood, respectively. For example, 11 basic amino acids were transported to the systemic circulation from the colonic lumen. Furthermore, many low-molecular-weight metabolites influenced by the intestinal microbiome are bioavailable. The present study is the first to report the transportation of metabolites from the colonic lumen to colonocytes and somatic blood in vivo, and the present findings are critical for clarifying host-intestinal bacterial interactions.

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

PubMed

Esparza-Soto, M; Westerhoff, P K

2001-01-01

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

Low-molecular-weight thiols in streptomycetes and their potential role as antioxidants.

PubMed Central

Newton, G L; Fahey, R C; Cohen, G; Aharonowitz, Y

1993-01-01

The intracellular low-molecular-weight thiols present in five gram-positive Streptomyces species and one Flavobacterium species were analyzed by high-performance liquid chromatography after fluorescence labeling with monobromobimane. Bacteria were chosen to include penicillin and cephalosporin beta-lactam producers and nonproducers. No significant amount of glutathione was found in any of the streptomycetes. Major intracellular thiols in all strains examined were cysteine, coenzyme A, sulfide, thiosulfate, and an unknown thiol designated U17. Those streptomycetes that make beta-lactam antibiotics also produce significant amounts of delta-(L-alpha-aminoadipyl)-L-cysteinyl-D-valine (ACV), a key intermediate in their biosynthesis. In Streptomyces clavuligerus, a potent producer of beta-lactams, the level of ACV was low during the early phase of growth and increased rapidly toward the end of exponential growth, paralleling that of antibiotic production. These and other observations indicate that ACV does not function as a protective thiol in streptomycetes. U17 may have this role since it was the major thiol in all streptomycetes and appeared to occur at levels about 10-fold higher than those of the other thiols measured, including ACV. Purification and amino acid analysis of U17 indicated that it contains cysteine and an unusual amine that is not one of the common amino acids. This thiol is identical to an unknown thiol found previously in Micrococcus roseus and Streptomyces griseus. A high level of ergothioneine was found in Streptomyces lactamdurans, and several unidentified thiols were detected in this and other streptomycetes. PMID:8478335

In vitro fermentation and prebiotic potential of novel low molecular weight polysaccharides derived from agar and alginate seaweeds.

PubMed

Ramnani, Priya; Chitarrari, Roberto; Tuohy, Kieran; Grant, John; Hotchkiss, Sarah; Philp, Kevin; Campbell, Ross; Gill, Chris; Rowland, Ian

2012-02-01

Fermentation properties and prebiotic potential of novel low molecular weight polysaccharides (LMWPs) derived from agar and alginate bearing seaweeds was investigated. Ten LMWPs were supplemented to pH, temperature controlled anaerobic batch cultures inoculated with human feces from three donors, in triplicate. Microbiota changes were monitored using Fluorescent in-situ hybridization and short chain fatty acids, the fermentation end products were analysed using gas chromatography. Of the ten LMWPs tested, Gelidium seaweed CC2253 of molecular weight 64.64 KDa showed a significant increase in bifidobacterial populations from log(10) 8.06 at 0 h to log(10) 8.55 at 24 h (p = 0.018). For total bacterial populations, alginate powder CC2238 produced a significant increase from log(10) 9.01 at 0 h to log(10) 9.58 at 24 h (p = 0.032). No changes were observed in the other bacterial groups tested viz. Bacteroides, Lactobacilli/Enterococci, Eubacterium rectale/Clostridium coccoides and Clostridium histolyticum. The polysaccharides also showed significant increases in total SCFA production, particularly acetic and propionic acids, indicating that they were readily fermented. In conclusion, some LMWPs derived from agar and alginate bearing seaweeds were fermented by gut bacteria and exhibited potential to be used a novel source of prebiotics. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

PubMed

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

2013-02-04

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

Yield, Esterification Degree and Molecular Weight Evaluation of Pectins Isolated from Orange and Grapefruit Peels under Different Conditions

PubMed Central

Sayah, Mohamed Yassine; Chabir, Rachida; Benyahia, Hamid; Rodi Kandri, Youssef; Ouazzani Chahdi, Fouad; Touzani, Hanan; Errachidi, Faouzi

2016-01-01

Orange (Citrus sinensis) and grapefruit (Citrus paradise) peels were used as a source of pectin, which was extracted under different conditions. The peels are used under two states: fresh and residual (after essential oil extraction). Organic acid (citric acid) and mineral acid (sulfuric acid) were used in the pectin extraction. The aim of this study is the evaluation the effect of extraction conditions on pectin yield, degree of esterification “DE” and on molecular weight “Mw”. Results showed that the pectin yield was higher using the residual peels. Moreover, both peels allow the obtainment of a high methoxyl pectin with DE >50%. The molecular weight was calculated using Mark-Houwink-Sakurada equation which describes its relationship with intrinsic viscosity. This later was determined using four equations; Huggins equation, kramer, Schulz-Blaschke and Martin equation. The molecular weight varied from 1.538 x1005 to 2.47x1005 g/mol for grapefruit pectin and from 1.639 x1005 to 2.471 x1005 g/mol for orange pectin. PMID:27644093

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

A first look at the turnover dynamics of low molecular weight organic carbon in shallow and deep soils of coastal prairie grassland ecosystem.

NASA Astrophysics Data System (ADS)

Mcfarland, J. W.; Lawrence, C. R.; Creamer, C.; Conaway, C. H.; Haw, M.; Waldrop, M. P.

