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1

Structure and function studies on enzymes with a catalytic carboxyl group(s): from ribonuclease T1 to carboxyl peptidases  

PubMed Central

A group of enzymes, mostly hydrolases or certain transferases, utilize one or a few side-chain carboxyl groups of Asp and/or Glu as part of the catalytic machinery at their active sites. This review follows mainly the trail of studies performed by the author and his colleagues on the structure and function of such enzymes, starting from ribonuclease T1, then extending to three major types of carboxyl peptidases including aspartic peptidases, glutamic peptidases and serine-carboxyl peptidases. PMID:23759941

TAKAHASHI, Kenji

2013-01-01

2

Adsorption of water vapor and carbon dioxide at carboxylic functional groups on the surface of coal  

Microsoft Academic Search

The adsorption of water vapor and carbon dioxide at room temperature in relation to carboxylic functional groups on the surfaces of 20 different types of coal was examined.The carboxylic functional groups on the surface of coal may be considered the preferential sites of adsorption when compared with the other groups. The adsorption of water vapor and carbon dioxide was found

J Nishino

2001-01-01

3

Carboxyl Group (?CO2 H) Functionalized Coordination Polymer Nanoparticles as Efficient Platforms for Drug Delivery.  

PubMed

Functionalization of nanoparticles can significantly influence their properties and potential applications. Although researchers can now functionalize metal, metal oxide, and organic polymer nanoparticles with a high degree of precision, controlled surface functionalization of nanoscale coordination polymer particles (CPPs) has remained a significant challenge. The lack of methodology is perhaps one of the greatest roadblocks to the advancement of CPPs into high added-value drug delivery applications. Here, we report having achieved this goal through a stepwise formation and functionalization protocol. We fabricated robust nanoparticles with enhanced thermal and colloidal stabilities by incorporation of carboxyl groups and these surface carboxyl groups could be subsequently functionalized through well-known peptide coupling reactions. The set of chemistries that we employed as proof-of-concept enabled a plethora of new functional improvements for the application of CPPs as drug delivery carriers, including enhanced colloidal stabilities and the incorporation of additional functional groups such as polyethylene glycol (PEG) or fluorescent dyes that enabled tracking of their cellular uptake. Finally, we ascertained the cytotoxicity of the new CPP nanoparticles loaded with camptothecin to human breast adenocarcinoma (MCF-7). Efflux measurements show that the encapsulation of camptothecin enhances the potency of the drug 6.5-fold and increases the drug retention within the cell. PMID:25284328

Novio, Fernando; Lorenzo, Julia; Nador, Fabiana; Wnuk, Karolina; Ruiz-Molina, Daniel

2014-11-17

4

Selected Functionality Changes of ?-Lactoglobulin upon Esterification of Side-Chain Carboxyl Groups  

Microsoft Academic Search

Free carboxyl groups of bovine ~34actoglobulin were esterified with meth- anol, ethanol, and n-butanol. The modified proteins showed increased positive charge as the number of ionizable carboxyl groups was reduced. The methyl, ethyl, and butyl esters of ~-lactoglobulin showed enhanced surface activity, determined with surface and interfacial tension measurements at an air\\/water and oil\\/ water interface, respectively. The methyl ester

Margaret I. Halpin; T. Richardson

1985-01-01

5

Functional carboxyl groups in the red cell anion exchange protein. Modification with an impermeant carbodiimide  

PubMed Central

Anion exchange in human red blood cell membranes was inactivated using the impermeant carbodiimide 1-ethyl-3-(4-azonia-4,4-dimethylpentyl)- carbodiimide (EAC). The inactivation time course was biphasic: at 30 mM EAC, approximately 50% of the exchange capacity was inactivated within approximately 15 min; this was followed by a phase in which irreversible exchange inactivation was approximately 100-fold slower. The rate and extent of inactivation was enhanced in the presence of the nucleophile tyrosine ethyl ester (TEE), suggesting that the inactivation is the result of carboxyl group modification. Inactivation (to a maximum of 10% residual exchange activity) was also enhanced by the reversible inhibitor of anion exchange 4,4'-dinitrostilbene-2,2'- disulfonate (DNDS) at concentrations that were 10(3)-10(4) times higher than those necessary for inhibition of anion exchange. The extracellular binding site for stilbenedisulfonates is essentially intact after carbodiimide modification: the irreversible inhibitor of anion exchange 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS) eliminated (most of) the residual exchange activity: DNDS inhibited the residual (DIDS-sensitive) Cl- at concentrations similar to those that inhibit Cl- exchange of unmodified membranes: and Cl- efflux is activated by extracellular Cl-, with half-maximal activation at approximately 3 mM Cl-, which is similar to the value for unmodified membranes. But the residual anion exchange function after maximum inactivation is insensitive to changes of extra- and intracellular pH between pH 5 and 7. The titratable group with a pKa of approximately 5.4, which must be deprotonated for normal function of the native anion exchanger, thus appears to be lost after EAC modification. PMID:2738575

1989-01-01

6

Adsorption of pesticidal compounds bearing a single carboxyl functional group and biogenic amines by humic fraction-immobilized silica gel.  

PubMed

Fractions collected from humic acids under acidic and basic conditions were immobilized on silica gel and used as adsorbents for a variety of agricultural pesticide compounds bearing a single carboxyl functional group and biogenic amines in acetonitrile. Among these compounds examined under the same conditions, the percentage of adsorption varies considerably from 0 to almost 100%. The percentage is found to be highly related to the structure of the analyte and the type of functional group attached to it. The adsorption, better performed on adsorbent immobilized with the fraction collected under acidic conditions, is believed to result from the reversible interaction between the functional moieties of the analyte and humic acids (e.g., amino or carboxyl group of analyte vs carboxyl group of humic acids, etc.) as no adsorption is observed under the same conditions for analytes that are derivatives of alcohol, amide, and ester. Given the nature of the analyte, the time needed to reach the maximum percent of adsorption decreases as the amount of adsorbent is increased. Also, the longer the time that has elapsed, the higher the percentage of analyte adsorbed, thus indicating that the adsorption process is surface-oriented. Factors such as the acidic or basic origin of the additive in the liquid phase of the matrix also affect the percentage of analyte adsorbed. PMID:23521499

Chen, Cheng-Sheng; Chen, Shushi

2013-04-17

7

Effect of Carboxylic Functional Group Functionalized on Carbon Nanotubes Surface on the Removal of Lead from Water  

PubMed Central

The adsorption mechanism of the removal of lead from water by using carboxylic functional group (COOH) functionalized on the surface of carbon nanotubes was investigated. Four independent variables including pH, CNTs dosage, contact time, and agitation speed were carried out to determine the influence of these parameters on the adsorption capacity of the lead from water. The morphology of the synthesized multiwall carbon nanotubes (MWCNTs) was characterized by using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) in order to measure the diameter and the length of the CNTs. The diameters of the carbon nanotubes were varied from 20 to 40?nm with average diameter at 24?nm and 10 micrometer in length. Results of the study showed that 100% of lead was removed by using COOH-MCNTs at pH 7, 150?rpm, and 2 hours. These high removal efficiencies were likely attributed to the strong affinity of lead to the physical and chemical properties of the CNTs. The adsorption isotherms plots were well fitted with experimental data. PMID:21350599

Atieh, Muataz Ali; Bakather, Omer Yehya; Al-Tawbini, Bassam; Bukhari, Alaadin A.; Abuilaiwi, Faraj Ahmad; Fettouhi, Mohamed B.

2010-01-01

8

Cyclopentane-1,3-dione: A Novel Isostere for the Carboxylic Acid Functional Group. Application to the Design of Potent Thromboxane (A2)-Receptor Antagonists  

PubMed Central

Cyclopentane-1,3-diones are known to exhibit pKa values typically in the range of carboxylic acids. To explore the potential of the cyclopentane-1,3-dione unit as a carboxylic acid isostere, the physical-chemical properties of representative congeners were examined and compared with similar derivatives bearing carboxylic acid or tetrazole residues. These studies suggested that cyclopentane-1,3-diones may effectively substitute for the carboxylic acid functional group. To demonstrate the use of the cyclopentane-1,3-dione isostere in drug-design, derivatives of a known thromboxane-A2 prostanoid (TP) receptor antagonist, 3-(3-(2-(4-chlorophenylsulfonamido)ethyl)-phenyl)propanoic acid (12), were synthesized and evaluated in both functional and radioligand-binding assays. A series of mono- and di-substituted cyclopentane-1,3-dione derivatives (41–45) were identified that exhibit nM IC50 and Kd values similar to 12. Collectively, these studies demonstrate that the cyclopentane-1,3-dione moiety comprises a novel isostere of the carboxylic acid functional group. Given the combination of the relatively strong acidity, tunable lipophilicity, and versatility of the structure, the cyclopentane-1,3-dione moiety may constitute a valuable addition to the palette of carboxylic acid isosteres. PMID:21863799

Ballatore, Carlo; Soper, James; Piscitelli, Francesco; James, Michael; Huang, Longchuan; Atasoylu, Onur; Huryn, Donna M.; Trojanowski, John Q.; Lee, Virginia M.-Y.; Brunden, Kurt R.; Smith, Amos B.

2011-01-01

9

Carboxyl group participation in sulfate and sulfamate group transfer reactions  

SciTech Connect

The pH dependence for the hydrolysis of N-(2-carboxyphenyl)sulfamic acid exhibits a plateau region corresponding to participation of the carboxyl function. A normal deuterium oxide solvent isotope effect indicates that proton transfer from the carboxylic acid is concerted with sulfamate group transfer to water. Hydrolysis of salicylic sulfate and N-(2-carboxyphenyl)sulfamate in /sup 18/O-enriched water yields salicylic acid and anthranilic acids with no enrichment, excluding catalysis by neighboring nucleophilic attack on sulfur by the carboxylate group. Intermolecular catalysis by carboxylic acids is demonstrated in the hydrolysis of N-(1-naphthyl)sulfamic acid; the mechanism is shown to involve preequilibrium protonation of the nitrogen followed by nucleophilic attack on sulfur by the carboxylate anion. Fast decomposition of the acyl sulfate completes the hydrolysis; this mechanism is considered to be the most efficient but is excluded in the intramolecular case which is constrained by the electronic requirements of displacement at the sulfur atom (6-ENDO-tet).

Hopkins, A.; Williams, A.

1982-04-23

10

An integrative technique based on synergistic coremoval and sequential recovery of copper and tetracycline with dual-functional chelating resin: roles of amine and carboxyl groups.  

PubMed

A novel chelating resin (R-AC) bearing dual-functional groups (amino and carboxyl groups) was self-synthesized and it showed superior properties on synergistic coremoval of Cu(II) and tetracycline (TC) to commercial resins (amine, carboxyl, and hydrophobic types), which was deeply investigated by equilibrium and kinetic tests in binary, preloading, and saline systems. The adsorption of TC on R-AC was markedly enhanced when coexisted with Cu(II), up to 13 times of that in sole system, whereas Cu(II) uptake seldom decreased in the copresence of TC. Decomplexing-bridging, which included [Cu-TC] decomplexing and [R-Cu] bridging for TC, was demonstrated as the leading mechanism for the synergistic coremoval of Cu(II) and TC. Carboxyl groups of R-AC played a dominant role in decomplexing of [Cu-TC] complex and releasing free TC. Cu(II) coordinated with amine groups of R-AC was further proved to participate in bridging interaction with free TC, and the bridging stoichiometric ratio ([NH-Cu]: TC) possibly was 2:1. About 96.9% of TC and 99.3% of Cu could be sequentially recovered with dilute NaOH followed by HCl. Considering stable application for five cycles in simulated and practical wastewater, R-AC shows great potential in green and simple coremoval of antibiotic and heavy metal ions. PMID:24168359

Ling, Chen; Liu, Fu-Qiang; Xu, Chao; Chen, Tai-Peng; Li, Ai-Min

2013-11-27

11

Functionality Distribution of Carboxyl and Hydroxyl-Terminated Polybutadiene  

Microsoft Academic Search

Elurion from silica gel was used to fractionate liquid polymers according to the number of chemically reactive groups per molecule (the functionality). Methods are presented for the functionality fractionation of high and low functionality carboxyl-terminated polybutadiene (CTPB). Results are also given on the fractionation of low functionality hydroxyl-terminated polybutadiene (HTPB) and of high functionality HTPB using a new elution series

M. S. Chang; D. M. French; P. L. Rogers

1973-01-01

12

Hybrid nanoparticles for drug delivery and bioimaging: mesoporous silica nanoparticles functionalized with carboxyl groups and a near-infrared fluorescent dye.  

PubMed

The development of a drug delivery system with fluorescent biolabels is important in anti-cancer drug delivery application due to the potential for simultaneous diagnosis and treatment of diseases. Here, we reported the synthesis and multiple functionalization of mesoporous silica nanoparticle (MSN) for bioimaging and controlled drug release. After the functionalization with carboxyl group, the nanoparticles exhibited much better dispersity and stability in aqueous solution than MSN. Furthermore, a substantial doxorubicin (DOX) loading level was achieved and DOX-loaded nanoparticles exhibited noticeable pH-sensitive behavior with accelerated release of DOX in acidic environment. Compared with native DOX-MSN, DOX-MSN/COOH-Cy5 exhibited enhanced intracellular uptake efficacy and stronger effect on killing tumor cells. Meanwhile, it was observed that the MSN/COOH-Cy5 was able to locate in the cytoplasm of MCF-7 cells and could accumulate in tumor tissues for a long period of time. Overall, the functional nanoparticle could potentially be used for simultaneous controlled drug release and near-infrared fluorescent bioimaging. PMID:23394807

Xie, Meng; Shi, Hui; Ma, Kun; Shen, Haijun; Li, Bo; Shen, Song; Wang, Xinshi; Jin, Yi

2013-04-01

13

Site identification of carboxyl groups on graphene edges with Pt derivatives.  

PubMed

Although chemical functionalization at carboxyl groups of nanocarbons has been vigorously investigated and the identities and quantities of the carboxyl groups have been well studied, the location of carboxyl groups had not previously been clarified. Here, we show that site identification of carboxyl groups is possible by using Pt-ammine complex as a stain. After Pt-ammine complexes were mixed with graphenes in ethanol, many Pt-ammine complex clusters with an average size of about 0.6 nm were found to exist at edges of graphene sheets, indicating that the carboxyl groups mainly existed at the graphene edges. These results will make it easier to add functionalities by chemical modifications for various applications of nanotubes and other nanocarbons. PMID:19206426

Yuge, Ryota; Zhang, Minfang; Tomonari, Mutsumi; Yoshitake, Tsutomu; Iijima, Sumio; Yudasaka, Masako

2008-09-23

14

Differences in Cytocompatibility Between MWCNTs and Carboxylic Functionalized MWCNTs  

NASA Astrophysics Data System (ADS)

Influence of carboxylic functionalization on the cytocompatibility of multiwalled carbon nanotubes (MWCNTs) was investigated in this work. Water contact angle assay showed that the surface of MWCNTs-containing carboxyl (MWCNTs-COOH) became much more hydrophilic compared with pure MWCNTs. In cell-adhesion assays, two cell lines, mouse fibroblast cells (L929) and human umbilical vein endothelial cells (EAHY926) were used to assess the cytocompatibility of materials. The MWCNTs-COOH displayed the improved cell proliferation, viability and adhesion due to the enhanced wettability, indicating their superior cytocompatibility over MWCNTs. The existence of carboxyl groups should be benefit to the adhesion and growth of both cells, which implied that MWCNTs-COOH were helpful for seeding both cells and could be used as the functional surface for the adhesion and growth of cells.

Zhang, Yiteng; Li, Dejun; Zhao, Mengli; Guo, Meixian; Deng, Xiangyun; Gu, Hanqing; Wan, Rongxin

2013-02-01

15

Characterization and diagenesis of strong-acid carboxyl groups in humic substances  

USGS Publications Warehouse

A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

Leenheer, J. A.; Wershaw, R. L.; Brown, G. K.; Reddy, M. M.

2003-01-01

16

IDENTIFICATION AND QUANTIFICATION OF AEROSOL POLAR OXYGENATED COMPOUNDS BEARING CARBOXYLIC AND/OR HYDROXYL GROUPS. 1. METHOD DEVELOPMENT  

EPA Science Inventory

In this study, a new analytical technique was developed for the identification and quantification of multi-functional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) ...

17

Improved antifouling properties of polyamide nanofiltration membranes by reducing the density of surface carboxyl groups.  

PubMed

Carboxyls are inherent functional groups of thin-film composite polyamide nanofiltration (NF) membranes, which may play a role in membrane performance and fouling. Their surface presence is attributed to incomplete reaction of acyl chloride monomers during the membrane active layer synthesis by interfacial polymerization. In order to unravel the effect of carboxyl group density on organic fouling, NF membranes were fabricated by reacting piperazine (PIP) with either isophthaloyl chloride (IPC) or the more commonly used trimesoyl chloride (TMC). Fouling experiments were conducted with alginate as a model hydrophilic organic foulant in a solution, simulating the composition of municipal secondary effluent. Improved antifouling properties were observed for the IPC membrane, which exhibited lower flux decline (40%) and significantly greater fouling reversibility or cleaning efficiency (74%) than the TMC membrane (51% flux decline and 40% cleaning efficiency). Surface characterization revealed that there was a substantial difference in the density of surface carboxyl groups between the IPC and TMC membranes, while other surface properties were comparable. The role of carboxyl groups was elucidated by measurements of foulant-surface intermolecular forces by atomic force microscopy, which showed lower adhesion forces and rupture distances for the IPC membrane compared to TMC membranes in the presence of calcium ions in solution. Our results demonstrated that a decrease in surface carboxyl group density of polyamide membranes fabricated with IPC monomers can prevent calcium bridging with alginate and, thus, improve membrane antifouling properties. PMID:23205860

Mo, Yinghui; Tiraferri, Alberto; Yip, Ngai Yin; Adout, Atar; Huang, Xia; Elimelech, Menachem

2012-12-18

18

?-Functionalization of Carboxylic Anhydrides with ?-Alkyl Substituents through Carbene Organocatalysis.  

PubMed

The first NHC-catalyzed functionalization of carboxylic anhydrides is described. In this reaction, the ??carbon behaves as a nucleophilic carbon and undergoes asymmetric reactions with electrophiles. Anhydrides with challenging ?-alkyl substituents work effectively. PMID:25284248

Jin, Zhichao; Chen, Shaojin; Wang, Yuhuang; Zheng, Pengcheng; Yang, Song; Chi, Yonggui Robin

2014-12-01

19

Functionalized carboxyl nanoparticles enhance mucus dispersion and hydration  

NASA Astrophysics Data System (ADS)

Luminal accumulation of viscous, poorly hydrated, and less transportable mucus has been associated with altered mucus rheology and reduced mucociliary clearance. These symptoms are some of the cardinal clinical manifestations found throughout major respiratory diseases as well as gastrointestinal and digestive disorders. Applications of current mucolytics may yield short-term improvements but are continuously challenged by undesirable side-effects. While nanoparticles (NPs) can interact with mucin polymers, whether functionalized NPs can rectify mucus rheology is unknown. Herein, we report that carboxyl-functionalized NPs (24 nm and 120 nm) dramatically reduced mucin gel size and accelerated mucin matrix hydration rate (diffusivity). Our results suggest that carboxyl-functionalized NPs disperse mucin gels possibly by enhancing network hydration. This report highlights the prospective usages of carboxyl-functionalized NPs as a novel mucus dispersant or mucolytic agent in adjusting mucus rheological properties and improving mucociliary transport to relieve clinical symptoms of patients suffering from relevant diseases.

Chen, Eric Y.; Daley, David; Wang, Yung-Chen; Garnica, Maria; Chen, Chi-Shuo; Chin, Wei-Chun

2012-01-01

20

Thermal stability of cellulose and their nanoparticles: Effect of incremental increases in carboxyl and aldehyde groups.  

PubMed

Oxidized cellulose containing carboxyl and aldehyde functional groups represent an important class of cellulose derivatives. In this study effect of incrementally increasing COOH and CHO groups at C2, C3, and C6 positions of cellulose and nanocellulose has been investigated, with a view to understanding their effect on thermal treatment of cellulose. The results show that 2,3-dialdehyde cellulose (DAC) is the most thermally stable oxidized product of cellulose while the most unstable derivatives contain carboxyl group at the C6 position (6CC). Carboxymethylcellulose (CMC), with carboxymethyl group on C6 position, is more stable than 6CC. Multi-functionalized celluloses 2,3,6-tricarboxycellulose and 6-carboxy-2,3-dialdehyde, have the same level of thermal stability as 6CC, showing that the presence of carboxyl at the C6 is a key destabilizing factor in the thermal stability of oxidized cellulose products. More the number of reducing end groups on the polymer chain, lower the thermal stability of the cellulose, as proved by comparing the TGA/DTG of monomeric analogs dextrose, cellobiose and glucuronic acid with the oxidized celluloses. The thermal stability trend observed for oxidized celluloses was DAC>DCC>nanoparticles>dextrose>glucuronic acid, caused by extent of reducing ends and COOH groups. PMID:25263899

Sharma, Priyanka R; Varma, Anjani J

2014-12-19

21

New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups  

NASA Astrophysics Data System (ADS)

We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.

Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

2011-09-01

22

New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups  

NASA Astrophysics Data System (ADS)

We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.

Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

2011-05-01

23

Water Sorption to Hydroxyl and Carboxylic Acid Groups in Carboxymethylcellulose (CMC) Studied with NIR-spectroscopy  

Microsoft Academic Search

In carbohydrate systems which contain polar groups such as hydroxyl and carboxylic acid groups, water molecules are adsorbed in a specific way which varies with the type of polar group. Near infrared Spectroscopy (NIR) combined with multivariate statistical analysis was used to study the interactions between water molecules and carboxymethylated cellulose (CMC) with various degrees of substitution of the carboxylic

Jesper Berthold; Ralf J. O. Olsson; Lennart Salmén

1998-01-01

24

Pancreatic Function in Carboxyl-Ester Lipase Knockout Mice  

Microsoft Academic Search

Background\\/Aims:CEL-MODY is a monogenic form of diabetes and exocrine pancreatic insufficiency due to mutations in the carboxyl-ester lipase (CEL) gene. We aimed to investigate endocrine and exocrine pancreatic function in CEL knockout mice (CELKO). Methods: A knockout mouse model with global targeted deletion of CEL was investigated physiologically and histopathologically, and compared to littermate control CEL+\\/+ mice at 7 and

Mette Vesterhus; Helge Ræder; Amarnath J. Kurpad; Dan Kawamori; Anders Molven; Rohit N. Kulkarni; C. Ronald Kahn; Pål Rasmus Njølstad

2010-01-01

25

Electrosynthesis and comparative studies on carboxyl-functionalized polythiophene derivatives  

Microsoft Academic Search

Electrochemical synthesis of a novel carboxylic acid functionalized polythiophene – poly(3-thiophene-butyric-acid), PTBA – has been realized. Its morphology, electrochemical, spectral and conducting properties have been compared to those of poly(3-thiophene-acetic-acid), PTAA, which is widely used to immobilise both bioactive molecules and inorganic nanoparticles. According to scanning electron microscopic (SEM) images, the difference in the real and geometric surface area of

Péter S. Tóth; Csaba Janáky; Zoltán Hiezl; Csaba Visy

2011-01-01

26

Density functional theory study of the oligomerization of carboxylic acids.  