2016-12-01

The functional importance of low molecular weight organic compounds (LMWOC) is in disproportion to their abundance within soil organic carbon (SOC) pools. LMWOC are critical in driving microbial metabolism, though microbial utilization is likely dependent on C chemistry. In this study, we examined the fate of two important, often plant-derived, components of soluble SOC: sugars and carboxylic acids, through an extended soil profile. Our objective was to evaluate the short-term (9 d) and long-term (16 mo) turnover dynamics of LMWOC under varying physical, biological, and chemical conditions through the soil column. Our study area is a coastal prairie near Santa Cruz, CA; soils are classified as fine-loamy, mixed thermic typic Argixerolls. The long-term component of this study was conducted in situ and replicated in the laboratory to quantify the short-term dynamics. We injected 13C-labeled glucose (GLU), 13C-labeled oxalic acid (OA), or deionized water into the A, B (argillic), and B/C (mottled) horizons at depths of 25, 75, and 125 cm, respectively. We sampled soil gas for 13CO2 intensively in the lab and at increasingly graduated intervals in the field. At the conclusion of each experiment, soils were harvested to assess total recovery of 13C in soil pools. Measures of extractable C indicated a significant priming effect in the A horizon, and an increase in microbial biomass C (MBC) in the argillic horizon in response to GLU and OA. In all instances, residence time was lower for GLU than OA and increased with depth for both substrates. In the short-term OA- C was mineralized to a greater degree than GLU- C in the A and argillic horizons, but in the deepest (mottled) soil horizon recovery of OA- C was substantially higher, and likely resulted from enhanced organo-metal complexation. Dissolved Al3+, which forms strong aqueous complexes with OA, may limit the availability of OA at depth compared to shallower soils. Long-term recovery favored GLU- C, which increased

Microcystin-LR Detected in a Low Molecular Weight Fraction from a Crude Extract of Zoanthus sociatus

PubMed Central

Domínguez-Pérez, Dany; Alexei Rodríguez, Armando; Osorio, Hugo; Azevedo, Joana; Castañeda, Olga; Vasconcelos, Vítor; Antunes, Agostinho

2017-01-01

Cnidarian constitutes a great source of bioactive compounds. However, research involving peptides from organisms belonging to the order Zoanthidea has received very little attention, contrasting to the numerous studies of the order Actiniaria, from which hundreds of toxic peptides and proteins have been reported. In this work, we performed a mass spectrometry analysis of a low molecular weight (LMW) fraction previously reported as lethal to mice. The low molecular weight (LMW) fraction was obtained by gel filtration of a Zoanthus sociatus (order Zoanthidea) crude extract with a Sephadex G-50, and then analyzed by matrix-assisted laser desorption/ionization time-of-flight/time-of-flight (MALDI-TOF/TOF) mass spectrometry (MS) in positive ion reflector mode from m/z 700 to m/z 4000. Afterwards, some of the most intense and representative MS ions were fragmented by MS/MS with no significant results obtained by Protein Pilot protein identification software and the Mascot algorithm search. However, microcystin masses were detected by mass-matching against libraries of non-ribosomal peptide database (NORINE). Subsequent reversed-phase C18 HPLC (in isocratic elution mode) and mass spectrometry analyses corroborated the presence of the cyanotoxin Microcystin-LR (MC-LR). To the best of our knowledge, this finding constitutes the first report of MC-LR in Z. sociatus, and one of the few evidences of such cyanotoxin in cnidarians. PMID:28257074

Conformations of low-molecular-weight lignin polymers in water

DOE PAGES

Petridis, Loukas; Smith, Jeremy C.

2016-01-13

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

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

PubMed

Petridis, Loukas; Smith, Jeremy C

2016-02-08

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

Study on antithrombotic and antiplatelet activities of low molecular weight fucoidan from Laminaria japonica

NASA Astrophysics Data System (ADS)

Chen, Anjin; Zhang, Fang; Shi, Jie; Zhao, Xue

2012-06-01

The antithrombotic and antiplatelet effects of two fucoidan fractions with low molecular weight and different sulfate content from Laminaria japonica were compared in order to examine the influence of chemical character on their antithrombotic activity and the possible mechanism. Both LMW fucoidan fractions exhibited favorable antithrombotic activity in an Fecl3-induced arterial thrombosis. The antithrombotic activity of LMW fucoidan was related with decrease of TXB2 and whole blood viscosity and hematocrit. LMW fucoidan showed a correlation between anticoagulant, antiaggregant and antithrombotic effects in vivo. For LMW fucoidan, antithrombotic activity required high dose of 5-10 nmol kg-1, concomitantly with increase in anticoagulant activity and inhibition of platelet aggregation. Administration of LMW fucoidan significantly promoted the 6-keto-PGF1α content and decreased the TXB2 content, indicating its inhibition of tissue factor pathway and regulation of metabolism of arachidonic acid. By comparison, highly sulfated fucoidan LF2 with Mw 3900 seemed to be a more suitable choice for antithrombotic drug for its antithrombotic activity accompanied with specific inhibitory activity on platelet aggregation, low anticoagulant activity and low hemorrhagic risk in vivo.

A low molecular weight protein tyrosine phosphatase from Synechocystis sp. strain PCC 6803: enzymatic characterization and identification of its potential substrates

PubMed Central

Mukhopadhyay, Archana; Kennelly, Peter J.

2011-01-01

The predicted protein product of open reading frame slr0328 from Synechocystis sp. PCC 6803, SynPTP, possesses significant amino acid sequence similarity with known low molecular weight protein tyrosine phosphatases (PTPs). To determine the functional properties of this hypothetical protein, open reading frame slr0328 was expressed in Escherichia coli. The purified recombinant protein, SynPTP, displayed its catalytic phosphatase activity towards several tyrosine, but not serine, phosphorylated exogenous protein substrates. The protein phosphatase activity of SynPTP was inhibited by sodium orthovanadate, a known inhibitor of tyrosine phosphatases, but not by okadaic acid, an inhibitor for many serine/threonine phosphatases. Kinetic analysis indicated that the Km and Vmax values for SynPTP towards p-nitrophenyl phosphate are similar to those of other known bacterial low molecular weight PTPs. Mutagenic alteration of the predicted catalytic cysteine of PTP, Cys7, to serine abolished enzyme activity. Using a combination of immunodetection, mass spectrometric analysis and mutagenically altered Cys7SerAsp125Ala-SynPTP, we identified PsaD (photosystem I subunit II), CpcD (phycocyanin rod linker protein) and phycocyanin-α and -β subunits as possible endogenous substrates of SynPTP in this cyanobacterium. These results indicate that SynPTP might be involved in the regulation of photosynthesis in Synechocystis sp. PCC 6803. PMID:21288886

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

PubMed

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

2016-10-01

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

Low molecular weight oligomers of amyloid peptides display β-barrel conformations: A replica exchange molecular dynamics study in explicit solvent

NASA Astrophysics Data System (ADS)

De Simone, Alfonso; Derreumaux, Philippe

2010-04-01

The self-assembly of proteins and peptides into amyloid fibrils is connected to over 40 pathological conditions including neurodegenerative diseases and systemic amyloidosis. Diffusible, low molecular weight protein and peptide oligomers that form in the early steps of aggregation appear to be the harmful cytotoxic species in the molecular etiology of these diseases. So far, the structural characterization of these oligomers has remained elusive owing to their transient and dynamic features. We here address, by means of full atomistic replica exchange molecular dynamics simulations, the energy landscape of heptamers of the amyloidogenic peptide NHVTLSQ from the beta-2 microglobulin protein. The simulations totaling 5 μs show that low molecular weight oligomers in explicit solvent consist of β-barrels in equilibrium with amorphous states and fibril-like assemblies. The results, also accounting for the influence of the pH on the conformational properties, provide a strong evidence of the formation of transient β-barrel assemblies in the early aggregation steps of amyloid-forming systems. Our findings are discussed in terms of oligomers cytotoxicity.

Anticancer, antioxidant, and antibacterial activities of low molecular weight bioactive subfractions isolated from cultures of wood degrading fungus Cerrena unicolor

PubMed Central

Jaszek, Magdalena; Stefaniuk, Dawid; Ciszewski, Tomasz; Matuszewski, Łukasz

2018-01-01

The aim of this study is to investigate in vitro the anticancer, antioxidant, and antibacterial activities of three low molecular weight subfractions I, II and III isolated from secondary metabolites produced by the wood degrading fungus Cerrena unicolor. The present study demonstrated that the low molecular weight subfractions III exhibited the strongest inhibitory activity towards breast carcinoma cells MDA-MB-231, prostatic carcinoma cells PC3, and breast cancer cells MCF7 with the half-maximal inhibitory concentration (IC50) value of 52,25 μg/mL, 60,66 μg/mL, and 54,92 μg/mL, respectively. The highest percentage of inhibition was noted at a concentration of 300 μg/mL in all the examined tumor lines. A significant percentage (59.08%) of ex-LMSIII inhibition of the MDA-MB-231 tumor line was reached at a concentration of 15 μg/ml, while the concentration applied did not affect normal human fibroblast cells. The low molecular weight subfraction III was the most effective and additionally showed the highest free radical 1,1-diphenyl-2-picryl-hydrazyl scavenging activity (IC50 20.39 μg/mL) followed by the low molecular weight subfraction I (IC50 64.14 μg/mL) and II (IC50 49.22 μg/mL). The antibacterial activity of the tested preparations was evaluated against three microorganisms: Bacillus subtilis, Staphylococcus aureus, and Escherichia coli. The MIC minimal inhibitory concentration (MIC) values for the low molecular weight subfraction I, II, and III showed a stronger inhibition effect on S. aureus than on B. subtilis and E. coli cells. The MIC values for the low molecular weight subfraction II against S. aureus, B. subtilis, and E. coli were 6.25, 12.5, and 100 mg/mL, respectively. PMID:29874240

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NO x conditions

DOE PAGES

D'Ambro, Emma L.; Lee, Ben H.; Liu, Jiumeng; ...

2017-01-04

Here, we present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO 2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C 5 compounds were major components (~50%) of SOA. The SOA composition and effective volatility evolved both as amore » function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.« less

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

PubMed

Bijan, Leila; Mohseni, Madjid

2005-10-01

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

Dicarboxylic acids generated by thermal alteration of kerogen and humic acids

NASA Technical Reports Server (NTRS)

Kawamura, Kimitaka; Kaplan, I. R.

1987-01-01

Significant amounts (up to 2 percent of organic geopolymers) of low-molecular-weight (LMW) dicarboxylic acids (C2-C10) have been detected during thermal alteration (270 C, 2 h) of kerogens and humic acids isolated from young or ancient lithified sediments. Their distribution is characterized by the predominance of oxalic acid followed by succinic, fumaric, and methylsuccinic acids. These acids are probably released by the breakdown of macromolecular structures, which have incorporated biogenic organic compounds, including diacids, during early digenesis in sediments. Because of their reactivity, LMW diacids may play geochemically important roles under natural conditions.

Water solubility enhancement of some organic pollutants and pesticides by dissolved humic and fulvic acids

USGS Publications Warehouse

Chiou, C.T.; Malcolm, R.L.; Brinton, T.I.; Kile, D.E.

1986-01-01

Water solubility enhancements by dissolved humic and fulvic acids from soil and aquatic origins and by synthetic organic polymers have been determined for selected organic pollutants and pesticides (p,p???-DDT, 2,4,5,2???,5???-PCB, 2,4,4???-PCB, 1,2,3-trichlorobenzene, and lindane). Significant solubility enhancements of relatively water-insoluble solutes by dissolved organic matter (DOM) of soil and aquatic origins may be described in terms of a partition-like interaction of the the solutes with the microscopic organic environment of the high-molecular-weight DOM species; the apparent solute solubilities increase linearly with DOM concentration and show no competitive effect between solutes. With a given DOM sample, the solute partition coefficient (Kdom) increases with a decrease of solute solubility (Sw) or with an increase of the solute's octanol-water partition coefficient (Kow). The Kdom values of solutes with soil-derived humic acid are approximately 4 times greater than with soil fulvic acid and 5-7 times greater than with aquatic humic and fulvic acids. The effectiveness of DOM in enhancing solute solubility appears to be largely controlled by the DOM molecular size and polarity. The relative inability of high-molecular-weight poly(acrylic acids) to enhance solute solubility is attributed to their high polarities and extended chain structures that do not permit the formation of a sizable intramolecular nonpolar environment.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

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

PubMed

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

2006-03-01

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

Plasma zinc's alter ego is a low-molecular-weight humoral factor.