PubMed

We present a density functional theory [M06-2X/6-31+G(d,p)] study of the structures and free energies of formation of oligomers of four carboxylic acids (formic acid, acetic acid, tetrolic acid, and benzoic acid) in water, chloroform, and carbon tetrachloride. Solvation effects were treated using the SMD continuum solvation model. The low-lying energy structures of molecular complexes were located by adopting an efficient search procedure to probe the potential energy surfaces of the oligomers of carboxylic acids (CA)n (n = 2-6). The free energies of the isomers of (CA)n in solution were determined as the sum of the electronic energy, vibrational-rotational-translational gas-phase contribution, and solvation free energy. The assessment of the computational protocol adopted in this study with respect to the dimerization of acetic acid, (AA)2, and formic acid, (FA)2, located new isomers of (AA)2 and (FA)2 and gave dimerization constants in good agreement with the experimental values. The calculation of the self-association of acetic acid, tetrolic acid, and benzoic acid shows the following: (i) Classic carboxylic dimers are the most stable isomer of (CA)2 in both the gas phase and solution. (ii) Trimers of carboxylic acid are stable in apolar aprotic solvents. (iii) Molecular clusters consisting of two interacting classic carboxylic dimers (CA)4,(D+D) are the most stable type of tetramers, but their formation from the self-association of classic carboxylic dimers is highly unfavorable. (iv) For acetic acid and tetrolic acid the reactions (CA)2 + 2CA ? (CA)4,(D+D) and (CA)3 + CA ? (CA)4,(D+D) are exoergonic, but these aggregation pathways go through unstable clusters that could hinder the formation of tetrameric species. (v) For tetrolic acid the prenucleation species that are more likely to form in solution are dimeric and trimeric structures that have encoded structural motifs resembling the ? and ? solid forms of tetrolic acid. (vi) Stable tetramers of benzoic acid could form in carbon tetrachloride from the aggregation of trimers and monomers. (vii) Higher order clusters such as acetic acid pentamers and tetrolic acid hexamers are highly unstable in all solvation environments. PMID:25357019

Di Tommaso, Devis; Watson, Ken L

2014-11-20

27

Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 1. Method development.  

PubMed

In this study, a new analytical technique was developed for the identification and quantification of multifunctional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) of the multifunctional compound using an alcohol (e.g., methanol, 1-butanol) in the presence of a relatively strong Lewis acid (BF3) as a catalyst. This esterification reaction quickly and quantitatively converts carboxylic acids to their ester forms. The second step is based on silylation of the ester compounds using bis(trimethylsilyl) trifluoroacetamide (BSTFA) as the derivatizing agent. For compounds bearing ketone groups in addition to carboxylic and hydroxyl groups, a third step was used based on PFBHA derivatization of the carbonyls. Different parameters including temperature, reaction time, and effect due to artifacts were optimized. A GC/MS in EI and in methane-CI mode was used for the analysis of these compounds. The new approach was tested on a number of multifunctional compounds. The interpretation of their EI (70 eV) and CI mass spectra shows that critical information is gained leading to unambiguous identification of unknown compounds. For example, when derivatized only with BF(3)-methanol, their mass spectra comprise primary ions at m/z M.+ + 1, M.+ + 29, and M.+ - 31 for compounds bearing only carboxylic groups and M.+ + 1, M.+ + 29, M.+ - 31, and M+. - 17 for those bearing hydroxyl and carboxylic groups. However, when a second derivatization (BSTFA) was used, compounds bearing hydroxyl and carboxylic groups simultaneously show, in addition to the ions observed before, ions at m/z M.+ + 73, M.+ - 15, M.+ - 59, M.+ - 75, M.+ - 89, and 73. To the best of our knowledge, this technique describes systematically for the first time a method for identifying multifunctional oxygenated compounds containing simultaneously one or more hydroxyl and carboxylic acid groups. PMID:15307788

Jaoui, M; Kleindienst, T E; Lewandowski, M; Edney, E O

2004-08-15

28

Polycarboxylation of carbon nanofibers under Friedel-Crafts condition: A simple route to direct binding of carboxylic functionalities to graphitic ?-system  

NASA Astrophysics Data System (ADS)

The functionalization of carbon nanofibers (CNFs) with oxalyl chloride, via Friedel-Crafts reaction in the presence of aluminum chloride, was first demonstrated as an efficient way to introduce carboxyl groups onto the nanofiber sidewalls. Octa-aminophenylsilsesquioxane (OASQ) was then covalently attached to the carboxylated nanocarbon CNF-(COOH)n through amide linkage. Taking into account the nature of the electrophilic aromatic substitution, this chemical functionalization may involve formation of conjugated carboxylic acid moiety. Structural analysis combined with electron microscopy observation of the robust octasilsesquioxane species show that carboxyl groups are uniformly distributed on the nanofibers surface.

Wu, Jiancheng; Cai, Hualun; Xu, Kai; Fu, Zien; Liu, Xin; Chen, Mingcai; Zhang, Xiuju

2012-11-01

29

Measuring the concentration of carboxylic acid groups in torrefied spruce wood.  

PubMed

Torrefaction is moderate thermal treatment (?200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction. PMID:22940339

Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

2012-11-01

30

Cowpea mosaic virus for material fabrication: addressable carboxylate groups on a programmable nanoscaffold.  

PubMed

For the first time, decoration of surface-exposed carboxylate groups on Cowpea mosaic virus particles is reported, thus increasing the number and types of addressable surface groups on this nanoscaffold. First, the addressabilty of carboxylates was demonstrated using a carboxylate-selective fluorescent dye, N-cyclohexyl-N'-(4-(dimethylamino)naphthyl)carbodiimide. Second, it was shown that the virions can be decorated with approximately 180 redox active, methyl(aminopropyl)viologen moieties by coupling to the surface carboxylates. The display of multiple redox centers on the virus particle surface may lead to the development of novel electron-transfer mediators in redox catalysis, to biosensors, and to nanoelectronic devices such as molecular batteries. PMID:16584217

Steinmetz, Nicole F; Lomonossoff, George P; Evans, David J

2006-04-11

31

Fabrication of carboxylic functionalized superparamagnetic mesoporous silica microspheres and their application for removal basic dye pollutants from water  

Microsoft Academic Search

Superparamagnetic mesoporous silica microspheres embedded with a silica-coated superparamagnetic iron oxide nanoparticles core and mesoporous silica shell have been prepared using stearyltrimethyl ammonium bromide (STAB) as surfactant template. The superparamagnetic mesoporous silica microspheres then were modified with anhydride functionalized silane to graft carboxylic groups and developed for removing basic dye pollutants, e.g., Methylene Blue (MB) and Acridine Orange (AO) from

Xucheng Fu; Xing Chen; Jin Wang; Jinhuai Liu

2011-01-01

32

Group Type Analysis of Carboxylic Acids Formed by Degradation of i-Dodecane and Kerosene with Nitric Acid  

Microsoft Academic Search

Quantitative analysis of carboxylic acids formed by diluent degradation with nitric acid was investigated by group type analysis.Based on Beer-Lambert's law and alkaline titration, the apparent molar extinction coefficient (E max) for C=0 stretching vibration (vc=0: 1,694 cm) of carboxylic acids in degraded diluents was determined to be 620±20 mole·\\/·cm. Using this value, the concentrations of carboxylic acids formed under

Ken OHWADA

1967-01-01

33

Preferential Interaction of Na+ over K+ to Carboxylate-functionalized Silver Nanoparticles  

EPA Science Inventory

Elucidating mechanistic interactions between specific ions (Na+/ K+) and nanoparticle surfaces to alter particle stability in polar media has received little attention. We investigated relative preferential binding of Na+ and K+ to carboxylate-functionalized silver nanoparticles ...

34

Nonlinear-optical properties of ?-diiminedithiolatonickel(II) complexes enhanced by electron-withdrawing carboxyl groups.  

PubMed

We report the synthesis, characterization, nonlinear-optical (NLO) properties, and density functional theory (DFT) calculations for three nickel diiminedithiolate complexes [Ni(4,4'-R2carboxy-bpy)(L)] [R = methyl, L = 1,2-benzenedithiolate (bdt), 1; R = ethyl, L = 5,6-dihydro-1,4-dithine-2,3-dithiolate (dddt), 2; R = ethyl, L = 1-(N-methylindol-5-yl)ethene-1,2-dithiolate (mi-5edt), 3]. The crystal structure of 1 shows a square-planar coordination for the nickel ion and bond distances consistent with a diiminedithiolate description for the complex. For all complexes, the cyclic voltammetry measurements show two reversible reduction processes (-1.353/-1.380 V and -0798/-0.830 V, respectively) and an anodic wave (+0.372/+0.601 V). The UV-vis spectra present a band around 600-700 nm (? = 4880-6000 dm(3) mol(-1) cm(-1)) mainly attributed to a charge-transfer highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) transition, which shows a large negative solvatochromic shift, characteristic of push-pull complexes, and is responsible for the NLO properties of these molecules. The charge-transfer character of this electronic transition is confirmed by DFT calculations, with the HOMO mainly centered on the dithiolate moiety and the LUMO on the bpy ligand, with important contribution given by the carboxyl groups (?13%). Small contributions from the nickel(II) ion are present in both of the frontier orbitals. The carboxyl groups enhance the optical properties of this class of complexes, confirmed by comparison with the corresponding unsubstituted compounds. The second-order NLO properties have been measured by an electric-field-induced second-harmonic-generation technique using a 10(-3) M solution in N,N-dimethylformamide and working with a 1.907 ?m incident wavelength, giving for ??1.907 (??0) values of -1095 (-581), -2760 (-954), and -1650 (-618) × 10(-48) esu for 1-3, respectively. These values are among the highest in the class of square-planar push-pull complexes, similar to those found for dithionedithiolate compounds. Moreover, spectroelectrochemical experiments demonstrate the possibility of using these complexes as redox-switchable NLO chromophores. PMID:24762131

Pilia, Luca; Pizzotti, Maddalena; Tessore, Francesca; Robertson, Neil

2014-05-01

35

Preparation and Characterization of Poly(methyl methacrylate)-functionalized Carboxyl Multi-walled Carbon Nanotubes  

NASA Astrophysics Data System (ADS)

An in situ polymerization process was used to prepare poly (methyl methacrylate) (PMMA)-functionalized carboxyl multi-walled carbon nanotubes using carboxylate carbon nanotubes and methyl methacrylate as reactants and benzoyl peroxide as an initiator agent. The functionalized multi-walled carbon nanotubes were characterized using transmission electron microscope, scanning electron microscope, nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis and Raman. The results indicate that the PMMA chains are covalently linked with the surface of carboxylate carbon nanotubes. The surface morphology is controlled by the content of carboxylate carbon nanotubes in the reactants. The PMMA functionalized multi-walled carbon nanotubes are soluble in deuterated chloroform. The storage modulus and tan? magnitude increase as the content of CCNTs increases up to 0.3%.

Meng, Qing-jie; Zhang, Xing-xiang; Bai, Shi-he; Wang, Xue-chen

2007-12-01

36

Electrochemical properties of polyolefin nonwoven fabric modified with carboxylic acid group for battery separator  

Microsoft Academic Search

Carboxylic acid group was introduced by radiation-induced grafting of acrylic acid (AAc) onto polyolefine nonwoven fabric (PNF), wherein the PNF comprises at least about 60% of a polyethylene having a melting temperature at ~132°C and no more than about 40% of a second polypropylene having a lower melting temperature at ~162°C, for a battery separator. The AAc-grafted PNF was characterized

S.-H. Choi; H.-J. Kang; E.-N. Ryu; K.-P. Lee

2001-01-01

37

Introduction of carboxylic acid group to polypropylene fabric for battery separator  

Microsoft Academic Search

Carboxylic acid group was introduced by radiation-induced grafting of acrylic acid (AAc) onto a polypropylene (PP) nonwoven\\u000a fabric for a battery separator. The AAc-grafted PP nonwoven fabric was characterized by IR, SEM, and TGA. The wetting speed,\\u000a electrolyte retention, electrical resistance, and tensile strength were evaluated after grafting of AAc. It was found that\\u000a the wetting speed, electrolyte retention, thickness,

Seong-Ho Choi; Young Chang Nho

1999-01-01

38

Electrochemical properties of polyolefin nonwoven fabric modified with carboxylic acid group for battery separator  

Microsoft Academic Search

Carboxylic acid group was introduced by radiation-induced grafting of acrylic acid (AAc) onto polyolefine nonwoven fabric (PNF), wherein the PNF comprises at least about 60% of a polyethylene having a melting temperature at ?132°C and no more than about 40% of a second polypropylene having a lower melting temperature at ?162°C, for a battery separator. The AAc-grafted PNF was characterized

Seong-Ho Choi; Hae-Jeong Kang; Eun-Nyoung Ryu; Kwang-Pill Lee

2001-01-01

39

Two types of essential carboxyl groups in Rhodospirillum rubrum proton ATPase.  

PubMed

Two different types of essential carboxyl groups were detected in the extrinsic component of the proton ATPase of Rhodospirillum rubrum. Chemical modification of R. rubrum chromatophores or its solubilized ATPase by Woodward's reagent K resulted in inactivation of photophosphorylating and ATPase activities. The apparent order of reaction was nearly 1 with respect to reagent concentration and similar K1 were obtained for the soluble and membrane-bound ATPases suggesting that inactivation was associated with modification of one essential carboxyl group located in the soluble component of the proton ATPase. Inactivation was prevented by adenine nucleotides but not by divalent cations. Dicyclohexylcarbodiimide completely inhibited the solubilized ATPase with a K1 of 5.2 mM and a K2 of 0.81 min-1. Mg2+ afforded nearly complete protection with a Kd of 2.8 mM. Two moles of [14C]dicyclohexylcarbodiimide were incorporated per mole of enzyme for complete inactivation but in the presence of 30 mM MgCl2 only one mole was incorporated and there was no inhibition. The labeling was recovered mostly from the beta subunit. The incorporation of the labeled reagent into the ATPase was not prevented by previous modification with Woodward's reagent K. It is concluded that both reagents modified two different essential carboxyl groups in the soluble ATPase from R. rubrum. PMID:6307154

Ceccarelli, E; Vallejos, R H

1983-07-01

40

Factors determining the pKa values of the ionizable groups in proteins: their intrinsic pKas and the effects of hydrogen bonding on buried carboxyl groups  

E-print Network

electrostatic interactions with other groups in the crystal structure, the perturbations on the pKas of these groups are small, demonstrating that surface charged groups typically are only marginally perturbed, due to high exposure to solvent. Charge... lysozyme between His31 and Asp70 results in highly perturbed pKas for both groups. The carboxyl group oxygens of the Asp70 side chain are ~81% buried and the imidazole nitrogens are ~87% buried. The interatomic distance between the carboxyl group...

Thurlkill, Richard Lee

2007-04-25

41

One-step preparation and pH-tunable self-aggregation of amphoteric aliphatic polycarbonates bearing plenty of amine and carboxyl groups.  

PubMed

This paper reports a novel amphoteric aliphatic polycarbonate bearing both amine and carboxyl groups. In the absence of protection-deprotection chemistry, the multi-functionalized copolymer is synthesized by one-step enzymatic copolymerization. The influences of the reaction conditions including monomer feed ratio and polymerization time are explored. The simultaneous incorporation of amine and carboxyl functionalities provides the copolymer with a pH-tunable self-aggregation feature, leading to various aggregation states including precipitated agglomerate, well-dispersed positively or negatively charged nanoparticles in a controlled manner. The copolymer displays minimal cytotoxicity to 293T and HeLa cells. PMID:23076737

Wang, Hua-Fen; Jia, Hui-Zhen; Zhu, Jing-Yi; Chu, Yan-Feng; Feng, Jun; Zhang, Xian-Zheng; Zhuo, Ren-Xi

2012-12-01

42

Specific effects of surface carboxyl groups on anionic polystyrene particles in their interactions with mesenchymal stem cells.  

PubMed

Nanoparticle uptake by living cells is governed by chemical interactions between functional groups on the nanoparticle as well as the receptors on cell surfaces. Here we have investigated the uptake of anionic polystyrene (PS) nanoparticles of ?100 nm diameter by mesenchymal stem cells (MSCs) using spinning-disk confocal optical microscopy combined with a quantitative analysis of the fluorescence images. Two types of anionic PS nanoparticles with essentially identical sizes and ?-potentials were employed in this study, carboxyl-functionalized nanoparticles (CPS) and plain PS nanoparticles, both coated with anionic detergent for stabilization. CPS nanoparticles were observed to internalize more rapidly and accumulate to a much higher level than plain PS nanoparticles. The relative importance of different uptake mechanisms for the two types of nanoparticles was investigated by using specific inhibitors. CPS nanoparticles were internalized mainly via the clathrin-mediated mechanism, whereas plain PS nanoparticles mainly utilized the macropinocytosis pathway. The pronounced difference in the internalization behavior of CPS and plain PS nanoparticles points to a specific interaction of the carboxyl group with receptors on the cell surface. PMID:21409242

Jiang, Xiue; Musyanovych, Anna; Röcker, Carlheinz; Landfester, Katharina; Mailänder, Volker; Nienhaus, G Ulrich

2011-05-01

43

Micelle ionization degree of anionic gemini surfactant having N,N -dialkylamide and carboxylate groups  

Microsoft Academic Search

The critical micelle concentration (cmc) behavior in aqueous NaCl solutions of the anionic gemini surfactant N,N?-ethylenebis(sodium N-dodecanoyl-?-alanate), (CH2)2[N-(COC11H23)CH2CH2(CO2Na)]2 (212), having N,N-dialkylamide and carboxylate groups in a molecule was investigated to measure the value of micelle ionization degree (?).\\u000a For comparison, the behavior of sodium N-dodecanoyl-N-methyl-?-alanate (SDMA), a monomer corresponding to 212, also was investigated. The ? value obtained from the

Kazuyuki Tsubone; Soumen Ghosh

2003-01-01

44

Polymer-Sensitized Solar Cells Using Polythiophene Derivatives with Directly Attached Carboxylic Acid Groups  

NASA Astrophysics Data System (ADS)

Polythiophene derivatives with carboxylic acid groups directly attached to the thiophene rings were synthesized for polymer-sensitized solar cells (PSSCs). The polymer layer densely and uniformly covering the surface of the TiO2 particle in the photoanode of the PSSCs allows excitons to diffuse to the polymer/TiO2 interface efficiently. The PSSCs yielded a maximum incident photon-to-current conversion efficiency of about 80% at 480 nm and the open-circuit voltage (VOC) values but also short-circuit current density (JSC) values increased with decreasing hydrolysis ratio of the polymer.

Akitsu, Kenta; Kubo, Takaya; Uchida, Satoshi; Segawa, Hiroshi; Otani, Naoki; Tomura, Misayo; Tamura, Takayuki; Matsumura, Mitsunobu

2012-10-01

45

Synthesis and characterization of a novel carboxyl group containing (co)polyimide with sulfur in the polymer backbone  

PubMed Central

Summary Soluble functional (co)polyimides are of great interest in the area of separation processes or optical applications, due to their excellent mechanical-, thermal- and optical properties, their superior processability and the ability to adapt their properties to a wide range of special applications. Therefore, two series of novel (co)polyimides containing fluorinated sulfur- and carboxylic acid groups consisting of 4,4?-(hexafluoroisopropylidene)di(phthalic anhydride) (6FDA), 3,5-diaminobenzoic acid (DABA), 4,4?-diaminodiphenylsulfide (4,4?-SDA) and 3,3?-diaminodiphenylsulfone (3,3?-DDS) were synthesized in a two-step polycondensation reaction. The synthesized copolymers were characterized by using NMR, FTIR, GPC, and DSC. Furthermore, with regard to processing and potential applications, the thermal stability, solubility in common organic solvents, moisture uptake, and transparency were investigated. Compared to commercially available transparent polymers, i.e., polymethylmethacrylate and cycloolefin polymers, the sulfur (co)polyimides containing carboxyl groups showed much higher glass-transition temperatures, comparably low moisture uptake and high transmission at the sodium D-line. Furthermore, good solubility in commonly used organic solvents makes them very attractive as high-performance coating materials. PMID:23015826

Mrsevic, Miroslav; Dusselberg, David

2012-01-01

46

Synthesis of novel functional polyolefin containing carboxylic acid via Friedel–Crafts acylation reaction  

Microsoft Academic Search

The strong polar group, carboxylic acid, has triumphantly been introduced into ethylene and allylbenzene copolymers without obvious degradation or crosslinking via Friedel–Crafts (F–C) acylation reaction with glutaric anhydride (GA), succinic anhydride (SA) and phthalic anhydride (PA) in the presence of anhydrous aluminum chloride in carbon disulfide. Some important reaction parameters were examined in order to optimize the acylation process. In

Yi Zheng; Yanguo Li; Li Pan; Yuesheng Li

2007-01-01

47

Detection of a CO and NH3 gas mixture using carboxylic acid-functionalized single-walled carbon nanotubes  

PubMed Central

Carbon nanotubes (CNT) are extremely sensitive to environmental gases. However, detection of mixture gas is still a challenge. Here, we report that 10 ppm of carbon monoxide (CO) and ammonia (NH3) can be electrically detected using a carboxylic acid-functionalized single-walled carbon nanotubes (C-SWCNT). CO and NH3 gases were mixed carefully with the same concentrations of 10 ppm. Our sensor showed faster response to the CO gas than the NH3 gas. The sensing properties and effect of carboxylic acid group were demonstrated, and C-SWCNT sensors with good repeatability and fast responses over a range of concentrations may be used as a simple and effective detection method of CO and NH3 mixture gas. PMID:23286690

2013-01-01

48

Adsorption of uranium ions by resins with amidoxime and amidoxime/carboxyl group prepared by radiation-induced polymerization  

NASA Astrophysics Data System (ADS)

In order to recover uranium ions from seawater, chelate-type resins with amidoxime and amidoxime/carboxylic acid groups were prepared by radiation-induced polymerization of acrylonitrile (AN) and AN/acrylic acid and by subsequent amidoximation of cyano group of poly(AN), respectively. The resins were characterized by FT-IR, FT-Raman, solid-state 13C-NMR, SEM, and elemental analysis, respectively. The adsorption rate of uranium ion by resins with the amidoxime/carboxylic acid group were higher than that of resins with the amidoxime group. The adsorption of uranium ions in artificial seawater to chelate-type resins was also examined.

Choi, Seong-Ho; Choi, Min-Seok; Park, Yong-Tae; Lee, Kwang-Pill; Kang, Hee-Dong

2003-06-01

49

5,6-dihydroxyindole-2-carboxylic acid (DHICA): a First Principles Density-Functional Study  

E-print Network

We report first principles density functional calculations for 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and several reduced forms. DHICA and 5,6-dihydroxyindole (DHI) are believed to be the basic building blocks of the eumelanins. Our results show that carboxylation has a significant effect on the physical properties of the molecules. In particular, the relative stabilities and the HOMO-LUMO gaps (calculated with the $\\Delta$SCF method) of the various redox forms are strongly affected. We predict that, in contrast to DHI, the density of unpaired electrons, and hence the ESR signal, in DHICA is negligibly small.