PubMed

Ou, Ou; Allen-Redpath, Keith; Urgast, Dagmar; Gordon, Margaret-Jane; Campbell, Gill; Feldmann, Jörg; Nixon, Graeme F; Mayer, Claus-Dieter; Kwun, In-Sook; Beattie, John H

2013-09-01

Mild dietary zinc deprivation in humans and rodents has little effect on blood plasma zinc levels, and yet cellular consequences of zinc depletion can be detected in vascular and other tissues. We proposed that a zinc-regulated humoral factor might mediate the effects of zinc deprivation. Using a novel approach, primary rat vascular smooth muscle cells (VSMCs) were treated with plasma from zinc-deficient (<1 mg Zn/kg) or zinc-adequate (35 mg Zn/kg, pair-fed) adult male rats, and zinc levels were manipulated to distinguish direct and indirect effects of plasma zinc. Gene expression changes were analyzed by microarray and qPCR, and incubation of VSMCs with blood plasma from zinc-deficient rats strongly changed the expression of >2500 genes, compared to incubation of cells with zinc-adequate rat plasma. We demonstrated that this effect was caused by a low-molecular-weight (∼2-kDa) zinc-regulated humoral factor but that changes in gene expression were mostly reversed by adding zinc back to zinc-deficient plasma. Strongly regulated genes were overrepresented in pathways associated with immune function and development. We conclude that zinc deficiency induces the production of a low-molecular-weight humoral factor whose influence on VSMC gene expression is blocked by plasma zinc. This factor is therefore under dual control by zinc.

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

PubMed Central

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

2012-01-01

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

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

PubMed

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

2012-01-01

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

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.

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

USGS Publications Warehouse

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

1997-01-01

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

Enhanced characterization of oil sands acid-extractable organics fractions using electrospray ionization-high-resolution mass spectrometry and synchronous fluorescence spectroscopy.

PubMed

Bauer, Anthony E; Frank, Richard A; Headley, John V; Peru, Kerry M; Hewitt, L Mark; Dixon, D George

2015-05-01

The open pit oil sands mining operations north of Fort McMurray, Alberta, Canada, are accumulating tailings waste at a rate approximately equal to 4.9 million m(3) /d. Naphthenic acids are among the most toxic components within tailings to aquatic life, but structural components have largely remained unidentified. In the present study, electrospray ionization high-resolution mass spectrometry (ESI-HRMS) and synchronous fluorescence spectroscopy (SFS) were used to characterize fractions derived from the distillation of an acid-extractable organics (AEO) mixture isolated from oil sands process-affected water (OSPW). Mean molecular weights of each fraction, and their relative proportions to the whole AEO extract, were as follows: fraction 1: 237 Da, 8.3%; fraction 2: 240 Da, 23.8%; fraction 3: 257 Da, 26.7%; fraction 4: 308 Da, 18.9%; fraction 5: 355 Da, 10.0%. With increasing mean molecular weight of the AEO fractions, a concurrent increase occurred in the relative abundance of nitrogen-, sulfur-, and oxygen-containing ions, double-bond equivalents, and degree of aromaticity. Structures present in the higher-molecular-weight fractions (fraction 4 and fraction 5) suggested the presence of heteroatoms, dicarboxyl and dihydroxy groups, and organic acid compounds with the potential to function as estrogens. Because organic acid compositions become dominated by more recalcitrant, higher-molecular-weight acids during natural degradation, these findings are important in the context of oil sands tailings pond water remediation. © 2015 SETAC.

Effect of low molecular weight heparin rectal suppository on experimental ulcerative colitis in mice.

PubMed

Luo, Junyong; Cao, Jichao; Jiang, Xueliang; Cui, Huifei

2010-09-01

The objective of this study was to investigate the effect and possible mechanism of rectally administered low molecular weight heparin (LMWH) on experimental ulcerative colitis. LMWH rectal suppository was prepared and its efficacy was studied by macroscopical and histological scoring systems as well as myeloperoxidase activity. Serum levels, including tumor necrosis factor-α (TNFα), interleukin-6 (IL-6) and a link factor of blood coagulation and inflammation factor Xa (FXa) were assayed by enzyme-linked immunosorbent assay. The expression of Musashi-1 (as an intestinal stem cell marker) in the colons was assessed by immunohistochemical analysis. The results showed that LMWH rectal suppository significantly decreased serum levels of TNF-α, IL-6 as well as FXa, while increased the expression of Musashi-1 in colon compared with acetic acid induced ulcerative colitis model group. All these preliminary results indicate LMWH rectal suppository is promising for treatment of ulcerative colitis. 2010 Elsevier Masson SAS. All rights reserved.

Thermally annealed gold nanoparticles for surface-assisted laser desorption ionisation-mass spectrometry of low molecular weight analytes.

PubMed

Pilolli, Rosa; Ditaranto, Nicoletta; Di Franco, Cinzia; Palmisano, Francesco; Cioffi, Nicola

2012-10-01

Metal nanomaterials have an emerging role in surface-assisted laser desorption ionisation-mass spectrometry (SALDI-MS) providing a useful tool to overcome some limitations intrinsically related to the use of conventional organic matrices in matrix-assisted LDI-MS. In this contribution, the possibility to use a stainless-steel-supported gold nanoparticle (AuNP) film as a versatile platform for SALDI-MS was assessed. A sacrificial anode electrosynthetic route was chosen in order to obtain morphologically controlled core-shell AuNPs; the colloidal AuNPs were, thereafter, drop cast onto a stainless-steel sample plate and the resulting AuNP film was thermally annealed in order to improve its effectiveness as LDI-MS promoter. Spectroscopic characterization of the nanostructured film by X-ray photoelectron spectroscopy was crucial for understanding how annealing induced changes in the surface chemistry and influenced the performance of AuNPs as desorption/ionisation promoter. In particular, it was demonstrated that the post-deposition treatments were essential to enhance the AuNP core/analyte interaction, thus resulting in SALDI-MS spectra of significantly improved quality. The AuNP films were applied to the detection of three different classes of low molecular weight (LMW) analytes, i.e. amino acids, peptides and LMW polymers, in order to demonstrate the versatility of this nanostructured material.

Laser-based methods for the analysis of low molecular weight compounds in biological matrices.