B. J. Powell

2004-08-24

50

Cluster functional renormalization group  

NASA Astrophysics Data System (ADS)

Functional renormalization group (FRG) has become a diverse and powerful tool to derive effective low-energy scattering vertices of interacting many-body systems. Starting from a free expansion point of the action, the flow of the RG parameter ? allows us to trace the evolution of the effective one- and two-particle vertices towards low energies by taking into account the vertex corrections between all parquet channels in an unbiased fashion. In this work, we generalize the expansion point at which the diagrammatic resummation procedure is initiated from a free UV limit to a cluster product state. We formulate a cluster FRG scheme where the noninteracting building blocks (i.e., decoupled spin clusters) are treated exactly, and the intercluster couplings are addressed via RG. As a benchmark study, we apply our cluster FRG scheme to the spin-1/2 bilayer Heisenberg model (BHM) on a square lattice where the neighboring sites in the two layers form the individual two-site clusters. Comparing with existing numerical evidence for the BHM, we obtain reasonable findings for the spin susceptibility, the spin-triplet excitation energy, and quasiparticle weight even in coupling regimes close to antiferromagnetic order. The concept of cluster FRG promises applications to a large class of interacting electron systems.

Reuther, Johannes; Thomale, Ronny

2014-01-01

51

Transition metal chemistry of main group hydrazides. Part 3:{sup 1} carboxylate appended phosphorus hydrazides as novel functionalized chelating systems. Synthesis and characterization of new cyclometallaphosphohydrazides. X-ray structure of a Palladium(II) representative  

SciTech Connect

The synthesis of new bifunctional chelating agents (BFCAs) based on the phosphorus hydrazide ligand family for potential {sup 109}Pd labeling of tumor-localizing biomolecules such as proteins/peptides is described. The new BFCAs were achieved in good yields (75-90%) by the reaction of the phosphorus hydrazide PhP(S)(NMeNH{sub 2}){sub 2} (1) with functionalized aldehydes to yield the Schiff-base products with the following chemical compositions as air-stable crystalline solids: PhP(S)(NMeNH{sub 2})(NMeNCHC{sub 6}H{sub 4}COOH), 2; PhP(S)(NMeNCHC{sub 6}H{sub 4}COOH){sub 2}, 3; PhP(S)(NMeNH{sub 2})(NMeNCHC{sub 6}H{sub 4}CH=CHCOOH), 4; PhP(S)(NMeNCHC{sub 6}H{sub 4}CH-CHCOOH){sub 2}, 5. The reactions of three of the new phosphorus hydrazides (2-4) with PdCl{sub 2}(PhCN){sub 2} resulted in the new Pd(II) metallacycles PhP(S)(NMeNH{sub 2})(NMeNCHC{sub 6}H{sub 4}COOH){center_dot}PdCl{sub 2}, 6; PhP(S)(NMeNCHC{sub 6}H{sub 4}COOH){sub 2}{center_dot}PdCl{sub 2}, 7; and PhP(S)(NMeNH{sub 2})(NMeNCHC{sub 6}H{sub 4}CH=CHCOOH){center_dot}PdCl{sub 2}, 8. The reactivity of 6 toward n-butylamine has been evaluated as a model for the preparation of new bioconjugates. The structural elucidation of all the new compounds has been carried out by analytical and complete NMR ({sup 1}H, {sup 31}P) and IR spectroscopic data. As a representative example, the X-ray structure of one of the Pd(II) complexes, 8, has been determined.

Singh, P.R.; Jimenez, H.; Barnes, C.L. [Missouri Univ. Research Reactor, Columbia, MO (United States); Katti, K.V. [Univ. of Missour, Columbia, MO (United States)]|[Missouri Univ. Research Reactor, Columbia, MO (United States); Volkert, W.A. [Missouri Univ. Research Reactor, Columbia, MO (United States)]|[Univ. of Missouri, Columbia, MO (United States)

1994-02-16

52

Spectroscopic and physicochemical behavior of magnesium phthalocyanine derivatives mono-substituted with a carboxylic acid group  

NASA Astrophysics Data System (ADS)

This work reports on the synthesis of novel unsymmetrically substituted magnesium phthalocyanine complexes containing one carboxyl group. The physicochemical behavior of these complexes were compared with those of their unmetallated and zinc counterparts. The MgPcs showed interesting absorption spectra with [8,15,22-Tris-(naphtho)-4,5-(3-carboxy-1,2-dioxyphenyl)phthalocyaninato]magnesium (II) showing a large split in the Q band whereas [8,15,22-Tris-(naphtho)-2-(carboxy) phthalocyaninato]magnesium(II) presented only a small splitting. The magnesium phthalocyanine derivatives displayed higher fluorescence quantum yields compared to unmetallated and zinc phthalocyanine counterparts. The latter gave admirable triplet and singlet oxygen quantum yields. These molecules can distinctly be employed in the field of photodynamic therapy in combination with fluorescence imaging.

Nombona, Nolwazi; Chidawanyika, Wadzanai; Nyokong, Tebello

2012-03-01

53

Whittaker functions on metaplectic groups  

E-print Network

The theory of Whittaker functions is of crucial importance in the classical study of automorphic forms on adele groups. Motivated by the appearance of Whittaker functions for covers of reductive groups in the theory of ...

McNamara, Peter James

2010-01-01

54

Carboxylic groups in mesoporous silica and ethane-bridged organosilica: effect of the surface on the reactivity.  

PubMed

Proton-donor ability of carboxylic groups incorporated by co-condensation into SBA-15 and ethane-bridged periodic mesoporous organosilica (PMO) has been studied through IR spectroscopy by dosing ammonia, which forms reversibly COO(-) groups and NH(4)(+) ions. The related equilibrium constants, determined by elaboration of IR data, reveal a lower reactivity of -COOH groups at the surface of PMO than on SBA-15, when the two samples have been outgassed at the same temperature. This finding is interpreted in terms of different dielectric constants and intermolecular interactions engaged with the surface species. Carboxylic groups on ethane-bridged organosilica react with silanols upon thermal treatment at 473 K to form a mixed anhydride species Si-O-C(O)-, at variance with the same groups on SBA-15. PMID:21079845

Fiorilli, Sonia; Camarota, Beatrice; Garrone, Edoardo; Onida, Barbara

2011-01-21

55

Facile one-step coating approach to magnetic submicron particles with poly(ethylene glycol) coats and abundant accessible carboxyl groups  

PubMed Central

Purpose Magnetic submicron particles (MSPs) are pivotal biomaterials for magnetic separations in bioanalyses, but their preparation remains a technical challenge. In this report, a facile one-step coating approach to MSPs suitable for magnetic separations was investigated. Methods Polyethylene glycol) (PEG) was derived into PEG-bis-(maleic monoester) and maleic monoester-PEG-succinic monoester as the monomers. Magnetofluids were prepared via chemical co-precipitation and dispersion with the monomers. MSPs were prepared via one-step coating of magnetofluids in a water-in-oil microemulsion system of aerosol-OT and heptane by radical co-polymerization of such monomers. Results The resulting MSPs contained abundant carboxyl groups, exhibited negligible nonspecific adsorption of common substances and excellent suspension stability, appeared as irregular particles by electronic microscopy, and had submicron sizes of broad distribution by laser scattering. Saturation magnetizations and average particle sizes were affected mainly by the quantities of monomers used for coating magnetofluids, and steric hindrance around carboxyl groups was alleviated by the use of longer monomers of one polymerizable bond for coating. After optimizations, MSPs bearing saturation magnetizations over 46 emu/g, average sizes of 0.32 ?m, and titrated carboxyl groups of about 0.21 mmol/g were obtained. After the activation of carboxyl groups on MSPs into N-hydroxysuccinimide ester, biotin was immobilized on MSPs and the resulting biotin-functionalized MSPs isolated the conjugate of streptavidin and alkaline phosphatase at about 2.1 mg/g MSPs; streptavidin was immobilized at about 10 mg/g MSPs and retained 81% ± 18% (n = 5) of the specific activity of the free form. Conclusion The facile approach effectively prepares MSPs for magnetic separations. PMID:23589687

Long, Gaobo; Yang, Xiao-lan; Zhang, Yi; Pu, Jun; Liu, Lin; Liu, Hong-bo; Li, Yuan-li; Liao, Fei

2013-01-01

56

Structural and Functional Models of Non-Heme Iron Enzymes : A Study of the 2His1Carboxylate Facial Triad Structural Motif  

Microsoft Academic Search

The structural and functional modeling of a specific group of non-heme iron enzymes by the synthesis of small synthetic analogues is the topic of this thesis. The group of non-heme iron enzymes with the 2-His-1-carboxylate facial triad has recently been established as a common platform for the activation of dioxygen in Nature. The oxidative transformations catalyzed by these enzymes are

P. C. A. Bruijnincx

2007-01-01

57

Preparation and characterization of TEMPO-oxidized cellulose nanofibrils with ammonium carboxylate groups.  

PubMed

Fibrous TEMPO-oxidized celluloses with 100% ammonium carboxylate groups (TOC-COONH4) were prepared by adding aqueous ammonia to fibrous TOC-COOH/water slurries. Using a gentle mechanical disintegration treatment in water, the obtained never-dried TOC-COONH4/water slurries could be converted to highly viscous and transparent gels consisting of mostly individualized TEMPO-oxidized cellulose nanofibrils. The self-standing TOCN-COONH4 film prepared from the aqueous TOCN-COONH4 dispersion via casting and drying had high optical transparency. When the self-standing TOCN-COONH4 film was heated at 105°C for 1 day, clear yellowing was observed on the film. FT-IR analysis of the heated TOCN-COONH4 films indicated the partial formation of TOCN-COOH type structures from the TOCN-COONH4 due to evaporation of NH3 gas from the films during heating. The heated TOCN-COONH4 films had lower moisture contents, higher film densities, and higher Young's moduli than the unheated TOCN-COONH4 films. PMID:23597708

Shimizu, Michiko; Fukuzumi, Hayaka; Saito, Tsuguyuki; Isogai, Akira

2013-08-01

58

Molecular level computational studies of polyethylene and polyacrylonitrile composites containing single walled carbon nanotubes: effect of carboxylic acid functionalization on nanotube-polymer interfacial properties  

PubMed Central

Molecular dynamics (MD) and molecular mechanics (MM) methods have been used to investigate additive-polymer interfacial properties in single walled carbon nanotube (SWNT)—polyethylene and SWNT—polyacrylonitrile composites. Properties such as the interfacial shear stress and bonding energy are similar for the two composites. In contrast, functionalizing the SWNT with carboxylic acid groups leads to an increase in these properties, with a larger increase for the polar polyacrylonitrile composite. Increasing the percentage of carbon atoms that were functionalized from 1 to 5% also leads to an increase in the interfacial properties. In addition, the interfacial properties depend on the location of the functional groups on the SWNT wall.

Haghighatpanah, Shayesteh; Bohlen, Martin; Bolton, Kim

2014-01-01

59

Carboxyl-terminal disulfide bond of acid sphingomyelinase is critical for its secretion and enzymatic function.  

PubMed

The human acid sphingomyelinase (ASM, EC 3.1.4.12), a lysosomal and secretory protein coded by the sphingomyelin phosphodiesterase 1 (SMPD-1) gene, catalyzes the degradation of sphingomyelin (SM) to ceramide and phosphorylcholine. We examined the structural-functional properties of its carboxyl-terminus (amino acids 462-629), which harbors approximately 1/3 of all mutations discovered in the SMPD-1 gene. We created four naturally occurring mutants (DeltaR608, R496L, G577A, and Y537H) and five serial carboxyl-terminal deletion mutants (N620, N590, N570, N510, and N490). Transient transfection of the His/V5-tagged wild-type and mutant recombinant ASM in Chinese hamster ovary cells showed that all the mutants were normally expressed. Nonetheless, none of them, except the smallest deletion mutant N620 that preserved all post-translational modifications, were found capable of secretion to the medium. Furthermore, only the N620 conserved functional integrity (100% activity of the wild type); all other mutants completely lost the ability to catalyze SM hydrolysis. Importantly, cell surface biotinylation revealed that mutant DeltaR608 transfected CHO cells and fibroblasts from a compound heterozygous Niemann-Pick disease type B (NPD-B) patient (DeltaR608 and R441X) have defective translocation to the plasma membrane. Furthermore, we demonstrated that the DeltaR608 and N590 were trapped in the endoplasmic reticulum (ER) quality control checkpoint in contrast to the wild-type lysosomal localization. Interestingly, while the steady-state levels of ubiquitination were minimal for the wild-type ASM, a significant amount of Lys63-linked polyubiquitinated DeltaR608 and N590 could be purified by S5a-affinity chromatography, indicating an important misfolding in the carboxyl-terminal mutants. Altogether, we provide evidence that the carboxyl-terminus of the ASM is crucial for its protein structure, which in turns dictates the enzymatic function and secretion. PMID:18052040

Lee, Ching Yin; Tamura, Taku; Rabah, Nadia; Lee, Dong-Young Donna; Ruel, Isabelle; Hafiane, Anouar; Iatan, Iulia; Nyholt, Dana; Laporte, Frédéric; Lazure, Claude; Wada, Ikuo; Krimbou, Larbi; Genest, Jacques

2007-12-25

60

Fatty acidomics: global analysis of lipid species containing a carboxyl group with a charge-remote fragmentation assisted approach  

PubMed Central

Charge-remote fragmentation has been well recognized as an effective approach for dissociation of long aliphatic chains. Herein, we exploited this approach for structural identification of all fatty acids including saturated, unsaturated, and modified ones by using electrospray ionization tandem mass spectrometry (ESI-MS/MS) after one-step derivatization of a charge-carried reagent through an amidation reaction. We tested the approach with different charge-carried reagents with respective to the hydrophobicity, charge strength, and distance from the charge to the carboxyl group. We found all the derivatives with these reagents could yield informative charge-remote fragmentation patterns regardless of the different chemical and physical properties of the reagents and these informative fragmentation patterns all could be effectively used for structural elucidation of lipid species containing a carboxyl group. We further found that the distinguished charge-remote fragmentations of fatty acid isomers enabled us to determine the composition of these isomers without any chromatographic separation. Finally, the abundant fragments yielded from individual derivatized moiety enabled us to sensitively quantify the individual species containing a carboxyl group. The described approach was a great extension to the multidimensional mass spectrometry-based shotgun lipidomics for global analysis of fatty acids including isomers and modifications. We believe that this approach could greatly facilitate the identification of the biochemical mechanisms underlying numerous pathological conditions. PMID:23971716

Wang, Miao; Han, Rowland H.; Han, Xianlin

2013-01-01

61

Variation in optoelectronic properties of azo dye-sensitized TiO2 semiconductor interfaces with different adsorption anchors: carboxylate, sulfonate, hydroxyl and pyridyl groups.  

PubMed

The optoelectronic properties of four azo dye-sensitized TiO2 interfaces are systematically studied as a function of a changing dye anchoring group: carboxylate, sulfonate, hydroxyl, and pyridyl. The variation in optoelectronic properties of the free dyes and those in dye/TiO2 nanocomposites are studied both experimentally and computationally, in the context of prospective dye-sensitized solar cell (DSSC) applications. Experimental UV/vis absorption spectroscopy, cyclic voltammetry, and DSSC device performance testing reveal a strong dependence on the nature of the anchor of the optoelectronic properties of these dyes, both in solution and as dye/TiO2 nanocomposites. First-principles calculations on both an isolated dye/TiO2 cluster model (using localized basis sets) and each dye modeled onto the surface of a 2D periodic TiO2 nanostructure (using plane wave basis sets) are presented. Detailed examination of these experimental and computational results, in terms of light harvesting, electron conversion and photovoltaic device performance characteristics, indicates that carboxylate is the best anchoring group, and hydroxyl is the worst, whereas sulfonate and pyridyl groups exhibit competing potential. Different sensitization solvents are found to affect critically the extent of dye adsorption achieved in the dye-sensitization of the TiO2 semiconductor, especially where the anchor is a pyridyl group. PMID:24786472

Zhang, Lei; Cole, Jacqueline M; Dai, Chencheng

2014-05-28

62

ATR-FTIR spectroscopic evidence for biomolecular phosphorus and carboxyl groups facilitating bacterial adhesion to iron oxides.  

PubMed

Attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy has been used to probe the binding of bacteria to hematite (?-Fe2O3) and goethite (?-FeOOH). In situ ATR-FTIR experiments with bacteria (Pseudomonas putida, Pseudomonas aeruginosa, Escherichia coli), mixed amino acids, polypeptide extracts, deoxyribonucleic acid (DNA), and a suite of model compounds were conducted. These compounds represent carboxyl, catecholate, amide, and phosphate groups present in siderophores, amino acids, polysaccharides, phospholipids, and DNA. Due in part to the ubiquitous presence of carboxyl groups in biomolecules, numerous IR peaks corresponding to outer-sphere or unbound (1400 cm(-1)) and inner-sphere (1310-1320 cm(-1)) coordinated carboxyl groups are noted following reaction of bacteria and biomolecules with ?-Fe2O3 and ?-FeOOH. However, the data also reveal that the presence of low-level amounts (i.e., 0.45-0.79%) of biomolecular phosphorous groups result in strong IR bands at ?1043 cm(-1), corresponding to inner-sphere Fe-O-P bonds, underscoring the importance of bacteria associated P-containing groups in biomolecule and cell adhesion. Spectral comparisons also reveal slightly greater P-O-Fe contributions for bacteria (Pseudomonad, E. coli) deposited on ?-FeOOH, as compared to ?-Fe2O3. This data demonstrates that slight differences in bacterial adhesion to Fe oxides can be attributed to bacterial species and Fe-oxide minerals. However, more importantly, the strong binding affinity of phosphate in all bacteria samples to both Fe-oxides results in the formation of inner-sphere Fe-O-P bonds, signifying the critical role of biomolecular P in the initiation of bacterial adhesion. PMID:24859052

Parikh, Sanjai J; Mukome, Fungai N D; Zhang, Xiaoming

2014-07-01

63

Response of human neutrophils to formyl-peptide modified at the terminal amino and carboxyl groups  

Microsoft Academic Search

Two analogs of chemotactic peptideN-formyl-l-methionyl-l-leucyl-l-phenylalanine were examined for their capacity to activate several functions of human neutrophils. The C-terminus methyl ester derivative of the chemotactic peptide was found to possess strong biological activity and was able to induce levels of chemotaxis, enzyme secretion, and Superoxide generation comparable to those observed with the same concentrations ofN-formyl-l-methionyl-l-leucyl-l-phenylalanine. The analog containing atert-butyloxycarbonyl group

Susanna Spisani; Teresa Cavalletti; Riccardo Gavioli; Angelo Scatturin; Gianni Vertuani; Serena Traniello

1986-01-01

64

THz and mid-IR spectroscopy of interstellar ice analogs: methyl and carboxylic acid groups.  

PubMed

A fundamental problem in astrochemistry concerns the synthesis and survival of complex organic molecules (COMs) throughout the process of star and planet formation. While it is generally accepted that most complex molecules and prebiotic species form in the solid phase on icy grain particles, a complete understanding of the formation pathways is still largely lacking. To take full advantage of the enormous number of available THz observations (e.g., Herschel Space Observatory, SOFIA, and ALMA), laboratory analogs must be studied systematically. Here, we present the THz (0.3-7.5 THz; 10-250 cm(-1)) and mid-IR (400-4000 cm(-1)) spectra of astrophysically-relevant species that share the same functional groups, including formic acid (HCOOH) and acetic acid (CH3COOH), and acetaldehyde (CH3CHO) and acetone ((CH3)2CO), compared to more abundant interstellar molecules such as water (H2O), methanol (CH3OH), and carbon monoxide (CO). A suite of pure and mixed binary ices are discussed. The effects on the spectra due to the composition and the structure of the ice at different temperatures are shown. Our results demonstrate that THz spectra are sensitive to reversible and irreversible transformations within the ice caused by thermal processing, suggesting that THz spectra can be used to study the composition, structure, and thermal history of interstellar ices. Moreover, the THz spectrum of an individual species depends on the functional group(s) within that molecule. Thus, future THz studies of different functional groups will help in characterizing the chemistry and physics of the interstellar medium (ISM). PMID:25302394

Ioppolo, S; McGuire, B A; Allodi, M A; Blake, G A

2014-01-01

65

Synthesis and herbicidal activity of isoindoline-1,3-dione substituted benzoxazinone derivatives containing a carboxylic ester group.  

PubMed

A carboxylic ester group was introduced to three series of isoindolinedione substituted benzoxazinone derivatives. Some of these analogues exhibited good herbicidal activities, and the injury symptoms against weeds included leaf cupping, crinkling, bronzing, and necrosis, typical of protox inhibitor herbicides. Structurally, they were classified as Chemical Group A (4-carboxylic ester group-6-isoindolinyl-benzoxazinones), B (4-carboxylic ester group-7-isoindolinyl-benzoxazinones), and C (4-carboxylic ester group-6- tetrahydroisoindolinyl-benzoxazinones). All of the tested compounds were structurally confirmed by (1)H NMR, IR, mass spectroscopy, and elemental analysis. Preliminary bioassay data of these three classes of compounds showed that, in general, the order of the herbicidal effectiveness is C > A > B. Several of the lead compounds, for example, C10 (methyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-2-methyl-3-oxo-2H-benzo[b][1,4] oxazin-4(3H)-yl) propano-ate), C12 (ethyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-2- methyl-3-oxo-2H-benzo[b][1,4]oxazin-4(3H)-yl) propanoate), and C13 (ethyl 2-(6-(1,3-dioxo-4,5,6,7-tetrahydro-1H-isoindol-2(3H)-yl)-7-fluoro-2-methyl-3-oxo-2H-benzo-[b][1,4]oxazin-4(3H)-yl) butanoate), exhibited greater than 80% control at 75 g a.i./ha in both pre- and postemergence treatments against dicotyledonous weeds, such as Abutilon theophrasti Medic, Chenopodium album L., and Amaranthus ascendens L., and monocotyledon weeds, such as Digitaria sanguinalis L., Echinochloa crus-galli L., and Setaria viridis L. On the basis of advanced screening tests and crop selectivity, compounds C10, C12, and C13 are safer to crops than flumioxazin. Compounds C10, C12, and C13 are potent to develop as pre-emergent herbicides used in peanut, soybean, maize, and cotton fields. PMID:19772294

Huang, Ming-Zhi; Luo, Fei-Xian; Mo, Hong-Bo; Ren, Ye-Guo; Wang, Xiao-Guang; Ou, Xiao-Ming; Lei, Man-Xiang; Liu, Ai-Ping; Huang, Lu; Xu, Man-Cai

2009-10-28

66

Floral benzenoid carboxyl methyltransferases: From in vitro to in planta function  

Microsoft Academic Search

Benzenoid carboxyl methyltransferases synthesize methyl esters (e.g., methyl benzoate and methyl salicylate), which are constituents of aromas and scents of many plant species and play important roles in plant communication with the surrounding environment. Within the past five years, eleven such carboxyl methyltransferases were isolated and most of them were comprehensively investigated at the biochemical, molecular and structural level. Two

Uta Effmert; Sandra Saschenbrecker; Jeannine Ross; Florence Negre; Chris M. Fraser; Joseph P. Noel; Natalia Dudareva; Birgit Piechulla

2005-01-01

67

Floral Benzenoid Carboxyl Methyltransferases: From in Vitro to in Planta Function  

Microsoft Academic Search

Benzenoid carboxyl methyltransferases synthesize methyl esters (e.g., methyl benzoate and methyl salicylate), which are constituents of aromas and scents of many plant species and play important roles in plant communication with the surrounding environment. Within the past five years, eleven such carboxyl methyltransferases were isolated and most of them were comprehensively investigated at the biochemical, molecular and structural level. Two

Uta Effmert; Sandra Saschenbrecker; Jeannine Ross; Florence Negre; Chris M. Fraser; Joseph P. Noel; Natalia Dudareva; Birgit Piechulla

2005-01-01

68

Synthesis and evaluation of novel dental monomer with branched carboxyl acid group.  

PubMed

To enhance the water miscibility and increase the mechanical properties of dentin adhesives, a new glycerol-based monomer with vinyl and carboxylic acid, 4-((1,3-bis(methacryloyloxy)propan-2-yl)oxy)-2-methylene-4-oxobutanoic acid (BMPMOB), was synthesized and characterized. Dentin adhesive formulations containing 2-hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]propane (BisGMA), and BMPMOB were characterized with regard to real-time photopolymerization behavior, water sorption, dynamic mechanical analysis, and microscale three-dimensional internal morphologies and compared with HEMA/BisGMA controls. The experimental adhesive copolymers showed higher glass transition temperature and rubbery moduli, as well as improved water miscibility compared to the controls. The enhanced properties of the adhesive copolymers indicated that BMPMOB is a promising comonomer for dental restorative materials. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 1473-1484, 2014. PMID:24596134

Song, Linyong; Ye, Qiang; Ge, Xueping; Misra, Anil; Laurence, Jennifer S; Berrie, Cynthia L; Spencer, Paulette

2014-10-01

69

Reinforcement of carboxyl groups in the surface of Corynebacterium glutamicum biomass for effective removal of basic dyes.  

PubMed

The biomass of Corynebacterium glutamicum was treated with poly(amic acid) to improve the biosorption of Basic Blue 3 (BB3) from aqueous solution. The grafting of poly(amic acid) onto the biomass surface increased the density of the carboxyl groups. The UV-spectrum revealed that strong acidic (pH2) and basic conditions (pH11) resulted in the precipitation of BB3. Therefore, pH edge experiments were conducted only within the range 3-10; these results indicated that electrostatic attraction between carboxyl groups of C. glutamicum and BB3 dye cations was favored under alkaline conditions. From the Langmuir model, poly(amic acid)-modified biomass gave a maximum uptake of 173.6 mg/g at pH 9, compared to 52.8 mg/g by the raw biomass. The biosorption kinetics was found to be fast; with equilibrium attained within 10 min. The increase in the ionic strength strongly affected the uptake of BB3 for both forms of C. glutamicum. PMID:19692228

Won, Sung Wook; Vijayaraghavan, K; Mao, Juan; Kim, Sok; Yun, Yeoung-Sang

2009-12-01

70

Learning the Functional Groups: Keys to Success.  

ERIC Educational Resources Information Center

Points out the difficulties students have when they are expected to learn functional groups, which are frameworks for chemical and physical properties of molecules. Presents a classification key for functional groups categorized by 10 common functional groups. (YDS)

Byrd, Shannon; Hildreth, David P.

2001-01-01

71

Regulating bioactivity of Cu2+ bis-1,10-phenanthroline artificial metallonucleases with sterically functionalized pendant carboxylates.  

PubMed

The synthetic chemical nuclease, [Cu(1,10-phenanthroline)2](2+), has stimulated research within metallonuclease development and in the area of cytotoxic metallodrug design. Our analysis reveals, however, that this agent is "promiscuous" as it binds both dsDNA and protein biomolecules, without specificity, and induces general toxicity to a diversity of cell lineages. Here, we describe the synthesis and characterization of small-molecule metallonucleases containing the redox-active cation, [Cu(RCOO)(1,10-phen)2](+), where 1,10-phen = 1,10-phenanthroline and R = -H, -CH3, -C2H5, -CH(CH3)2, and -C(CH3)3. The presence of coordinated carboxylate groups in the complex cation functions to enhance dsDNA recognition, reduce serum albumin binding, and offer control of toxicity toward human cancer cells, Gram positive and negative bacteria, and fungal pathogens. The induction of genomic dsDNA breaks (DSBs) were identified in ovarian adenocarcinoma cells using immunodetection of ?-H2AX. Formate, acetate, and pivalate functionalized complexes induced DSBs in a higher percentage of cells compared with [Cu(1,10-phen)2](2+), which supports the importance of inner-sphere modification toward enhancing targeted biological application. PMID:24131470

Prisecaru, Andreea; McKee, Vickie; Howe, Orla; Rochford, Garret; McCann, Malachy; Colleran, John; Pour, Milan; Barron, Niall; Gathergood, Nicholas; Kellett, Andrew

2013-11-14

72

Analysis of carboxyl tail function in the skeletal muscle Cl- channel hClC-1.  

PubMed

Human ClC-1 (skeletal muscle Cl- channel) has a long cytoplasmic C-tail (carboxyl tail), containing two CBS (cystathionine beta-synthase) domains, which is very important for channel function. We have now investigated its significance further, using deletion and alanine-scanning mutagenesis, split channels, GST (glutathione transferase)-pull-down and whole-cell patch-clamping. In tagged split-channel experiments, we have demonstrated strong binding between an N-terminal membrane-resident fragment (terminating mid-C-tail at Ser(720) and containing CBS1) and its complement (containing CBS2). This interaction is not affected by deletion of some sequences, suggested previously to be important, particularly in channel gating. Contact between CBS1 and CBS2, however, may make a major contribution to assembly of functional channels from such co-expressed complements, although the possibility that C-tail fragments could, in addition, bind to other parts of the membrane-resident component has not been eliminated. We now show such an interaction between a membrane-resident component terminating at Ser(720) (but with CBS1 deleted) and a complete C-tail beginning at Leu(598). Channel function is rescued in patch-clamped HEK-293T (human embryonic kidney) cells co-expressing these same fragments. From our own results and those of others, we conclude that the CBS1-CBS2 interaction is not sufficient, in itself, for channel assembly, but rather that this might normally assist in bringing some part of the CBS2/C-tail region into appropriate proximity with the membrane-resident portion of the protein. Previously conflicting and anomalous results can now be explained by an hypothesis that, for split channels to be functional, at least one membrane-resident component must include a plasma membrane trafficking signal between Leu(665) and Lys(680). PMID:18321245

Ma, Linlin; Rychkov, Grigori Y; Hughes, Bernard P; Bretag, Allan H

2008-07-01

73

Solid phase extraction of petroleum carboxylic acids using a functionalized alumina as stationary phase.  

PubMed

Petroleum essentially consists of a mixture of organic compounds, mainly containing carbon and hydrogen, and, in minor quantities, compounds with nitrogen, sulphur, and oxygen. Some of these compounds, such as naphthenic acids, can cause corrosion in pipes and equipment used in processing plants. Considering that the methods of separation or clean up the target compounds in low concentrations and in complex matrix use large amounts of solvents or stationary phases, is necessary to study new methodologies that consume smaller amounts of solvent and stationary phases to identify the acid components present in complex matrix, such as crude oil samples. The proposed study aimed to recover acid compounds using the solid phase extraction method, employing different types of commercial stationary ion exchange phases (SAX and NH(2)) and new phase alumina functionalized with 1,4-bis(n-propyl)diazoniabicyclo[2.2.2]octane chloride silsesquioxane (Dab-Al(2)O(3)), synthesized in this work. Carboxylic acids were used as standard mixture in the solid phase extraction for further calculation of recovery yield. Then, the real sample (petroleum) was fractionated into saturates, aromatics, resins, and asphaltenes, and the resin fraction of petroleum (B1) was eluted through stationary ion exchange phases. The stationary phase synthesized in this work showed an efficiency of ion exchange comparable to that of the commercial stationary phases. PMID:22589166

de Conto, Juliana Faccin; Nascimento, Juciara dos Santos; de Souza, Driele Maiara Borges; da Costa, Luiz Pereira; Egues, Silvia Maria da Silva; Freitas, Lisiane Dos Santos; Benvenutti, Edilson Valmir

2012-04-01

74

Surface functional groups of carbon nanotubes to manipulate capacitive behaviors.  

PubMed

The covalent functionalization of carbon nanotubes (CNTs) is a basic but important chemistry that can modify their physicochemical properties, resolve their poor dispersion capability, and improve their capacitance to enable their use as high-energy supercapacitors. However, the relationship between functional groups on the CNT surface and their capacitive characteristics has not yet been explored. Here, we demonstrate the influence of carboxylic, sulfonic, and amine groups tethered to CNTs (Cf-CNTs, Sf-CNTs, and Nf-CNTs, respectively) on capacitor performance in an organic electrolyte. The Cf-CNTs show the highest specific capacitance of 129.4 F g(-1), four-fold greater than 31.2 F g(-1) of pristine CNTs, but they reveal the lowest rate capability of 57%. In contrast, the Sf- and Nf-CNTs exhibit specific capacitances of 70.9 F g(-1) and 83.6 F g(-1), two-fold greater than that of pristine CNTs, along with a good rate capability greater than 80%. Despite their pseudocapacitive nature, all functionalized CNTs show a cyclic stability of more than 80% after 500 cycles due to the electrochemical stability of the functional groups. As demonstrated by spectroscopic analysis, the supercapacitive behaviors of the functionalized CNTs originate from specific interactions between functional groups and lithium ions and the alteration of the electronic structure arising from covalent functionalization. PMID:24162723

Park, Sul Ki; Mahmood, Qasim; Park, Ho Seok

2013-12-21

75

Functional groups on waste beer yeast involved in chromium biosorption from electroplating effluent  

Microsoft Academic Search

Waste yeast Saccharomyces cerevisiae from the beer fermentation industry was used for the biosorption of chromium from electroplating effluent. The role played\\u000a by functional groups such as carboxyl, amino, sulfhydryl, phosphate and lipids present on the yeast were evaluated by potentiometric\\u000a titration and chemical modification. The extent of contribution of the functional groups and lipids to chromium biosorption\\u000a was found

K. Parvathi; R. Nagendran

2008-01-01

76

Floral benzenoid carboxyl methyltransferases: From in vitro to in planta function  

PubMed Central

Benzenoid carboxyl methyltransferases synthesize methyl esters (e.g., methyl benzoate and methyl salicylate), which are constituents of aromas and scents of many plant species and play important roles in plant communication with the surrounding environment. Within the past five years, eleven such carboxyl methyltransferases were isolated and most of them were comprehensively investigated at the biochemical, molecular and structural level. Two types of enzymes can be distinguished according to their substrate preferences: the SAMT-type enzymes isolated from Clarkia breweri, Stephanotis floribunda, Antirrhinum majus, Hoya carnosa, and Petunia hybrida, which have a higher catalytic efficiency and preference for salicylic acid, while BAMT-type enzymes from A. majus, Arabidopsis thaliana, Arabidopsis lyrata, and Nicotiana suaveolens prefer benzoic acid. The elucidation of C. breweri SAMT’s three-dimensional structure allowed a detailed modelling of the active sites of the carboxyl methyltransferases and revealed that the SAM binding pocket is highly conserved among these enzymes while the methyl acceptor binding site exhibits some variability, allowing a classification into SAMT-type and BAMT-type enzymes. The analysis of expression patterns coupled with biochemical characterization showed that these carboxyl methyltransferases are involved either in floral scent biosynthesis or in plant defense responses. While the latter can be induced by biotic or abiotic stress, the genes responsible for floral scent synthesis exhibit developmental and rhythmic expression pattern. The nature of the product and efficiency of its formation in planta depend on the availability of substrates, the catalytic efficiency of the enzyme toward benzoic acid and/or salicylic acid, and the transcriptional, translational, and post-translational regulation at the enzyme level. The biochemical properties of benzenoid carboxyl methyltransferases suggest that the genes involved in plant defenses might represent the ancestor for the presently existing floral genes which during evolution gained different expression profiles and encoded enzymes with the ability to accept structurally similar substrates. PMID:15946712

Effmert, Uta; Saschenbrecker, Sandra; Ross, Jeannine; Negre, Florence; Fraser, Chris M.; Noel, Joseph P.; Dudareva, Natalia; Piechulla, Birgit

2010-01-01

77

New analytical approaches to organic geochemistry: solid phase functional group extraction for bitumens and functional group markers for kerogens  

NASA Astrophysics Data System (ADS)

The first step of a general strategy for the analysis of bitumens and kerogens is based on specific functional group reactions carried out on solid surfaces: for soluble materials (bitumens, tars, etc.) a fractionation of the sample into isofunctional sets of compounds was accomplished by means of the Solid Phase Functional Group Extraction technique. This paper describes the use of the functional reagents diphenylenediamine and carboxyhydrazide bound to a solid (polymer) matrix for the selective isolation of aldehydes and ketones, respectively. The individual compounds were further separated and identified by combined gas chromatography-mass spectrometry. Functional groups of insoluble materials (kerogens) were determined through reactions of specific functional reagents (containing a marker) directly with the solid surface of the kerogen. In this paper, bromine or chlorine were chosen as markers, and the reagents p-bromophenacylbromide, p-chloroaniline, p-chlorobenzenediazonium sulphate, p-chlorobenzaldehyde, N-bromosuccinimide, p-bromobenzoyl chloride, N, N-di( p-bromophenyl)ethylenediamine, and p-bromobenzhydrazide, were used for the determination of the groups carboxylic acid, aldehyde, phenol/aromatic amines, primary amines, allylic/hydrogen, alcohols/primary-secondary amines, aldehydes and carbonyl compounds, respectively. Results are discussed for Brazilian oil shales from the Irati, Tremembé and Maraú Formations.

Neto, C. Costa; Maçaira, A. M. P.; Pinto, R. C. P.; Nakayama, H. T.; Cardoso, J. N.

78

A Functional Analytic Approach to Group Psychotherapy  

ERIC Educational Resources Information Center

This article provides a particular view on the use of Functional Analytical Psychotherapy (FAP) in a group therapy format. This view is based on the author's experiences as a supervisor of Functional Analytical Psychotherapy Groups, including groups for women with depression and groups for chronic pain patients. The contexts in which this approach…

Vandenberghe, Luc

2009-01-01

79

Functional Polymers with Biologically Active Groups  

Microsoft Academic Search

Synthetic polymers with functional groups, especially where the functional group is a biologically active group, are receiving considerable attention, since such polymeric drugs represent novel drug delivery systems. In this paper methods for the preparation of typical classes of polymers with biologically active groups were explored. As an example of a condensation polymer, primaquine was incorporated in a polymer chain

Otto Vogl; David Tirrell

1979-01-01

80

A simple colorimetric chemosensor bearing a carboxylic acid group with high selectivity for CN-  

NASA Astrophysics Data System (ADS)

A new simple ‘naked eye' chemosensor 1 (sodium (E)-2-((2-(3-hydroxy-2-naphthoyl)hydrazono)methyl)benzoate) has been synthesized for detection of CN- in a mixture of DMF/H2O (9:1). The sensor 1 comprises of a naphthoic hydrazide as efficient hydrogen bonding donor group and a benzoic acid as the moiety with the water solubility. The receptor 1 showed high selectivity toward cyanide ions in a 1:1 stoichiometric manner, which induces a fast color change from colorless to yellow for CN- over other anions. Therefore, receptor 1 could be useful for cyanide detection in aqueous environment, displaying a high distinguishable selectivity from hydrogen bonded anions and being clearly visible to the naked eye.

Park, Gyeong Jin; Choi, Ye Won; Lee, Dongkuk; Kim, Cheal

2014-11-01

81

Functional Reconstitution of the Integral Membrane Enzyme, Isoprenylcysteine Carboxyl Methyltransferase, in Synthetic Bolalipid Membrane Vesicles†  

PubMed Central

Three bipolar archaeal-type diglycerophosphocholine tetraether lipids (a.k.a., bolalipids) have been prepared to determine 1) the influence of molecular structure on the physical properties of bolalipid membranes and 2) their impact on the functional reconstitution of Ste14p, a membrane-associated isoprenylcysteine carboxyl methyltransferase from Saccharomyces cerevisiae. The three bolalipids synthesized were: C20BAS, C32BAS, and C32phytBAS. These bolalipid structures differ in that the C20BAS derivative has a short sn-1 glyceryl diether C20H40 transmembrane alkyl chain and two ether-linked sn-2 n-decyl chains, whereas the C32BAS and C32phytBAS derivatives have a longer sn-1 diether C32H64 membrane-spanning chain and two ether-linked sn-2 n-hexadecyl or phytanyl chains, respectively. Differential scanning calorimetry and temperature-dependent 31P NMR was used to determine the gel-to-liquid crystalline phase transition temperatures of the bolalipids (C32BAS Tm > 85 °C; C32phytBAS Tm = 14 °C; C20BAS Tm = 17°C). The bolalipid lateral diffusion coefficients, determined by fluorescence recovery after photobleaching at 20 °C, were 1.5 × 10?8 and 1.8 × 10?9 cm2/s for C20BAS and C32phytBAS, respectively. The mobility of C32BAS could not be measured at this temperature. Ste14p activity was monitored by an in vitro methyltransferase assay in reconstituted vesicle dispersions composed of DMPC, C20BAS:E. coli polar lipid, C20BAS:POPC, C32phytBAS:E. coli polar lipid, and C32phytBAS:POPC. Ste14p activity was lost in vesicles composed of 75–100 mol% C20BAS and 0–100 mol% C32BAS, but retained in vesicles with 0–50 mol% C20BAS and 0–100 mol% C32phytBAS. Confocal immunofluorescence microscopy confirmed the presence of Ste14p in 100 mol% C20BAS and 100 mol% C32phytBAS vesicle dispersions, even though the lamellar liquid crystalline phase thickness of C20BAS is only 32 Å. Since Ste14p activity was not affected by either the gel to liquid-crystal phase transition temperature of the lipid or the temperature of the assay, the low activity observed in 75–100 mol% C20BAS membranes can be attributed to hydrophobic mismatch between this bolalipid and the hydrophobic surface of Ste14p. PMID:17144661

Febo-Ayala, Wilma; Morera-Felix, Shakira L.

2008-01-01

82

Synthesis, characterization, and bioactivity of carboxylic acid-functionalized titanium dioxide nanobelts  

PubMed Central

Background Surface modification strategies to reduce engineered nanomaterial (ENM) bioactivity have been used successfully in carbon nanotubes. This study examined the toxicity and inflammatory potential for two surface modifications (humic acid and carboxylation) on titanium nanobelts (TNB). Methods The in vitro exposure models include C57BL/6 alveolar macrophages (AM) and transformed human THP-1 cells exposed to TNB for 24 hrs in culture. Cell death and NLRP3 inflammasome activation (IL-1? release) were monitored. Short term (4 and 24 hr) in vivo studies in C57BL/6, BALB/c and IL-1R null mice evaluated inflammation and cytokine release, and cytokine release from ex vivo cultured AM. Results Both in vitro cell models suggest that the humic acid modification does not significantly affect TNB bioactivity, while carboxylation reduced both toxicity and NLRP3 inflammasome activation. In addition, short term in vivo exposures in both C57BL/6 and IL-1R null mouse strains demonstrated decreased markers of inflammation, supporting the in vitro finding that carboxylation is effective in reducing bioactivity. TNB instillations in IL-1R null mice demonstrated the critical role of IL-1? in initiation of TNB-induced lung inflammation. Neutrophils were completely absent in the lungs of IL-1R null mice instilled with TNB for 24 hrs. However, the cytokine content of the IL-1R null mice lung lavage samples indicated that other inflammatory agents, IL-6 and TNF-? were constitutively elevated indicating a potential compensatory inflammatory mechanism in the absence of IL-1 receptors. Conclusions Taken together, the data suggests that carboxylation, but not humic acid modification of TNB reduces, but does not totally eliminate bioactivity of TNB, which is consistent with previous studies of other long aspect ratio nanomaterials such as carbon nanotubes. PMID:25179214

2014-01-01

83

Surface functional groups of carbon nanotubes to manipulate capacitive behaviors  

NASA Astrophysics Data System (ADS)

The covalent functionalization of carbon nanotubes (CNTs) is a basic but important chemistry that can modify their physicochemical properties, resolve their poor dispersion capability, and improve their capacitance to enable their use as high-energy supercapacitors. However, the relationship between functional groups on the CNT surface and their capacitive characteristics has not yet been explored. Here, we demonstrate the influence of carboxylic, sulfonic, and amine groups tethered to CNTs (Cf-CNTs, Sf-CNTs, and Nf-CNTs, respectively) on capacitor performance in an organic electrolyte. The Cf-CNTs show the highest specific capacitance of 129.4 F g-1, four-fold greater than 31.2 F g-1 of pristine CNTs, but they reveal the lowest rate capability of 57%. In contrast, the Sf- and Nf-CNTs exhibit specific capacitances of 70.9 F g-1 and 83.6 F g-1, two-fold greater than that of pristine CNTs, along with a good rate capability greater than 80%. Despite their pseudocapacitive nature, all functionalized CNTs show a cyclic stability of more than 80% after 500 cycles due to the electrochemical stability of the functional groups. As demonstrated by spectroscopic analysis, the supercapacitive behaviors of the functionalized CNTs originate from specific interactions between functional groups and lithium ions and the alteration of the electronic structure arising from covalent functionalization.The covalent functionalization of carbon nanotubes (CNTs) is a basic but important chemistry that can modify their physicochemical properties, resolve their poor dispersion capability, and improve their capacitance to enable their use as high-energy supercapacitors. However, the relationship between functional groups on the CNT surface and their capacitive characteristics has not yet been explored. Here, we demonstrate the influence of carboxylic, sulfonic, and amine groups tethered to CNTs (Cf-CNTs, Sf-CNTs, and Nf-CNTs, respectively) on capacitor performance in an organic electrolyte. The Cf-CNTs show the highest specific capacitance of 129.4 F g-1, four-fold greater than 31.2 F g-1 of pristine CNTs, but they reveal the lowest rate capability of 57%. In contrast, the Sf- and Nf-CNTs exhibit specific capacitances of 70.9 F g-1 and 83.6 F g-1, two-fold greater than that of pristine CNTs, along with a good rate capability greater than 80%. Despite their pseudocapacitive nature, all functionalized CNTs show a cyclic stability of more than 80% after 500 cycles due to the electrochemical stability of the functional groups. As demonstrated by spectroscopic analysis, the supercapacitive behaviors of the functionalized CNTs originate from specific interactions between functional groups and lithium ions and the alteration of the electronic structure arising from covalent functionalization. Electronic supplementary information (ESI) available: Optical images, XPS spectra, N2 adsorption/desorption isotherms, CV curves, and impedance spectra. See DOI: 10.1039/c3nr04858f

Park, Sul Ki; Mahmood, Qasim; Park, Ho Seok

2013-11-01

84

Carboxyl-Group Footprinting Maps the Dimerization Interface and Phosphorylation-induced Conformational Changes of a Membrane-associated Tyrosine Kinase*  

PubMed Central

Her4 is a transmembrane receptor tyrosine kinase belonging to the ErbB-EGFR family. It plays a vital role in the cardiovascular and nervous systems, and mutations in Her4 have been found in melanoma and lung cancer. The kinase domain of Her4 forms a dimer complex, called the asymmetric dimer, which results in kinase activation. Although a crystal structure of the Her4 asymmetric dimer is known, the dimer affinity and the effect of the subsequent phosphorylation steps on kinase domain conformation are unknown. We report here the use of carboxyl-group footprinting MS on a recombinant expressed, Her4 kinase-domain construct to address these questions. Carboxyl-group footprinting uses a water-soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, in the presence of glycine ethyl ester, to modify accessible carboxyl groups on glutamate and aspartate residues. Comparisons of Her4 kinase-domain monomers versus dimers and of unphosphorylated versus phosphorylated dimers were made to map the dimerization interface and to determine phosphorylation induced-conformational changes. We detected 37 glutamate and aspartate residues that were modified, and we quantified their extents of modification by liquid chromatography MS. Five residues showed changes in carboxyl-group modification. Three of these residues are at the predicted dimer interface, as shown by the crystal structure, and the remaining two residues are on loops that likely have altered conformation in the kinase dimer. Incubating the Her4 kinase dimers with ATP resulted in dramatic increase in Tyr-850 phosphorylation, located on the activation loop, and this resulted in a conformational change in this loop, as evidenced by reduction in carboxyl-group modification. The kinase monomer-dimer equilibrium was measured using a titration format in which the extent of carboxyl-group footprinting was mathematically modeled to give the dimer association constant (1.5–6.8 × 1012 dm2/mol). This suggests that the kinase-domain makes a significant contribution to the overall dimerization affinity of the full-length Her4 protein. PMID:21422241

Zhang, Hao; Shen, Wei; Rempel, Don; Monsey, John; Vidavsky, Ilan; Gross, Michael L.; Bose, Ron

2011-01-01

85

Localization of functions defined on cantor group  

NASA Astrophysics Data System (ADS)

We introduce a notion of localization for dyadic functions, i. e. functions defined on Cantor group. Both non-periodic and periodic cases are discussed. Localization is characterized by functionals UCd and UCdp similar to the Heisenberg (the Breitenberger) uncertainty constants used for real-line (periodic) functions. We are looking for dyadic analogs of uncertainty principles. To justify definition we use some test functions including dyadic scaling and wavelet functions.