PubMed

Kiss, András; Hopfgartner, Gérard

2016-07-15

Laser-based desorption and/or ionization methods play an important role in the field of the analysis of low molecular-weight compounds (LMWCs) because they allow direct analysis with high-throughput capabilities. In the recent years there were several new improvements in ionization methods with the emergence of novel atmospheric ion sources such as laser ablation electrospray ionization or laser diode thermal desorption and atmospheric pressure chemical ionization and in sample preparation methods with the development of new matrix compounds for matrix-assisted laser desorption/ionization (MALDI). Also, the combination of ion mobility separation with laser-based ionization methods starts to gain popularity with access to commercial systems. These developments have been driven mainly by the emergence of new application fields such as MS imaging and non-chromatographic analytical approaches for quantification. This review aims to present these new developments in laser-based methods for the analysis of low-molecular weight compounds by MS and several potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

The low-molecular-weight fraction of exopolysaccharide II from Sinorhizobium meliloti is a crucial determinant of biofilm formation.

PubMed

Rinaudi, Luciana V; González, Juan E

2009-12-01

Sinorhizobium meliloti is a soil bacterium that elicits the formation of root organs called nodules on its host plant, Medicago sativa. Inside these structures, the bacteria are able to convert atmospheric nitrogen into ammonia, which is then used by the plant as a nitrogen source. The synthesis by S. meliloti of at least one exopolysaccharide, succinoglycan or EPS II, is essential for a successful symbiosis. While exopolysaccharide-deficient mutants induce the formation of nodules, they fail to invade them, and as a result, no nitrogen fixation occurs. Interestingly, the low-molecular-weight fractions of these exopolysaccharides are the symbiotically active forms, and it has been suggested that they act as signals to the host plant to initiate infection thread formation. In this work, we explored the role of these rhizobial exopolysaccharides in biofilm formation and their importance in the symbiotic relationship with the host. We showed that the ExpR/Sin quorum-sensing system controls biofilm formation in S. meliloti through the production of EPS II, which provides the matrix for the development of structured and highly organized biofilms. Moreover, the presence of the low-molecular-weight fraction of EPS II is vital for biofilm formation, both in vitro and in vivo. This is the first report where the symbiotically active fraction of EPS II is shown to be a critical factor for biofilm formation and root colonization. Thus, the ability of S. meliloti to properly attach to root surfaces and form biofilms conferred by the synthesis of exopolysaccharides may embody the main function of these symbiotically essential molecules.

Development of gel-filter method for high enrichment of low-molecular weight proteins from serum.

PubMed

Chen, Lingsheng; Zhai, Linhui; Li, Yanchang; Li, Ning; Zhang, Chengpu; Ping, Lingyan; Chang, Lei; Wu, Junzhu; Li, Xiangping; Shi, Deshun; Xu, Ping

2015-01-01

The human serum proteome has been extensively screened for biomarkers. However, the large dynamic range of protein concentrations in serum and the presence of highly abundant and large molecular weight proteins, make identification and detection changes in the amount of low-molecular weight proteins (LMW, molecular weight ≤ 30kDa) difficult. Here, we developed a gel-filter method including four layers of different concentration of tricine SDS-PAGE-based gels to block high-molecular weight proteins and enrich LMW proteins. By utilizing this method, we identified 1,576 proteins (n = 2) from 10 μL serum. Among them, 559 (n = 2) proteins belonged to LMW proteins. Furthermore, this gel-filter method could identify 67.4% and 39.8% more LMW proteins than that in representative methods of glycine SDS-PAGE and optimized-DS, respectively. By utilizing SILAC-AQUA approach with labeled recombinant protein as internal standard, the recovery rate for GST spiked in serum during the treatment of gel-filter, optimized-DS, and ProteoMiner was 33.1 ± 0.01%, 18.7 ± 0.01% and 9.6 ± 0.03%, respectively. These results demonstrate that the gel-filter method offers a rapid, highly reproducible and efficient approach for screening biomarkers from serum through proteomic analyses.

Low-molecular-weight heparin biosimilars: potential implications for clinical practice. Australian Low-Molecular-Weight Heparin Biosimilar Working Group (ALBW).

PubMed

Nandurkar, H; Chong, B; Salem, H; Gallus, A; Ferro, V; McKinnon, R

2014-05-01

A working group of clinicians and scientists was formed to review the clinical considerations for use of low-molecular-weight heparin (LMWH) biosimilars. LMWH are biological molecules of significant complexity; the full complexity of chemical structure is still to be elucidated. LMWH biosimilars are products that are biologically similar to their reference product and rely on clinical data from a reference product to establish safety and efficacy. The complex nature of LMWH molecules means that it is uncertain whether a LMWH biosimilar is chemically identical to its reference product; this introduces the possibility of differences in activity and immunogenicity. The challenge for regulators and clinicians is to evaluate the level of evidence required to demonstrate that a LMWH is sufficiently similar to the reference product. The consensus opinion of the working group is that prior to clinical use a LMWH biosimilar should have proven efficacy and safety, similar to the reference product with prospective studies, which should be confirmed with a proactive post-marketing pharmacovigilance programme. © 2014 The Authors; Internal Medicine Journal © 2014 Royal Australasian College of Physicians.

[The low-molecular weight antioxidants of microorganisms].

PubMed

Skorokhod, I O; Kurdysh, I K

2014-01-01

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

Hydrophilic interaction chromatography-multiple reaction monitoring mass spectrometry method for basic building block analysis of low molecular weight heparins prepared through nitrous acid depolymerization.

PubMed

Sun, Xiaojun; Guo, Zhimou; Yu, Mengqi; Lin, Chao; Sheng, Anran; Wang, Zhiyu; Linhardt, Robert J; Chi, Lianli

2017-01-06

Low molecular weight heparins (LMWHs) are important anticoagulant drugs that are prepared through depolymerization of unfractionated heparin. Based on the types of processing reactions and the structures of the products, LMWHs can be divided into different classifications. Enoxaparin is prepared by benzyl esterification and alkaline depolymerization, while dalteparin and nadroparin are prepared through nitrous acid depolymerization followed by borohydride reduction. Compositional analysis of their basic building blocks is an effective way to provide structural information on heparin and LMWHs. However, most current compositional analysis methods have been limited to heparin and enoxaparin. A sensitive and comprehensive approach is needed for detailed investigation of the structure of LMWHs prepared through nitrous acid depolymerization, especially their characteristic saturated non-reducing end (NRE) and 2,5-anhydro-d-mannitol reducing end (RE). A maltose modified hydrophilic interaction column offers improved separation of complicated mixtures of acidic disaccharides and oligosaccharides. A total of 36 basic building blocks were unambiguously identified by high-resolution tandem mass spectrometry (MS). Multiple reaction monitoring (MRM) MS/MS quantification was developed and validated in the analysis of dalteparin and nadroparin samples. Each group of building blocks revealed different aspects of the properties of LMWHs, such as functional motifs required for anticoagulant activity, the structure of heparin starting materials, cleavage sites in the depolymerization reaction, and undesired structural modifications resulting from side reactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular and functional characterization of the American cockroach, Periplaneta americana, Rab5: the first exopterygotan low molecular weight ovarian GTPase during oogenesis.

PubMed

Elmogy, Mohamed; Mohamed, Amr A; Tufail, Muhammad; Uno, Tomohide; Takeda, Makio

2017-05-26

The small Rab GTPases are key regulators of membrane vesicle trafficking. Ovaries of Periplaneta americana (Linnaeus) (Blattodea: Blattidae) have small molecular weight GTP/ATP-binding proteins during early and late vitellogenic periods of oogenesis. However, the identification and characterization of the detected proteins have not been yet reported. Herein, we cloned a cDNA encoding Rab5 from the American cockroach, P. americana, ovaries (PamRab5). It comprises 796 bp, encoding a protein of 213 amino acid residues with a predicted molecular weight of 23.5 kDa. PamRab5 exists as a single-copy gene in the P. americana genome, as revealed by Southern blot analysis. An approximate 2.6 kb ovarian mRNA was transcribed especially at high levels in the previtellogenic ovaries, detected by Northern blot analysis. The muscle and head tissues also showed high levels of PamRab5 transcript. PamRab5 protein was localized, via immunofluorescence labeling, to germline-derived cells of the oocytes, very early during oocyte differentiation. Immunoblotting detected a ∼25 kDa signal as a membrane-associated form revealed after application of detergent in the extraction buffer, and 23 kDa as a cytosolic form consistent with the predicted molecular weight from amino acid sequence in different tissues including ovary, muscles and head. The PamRab5 during late vitellogenic periods is required to regulate the endocytotic machinery during oogenesis in this cockroach. This is the first report on Rab5 from a hemimetabolan, and presents an inaugural step in probing the molecular premises of insect oocyte endocytotic trafficking important for oogenesis and embryonic development. © 2017 Institute of Zoology, Chinese Academy of Sciences.

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.

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.

Release of low molecular weight silicones and platinum from silicone breast implants.

PubMed

Lykissa, E D; Kala, S V; Hurley, J B; Lebovitz, R M

1997-12-01

We have conducted a series of studies addressing the chemical composition of silicone gels from breast implants as well as the diffusion of low molecular weight silicones (LM-silicones) and heavy metals from intact implants into various surrounding media, namely, lipid-rich medium (soy oil), aqueous tissue culture medium (modified Dulbecco's medium, DMEM), or an emulsion consisting of DMEM plus 10% soy oil. LM-silicones in both implants and surrounding media were detected and quantitated using gas chromatography (GC) coupled with atomic emission (GC-AED) as well as mass spectrometric (GC/MS) detectors, which can detect silicones in the nanogram range. Platinum, a catalyst used in the preparation of silicone gels, was detected and quantitated using inductive argon-coupled plasma/mass spectrometry (ICP-MS), which can detect platinum in the parts per trillion range. Our results indicate that GC-detectable low molecular weight silicones contribute approximately 1-2% to the total gel mass and consist predominantly of cyclic and linear poly-(dimethylsiloxanes) ranging from 3 to 20 siloxane [(CH3)2-Si-O] units (molecular weight 200-1500). Platinum can be detected in implant gels at levels of approximately 700 micrograms/kg by ICP-MS. The major component of implant gels appears to be high molecular weight silicone polymers (HM-silicones) too large to be detected by GC. However, these HM-silicones can be converted almost quantitatively (80% by mass) to LM-silicones by heating implant gels at 150-180 degrees C for several hours. We also studied the rates at which LM-silicones and platinum leak through the intact implant outer shell into the surrounding media under a variety of conditions. Leakage of silicones was greatest when the surrounding medium was lipid-rich, and up to 10 mg/day LM-silicones was observed to diffuse into a lipid-rich medium per 250 g of implant at 37 degrees C. This rate of leakage was maintained over a 7-day experimental period. Similarly, platinum was

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

PubMed

Greening, David W; Simpson, Richard J

2017-01-01

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

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

PubMed Central

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

2016-01-01

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

Rheological Properties of Gels from Pyrene Based Low Molecular Weight Gelators

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

Leivo, Kimmo T.; Hahma, Arno P.

2008-07-07

Gels of pyrene derived low molecular weight organogelators (LMOGs) in primary alcohols have been characterized by rheometry and scanning electron microscopy. Total gelator concentration was 1-2.7 % w/w depending on the solvent and the gelator, including equimolar amounts of the gelator and 2,4,7-trinitrofluorenone (TNF), which is necessary for gelation. Thermoreversible and strongly shear thinning gels were achieved as the two components interact non-covalently to form a gel network. A qualitative correlation between the rheological properties and the nanoscale gel structure were found.

Rheological Properties of Gels from Pyrene Based Low Molecular Weight Gelators

NASA Astrophysics Data System (ADS)

Leivo, Kimmo T.; Hahma, Arno P.

2008-07-01

Gels of pyrene derived low molecular weight organogelators (LMOGs) in primary alcohols have been characterized by rheometry and scanning electron microscopy. Total gelator concentration was 1-2.7 % w/w depending on the solvent and the gelator, including equimolar amounts of the gelator and 2,4,7-trinitrofluorenone (TNF), which is necessary for gelation. Thermoreversible and strongly shear thinning gels were achieved as the two components interact non-covalently to form a gel network. A qualitative correlation between the rheological properties and the nanoscale gel structure were found.