Krivoshein, Aleksander V.; Lebedeva, Elena A.

2013-10-01

86

Relating Functional Groups to the Periodic Table  

ERIC Educational Resources Information Center

An introduction to organic chemistry functional groups and their ionic variants is presented. Functional groups are ordered by the position of their specific (hetero) atom in the periodic table. Lewis structures are compared with their corresponding condensed formulas. (Contains 5 tables.)

Struyf, Jef

2009-01-01

87

Copper-Catalyzed Carboxylation of Aryl Iodides with Carbon Dioxide  

PubMed Central

A method for carboxylation of aryl iodides with carbon dioxide has been developed. The reaction employs low loadings of copper iodide/TMEDA or DMEDA catalyst, 1 atm of CO2, DMSO or DMA solvent, and proceeds at 25–70 °C. Good functional group tolerance is observed, with ester, bromide, chloride, fluoride, ether, hydroxy, amino, and ketone functionalities tolerated. Additionally, hindered aryl iodides such as iodomesitylene can also be carboxylated PMID:24288654

Tran-Vu, Hung; Daugulis, Olafs

2013-01-01

88

Determination of binding constants of labile ligands in metal–ligand complexes containing carboxylic groups bound polymer by using breakthrough technique  

Microsoft Academic Search

This study was conducted to confirm the possibilities of determining the binding constants of ligands in metal–ligand complexes containing carboxylic groups bound polymer by using breakthrough technique. Aniline and o-anisidine were selected as model ligands. A mini column apparatus was used to study sorption of ligands onto ligand exchange resin. The experiments were conducted in a constant temperature at 25°C.

Ahmet Ayar; A. Ihsan Pekacar; Bedrettin Mercimek

2003-01-01

89

Effects of the density of carboxyl groups in organic compounds on the photocatalytic reduction of Cr(VI) in a TiO2 suspension  

Microsoft Academic Search

Photocatalytic reduction (PCR) of Cr(VI) in a TiO2 suspension was studied at pH 4 in the presence of organic compounds containing different numbers of carboxyl groups. The compounds studied were glycine (Gly), iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA). In all the cases, near complete Cr(VI) removal was observed after 60 minutes. During PCR process, the aqueous Cr(VI)

Seung-Mok Lee; Il-Hyoung Cho; Yoon-Young Chang; Jae-Kyu Yang

2007-01-01

90

The central role of ketones in reversible and irreversible hydrothermal organic functional group transformations  

NASA Astrophysics Data System (ADS)

Studies of hydrothermal reactions involving organic compounds suggest complex, possibly reversible, reaction pathways that link functional groups from reduced alkanes all the way to oxidized carboxylic acids. Ketones represent a critical functional group because they occupy a central position in the reaction pathway, at the point where Csbnd C bond cleavage is required for the formation of the more oxidized carboxylic acids. The mechanisms for the critical bond cleavage reactions in ketones, and how they compete with other reactions are the focus of this experimental study. We studied a model ketone, dibenzylketone (DBK), in H2O at 300 °C and 70 MPa for up to 528 h. Product analysis was performed as a function of time at low DBK conversions to reveal the primary reaction pathways. Reversible interconversion between ketone, alcohol, alkene and alkane functional groups is observed in addition to formation of radical coupling products derived from irreversible Csbnd C and Csbnd H homolytic bond cleavage. The product distributions are time-dependent but the bond cleavage products dominate. The major products that accumulate at longer reaction times are toluene and larger, dehydrogenated structures that are initially formed by radical coupling. The hydrogen atoms generated by dehydrogenation of the coupling products are predominantly consumed in the formation of toluene. Even though bond cleavage products dominate, no carboxylic acids were observed on the timescale of the reactions under the chosen experimental conditions.

Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

2012-12-01

91

Liapunov functions Nonlinear dynamics reading group  

E-print Network

Liapunov functions revisited Nonlinear dynamics reading group Maria Joao 1st October, 2009 #12;Nonlinear dynamics reading group I. Introduction Non-linear dynamical system: Autonomous: Non;Nonlinear dynamics reading group I. Introduction Good place to start: (1) determine equilibrium points (2

Daunizeau, Jean

92

Preparation and characterization of multi-carboxyl-functionalized silica gel for removal of Cu (II), Cd (II), Ni (II) and Zn (II) from aqueous solution  

NASA Astrophysics Data System (ADS)

In this paper, the multi-carboxyl-functionalized silica gel was prepared by surface grafting method and applied for the removal of Cu (II), Cd (II), Ni (II) and Zn (II) from aqueous solution. The adsorbent was characterized by FT-IR, thermogravimetry, Brunauer-Emmett-Teller surface area measurement and elemental analysis, and it proved that the organic functional group, carboxyl group, was grafted successfully onto the silica gel surface. The effect of solution pH on removal efficiencies of Cu (II), Cd (II), Ni (II) and Zn (II) was investigated and it was found that with the exception of Zn (II), the removal efficiencies of the rest of metal ions increased with the increasing of pH in the solution, the maximum removal efficiency occurred at pH 6.0, whereas the maximum removal efficiency for Zn (II) was found to be at pH 7.0. Adsorption equilibrium data were well fitted to Langmuir than Freundlich isotherm model and the maximum adsorption capacity for Cu (II), Cd (II), Ni (II) and Zn (II) was 47.07, 41.48, 30.80 and 39.96 mg/g, respectively. Competitive adsorption experiments demonstrated that the adsorbent material had excellent adsorption amount and high affinity for the Cu (II) in the binary systems. In addition, the column experiments were used to investigate stability and reusability of the adsorbent, the dynamic adsorption performance, and desorption of metal ions absorbed from the adsorbent. The results confirmed that the adsorbent presents good dynamic adsorption performance for Cu (II), Cd (II), Ni (II) and Zn (II) and these metal ions adsorbed were easy to be desorbed from the adsorbent. The adsorption capacities of metal ions did not present an obvious decrease after five cycles of adsorption-desorption.

Li, Min; Li, Ming-yu; Feng, Chang-gen; Zeng, Qing-xuan

2014-09-01

93

Macroevolutionary trends of atomic composition and related functional group proportion in eukaryotic and prokaryotic proteins.  

PubMed

To fully explore the trends of atomic composition during the macroevolution from prokaryote to eukaryote, five atoms (oxygen, sulfur, nitrogen, carbon, hydrogen) and related functional groups in prokaryotic and eukaryotic proteins were surveyed and compared. Genome-wide analysis showed that eukaryotic proteins have more oxygen, sulfur and nitrogen atoms than prokaryotes do. Clusters of Orthologous Groups (COG) analysis revealed that oxygen, sulfur, carbon and hydrogen frequencies are higher in eukaryotic proteins than in their prokaryotic orthologs. Furthermore, functional group analysis demonstrated that eukaryotic proteins tend to have higher proportions of sulfhydryl, hydroxyl and acylamino, but lower of sulfide and carboxyl. Taken together, an apparent trend of increase was observed for oxygen and sulfur atoms in the macroevolution; the variation of oxygen and sulfur compositions and their related functional groups in macroevolution made eukaryotic proteins carry more useful functional groups. These results will be helpful for better understanding the functional significances of atomic composition evolution. PMID:24262937

Zhang, Yu-Juan; Yang, Chun-Lin; Hao, You-Jin; Li, Ying; Chen, Bin; Wen, Jian-Fan

2014-01-25

94

Identifying organic aerosol sources by comparing functional group composition in chamber and atmospheric particles.  

PubMed

Measurements of submicron particles by Fourier transform infrared spectroscopy in 14 campaigns in North America, Asia, South America, and Europe were used to identify characteristic organic functional group compositions of fuel combustion, terrestrial vegetation, and ocean bubble bursting sources, each of which often accounts for more than a third of organic mass (OM), and some of which is secondary organic aerosol (SOA) from gas-phase precursors. The majority of the OM consists of alkane, carboxylic acid, hydroxyl, and carbonyl groups. The organic functional groups formed from combustion and vegetation emissions are similar to the secondary products identified in chamber studies. The near absence of carbonyl groups in the observed SOA associated with combustion is consistent with alkane rather than aromatic precursors, and the absence of organonitrate groups can be explained by their hydrolysis in humid ambient conditions. The remote forest observations have ratios of carboxylic acid, organic hydroxyl, and nonacid carbonyl groups similar to those observed for isoprene and monoterpene chamber studies, but in biogenic aerosols transported downwind of urban areas the formation of esters replaces the acid and hydroxyl groups and leaves only nonacid carbonyl groups. The carbonyl groups in SOA associated with vegetation emissions provides striking evidence for the mechanism of esterification as the pathway for possible oligomerization reactions in the atmosphere. Forest fires include biogenic emissions that produce SOA with organic components similar to isoprene and monoterpene chamber studies, also resulting in nonacid carbonyl groups in SOA. PMID:21317360

Russell, Lynn M; Bahadur, Ranjit; Ziemann, Paul J

2011-03-01

95

Department and function Group Leader, Cell Biology  

E-print Network

processing; lipid rafts and their function in MHC II biology; roles of intestinal epithelial cells in mucosalDepartment and function Group Leader, Cell Biology Education: 1982-1987 Biology, Technical of Bonn since 2000 Assistant in the Department of Cell Biology Major research interests: Antigen

Manstein, Dietmar J.

96

Effect of carbon nanofiber surface functional groups on oxygen reduction in alkaline solution  

NASA Astrophysics Data System (ADS)

Carbon nanofibers (CNFs) with different content of surface functional groups which are carboxyl groups (CNF-OX), carbonyl groups (CNF-CO) and hydroxyl groups (CNF-OH) and nitrogen-containing groups (CNF-ON) are synthesized, and their electrocatalytic activities toward oxygen reduction reaction (ORR) in alkaline solution are investigated. The result of X-ray photoelectron spectroscopy (XPS) characterization indicates that a higher concentration of carboxyl groups, carbonyl groups and hydroxyl groups are imported onto the CNF-OX, CNF-CO and CNF-OH, respectively. Cyclic voltammetry shows that both the oxygen- and nitrogen-containing groups can improve the electrocatalytic activity of CNFs for ORR. The CNF-ON/GC electrode, which has nitrogen-containing groups, exhibits the highest current density of ORR. Rotating disk electrode (RDE) characterization shows that the oxygen reduction on CNF-ON/GC electrode proceeds almost entirely through the four-electron reduction pathway, the CNF-OX/GC, CNF-CO/GC and CNF-OH/GC electrodes proceed a two-electron reduction pathway at low potentials (-0.2 V to -0.6 V) followed by a gradual four-electron reduction pathway at more negative potentials, while the untreated carbon nanofiber (CNF-P/GC) electrode proceeds predominantly by a two-electron reduction pathway within the whole range of potential studied.

Zhong, Ren-Sheng; Qin, Yuan-Hang; Niu, Dong-Fang; Tian, Jing-Wei; Zhang, Xin-Sheng; Zhou, Xin-Gui; Sun, Shi-Gang; Yuan, Wei-Kang

2013-03-01

97

Functional Groups in the Avian Auditory System  

PubMed Central

Auditory perception depends on the coding and organization of the information-bearing acoustic features of sounds by auditory neurons. We report here that auditory neurons can be classified into functional groups each of which plays a specific role in extracting distinct complex sound features. We recorded the electrophysiological responses of single auditory neurons in the songbird midbrain and forebrain to conspecific song, measured their tuning by calculating spectrotemporal receptive fields (STRFs) and classified them using multiple cluster analysis methods. Based on STRF shape, cells clustered into functional groups that divided the space of acoustical features into regions that represent cues for the fundamental acoustic percepts of pitch, timbre and rhythm. Four major groups were found in the midbrain and five major groups were found in the forebrain. Comparing STRFs in midbrain and forebrain neurons suggested that both inheritance and emergence of tuning properties occur as information ascends the auditory processing stream. PMID:19261874

Woolley, Sarah M. N.; Gill, Patrick R.; Fremouw, Thane; Theunissen, Frederic E.

2009-01-01

98

Ising exponents from the functional renormalization group  

SciTech Connect

We study the 3d Ising universality class using the functional renormalization group. With the help of background fields and a derivative expansion up to fourth order we compute the leading index, the subleading symmetric and antisymmetric corrections to scaling, the anomalous dimension, the scaling solution, and the eigenperturbations at criticality. We also study the cross correlations of scaling exponents, their dependence on dimensionality, and the numerical convergence of the derivative expansion. Collecting all available data from functional renormalization group studies to date, we estimate that systematic errors are in good agreement with findings from Monte Carlo simulations, {epsilon}-expansion techniques, and resummed perturbation theory.

Litim, Daniel F. [Department of Physics and Astronomy, University of Sussex, BN1 9QH, Brighton (United Kingdom); Zappala, Dario [INFN, Sezione di Catania, 64 via S. Sofia, I-95123, Catania (Italy)

2011-04-15

99

Functional groups grafted nonwoven fabrics for blood filtration-The effects of functional groups and wettability on the adhesion of leukocyte and platelet  

NASA Astrophysics Data System (ADS)

In this work, the effects of grafted functional groups and surface wettability on the adhesion of leukocyte and platelet were investigated by the method of blood filtration. The filter materials, poly(butylene terephthalate) nonwoven fabrics bearing different functional groups including hydroxyl (OH), carboxyl (COOH), sulfonic acid group (SO3H) and zwitterionic sulfobetaine group (?N((CH3)2)(CH2)3SO3?) with controllable wettability were prepared by UV radiation grafting vinyl monomers with these functional groups. Our results emphasized that both surface functional groups and surface wettability had significant effects on the adhesion of leukocyte and platelet. In the case of filter materials with the same wettability, leukocytes adhering to filter materials decreased in the order: the surface bearing OH only > the surface bearing both OH and COOH > the surface bearing sulfobetaine group > the surface bearing SO3H, while platelets adhering to filter materials decreased as the following order: the surface bearing SO3H > the surface bearing both OH and COOH > the surface bearing OH only > the surface bearing sulfobetaine group. As the wettability of filter materials increased, both leukocyte and platelet adhesion to filter materials declined, except that leukocyte adhesion to the surface bearing OH only remained unchanged.

Yang, Chao; Cao, Ye; Sun, Kang; Liu, Jiaxin; Wang, Hong

2011-01-01

100

Department and function: Group Leader, Clinical Immunology  

E-print Network

Department and function: Group Leader, Clinical Immunology Education: 1981-1986 Biology in Hannover Positions: 1987-recent Scientist in the Division of Clinical Immunology, MHH 1992 PhD in Biology, MHH 2003 Habilitation in Immunology, MHH Major research interests: Analysis of Natural Killer (NK) cell subpopulations

Manstein, Dietmar J.

101

Influence of functional groups on the C ?-C ? chain of L-phenylalanine and its derivatives  

NASA Astrophysics Data System (ADS)

L-phenylalanine ( L-phe) consists of three different functional groups, i.e., phenyl, carboxyl (-COOH) and amino (-NH 2), joining through the C ?-C ? bridge. Substitution of these groups produces 2-phenethylamine (PEA) and 3-phenylpropionic acid (PPA). Electronic structures of L-phe, PEA and PPA together with smaller "fragments" L-alanine and benzene were determined using density functional theory (DFT), from which core and valence shell ionization spectra were simulated. Comparison of the spectra reveals that core shell ionization energies clearly indicate that the carbon bridge is significantly affected by their functional group substitutions particularly at the C ? site. In the valence space, quite unexpectedly, the frontier orbitals are concentrated on the benzene group although some energy splitting is observed. The orbitals which significantly affect the C ?-C ? carbon backbone are from the inner valence shell in the ionization energy region of 20-26 eV of the molecules.

Ganesan, Aravindhan; Brunger, Michael; Wang, Feng

2010-07-01

102

Interaction network among functional drug groups  

PubMed Central

Background More attention has been being paid to combinatorial effects of drugs to treat complex diseases or to avoid adverse combinations of drug cocktail. Although drug interaction information has been increasingly accumulated, a novel approach like network-based method is needed to analyse that information systematically and intuitively Results Beyond focussing on drug-drug interactions, we examined interactions between functional drug groups. In this work, functional drug groups were defined based on the Anatomical Therapeutic Chemical (ATC) Classification System. We defined criteria whether two functional drug groups are related. Then we constructed the interaction network of drug groups. The resulting network provides intuitive interpretations. We further constructed another network based on interaction sharing ratio of the first network. Subsequent analysis of the networks showed that some features of drugs can be well described by this kind of interaction even for the case of structurally dissimilar drugs. Conclusion Our networks in this work provide intuitive insights into interactions among drug groups rather than those among single drugs. In addition, information on these interactions can be used as a useful source to describe mechanisms and features of drugs. PMID:24555875

2013-01-01

103

The Circular Velocity Function of Group Galaxies  

NASA Astrophysics Data System (ADS)

A robust prediction of ?CDM cosmology is the halo circular velocity function (CVF), a dynamical cousin of the halo mass function. The correspondence between theoretical and observed CVFs is uncertain, however: cluster galaxies are reported to exhibit a power-law CVF consistent with N-body simulations, but that of the field is distinctly Schechter-like, flattened compared to ?CDM expectations at circular velocities v c <~ 200 km s–1. Groups offer a powerful probe of the role environment plays in this discrepancy as they bridge the field and clusters. Here, we construct the CVF for a large, mass- and multiplicity-complete sample of group galaxies from the Sloan Digital Sky Survey. Using independent photometric v c estimators, we find no transition from field to ?CDM-shaped CVF above v c = 50 km s–1 as a function of group halo mass. All groups with 12.4 <~ log M halo/M ? <~ 15.1 (Local Group analogs to rich clusters) display similar Schechter-like CVFs marginally suppressed at low v c compared to that of the field. Conversely, some agreement with N-body results emerges for samples saturated with late-type galaxies, with isolated late-types displaying a CVF similar in shape to ?CDM predictions. We conclude that the flattening of the low-v c slope in groups is due to their depressed late-type fractions—environment affecting the CVF only to the extent that it correlates with this quantity—and that previous cluster analyses may suffer from interloper contamination. These results serve as useful benchmarks for cosmological simulations of galaxy formation.

Abramson, Louis E.; Williams, Rik J.; Benson, Andrew J.; Kollmeier, Juna A.; Mulchaey, John S.

2014-09-01

104

Functional renormalization group approach to neutron matter  

NASA Astrophysics Data System (ADS)

The chiral nucleon-meson model, previously applied to systems with equal number of neutrons and protons, is extended to asymmetric nuclear matter. Fluctuations are included in the framework of the functional renormalization group. The equation of state for pure neutron matter is studied and compared to recent advanced many-body calculations. The chiral condensate in neutron matter is computed as a function of baryon density. It is found that, once fluctuations are incorporated, the chiral restoration transition for pure neutron matter is shifted to high densities, much beyond three times the density of normal nuclear matter.

Drews, Matthias; Weise, Wolfram

2014-11-01

105

2-(4-Carb-oxy-piperidinium-1-yl)pyridine-3-carboxyl-ate  

PubMed Central

The title compound, C12H14N2O4, crystallizes as a zwitterion. A negative charge is delocalized in the deprotonated carboxyl group attached to the pyridine ring. The piperidine N atom accepts a proton and the ring is transformed into a piperidinium cation. There is an intra­molecular N—H?O hydrogen bond between the protonated NH and a carboxyl­ate O atom. In the crystal, an O—H?O hydrogen bond between the carboxyl group and the carboxyl­ate O atom of another mol­ecule generates a helix along the b axis. PMID:22412757

Fan, Ping; Ge, Chunhua; Sun, Mingjun; Li, Weiwei; Shang, Runshan

2012-01-01

106

Effect of functional groups on sludge for biosorption of reactive dyes.  

PubMed

The sludge, which was collected from a biological coke wastewater treatment plant, was used as a low-cost adsorbent in the removal of reactive dyes (Methylene Blue (MB) and Reactive Red 4 (RR4)) from aqueous solution. The pH of dye solution played an important role on the dye uptake. With the solution pH increase, the MB uptake increased; whereas the RR4 uptake decreased. The maximum uptake of RR4 by protonated sludge was 73.7 mg/g at pH 1, and the maximum uptake of MB by sludge was 235.3 mg/g at pH 9. Three functional groups, including carboxyl, phosphonate, and amine group, were identified by potentiometric titration, fourier transform infrared (FT-IR) spectrometry, and X-ray photoelectron spectroscopy (XPS). The anionic functional groups, phosphonate and carboxyl group, were identified as the binding sites for the cationic MB. Amine groups were identified to bind RR4. The main mechanism of the reactive dyestuffs adsorption is electrostatic interaction. PMID:19634431

Cai, Junxiong; Cui, Longzhe; Wang, Yanxin; Liu, Chengfu

2009-01-01

107

Modeling the hydrolysis of perfluorinated compounds containing carboxylic and phosphoric acid ester functions and sulfonamide groups  

Microsoft Academic Search

Temperature-dependent rate constants were estimated for the acid- and base-catalyzed and neutral hydrolysis reactions of perfluorinated telomer acrylates (FTAcrs) and phosphate esters (FTPEs), and the SN1 and SN2 hydrolysis reactions of fluorotelomer iodides (FTIs). Under some environmental conditions, hydrolysis of monomeric FTAcrs could be rapid (half-lives of several years in marine systems and as low as several days in some

Sierra Rayne; Kaya Forest

2010-01-01

108

A carboxyl-terminal hydrophobic interface is critical to sodium channel function. Relevance to inherited disorders.  

PubMed

Perturbation of sodium channel inactivation, a finely tuned process that critically regulates the flow of sodium ions into excitable cells, is a common functional consequence of inherited mutations associated with epilepsy, skeletal muscle disease, autism, and cardiac arrhythmias. Understanding the structural basis of inactivation is key to understanding these disorders. Here we identify a novel role for a structural motif in the COOH terminus of the heart NaV1.5 sodium channel in determining channel inactivation. Structural modeling predicts an interhelical hydrophobic interface between paired EF hands in the proximal region of the NaV1.5 COOH terminus. The predicted interface is conserved among almost all EF hand-containing proteins and is the locus of a number of disease-associated mutations. Using the structural model as a guide, we provide biochemical and biophysical evidence that the structural integrity of this interface is necessary for proper Na+ channel inactivation gating. We thus demonstrate a novel role of the sodium channel COOH terminus structure in the control of channel inactivation and in pathologies caused by inherited mutations that disrupt it. PMID:16798729

Glaaser, Ian W; Bankston, John R; Liu, Huajun; Tateyama, Michihiro; Kass, Robert S

2006-08-18

109

Simultaneous determination of interfacial molarities of amide bonds, carboxylate groups, and water by chemical trapping in micelles of amphiphiles containing peptide bond models.  

PubMed

Chemical trapping is a powerful approach for obtaining experimental estimates of interfacial molarities of weakly basic nucleophiles in the interfacial regions of amphiphile aggregates. Here, we demonstrate that the chemical probe 4-hexadecyl-2,6-dimethylbenzenediazonium ion (16-ArN(2)(+)) reacts competitively with interfacial water, with the amide carbonyl followed by cleavage of the headgroups from the tail at the amide oxygen, and with the terminal carboxylate groups in micelles of two N-acyl amino-acid amphiphiles, sodium N-lauroylsarcosinate (SLS) and sodium N-lauroylglycinate (SLG), simple peptide bond model amphiphiles. Interfacial molarities (in moles per liter of interfacial volume) of these three groups were obtained from product yields, assuming that selectivity toward a particular nucleophile compared to water is the same in an aqueous reference solution and in the interfacial region. Interfacial carboxylate group molarities are ~1.5 M in both SLS and SLG micelles, but the concentration of the amide carbonyl for SLS micelles is ~4.6-5 times less (ca. 0.7 M) than that of SLG micelles (~3 M). The proton on the secondary N of SLG helps solubilize the amide bond in the aqueous region, but the methyl on the tertiary N of SLS helps solubilize the amide bond in the micellar core, reducing its reaction with 16-ArN(2)(+). Application of chemical trapping to proteins in membrane mimetic interfaces should provide insight into the topology of the protein within the interface because trapping of the amide carbonyl and cleavage at the C-N bond occurs only within the interface, and fragment characterization marks those peptide bonds located within the interface. PMID:23237147

Zhang, Yongliang; Romsted, Laurence S; Zhuang, Lanzhen; de Jong, Sander

2013-01-15

110

Identification and quantification of aerosol polar oxygenated compounds bearing carboxylic or hydroxyl groups. 2. Organic tracer compounds from monoterpenes.  

PubMed

In this study, a comparison is made of polar organic compounds found in the field with those produced in secondary organic aerosol from laboratory irradiations of natural hydrocarbons and oxides of nitrogen (NOx). The field samples comprised atmospheric particulate matter (PM2.5) collected at Research Triangle Park (RTP), NC, during the summer of 2003, and the laboratory samples originated from the photooxidation of the following monoterpenes: alpha-pinene, beta-pinene, and d-limonene. To determine the structural characteristics of the polar compounds, the filter samples were solvent extracted and derivatized using a technique based on single and multistep derivatizations. The resulting compound derivatives were analyzed by GC-MS in the methane-Cl and El modes. In addition to previously reported biogenic oxidation products (pinic acid, pinonic acid, norpinic acid, nopinone, and pinonaldehyde), seven multifunctional organic compounds were found in both field and laboratory samples. These compounds, which are proposed as possible atmospheric tracers for secondary organic aerosol from monoterpenes, were consistent with the following identifications: 3-isopropyl pentanedioic acid; 3-acetyl pentanedioic acid; 3-carboxy heptanedioic acid; 3-acetyl hexanedioic acid; 2-isopropyl-1,2-dihydroxybutanol; 4-isopropyl-2,4-dihydroxyhexanol; and 3-(2-hydroxy-ethyl)-2,2-dimethyl-cyclobutane carboxylic acid. Initial attempts have been made to quantify the concentrations of these tracer compounds on the basis of surrogate compound calibrations. The occurrence of these compounds in both laboratory and field measurements suggests that secondary organic aerosol originating from biogenic hydrocarbons are contributing to the regional aerosol burden in the southeastern United States. Several of these compounds also appear to contribute to the global aerosol burden in that they have also been identified in Europe and Brazil. PMID:16124301

Jaoui, M; Kleindienst, T E; Lewandowski, M; Offenberg, J H; Edney, E O

2005-08-01

111

POLYCOMB GROUP COMPLEXES - MANY COMBINATIONS, MANY FUNCTIONS  

PubMed Central

Polycomb Group (PcG) proteins are transcription regulatory proteins that control the expression of a variety of genes from early embryogenesis through birth to adulthood. PcG proteins form several complexes that are thought to collaborate to repress gene transcription. Individual PcG proteins have unique characteristics and mutations in genes encoding different PcG proteins cause distinct phenotypes. Histone modifications have important roles in some PcG protein functions, but they are not universally required. The mechanisms of gene-specific recruitment, transcription repression, and selective derepression of genes by vertebrate PcG proteins are incompletely understood. Future studies of this enigmatic group of developmental regulators are certain to produce unanticipated discoveries. PMID:19889541

Kerppola, Tom K

2010-01-01

112

rac-Ammonium cis-2-carb-oxy-cyclo-hexane-1-carboxyl-ate  

PubMed Central

In the structure of the title compound, NH4 +·C8H11O4 ?, the carboxyl and carboxyl­ate groups of the cation adopt C—C—C—O torsion angles of 174.9?(2) and ?145.4?(2)°, respectively, with the alicyclic ring. The ammonium H atoms of the cations give a total of five hydrogen-bonding associations with carboxyl­ate O-atom acceptors of the anion which, together with a carboxyl O—H?Ocarboxyl­ate inter­action give sheet structures which lie in the (101) planes. PMID:21522680

Smith, Graham; Wermuth, Urs D.

2011-01-01

113

High-throughput aided synthesis of the porous metal-organic framework-type aluminum pyromellitate, MIL-121, with extra carboxylic acid functionalization.  

PubMed

A new porous metal-organic framework (MOF)-type aluminum pyromellitate (MIL-121 or Al(OH)[H(2)btec]·(guest), (guest = H(2)O, H(4)btec = pyromellitic acid) has been isolated by using a high-throughput synthesis method under hydrothermal conditions. Its structure was determined from powder X-ray diffraction analysis using synchrotron radiation (Soleil, France) and exhibits a network closely related to that of the MIL-53 series. It is a three-dimensional (3D) framework containing one-dimensional (1D) channels delimited by infinite trans-connected aluminum-centered octahedra AlO(4)(OH)(2) linked through the pyromellitate ligand. Here the organic ligand acts as tetradendate linker via two of the carboxylate groups. The two others remain non-bonded in their protonated form, and this constitutes a rare case of the occurrence of both bonding and non-bonding organic functionalities of the MOF family. The non-coordinated -COOH groups points toward the channels to get them an open form configuration. Within the tunnels are located unreacted pyromellitic acid and water species, which are evacuated upon heating, and a porous MIL-121 phase is obtained with a Brunauer-Emmett-Teller (BET) surface area of 162 m(2) g(-1). MIL-121 has been characterized by IR, thermogravimetry (TG) analyses, and solid state NMR spectroscopy employing a couple of two-dimensional (2D) techniques such as (1)H-(1)H SQ-DQ BABA, (1)H-(1)H SQ-SQ RFDR, (27)Al{(1)H} CPHETCOR and (27)Al MQMAS. PMID:20923169

Volkringer, Christophe; Loiseau, Thierry; Guillou, Nathalie; Férey, Gérard; Haouas, Mohamed; Taulelle, Francis; Elkaim, Erik; Stock, Norbert

2010-11-01

114

Structural Synergism in Functionalized Polymers: New Catalysts for Transacylation Reactions of Derivatives of Carboxylic and Phosphoric Acids.  

National Technical Information Service (NTIS)

This project has focused on the development of new highly-efficient, selective catalysts for widely-used commercial and biological reactions of carboxylic and phosphoric acids and their derivatives. The first phase of the project included the design and s...

M. Zeldin, W. K. Fife

1991-01-01

115

A simple one-step modification of various materials for introducing effective multi-functional groups.  

PubMed

Covalent immobilization of various biomolecules is a desired strategy for bio-multifunctional surface modification. Multi-functionalization of a material surface is considered to be the premise of immobilizing a variety of biomolecules. However, currently adopted methods, used to introduce proper reactive functional groups on material surfaces, mostly are hard to be carried out and frequently can only introduce insufficient functional groups. In this work, we successfully develop the films (GAHD films) prepared via the simple copolymerization of gallic acid (GA) and hexamethylenediamine (HD), which can be deposited on different kinds of material surfaces including metals, ceramics and polymers by a one-step dip-coating method. Moreover, these copolymerized GAHD films possess high concentration of multi-functional groups like carboxyl (COOH), primary amine (-NH2) and quinone groups on the surfaces. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results prove either the occurrence of Michael addition reaction, Schiff base reaction in the film-forming process, or the existence of COOH, NH2 and quinone groups on the surfaces. The maximum contents of carboxyl and amine on the GAHD film are 24.9 nmol/cm(2) and 31.7 nmol/cm(2) respectively. After dynamical immersion for 30 days, slight swellings can be observed, which reveals that the GAHD films possess good stability. Moreover, Heparin (Hep), fibronectin (Fn) and laminin (Ln) are successfully immobilized on the GAHD film surfaces. The results of cell counting kit-8 (CCK-8) and rhodamine fluorescence photograph indicate that the 1:1.62 GAHD film has good cytocompatibility. PMID:24064415

Chen, Si; Li, Xin; Yang, Zhilu; Zhou, Shuo; Luo, Rifang; Maitz, Manfred F; Zhao, Yuancong; Wang, Jin; Xiong, Kaiqin; Huang, Nan

2014-01-01

116

Carboxylic acid functionalization prevents the translocation of multi-walled carbon nanotubes at predicted environmentally relevant concentrations into targeted organs of nematode Caenorhabditis elegans  

NASA Astrophysics Data System (ADS)

Carboxyl (-COOH) surface modified multi-walled carbon nanotubes (MWCNTs-COOH) can be used for targeted delivery of drugs and imaging. However, whether MWCNTs-COOH at environmentally relevant concentrations exert certain toxic effects on multicellular organisms and the underlying mechanisms are still largely unclear. In the present study, we applied the nematode Caenorhabditis elegans to evaluate the properties of MWCNTs-COOH at environmentally relevant concentrations by comparing the effects of MWCNTs and MWCNTs-COOH exposure on C. elegans from L1-larvae to adult at concentrations of 0.001-1000 ?g L-1. Exposure to MWCNTs could potentially damage the intestine (primary targeted organ) at concentrations greater than 0.1 ?g L-1 and functions of neurons and reproductive organ (secondary targeted organs) at concentrations greater than 0.001 ?g L-1. Carboxyl modification prevented the toxicity of MWCNTs on the primary and the secondary targeted organs at concentrations less than 100 ?g L-1, suggesting that carboxyl modification can effectively prevent the adverse effects of MWCNTs at environmentally relevant concentrations. After exposure, MWCNTs-COOH (1 mg L-1) were translocated into the spermatheca and embryos in the body through the primary targeted organs. However, MWCNTs-COOH (10 ?g L-1) were not observed in spermatheca and embryos in the body of nematodes. Moreover, relatively high concentrations of MWCNTs-COOH exposed nematodes might have a hyper-permeable intestinal barrier, whereas MWCNTs-COOH at environmentally relevant concentrations effectively sustained the normally permeable state for the intestinal barrier. Therefore, we elucidated the cellular basis of carboxyl modification to prevent toxicity of MWCNTs at environmentally relevant concentrations. Our data highlights the key role of biological barriers in the primary targeted organs to block toxicity formation from MWCNTs, which will be useful for the design of effective prevention strategies against MWCNTs toxicity.Carboxyl (-COOH) surface modified multi-walled carbon nanotubes (MWCNTs-COOH) can be used for targeted delivery of drugs and imaging. However, whether MWCNTs-COOH at environmentally relevant concentrations exert certain toxic effects on multicellular organisms and the underlying mechanisms are still largely unclear. In the present study, we applied the nematode Caenorhabditis elegans to evaluate the properties of MWCNTs-COOH at environmentally relevant concentrations by comparing the effects of MWCNTs and MWCNTs-COOH exposure on C. elegans from L1-larvae to adult at concentrations of 0.001-1000 ?g L-1. Exposure to MWCNTs could potentially damage the intestine (primary targeted organ) at concentrations greater than 0.1 ?g L-1 and functions of neurons and reproductive organ (secondary targeted organs) at concentrations greater than 0.001 ?g L-1. Carboxyl modification prevented the toxicity of MWCNTs on the primary and the secondary targeted organs at concentrations less than 100 ?g L-1, suggesting that carboxyl modification can effectively prevent the adverse effects of MWCNTs at environmentally relevant concentrations. After exposure, MWCNTs-COOH (1 mg L-1) were translocated into the spermatheca and embryos in the body through the primary targeted organs. However, MWCNTs-COOH (10 ?g L-1) were not observed in spermatheca and embryos in the body of nematodes. Moreover, relatively high concentrations of MWCNTs-COOH exposed nematodes might have a hyper-permeable intestinal barrier, whereas MWCNTs-COOH at environmentally relevant concentrations effectively sustained the normally permeable state for the intestinal barrier. Therefore, we elucidated the cellular basis of carboxyl modification to prevent toxicity of MWCNTs at environmentally relevant concentrations. Our data highlights the key role of biological barriers in the primary targeted organs to block toxicity formation from MWCNTs, which will be useful for the design of effective prevention strategies against MWCNTs toxicity. Electronic supplementary information (ESI) available. See DOI: 10

Nouara, Abdelli; Wu, Qiuli; Li, Yinxia; Tang, Meng; Wang, Haifang; Zhao, Yuliang; Wang, Dayong

2013-06-01

117

Controlling the mechanism of trypsin inhibition by the numbers of ?-cyclodextrins and carboxyl groups in carboxyethylester-polyrotaxanes  

Microsoft Academic Search

Carboxyethylester-polyrotaxanes (CEE-polyrotaxanes) with the various number of CEE-modified ?-cyclodextrins (CEE-?-CDs) were synthesized, and the effects of the number of CEE-?-CDs on calcium binding and trypsin inhibition were investigated. Calcium binding affinity was dependent on the density of the CEE groups accompanied with the number of ?-CD threading in the CEE-polyrotaxanes. The high number of CEE-?-CDs leads to greater inhibition of

Masaru Eguchi; Tooru Ooya; Nobuhiko Yui

2004-01-01

118

Analysis of carboxyl group in coal and coal aromaticity by Fourier transform infrared (FT-IR) spectrometry  

Microsoft Academic Search

Thirty-five SS coals as well as two Australian lignites were analyzed by Fourier transform infrared (FT-IR) spectrometry using the KBr tablet method; the SS coals are a series of standard coals produced in various countries. A selected zone 1800–1500cm?1 of the FT-IR spectrum obtained was deconvoluted, and the peak area for COOH group in coal was obtained. The content of

Wenhua Geng; Tsunenori Nakajima; Hirokazu Takanashi; Akira Ohki

2009-01-01

119

A Mononuclear Carboxylate-Rich Oxoiron(IV) Complex: a Structural and Functional Mimic of TauD Intermediate 'J'  

PubMed Central

The pentadentate ligand nBu-P2DA (2(b), nBu-P2DA = N-(1?,1?-bis(2-pyridyl)pentyl)iminodiacetate) was designed to bind an iron center in a carboxylate-rich environment similar to that found in the active sites of TauD and other ?-ketoglutarate-dependent mononuclear non-heme iron enzymes. The iron(II) complex nBu4N[FeII(Cl)(nBu-P2DA)] (3(b)-Cl) was synthesized and crystallographically characterized to have a 2-pyridine-2-carboxylate donor set in the plane perpendicular to the Fe-Cl bond. Reaction of 3(b)-Cl with N-heterocyclic amines such as pyridine or imidazole yielded the N-heterocyclic amine adducts [FeII(N)(nBu-P2DA)]. These adducts in turn reacted with oxo-transfer reagents at ?95 °C to afford a short-lived oxoiron(IV) complex [FeIV(O)(nBu-P2DA)] (5(b)) in yields as high as 90% depending on the heterocycle used. Complex 5(b) exhibits near-IR absorption features (?max = 770 nm) and Mossbauer parameters (? = 0.04 mm/s; ?EQ = 1.13 mm/s; D = 27±2 cm?1) characteristic of an S = 1 oxoiron(IV) species. Direct evidence for an Fe=O bond of 1.66 Å was found from EXAFS analysis. DFT calculations on 5(b) in its S =1 spin state afforded a geometry-optimized structure consistent with the EXAFS data. They further demonstrated that the replacement of two pyridine donors in [FeIV(O)(N4Py)]2+ (N4Py = N,N-(bis(2-pyridyl)methyl)N-bis(2-pyridylmethyl)amine) with carboxylate donors in 5(b) decreased the energy gap between the ground S = 1 and the excited S = 2 states, reflecting the weaker equatorial ligand field of 5(b) and accounting for its larger D value. Complex 5(b) reacted readily with dihydrotoluene, methyldiphenylphosphine and ferrocene at ?60 °C, and in all cases was approximately a 5-fold more reactive oxidant than [FeIV(O)(N4Py)]2+. The reactivity differences between these two complexes may arise from a combination of electronic and steric factors. Carboxylate-rich 5(b) represents the closest structural mimic reported thus far of the oxoiron(IV) intermediate (‘J’) found in TauD and provides us with vital insights into the role carboxylate ligands play in modulating the spectroscopic and reactivity properties of the non-heme oxoiron(IV) moiety. PMID:23267430

McDonald, Aidan R.; Guo, Yisong; Vu, Van V.; Bominaar, Emile L.; Munck, Eckard; Que, Lawrence

2012-01-01

120

Amatoxins bearing amino and carboxyl groups prepared by selective alteration of the aldehyde generated by periodate oxidation of methylated alpha-amanitin.  

PubMed

Amatoxins are cyclic peptides which can be purified from the carpophores of various mushroom species. Since they were first recognized as potent inhibitors of the nuclear RNA polymerases of most eukaryotes these peptides have served as important tools in the study of transcription. The presence of unusual amino acid residues in these peptides has provided opportunities to attempt a variety of semisynthetic modifications. We describe several new amatoxin derivatives that were prepared by selective modification of an aldehyde group which can be generated by periodate oxidation of 6'-O-methyl-alpha-amanitin. The derivatives which resulted from sodium cyanoborohydride-mediated coupling to the toxin of ammonia, glycine, and L-proline exhibited Ki values for calf thymus RNA polymerase II of 1.7 x 10(-7) M, 2.5 x 10(-7) M and 7.0 x 10(-6) M, respectively. Treatment of the aldehyde with sodium chlorite or hydroxylamine-O-sulfonic acid converted the amanitin aldehyde to the corresponding carboxyl or nitrile compounds with Ki values of 1.0 x 10(-7) M and 3.0 x 10(-9) M, respectively. Difficulties which were encountered in the preparation of these derivatives are discussed relative to peculiarities in the chemical behavior of the amanitin aldehyde. PMID:1655668

Mullersman, J E; Preston, J F

1991-06-01

121

Parameterization of Leaf-Level Gas Exchange for Plant Functional Groups From Amazonian Seasonal Tropical Rain Forest  

NASA Astrophysics Data System (ADS)

Plant communities exert strong influence over the magnitude of carbon and water cycling through ecosystems by controlling photosynthetic gas exchange and respiratory processes. Leaf-level gas exchange fluxes result from a combination of physiological properties, such as carboxylation capacity, respiration rates and hydraulic conductivity, interacting with environmental drivers such as water and light availability, leaf-to-air vapor pressure deficit, and temperature. Carbon balance models concerned with ecosystem-scale responses have as a common feature the description of eco-physiological properties of vegetation. Here we focus on the parameterization of ecophysiological gas-exchange properties of plant functional groups from a pristine Amazonian seasonally dry tropical rain forest ecosystem (FLONA-Tapajós, Santarém, PA, Brazil). The parameters were specific leaf weight, leaf nitrogen content, leaf carbon isotope ratio, maximum photosynthetic assimilation rate, photosynthetic carboxylation capacity, dark respiration rates, and stomatal conductance to water vapor. Our plant functional groupings were lianas at the top of the canopy, trees at the top of the canopy, mid-canopy trees and undestory trees. Within the functional groups, we found no evidence that leaves acclimated to seasonal changes in precipitation. However, there were life-form dependent distinctions when a combination of parameters was included. Top-canopy lianas were statistically different from top-canopy trees for leaf carbon isotope ratio, maximum photosynthetic assimilation rate, and stomatal conductance to water vapor, suggesting that lianas are more conservative in the use of water, causing a stomatal limitation on photosynthetic assimilation. Top-canopy, mid canopy and understory groupings were distinct for specific leaf weight, leaf nitrogen content, leaf carbon isotope ratio, maximum photosynthetic assimilation rate, and photosynthetic carboxylation capacity. The recognition that plant functional groups have distinct impacts on ecosystem-scale gas exchange can increase the accuracy of process-based carbon balance models where structure is known and when logging activities are incorporated into production models.

Domingues, T. F.; Berry, J. A.; Ometto, J. P.; Martinelli, L. A.; Ehleringer, J. R.