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…

Production of High Molecular Weight Organic Compounds on the Surfaces of Amorphous Iron Silicate Catalysts: Implications for Organic Synthesis in the Solar Nebula

NASA Technical Reports Server (NTRS)

Gilmour, I.; Hill, H. G. M.; Pearson, V. K.; Sephton, M. A.; Nuth, J. A., III

2002-01-01

The high molecular weight organic products of Fischer-Tropsch/Haber-Bosch syntheses on the surfaces of Fe-silicate catalysts have been studied by GCMS. Additional information is contained in the original extended abstract.

Approaches for the analysis of low molecular weight compounds with laser desorption/ionization techniques and mass spectrometry.

PubMed

Bergman, Nina; Shevchenko, Denys; Bergquist, Jonas

2014-01-01

This review summarizes various approaches for the analysis of low molecular weight (LMW) compounds by different laser desorption/ionization mass spectrometry techniques (LDI-MS). It is common to use an agent to assist the ionization, and small molecules are normally difficult to analyze by, e.g., matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) using the common matrices available today, because the latter are generally small organic compounds themselves. This often results in severe suppression of analyte peaks, or interference of the matrix and analyte signals in the low mass region. However, intrinsic properties of several LDI techniques such as high sensitivity, low sample consumption, high tolerance towards salts and solid particles, and rapid analysis have stimulated scientists to develop methods to circumvent matrix-related issues in the analysis of LMW molecules. Recent developments within this field as well as historical considerations and future prospects are presented in this review.

Microwave-assisted organic acid extraction of lignin from bamboo: structure and antioxidant activity investigation.

PubMed

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

2012-10-01

Microwave-assisted extraction in organic acid aqueous solution (formic acid/acetic acid/water, 3/5/2, v/v/v) was applied to isolate lignin from bamboo. Additionally, the structural features of the extracted lignins were thoroughly investigated in terms of C₉ formula, molecular weight distribution, FT-IR, (1)H NMR and HSQC spectroscopy. It was found that with an increase in the severity of microwave-assisted extraction, there was an increase of phenolic hydroxyl content in the lignin. In addition, an increase of the severity resulted in a decrease of the bound carbohydrate content as well as molecular weight of the lignin. Antioxidant activity investigation indicated that the radical scavenging index of the extracted lignins (0.35-1.15) was higher than that of BHT (0.29) but lower than that of BHA (3.85). The results suggested that microwave-assisted organic acid extraction provides a promising way to prepare lignin from bamboo with good antioxidant activity for potential application in the food industry. Copyright © 2012 Elsevier Ltd. All rights reserved.

Seasonal variations, molecular distributions, and stable carbon isotopic compositions of dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls in PM2.5 from Beijing, China

NASA Astrophysics Data System (ADS)

Zhao, W.; Kawamura, K.; Fu, P.

2016-12-01

Low molecular weight (LMW) dicarboxylic acids and related polar compounds comprise a significant fraction of atmospheric aerosols. Seasonal variations, molecular distributions, and stable carbon isotopic compositions of dicarboxylic acids, ketocarboxylic acids, and α-dicarbonyls, as well as organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC) and inorganic ionic species, were determined to better understand the sources and photochemical aging processes of carbonaceous aerosols in urban Beijing from Sept. 2013 to Jul. 2014 (n=65). Concentrations of total diacids ranged from 110-2580 ng m-3, while ketoacids (9.5-353 ng m-3) and dicarbonyls (1.5-85.9 ng m-3) were less abundant. Higher ambient concentrations of phthalic (Ph) (37.9±27.3 ng m-3), terephthalic (tPh) (48.7±51.1 ng m-3), and glyoxylic (ωC2) (44.3±69 ng m-3) acids were found in winter than other seasons. The temporal variations of malonic acid to succinic acid (C3/C4) ratios were relatively low throughout the whole year, most of which were less than or equal to unity, even in summer, implying more contributions of dicarboxylic acids from primary emissions, rather than aging processes during long-range atmospheric transport. The δ13C mean values of malonic acid (-18.7% to -17.3%) and succinic acid (-28.6% to -17.1%) were larger than those of oxalic acid (-22.9% to -20.1%) in both seasons, except for δ13C of succinic acid in summer. Lower δ13C values of these compounds in Beijing than those in marine areas may be mainly associated with primary emissions, such as biomass burning, vehicular exhaust, incomplete fossil fuel combustion and plastic wastes.

Low-Molecular-Weight Protein Tyrosine Phosphatase Predicts Prostate Cancer Outcome by Increasing the Metastatic Potential.

PubMed

Ruela-de-Sousa, Roberta R; Hoekstra, Elmer; Hoogland, A Marije; Queiroz, Karla C Souza; Peppelenbosch, Maikel P; Stubbs, Andrew P; Pelizzaro-Rocha, Karin; van Leenders, Geert J L H; Jenster, Guido; Aoyama, Hiroshi; Ferreira, Carmen V; Fuhler, Gwenny M

2016-04-01

Low-risk patients suffering from prostate cancer (PCa) are currently placed under active surveillance rather than undergoing radical prostatectomy. However, clear parameters for selecting the right patient for each strategy are not available, and new biomarkers and treatment modalities are needed. Low-molecular-weight protein tyrosine phosphatase (LMWPTP) could present such a target. To correlate expression levels of LMWPTP in primary PCa to clinical outcome, and determine the role of LMWPTP in prostate tumor cell biology. Acid phosphatase 1, soluble (ACP1) expression was analyzed on microarray data sets, which were subsequently used in Ingenuity Pathway Analysis. Immunohistochemistry was performed on a tissue microarray containing material of 481 PCa patients whose clinicopathologic data were recorded. PCa cell line models were used to investigate the role of LMWPTP in cell proliferation, migration, adhesion, and anoikis resistance. The association between LMWPTP expression and clinical and pathologic outcomes was calculated using chi-square correlations and multivariable Cox regression analysis. Functional consequences of LMWPTP overexpression or downregulation were determined using migration and adhesion assays, confocal microscopy, Western blotting, and proliferation assays. LMWPTP expression was significantly increased in human PCa and correlated with earlier recurrence of disease (hazard ratio [HR]:1.99; p<0.001) and reduced patient survival (HR: 1.53; p=0.04). Unbiased Ingenuity analysis comparing cancer and normal prostate suggests migratory propensities in PCa. Indeed, overexpression of LMWPTP increases PCa cell migration, anoikis resistance, and reduces activation of focal adhesion kinase/paxillin, corresponding to decreased adherence. Overexpression of LMWPTP in PCa confers a malignant phenotype with worse clinical outcome. Prospective follow-up should determine the clinical potential of LMWPTP overexpression. These findings implicate low-molecular-weight

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.