2004-12-01

122

Hierarchical Grouping to Optimize an Objective Function  

Microsoft Academic Search

A procedure for forming hierarchical groups of mutually exclusive subsets, each of which has members that are maximally similar with respect to specified characteristics, is suggested for use in large-scale (n > 100) studies when a precise optimal solution for a specified number of groups is not practical. Given n sets, this procedure permits their reduction to n ? 1

Joe H. Ward Jr

1963-01-01

123

Use of sterically hindered carboxylate ligands to model structural and functional features of dioxygen-activating centers in non-heme diiron enzymes  

E-print Network

Chapter I. Modeling Dioxygen-Activating Centers in Non-Heme Diiron Enzymes: Carboxylate Shifts in Diiron(II) Complexes Supported by Sterically Hindered Carboxylate Ligands General synthetic routes are described for a series ...

Lee, Dongwhan, 1970-

2002-01-01

124

Functional group composition of organic aerosol from combustion emissions and secondary processes at two contrasted urban environments  

NASA Astrophysics Data System (ADS)

The quantification of major functional groups in atmospheric organic aerosol (OA) provides a constraint on the types of compounds emitted and formed in atmospheric conditions. This paper presents functional group composition of organic aerosol from two contrasted urban environments: Marseille during summer and Grenoble during winter. Functional groups were determined using a tandem mass spectrometry approach, enabling the quantification of carboxylic (RCOOH), carbonyl (RCOR?), and nitro (RNO2) functional groups. Using a multiple regression analysis, absolute concentrations of functional groups were combined with those of organic carbon derived from different sources in order to infer the functional group contents of different organic aerosol fractions. These fractions include fossil fuel combustion emissions, biomass burning emissions and secondary organic aerosol (SOA). Results clearly highlight the differences between functional group fingerprints of primary and secondary OA fractions. OA emitted from primary sources is found to be moderately functionalized, as about 20 carbons per 1000 bear one of the functional groups determined here, whereas SOA is much more functionalized, as in average 94 carbons per 1000 bear a functional group under study. Aging processes appear to increase both RCOOH and RCOR? functional group contents by nearly one order of magnitude. Conversely, RNO2 content is found to decrease with photochemical processes. Finally, our results also suggest that other functional groups significantly contribute to biomass smoke and SOA. In particular, for SOA, the overall oxygen content, assessed using aerosol mass spectrometer measurements by an O:C ratio of 0.63, is significantly higher than the apparent O:C* ratio of 0.17 estimated based on functional groups measured here. A thorough examination of our data suggests that this remaining unexplained oxygen content can be most probably assigned to alcohol (ROH), organic peroxides (ROOH), organonitrates (RONO2) and/or organosulfates (ROSO3H).

El Haddad, Imad; Marchand, Nicolas; D'Anna, Barbara; Jaffrezo, Jean Luc; Wortham, Henri

2013-08-01

125

Synthesis of carboxylate-functionalized graphene nanosheets for high dispersion of platinum nanoparticles based on the reduction of graphene oxide via 1-pyrenecarboxaldehyde  

NASA Astrophysics Data System (ADS)

A one-step reduction/functionalization strategy for the synthesis of carboxylate-functionalized graphene nanosheets is reported in this paper. 1-pyrenecarboxaldehyde (PCA) is introduced as a new reductant for the chemical reduction of graphene oxide (GO), serving three roles: reducing GO to graphene nanosheets (GNs), stabilizing the as-prepared GNs due to the electrostatic repulsion of the oxidation products of PCA (1-pyrenecarboxylate, PC-) on the surface of the GNs and anchoring Pt nanoparticles (Pt NPs) with high dispersion and small particle size. Transmission electron microscopy shows that Pt NPs with an average diameter of 1.3 ± 0.2 nm are uniformly dispersed on the surface of the PC--functionalized GNs (PC--GNs). The obtained Pt NPs/PC--GNs nanohybrids have higher electrocatalytic activity and stability towards methanol oxidation in comparison with Pt NPs supported on GNs obtained by the chemical reduction of GO with the typical reductant, hydrazine.

Kuang, Yinjie; Chen, Jinhua; Zheng, Xingliang; Zhang, Xiaohua; Zhou, Qionghua; Lu, Cuihong

2013-10-01

126

Synthesis of carboxylate-functionalized graphene nanosheets for high dispersion of platinum nanoparticles based on the reduction of graphene oxide via 1-pyrenecarboxaldehyde.  

PubMed

A one-step reduction/functionalization strategy for the synthesis of carboxylate-functionalized graphene nanosheets is reported in this paper. 1-pyrenecarboxaldehyde (PCA) is introduced as a new reductant for the chemical reduction of graphene oxide (GO), serving three roles: reducing GO to graphene nanosheets (GNs), stabilizing the as-prepared GNs due to the electrostatic repulsion of the oxidation products of PCA (1-pyrenecarboxylate, PC?) on the surface of the GNs and anchoring Pt nanoparticles (Pt NPs) with high dispersion and small particle size. Transmission electron microscopy shows that Pt NPs with an average diameter of 1.3 ± 0.2 nm are uniformly dispersed on the surface of the PC?-functionalized GNs (PC?-GNs). The obtained Pt NPs/PC?-GNs nanohybrids have higher electrocatalytic activity and stability towards methanol oxidation in comparison with Pt NPs supported on GNs obtained by the chemical reduction of GO with the typical reductant, hydrazine. PMID:24013585

Kuang, Yinjie; Chen, Jinhua; Zheng, Xingliang; Zhang, Xiaohua; Zhou, Qionghua; Lu, Cuihong

2013-10-01

127

Photochemical and antimicrobial properties of silver nanoparticle-encapsulated chitosan functionalized with photoactive groups.  

PubMed

Chitosan was functionalized with 4-((E)-2-(3-hydroxynaphthalen-2-yl)diazen-1-yl)benzoic acid by the coupling of the hydroxyl functional groups of chitosan with carboxylic acid group of the dye by DCC coupling method. The silver nanoparticles were prepared by sol-gel method of nanoparticle synthesis. Silver nanoparticle-encapsulated functionalized chitosan was prepared by the phase transfer method. The products were characterized by FTIR, UV-Vis, fluorescence and NMR spectroscopic methods and by SEM and TEM analysis. The photochemical properties of silver nanoparticle-encapsulated chitosan functionalized with 4-((E)-2-(3-hydroxynaphthalen-2-yl)diazen-1-yl)benzoic acid was studied in detail. The light-fastening properties of the chromophoric system was enhanced when attached to chitosan, and it can be further improved by the encapsulation of silver nanoparticles. The antibacterial analysis of silver nanoparticle-encapsulated functionalized chitosan was carried out against Staphylococcus aureus and Escherichia coli and against fungal species such as Aspergillus flavus and Aspergillus terreus. This study showed that silver nanoparticles-encapsulated functionalized chitosan can be used for antibacterial and antifungal applications. PMID:23910360

Mathew, Thomas V; Kuriakose, Sunny

2013-10-01

128

Hermite Functions on Compact Lie Groups, II  

Microsoft Academic Search

The usual formula for Hermite polynomials on Rd is extended to a compact Lie group G, yielding an isometry of L2(G, p1), where p1 is the heat kernel measure at time one, with a natural completion of the universal enveloping algebra of G. The existence of such an isometry was first established by L. Gross; here we present a simplified

O. Hijab

1995-01-01

129

1H-Imidazol-3-ium-4-carboxyl-ate  

PubMed Central

In the title compound, C4H4N2O2, both imidazole N atoms are protonated and carboxyl­ate group is deprotonated, resulting in a zwitterion. The mol­ecule is essentially planar, with an r.m.s. deviation of 0.012?(1)?Å. In the crystal, N—H?O hydrogen bonds and ?–? stacking inter­actions [centroid–centroid distance = 3.674?(2)?Å] between the imidazole rings link the mol­ecules into a three-dimensional supra­molecular network. PMID:22259422

Cao, Qiang; Duan, Bao-Rong; Zhu, Bin; Cao, Zhen

2012-01-01

130

ATR-FTIR characterization of organic functional groups and inorganic ions in ambient aerosols at a rural site  

NASA Astrophysics Data System (ADS)

An Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopic method was used to measure organic functional groups and inorganic ions at Tonto National Monument (TNM), an Interagency Monitoring of Protected Visual Environments (IMPROVE) sampling site in a rural area near Phoenix, Arizona. Functional groups and ions from common aerosol compound classes such as aliphatic and aromatic CH, methylene, methyl, aldehydes/ketones, carboxylic acids, ammonium sulfate and nitrate as well as functional groups from difficult to measure compound classes such as esters/lactones, acid anhydrides, carbohydrate hydroxyl and ethers, amino acids, and amines were quantified. On average, ˜33% of the PM 1.0 mass was composed of organic aerosol. The average (standard deviation) composition of the organic aerosol at TNM was 34% (6%) biogenic functional groups, 21% (5%) oxygenated functional groups, 28% (7%) aliphatic hydrocarbon functional groups (aliphatic CH, methylene and methyl) and 17% (1%) aromatic hydrocarbon functional groups. Compositional analysis, functional group correlations, and back trajectories were used to identify three types of events with source signatures: primary biogenic-influenced, urban-influenced, and regional background. The biogenic-influenced event had high concentrations of amino acids and carbohydrate hydroxyl and ether, as well as aliphatic CH and aromatic CH functional groups and qualitatively high levels of silicate. The urban-influenced events had back trajectories traveling directly from the Phoenix area and high concentrations of hydrocarbons, oxygenated functional groups, and inorganic ions. This aerosol characterization suggests that both primary emissions in Phoenix and secondary formation of aerosols from Phoenix emissions had a major impact on the aerosol composition and concentration at TNM. The regional background source had low concentrations of all functional groups, but had higher concentrations of biogenic functional groups than the urban source.

Coury, Charity; Dillner, Ann M.

131

Pd/light-accelerated atom-transfer carbonylation of alkyl iodides: applications in multicomponent coupling processes leading to functionalized carboxylic acid derivatives.  

PubMed

The atom-transfer carbonylation reaction of various alkyl iodides thereby leading to carboxylic acid esters was effectively accelerated by the addition of transition-metal catalysts under photoirradiation conditions. By using a combined Pd/h? reaction system, vicinal C-functionalization of alkenes was attained in which ?-substituted iodoalkanes, alkenes, carbon monoxide, and alcohols were coupled to give functionalized esters. When alkenyl alcohols were used as acceptor alkenes, three-component coupling reactions, which were accompanied by intramolecular esterification, proceeded to give lactones. Pd-dimer complex [Pd(2)(CNMe)(6)][PF(6)](2), which is known to undergo homolysis under photoirradiation conditions, worked quite well as a catalyst in these three- or four-component coupling reactions. In this metal/radical hybrid system, both Pd radicals and acyl radicals are key players and a stereochemical study confirmed the carbonylation step proceeded through a radical carbonylation mechanism. PMID:22733719

Fusano, Akira; Sumino, Shuhei; Nishitani, Satoshi; Inouye, Takaya; Morimoto, Keisuke; Fukuyama, Takahide; Ryu, Ilhyong

2012-07-23

132

Analysis of functionalized polyethylene terephthalate with immobilized NTPDase and cysteine  

Microsoft Academic Search

Polyethylene terephthalate (PET) was functionalized to introduce carboxyl groups onto its surface by a carboxylation technique. Surface and bulk properties, such as possible surface deterioration, surface roughness and the mechanical strength of the carboxylated polymers, were studied and compared with those of aminolyzed and hydrolyzed PET. Atomic force microscopy studies showed that unlike aminolysis and hydrolysis, which increased the surface

Vignesh Muthuvijayan; Jun Gu; Randy S. Lewis

2009-01-01

133

Mass spectrometry-based carboxyl footprinting of proteins: method evaluation  

PubMed Central

Protein structure determines function in biology, and a variety of approaches have been employed to obtain structural information about proteins. Mass spectrometry-based protein footprinting is one fast-growing approach. One labeling-based footprinting approach is the use of a water-soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and glycine ethyl ester (GEE) to modify solvent-accessible carboxyl groups on glutamate (E) and aspartate (D). This paper describes method development of carboxyl-group modification in protein footprinting. The modification protocol was evaluated by using the protein calmodulin as a model. Because carboxyl-group modification is a slow reaction relative to protein folding and unfolding, there is an issue that modifications at certain sites may induce protein unfolding and lead to additional modification at sites that are not solvent-accessible in the wild-type protein. We investigated this possibility by using hydrogen deuterium amide exchange (H/DX). The study demonstrated that application of carboxyl group modification in probing conformational changes in calmodulin induced by Ca2+ binding provides useful information that is not compromised by modification-induced protein unfolding. PMID:22408386

Zhang, Hao; Wen, Jianzhong; Huang, Richard Y-C; Blankenship, Robert E.; Gross, Michael L.

2011-01-01

134

Functional Renormalization Group Approach to the Sine-Gordon Model  

SciTech Connect

The renormalization group flow is presented for the two-dimensional sine-Gordon model within the framework of the functional renormalization group method by including the wave-function renormalization constant. The Kosterlitz-Thouless-Berezinski type phase structure is recovered as the interpolating scaling law between two competing IR attractive area of the global renormalization group flow.

Nagy, S.; Sailer, K. [Department of Theoretical Physics, University of Debrecen, Debrecen (Hungary); Nandori, I. [Institute of Nuclear Research, P.O. Box 51, H-4001 Debrecen (Hungary); Polonyi, J. [Strasbourg University, CNRS-IPHC, BP28 67037 Strasbourg Cedex 2 (France)

2009-06-19

135

Adapting Reinforcement Learning for Computer Games: Using Group Utility Functions  

Microsoft Academic Search

Group utility functions are an extension of the common team utility function for providing multi- ple agents with a common reinforcement learn- ing signal for learning cooperative behaviour. In this paper we describe what group utility functions are and suggest using them to pro- vide non-player computer game character be- haviours. As yet, reinforcement learning tech- niques have very rarely

Jay Bradley; Gillian Hayes

2005-01-01

136

1-Azaniumylcyclobutane-1-carboxylate monohydrate  

NASA Technical Reports Server (NTRS)

In the title compound, C5H9NO2H2O, the amino acid is in the usual zwitterionic form involving the carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7) and0.118 (7). In the crystal, NH O and OH O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+) and donor (through a single carboxylate O from two different aminocyclobutane carboxylatemoities)], resulting in a two-dimensional layered structure lying parallel to (100).

Butcher, Ray J.; Brewer, Greg; Burton, Aaron S.; Dworkin, Jason

2014-01-01

137

Complexation of cadmium to sulfur and oxygen functional groups in an organic soil  

NASA Astrophysics Data System (ADS)

Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd) to soil organic matter (SOM) was determined in an organic (49% organic C) soil as a function of reaction time, pH and Cd concentration. In experiments conducted at native Cd concentrations in soil (0.23 ?g g -1 dry soil), halides (Cl, Br) were used as competing ligands to functional groups in SOM. The concentration of Cd in the aqueous phase was determined by isotope-dilution (ID) inductively-coupled-plasma-mass-spectrometry (ICP-MS), and the activity of Cd 2+ was calculated from the well-established Cd-halide constants. At higher Cd loading (500-54,000 ?g g -1), the Cd 2+ activity was directly determined by an ion-selective electrode (ISE). On the basis of results from extended X-ray absorption fine structure (EXAFS) spectroscopy, a model with one thiolate group (RS -) was used to describe the complexation (Cd 2+ + RS - ? CdSR +; log KCdSR) at native Cd concentrations. The concentration of thiols (RSH; 0.047 mol kg -1 C) was independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. Log KCdSR values of 11.2-11.6 (p Ka for RSH = 9.96), determined in the pH range 3.1-4.6, compare favorably with stability constants for the association between Cd and well-defined thiolates like glutathione. In the concentration range 500-54,000 ?g Cd g -1, a model consisting of one thiolate and one carboxylate (RCOO -) gave the best fit to data, indicating an increasing role for RCOOH groups as RSH groups become saturated. The determined log KCdOOCR of 3.2 (Cd 2+ + RCOO - ? CdOOCR +; log KCdOOCR; p Ka for RCOOH = 4.5) is in accordance with stability constants determined for the association between Cd and well-defined carboxylates. Given a concentration of reduced sulfur groups of 0.2% or higher in NOM, we conclude that the complexation to organic RSH groups may control the speciation of Cd in soils, and most likely also in surface waters, with a total concentration less than 5 mg Cd g -1 organic C.

Karlsson, Torbjörn; Elgh-Dalgren, Kristin; Björn, Erik; Skyllberg, Ulf

2007-02-01

138

The human immunodeficiency virus Tat proteins specifically associate with TAK in vivo and require the carboxyl-terminal domain of RNA polymerase II for function.  

PubMed Central

Human immunodeficiency virus types 1 and 2 encode closely related proteins, Tat-1 and Tat-2, that stimulate viral transcription. Previously, we showed that the activation domains of these proteins specifically interact in vitro with a cellular protein kinase named TAK. In vitro, TAK phosphorylates the Tat-2 but not the Tat-1 protein, a 42-kDa polypeptide of unknown identity, and the carboxyl-terminal domain (CTD) of RNA polymerase II (RNAP II). We now show that the 42-kDa substrate of TAK cochromatographs with TAK activity, suggesting that this 42-kDa polypeptide is a subunit of TAK. We also show that the Tat proteins specifically associate with TAK in vivo, since wild-type Tat-1 and Tat-2 proteins expressed in mammalian cells, but not mutant Tat proteins containing a nonfunctional activation domain, can be coimmunoprecipitated with TAK. We also mapped the in vivo phosphorylation sites of Tat-2 to the carboxyl terminus of the protein, but analysis of proteins with mutations at these sites suggests that phosphorylation is not essential for Tat-2 transactivation function. We further investigated whether the CTD of RNAP II is required for Tat function in vivo. Using plasmid constructs that express an alpha-amanitin-resistant RNAP II subunit with a truncated or full-length CTD, we found that an intact CTD is required for Tat function. These observations strengthen the proposal that the mechanism of action of Tat involves the recruitment or activation of TAK, resulting in activated transcription through phosphorylation of the CTD. PMID:8676484

Yang, X; Herrmann, C H; Rice, A P

1996-01-01

139

End Group Modification of Regioregular Polythiophene through Postpolymerization Functionalization  

E-print Network

of the conjugated polymers. Literature procedures to function- alize end groups of conjugated polymers, however electroactive end groups, the grafting of conjugated polymers onto surfaces, or access of -conjugated building

McCullough, Richard D.

140

Ionization behavior, stoichiometry of association, and accessibility of functional groups in the active layers of reverse osmosis and nanofiltration membranes.  

PubMed

We characterized the fully aromatic polyamide (PA) active layers of six commercial reverse osmosis (RO) and nanofiltration (NF) membranes and found that in contrast to their similar elemental composition, total concentration of functional groups, and degree of polymerization, the ionization behavior and spatial distribution of carboxylic (R-COOH) groups within the active layers can be significantly different. We also studied the steric effects experienced by barium ion (Ba2+) in the active layers by determining the fraction of carboxylate (R-COO-) groups accessible to Ba2+; such fraction, referred to as the accessibility ratio (AR), was found to vary within the range AR=0.40-0.81, and to be generally independent of external solution pH. Additionally, we studied an NF membrane with a sulfonated polyethersulfone (SPES) active layer, and found that the concentration of sulfonate (R-SO3-) groups in the active layer was 1.67 M, independent of external solution pH and approximately three times higher than the maximum concentration (approximately 0.45+/-0.25 M) of R-COO- groups in PA active layers. The R-SO3- groups were found to be highly accessible to Ba2+ (AR=0.95+/-0.01). PMID:20701293

Coronell, Orlando; González, Mari I; Mariñas, Benito J; Cahill, David G

2010-09-01

141

Peptide Coupling between Amino Acids and the Carboxylic Acid of a Functionalized Chlorido-gold(I)-phosphane.  

PubMed

We have developed a protocol for the direct coupling between methyl ester protected amino acids and the chlorido-gold(I)-phosphane (p-HOOC(C6H4)PPh2)AuCl. By applying the EDC·HCl/NHS strategy (EDC·HCl = N-ethyl-N'-(3-(dimethylamino)propyl)carbodiimide hydrochloride, NHS = N-hydroxysuccinimide), the methyl esters of l-phenylalanine, glycine, l-leucine, l-alanine, and l-methionine are coupled with the carboxylic acid of the gold complex in moderate to good yields (62-88%). All amino acid tagged gold complexes were characterized by (1)H and (13)C NMR spectroscopy and high-resolution mass spectrometry. As corroborated by measurement of the angle of optical rotation, no racemization occurred during the reaction. The molecular structure of the leucine derivative was determined by single-crystal X-ray diffraction. In the course of developing an efficient coupling protocol, the acyl chlorides (p-Cl(O)C(C6H4)PPh2)AuX (X = Cl, Br) were also prepared and characterized. PMID:25203269

Kriechbaum, Margit; List, Manuela; Himmelsbach, Markus; Redhammer, Günther J; Monkowius, Uwe

2014-10-01

142

Various fates of neuronal progenitor cells observed on several different chemical functional groups  

NASA Astrophysics Data System (ADS)

Neuronal progenitor cells cultured on gold-coated glass surfaces modified by different chemical functional groups, including hydroxyl (-OH), carboxyl (-COOH), amino (-NH2), bromo (-Br), mercapto (-SH), - Phenyl and methyl (-CH3), were studied here to investigate the influence of surface chemistry on the cells' adhesion, morphology, proliferation and functional gene expression. Focal adhesion staining indicated in the initial culture stage cells exhibited morphological changes in response to different chemical functional groups. Cells cultured on -NH2 grafted surface displayed focal adhesion plaque and flattened morphology and had the largest contact area. However, their counter parts on -CH3 grafted surface displayed no focal adhesion and rounded morphology and had the smallest contact area. After 6 days culture, the proliferation trend was as follows: -NH2 > -SH> -COOH> - Phenyl > - Br > -OH> -CH3. To determine the neural functional properties of the cells affected by surface chemistry, the expression of glutamate decarboxylase (GAD67), nerve growth factor (NGF) and brainderived neurotrophic factor (BDNF) were characterized. An increase of GAD67 expression was observed on -NH2, -COOH and -SH grafted surfaces, while no increase in NGF and BDNF expression was observed on any chemical surfaces. These results highlight the importance of surface chemistry in the fate determination of neuronal progenitor cells, and suggest that surface chemistry must be considered in the design of biomaterials for neural tissue engineering.

Liu, Xi; Wang, Ying; He, Jin; Wang, Xiu-Mei; Cui, Fu-Zhai; Xu, Quan-Yuan

2011-12-01

143

[2]rotaxane with multiple functional groups.  