Stabilization of coacervate systems by products of abiogenic oxidation of low-molecular-weight compounds using the energy of. gamma. radiation

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

Evreinova, T.N.; Kuzin, A.M.; Kryukova, L.M.

1976-01-01

The purpose of the study was to determine the possibility of stabilization of protein-carbohydrate and protein-nucleic acid systems by products of the abiogenic oxidation of pyrocatechol, pyrogallol, and o-dianisidine using the energy of gamma radiation. The protein-nucleic acid system was produced by mixing the following reagents: histone, DNA, acetate buffer, and a solution of oxidized compounds. The protein-carbohydrate system was produced by mixing the following reagents: histone, gum arabic, acetate buffer, and a solution of oxidized compounds. Results indicated that the stabilization of coacervate systems occurs when stabilizing low-molecular-weight compounds of the type of quinones and the imino form ofmore » o-dianisidine are included in them. These compounds may be formed under the action of physical factors without the participation of enzymes. (HLW)« less

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

PubMed

Balch, J; Guéguen, C

2015-01-01

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

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

NASA Technical Reports Server (NTRS)

Gange, Robert Allen (Inventor)

1977-01-01

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

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.

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

PubMed

Xu, Lu; Liu, Lei; Li, Xinjian

2017-11-01

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

Competitive stereocomplexation, homocrystallization, and polymorphic crystalline transition in poly(L-lactic acid)/poly(D-lactic acid) racemic blends: molecular weight effects.

PubMed

Pan, Pengju; Han, Lili; Bao, Jianna; Xie, Qing; Shan, Guorong; Bao, Yongzhong

2015-05-28

Competitive crystallization kinetics, polymorphic crystalline structure, and transition of poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic blends with a wide range of molecular weights (MWs) were symmetrically investigated. Stereocomplex (sc) crystallites are exclusively formed in the low-MW racemic blends. However, stereocomplexation is remarkably depressed, and homocrystallization becomes prevailing with increasing MWs of PLLA and PDLA. Suppressed stereocomplexation in high-MW (HMW) racemic blends is proposed to be due to the low chain diffusion ability and restricted intermolecular crystal nucleation/growth. Equilibrium melting point of sc crystallites first increases and then decreases as MW increases. Crystallinity and relative fraction of sc crystallites in racemic blends enhance with crystallization temperature (Tc), and the sc crystallites are merely formed at Tc > 170 °C because of their higher thermodynamic stability. In situ wide-angle X-ray diffraction (WAXD) analysis reveals that the stereocomplexation and homocrystallization are successive rather than completely simultaneous, and the stereocomplexation is preceding homocrystallization in isothermal crystallization of HMW racemic blends. Both initial crystalline structure of homocrystallites (hc) and MW influence the heating-induced hc-to-sc transition of HMW racemic blend drastically; the hc-to-sc transition becomes easier with decreasing Tc and MW. After crystallization at the same temperature, sc crystallites show smaller long period than their hc counterparts.

Isolation of hydrophilic organic acids from water using nonionic macroporous resins

USGS Publications Warehouse

Aiken, G.R.; McKnight, Diane M.; Thorn, K.A.; Thurman, E.M.

1992-01-01

A method has been developed for the isolation of hydrophilic organic acids from aquatic environments using Amberlite* * Use of trade names in this report is for identification purposes only and does not constitute endorsement by the U.S. Geological Survey. XAD-4 resin. The method uses a two column array of XAD-8 and XAD-4 resins in series. The hydrophobic organic acids, composed primarily of aquatic fulvic acid, are removed from the sample on XAD-8, followed by the isolation of the more hydrophilic organic acids on XAD-4. For samples from a number of diverse environments, more of the dissolved organic carbon was isolated on the XAD-8 resin (23-58%) than on the XAD-4 resin (7-25%). For these samples, the hydrophilic acids have lower carbon and hydrogen contents, higher oxygen and nitrogen contents, and are lower in molecular weight than the corresponding fulvic acids. 13C NMR analyses indicate that the hydrophilic acids have a lower concentration of aromatic carbon and greater heteroaliphatic, ketone and carboxyl content than the fulvic acid. ?? 1992.

Analysis of low molecular weight metabolites in tea using mass spectrometry-based analytical methods.

PubMed

Fraser, Karl; Harrison, Scott J; Lane, Geoff A; Otter, Don E; Hemar, Yacine; Quek, Siew-Young; Rasmussen, Susanne

2014-01-01

Tea is the second most consumed beverage in the world after water and there are numerous reported health benefits as a result of consuming tea, such as reducing the risk of cardiovascular disease and many types of cancer. Thus, there is much interest in the chemical composition of teas, for example; defining components responsible for contributing to reported health benefits; defining quality characteristics such as product flavor; and monitoring for pesticide residues to comply with food safety import/export requirements. Covered in this review are some of the latest developments in mass spectrometry-based analytical techniques for measuring and characterizing low molecular weight components of tea, in particular primary and secondary metabolites. The methodology; more specifically the chromatography and detection mechanisms used in both targeted and non-targeted studies, and their main advantages and disadvantages are discussed. Finally, we comment on the latest techniques that are likely to have significant benefit to analysts in the future, not merely in the area of tea research, but in the analytical chemistry of low molecular weight compounds in general.

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

PubMed

McGlory, Chris; Morton, James P

2010-10-01

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