PubMed

High-yield syntheses of Cu(II)- and Ni(II)-templated [2]pseudorotaxane precursors (CuPRT and NiPRT, respectively) were achieved by threading bis(azide)bis(amide)-2,2'-bipyridine axle into a bis(amide)tris(amine) macrocycle. Single-crystal X-ray structural analysis of CuPRT revealed complete threading of the axle fragment into the wheel cavity, where strong aromatic ?-? stacking interactions between two parallel arene moieties of the wheel and the pyridyl unit of axle are operative in addition to metal ion templation. Attachment of a newly developed bulky stopper molecule with a terminal alkyne to CuPRT via a Cu(I)-catalyzed azide-alkyne cycloaddition reaction failed as a result of dethreading of the azide-terminated axle under the reaction conditions. However, the synthesis of a metal-free [2]rotaxane containing triazole with other functionalities in the axle was achieved in ?45% yield upon coupling between azide-terminated NiPRT and the alkyne-terminated stopper. The [2]rotaxane was characterized by mass spectrometry, 1D and 2D NMR (COSY, DOSY, and ROESY) experiments. Comparative solution-state NMR studies of the [2]rotaxane in its unprotonated and protonated states were carried out to locate the position of the wheel on the axle of the metal-free [2]rotaxane. Furthermore, a variable-temperature (1)H NMR study in DMSO-d6 of [2]rotaxane supported the kinetic inertness of the interlocked structure, where the newly developed stopper prevents dethreading of the 30-membered wheel from the axle. PMID:25353057

Saha, Subrata; Santra, Saikat; Akhuli, Bidyut; Ghosh, Pradyut

2014-11-21

144

How functional is functional? Ecological groupings in terrestrial animal ecology: towards an animal functional type approach  

Microsoft Academic Search

Understanding mechanisms to predict changes in plant and animal communities is a key challenge in ecology. The need to transfer\\u000a knowledge gained from single species to a more generalized approach has led to the development of categorization systems where\\u000a species’ similarities in life strategies and traits are classified into ecological groups (EGs) like functional groups\\/types\\u000a or guilds. While approaches in

Niels Blaum; Eva Mosner; Monika Schwager; Florian Jeltsch

145

Poly(ethylene glycol)- and carboxylate-functionalized gold nanoparticles using polymer linkages: single-step synthesis, high stability, and plasmonic detection of proteins.  

PubMed

Gold nanoparticles with suitable surface functionalities have been widely used as a versatile nanobioplatform. However, functionalized gold nanoparticles using thiol-terminated ligands have a tendency to aggregate, particularly in many enzymatic reaction buffers containing biological thiols, because of ligand exchange reactions. In the present study, we developed a one-step synthesis of poly(ethylene glycol) (PEG)ylated gold nanoparticles using poly(dimethylaminoethyl methacrylate) (PDMAEMA) in PEG as a polyol solvent. Because of the chelate effect of polymeric functionalities on the gold surface, the resulting PEGylated gold nanoparticles (Au@P-PEG) are very stable under the extreme conditions at which the thiol-monolayer-protected gold nanoparticles are easily coagulated. Using the solvent mixture of PEG and ethylene glycol (EG) and subsequent hydrolysis, gold nanoparticles bearing mixed functionalities of PEG and carboxylate are generated. The resulting particles exhibit selective adsorption of positively charged chymotrypsin (ChT) without nonselective adsorption of bovine serum albumin (BSA). The present nanoparticle system has many advantages, including high stability, simple one-step synthesis, biocompatibility, and excellent binding specificity; thus, this system can be used as a versatile platform for potential bio-related applications, such as separation, sensing, imaging, and assays. PMID:24090031

Park, Garam; Seo, Daeha; Chung, Im Sik; Song, Hyunjoon

2013-11-01

146

Replicating Small Group Research Using the Functional Theory.  

ERIC Educational Resources Information Center

A replication study tested functional theory utilizing untrained full-fledged groups. One hundred forty undergraduate students who were enrolled in a small group communication course at a large midwestern university participated in small group discussions analyzing a plagiarism case used in an original study by R. Y. Hirokawa. Results indicated…

Cragan, John F.; Wright, David W.

147

Some functional inequalities on polynomial volume growth Lie groups  

E-print Network

Some functional inequalities on polynomial volume growth Lie groups Diego Chamorro January 21, 2011 Abstract We study in this article some Sobolev-type inequalities on polynomial volume growth Lie groups. We-Paley decomposition to this general framework. Keywords: Sobolev inequalities, polynomial volume growth Lie groups. 1

Boyer, Edmond

148

1-Aza-niumyl-cyclo-butane-1-carboxyl-ate monohydrate.  

PubMed

In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the ?-carboxyl-ate group. The cyclo-butane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882?(7) and 0.118?(7). In the crystal, N-H?O and O-H?O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3 (+)) and donor (through a single carboxylate O from two different aminocyclobutane carb-oxylate moities)], resulting in a two-dimensional layered structure lying parallel to (100). PMID:24764920

Butcher, Ray J; Brewer, Greg; Burton, Aaron S; Dworkin, Jason P

2014-02-01

149

Electrical transport and field-effect transistors using inkjet-printed SWCNT films having different functional side groups.  

PubMed

The electrical properties of random networks of single-wall carbon nanotubes (SWNTs) obtained by inkjet printing are studied. Water-based stable inks of functionalized SWNTs (carboxylic acid, amide, poly(ethylene glycol), and polyaminobenzene sulfonic acid) were prepared and applied to inkjet deposit microscopic patterns of nanotube films on lithographically defined silicon chips with a back-side gate arrangement. Source-drain transfer characteristics and gate-effect measurements confirm the important role of the chemical functional groups in the electrical behavior of carbon nanotube networks. Considerable nonlinear transport in conjunction with a high channel current on/off ratio of approximately 70 was observed with poly(ethylene glycol)-functionalized nanotubes. The positive temperature coefficient of channel resistance shows the nonmetallic behavior of the inkjet-printed films. Other inkjet-printed field-effect transistors using carboxyl-functionalized nanotubes as source, drain, and gate electrodes, poly(ethylene glycol)-functionalized nanotubes as the channel, and poly(ethylene glycol) as the gate dielectric were also tested and characterized. PMID:20481513

Gracia-Espino, Eduardo; Sala, Giovanni; Pino, Flavio; Halonen, Niina; Luomahaara, Juho; Mäklin, Jani; Tóth, Géza; Kordás, Krisztián; Jantunen, Heli; Terrones, Mauricio; Helistö, Panu; Seppä, Heikki; Ajayan, Pulickel M; Vajtai, Robert

2010-06-22

150

Structure Functions and Low-x -- Working Group Summary  

E-print Network

A summary of recent results reported in the Structure Functions and Low-x working group at the DIS 2009 Workshop is given. Recent measurements of deep inelastic scattering cross sections and structure functions at HERA and of proton anti-proton collisions at Tevatron are presented. New developments of the extraction of parton distribution functions and of new theoretical developments are discussed.

Burkard Reisert; Agustin Sabio Vera; Zhiqing Zhang

2009-08-15

151

Poly[?2-aqua-?2-(pyrazine-2-carboxyl-ato)-lithium  

PubMed Central

The structure of the title compound, [Li(C5H3N2O2)(H2O)]n, contains an LiI ion with a distorted trigonal–bipyramidal coordination environment involving the N and O atoms of pyrazine-2-carboxyl­ate ligands with a bridging carboxyl­ate group, and two aqua O atoms also in a bridging mode. The symmetry-related LiI ions bridged by a carboxyl­ate O atom and a coordinating water O atom form an Li2O2 unit with an Li?Li distance of 3.052?(4)?Å, which generates mol­ecular ribbons propagating in the c-axis direction. The ribbons are held together by a network of O—H?O hydrogen bonds in which the coordinating water mol­ecules act as donors and the carboxyl­ate O atoms as acceptors. PMID:22807764

Starosta, Wojciech; Leciejewicz, Janusz

2012-01-01

152

Hypervalent Iodine Iodinative Decarboxylation Of Cubyl And Homocubyl Carboxylic Acids  

NASA Astrophysics Data System (ADS)

The hypervalent iodine oxidative decarboxylation of homocubyl and cubyl mono- and di-carboxylic acids is reported; the carboxylic acid is treated with PhI(OAc)2CC14-I2 under irradiation conditions and 80-90% of the derived iodo compound is obtained. Systematic functionalization of cubane is an important synthetic goal. The two main methods of cubane synthesis involve sequential Favorskii ring contractions to yield first a homocubyl carboxylic acid, and theh after a second Favorskii reaction, a 1,41,2 or 1,33 cubyl dicarboxylic acid. As a consequence of this synthetic procedure the carboxy group is a logical starting functionality for subsequent synthetic transformation in the cubyl ring system. The carboxy group has been converted ,into a nitro group in the synthesis of 1,4-dinitrocubane4 and halogenodecarboxylation has been effected.596 In a basically different approach Eaton et al., used ortho-lithiation of the der td carboxamide etc a site for ortho-iodination.7 Introduction of an iodo group onto the cubyl system is especially desirable because hypervalent iodine synthetic methodology may be employed in order to effect displacement reactions. This scheme has been successfully applied by Eaton et al.8 in tim cubyl system for R-IC12+ R-C1 R-I(OAC)2+ R-OAc where R=1- iodo-2-N,N-di-isopropylcarbox-amido-5-methylcubane.

Moriarty, Robert M.; Khosrowshahi, Jaffar S.; Dalecki, Tomasz

1988-05-01

153

Acid-base titrations of functional groups on the surface of the thermophilic bacterium Anoxybacillus flavithermus: comparing a chemical equilibrium model with ATR-IR spectroscopic data.  

PubMed

Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength. PMID:17243732

Heinrich, Hannah T M; Bremer, Phil J; Daughney, Christopher J; McQuillan, A James

2007-02-27

154

Probing pH-dependent functional elements in proteins: modification of carboxylic acid pairs in Trichoderma reesei cellobiohydrolase Cel6A.  

PubMed

Two carboxylic acid side chains can, depending on their geometry and environment, share a proton in a hydrogen bond and form a carboxyl-carboxylate pair. In the Trichoderma reesei cellobiohydrolase Cel6A structure, five carboxyl-carboxylate pairs are observed. One of these pairs (D175-D221) is involved in catalysis, and three other pairs are found in, or close to the two surface loops covering the active site tunnel of the catalytic domain. To stabilize Cel6A at alkaline pH values, where deprotonation of the carboxylic acids leads to repulsion of their side chains, we designed two mutant enzymes. In the first mutant, one carboxyl-carboxylate pair (E107-E399) was replaced by a corresponding amide-carboxylate pair (Q107-E399), and in the second mutant, all three carboxyl-carboxylate pairs (E107-E399, D170-E184, and D366-D419) were mutated in a similar manner. The unfolding studies using both intrinsic tryptophan fluorescence and far-ultraviolet circular dichroism spectroscopy at different pH values demonstrate that the unfolding temperature (T(m)) of both mutants has changed, resulting in destabilization of the mutant enzymes at acidic pH and stabilization at alkaline pH. The effect of stabilization seems additive, as a Cel6A triple mutant is the most stable enzyme variant. This increased stability is also reflected in the 2- or 4-fold increased half-life of the two mutants at alkaline pH, while the catalytic rate on cellotetraose (at t = 0) has not changed. Increased operational stability at alkaline pH was also observed on insoluble cellulosic substrates. Local conformational changes are suggested to take place in the active site loops of Cel6A wild-type enzyme at elevated pHs (pH 7), affecting to the end-product spectrum on insoluble cellulose. The triple mutant does not show such pH-dependent behavior. Overall, our results demonstrate that carboxyl-carboxylate pair engineering is a useful tool to alter pH-dependent protein behavior. PMID:12939137

Wohlfahrt, Gerd; Pellikka, Tarmo; Boer, Harry; Teeri, Tuula T; Koivula, Anu

2003-09-01

155

Single or functionalized fullerenes interacting with heme group  

NASA Astrophysics Data System (ADS)

The heme group is responsible for iron transportation through the bloodstream, where iron participates in redox reactions, electron transfer, gases detection etc. The efficiency of such processes can be reduced if the whole heme molecule or even the iron is somehow altered from its original oxidation state, which can be caused by interactions with nanoparticles as fullerenes. To verify how such particles alter the geometry and electronic structure of heme molecule, here we report first principles calculations based on density functional theory of heme group interacting with single C60 fullerene or with C60 functionalized with small functional groups (-CH3, -COOH, -NH2, -OH). The calculations shown that the system heme + nanoparticle has a different spin state in comparison with heme group if the fullerene is functionalized. Also a functional group can provide a stronger binding between nanoparticle and heme molecule or inhibit the chemical bonding in comparison with single fullerene results. In addition heme molecule loses electrons to the nanoparticles and some systems exhibited a geometry distortion in heme group, depending on the binding energy. Furthermore, one find that such nanoparticles induce a formation of spin up states in heme group. Moreover, there exist modifications in density of states near the Fermi energy. Although of such changes in heme electronic structure and geometry, the iron atom remains in the heme group with the same oxidation state, so that processes that involve the iron might not be affected, only those that depend on the whole heme molecule.

Costa, Wallison Chaves; Diniz, Eduardo Moraes

2014-09-01

156

The Luminosity Function of Galaxies in Compact Groups  

E-print Network

From R-band images of 39 Hickson compact groups (HCGs), we use galaxy counts to determine a luminosity function extending to M_R=-14.0, approximately two magnitudes deeper than previous compact group luminosity functions. We find that a single Schechter function is a poor fit to the data, so we fit a composite function consisting of separate Schechter functions for the bright and faint galaxies. The bright end is best fit with M^*=-21.6 and alpha=-0.52 and the faint end with M^*=-16.1 and alpha=-1.17. The decreasing bright end slope implies a deficit of intermediate luminosity galaxies in our sample of HCGs and the faint end slope is slightly steeper than that reported for earlier HCG luminosity functions. Furthermore, luminosity functions of subsets of our sample reveal more substantial dwarf populations for groups with x-ray halos, groups with tidal dwarf candidates, and groups with a dominant elliptical or lenticular galaxy. Collectively, these results support the hypothesis that within compact groups, the initial dwarf galaxy population is replenished by "subsequent generations" formed in the tidal debris of giant galaxy interactions.

Sally D. Hunsberger; Jane C. Charlton; Dennis Zaritsky

1998-05-13

157

Coordination modes of bridge carboxylates in dinuclear manganese compounds determine their catalase-like activities.  

PubMed

To explore the role of bridge carboxylate coordination modes on the catalase-like activities of dinuclear manganese compounds, [Mn(II)2(bpmapa)2(H2O)2](ClO4)2 (1), [Mn(II)2(pbpmapa)2(H2O)2](ClO4)2 (2), and [Mn(II)2(bpmaa)2(H2O)3](ClO4)2 (3) (bpmapa = [bis(2-pyridylmethyl)amino]propionic acid, pbpmapa = alpha-phenyl-beta-[bis(2-pyridylmethyl)amino]propionic acid, and bpmaa = [bis(2-pyridylmethyl)amino]acetic acid), in which Mn(II)-Mn(II) centers have a similar coordination sphere but different carboxylate-Mn bridging modes have been synthesized and structurally characterized by single X-ray diffraction, UV-visible, IR, and EPR spectroscopies, and their catalase-like activities were investigated. Studies of their catalytic activities and the influence of the nitrogenous bases on their catalytic activities indicated that the carboxylate-Mn coordination mode was crucial in H2O2 deprotonation, and eventually in H2O2 disproportionation. Compound 1 with a bidentate carboxylate bridge showed higher catalase-like activity than 2 and 3, in which the carboxylate groups have a monodentate bridging mode. The deprotonation ability of the carboxylate anion was determined by the O-C-O angle and the distance between the weakly bound oxygen of the bridging carboxylate to the manganese ion. The smaller the angle, and the shorter the distance, the stronger the basicity that the carboxylate anion exhibits. The bidentate mu-1,1 bridging coordination mode functionally mimicked the glutamate residues at the manganese catalase active site. Our results suggested that increasing the basicity of the bridging carboxylate ligand of the catalase model compounds will increase their deprotonation ability and lead to more active catalase mimics. PMID:19809747

Jiang, Xiaojun; Liu, Hui; Zheng, Bing; Zhang, Jingyan

2009-10-28

158

Analysis of Functional Groups by Solubility and Infrared Analysis.  

ERIC Educational Resources Information Center

An experiment which introduces students to infrared spectroscopy and the solubility behavior of various organic compounds is described. The experiment also serves to integrate some of the basic chemical reactions of functional groups with their spectral properties. (JN)

Turek, William N.

1984-01-01

159

Department and function: Group Leader, Laboratory of Molecular Immunology; Clinical  

E-print Network

Department and function: Group Leader, Laboratory of Molecular Immunology; Clinical Immunology in Immunology, Hannover Medical School Positions: 1994-1996: Research Associate, Dept. of Clinical Immunology, Hannover Medical School 1994: Visiting Scientist, Dept. of Immunology, University of Utrecht

Manstein, Dietmar J.

160

Can functional groups be used to indicate estuarine ecological status?  

Microsoft Academic Search

International legislation demands that statutory bodies report on the health of aquatic ecosystems. Traditionally, ecosystem\\u000a components have been characterised according to species assemblages but with limited success in predicting health. On the\\u000a other hand, many studies based upon functional groupings that include trophic relationships and bioturbation potential have\\u000a shown response to pollution. However, these and other functional group responses have

Jeanette L. Sanders; Mike A. Kendall; Anthony J. S. Hawkins; John I. Spicer

2007-01-01

161

Thermodynamic characterization of proton-ionizable functional groups on the cell surfaces of ammonia-oxidizing bacteria and archaea.  

PubMed

The ammonia-oxidizing archaeon Nitrosopumilus maritimus strain SCM1 (strain SCM1), a representative of the Thaumarchaeota archaeal phylum, can sustain high specific rates of ammonia oxidation at ammonia concentrations too low to sustain metabolism by ammonia-oxidizing bacteria (AOB). One structural and biochemical difference between N. maritimus and AOB that might be related to the oligotrophic adaptation of strain SCM1 is the cell surface. A proteinaceous surface layer (S-layer) comprises the outermost boundary of the strain SCM1 cell envelope, as opposed to the lipopolysaccharide coat of Gram-negative AOB. In this work, we compared the surface reactivities of two archaea having an S-layer (strain SCM1 and Sulfolobus acidocaldarius) with those of four representative AOB (Nitrosospira briensis, Nitrosomonas europaea, Nitrosolobus multiformis, and Nitrosococcus oceani) using potentiometric and calorimetric titrations to evaluate differences in proton-ionizable surface sites. Strain SCM1 and S. acidocaldarius have a wider range of proton buffering (approximately pH 10-3.5) than the AOB (approximately pH 10-4), under the conditions investigated. Thermodynamic parameters describing proton-ionizable sites (acidity constants, enthalpies, and entropies of protonation) are consistent with these archaea having proton-ionizable amino acid side chains containing carboxyl, imidazole, thiol, hydroxyl, and amine functional groups. Phosphorous-bearing acidic functional groups, which might also be present, could be masked by imidazole and thiol functional groups. Parameters for the AOB are consistent with surface structures containing anionic oxygen ligands (carboxyl- and phosphorous-bearing acidic functional groups), thiols, and amines. In addition, our results showed that strain SCM1 has more reactive surface sites than the AOB and a high concentration of sites consistent with aspartic and/or glutamic acid. Because these alternative boundary layers mediate interaction with the local external environment, these data provide the basis for further comparisons of the thermodynamic behavior of surface reactivity toward essential nutrients. PMID:24589203

Gorman-Lewis, D; Martens-Habbena, W; Stahl, D A

2014-03-01

162

Asymptotic Expansions of Hermite Functions on Compact Lie Groups  

Microsoft Academic Search

Let G be a compact, connected Lie group endowed with a bi-invariant Riemannian metric. Let ?t be the heat kernel on G; that is, ?t is the fundamental solution to the heat equation on the group determined by the Laplace–Beltrami operator. Recent work of Gross (1993) and Hijab (1994) has led to the study of a new family of functions

Jeffrey J. Mitchell

2002-01-01

163

Personalizing Group Environments: A Conceptual Approach Toward More Effective Small Group Functioning.  

ERIC Educational Resources Information Center

A conceptual approach toward more effective small group functioning is undertaken in this paper to provide a basis from which empirically relevant hypotheses can be drawn and tested. This analysis views actualizing individuals as possessing the unique ability to perceive and utilize the types of behaviors which are conducive to personalizing group

Beach, Wayne A.

164

Intracellular localization of a group II chaperonin indicates a membrane-related function  

NASA Technical Reports Server (NTRS)

Chaperonins are protein complexes that are believed to function as part of a protein folding system in the cytoplasm of the cell. We observed, however, that the group II chaperonins known as rosettasomes in the hyperthermophilic archaeon Sulfolobus shibatae, are not cytoplasmic but membrane associated. This association was observed in cultures grown at 60 degrees C and 76 degrees C or heat-shocked at 85 degrees C by using immunofluorescence microscopy and in thick sections of rapidly frozen cells grown at 76 degrees C by using immunogold electron microscopy. We observed that increased abundance of rosettasomes after heat shock correlated with decreased membrane permeability at lethal temperature (92 degrees C). This change in permeability was not seen in cells heat-shocked in the presence of the amino acid analogue azetidine 2-carboxylic acid, indicating functional protein synthesis influences permeability. Azetidine experiments also indicated that observed heat-induced changes in lipid composition in S. shibatae could not account for changes in membrane permeability. Rosettasomes purified from cultures grown at 60 degrees C and 76 degrees C or heat-shocked at 85 degrees C bind to liposomes made from either the bipolar tetraether lipids of Sulfolobus or a variety of artificial lipid mixtures. The presence of rosettasomes did not significantly change the transition temperature of liposomes, as indicated by differential scanning calorimetry, or the proton permeability of liposomes, as indicated by pyranine fluorescence. We propose that these group II chaperonins function as a structural element in the natural membrane based on their intracellular location, the correlation between their functional abundance and membrane permeability, and their potential distribution on the membrane surface.

Trent, Jonathan D.; Kagawa, Hiromi K.; Paavola, Chad D.; McMillan, R. Andrew; Howard, Jeanie; Jahnke, Linda; Lavin, Colleen; Embaye, Tsegereda; Henze, Christopher E.

2003-01-01

165

Ammonia capture in porous organic polymers densely functionalized with Brønsted acid groups.  

PubMed

The elimination of specific environmental and industrial contaminants, which are hazardous at only part per million to part per billion concentrations, poses a significant technological challenge. Adsorptive materials designed for such processes must be engendered with an exceptionally high enthalpy of adsorption for the analyte of interest. Rather than relying on a single strong interaction, the use of multiple chemical interactions is an emerging strategy for achieving this requisite physical parameter. Herein, we describe an efficient, catalytic synthesis of diamondoid porous organic polymers densely functionalized with carboxylic acids. Physical parameters such as pore size distribution, application of these materials to low-pressure ammonia adsorption, and comparison with analogous materials featuring functional groups of varying acidity are presented. In particular, BPP-5, which features a multiply interpenetrated structure dominated by <6 Å pores, is shown to exhibit an uptake of 17.7 mmol/g at 1 bar, the highest capacity yet demonstrated for a readily recyclable material. A complementary framework, BPP-7, features slightly larger pore sizes, and the resulting improvement in uptake kinetics allows for efficient adsorption at low pressure (3.15 mmol/g at 480 ppm). Overall, the data strongly suggest that the spatial arrangement of acidic sites allows for cooperative behavior, which leads to enhanced NH3 adsorption. PMID:24456083

Van Humbeck, Jeffrey F; McDonald, Thomas M; Jing, Xiaofei; Wiers, Brian M; Zhu, Guangshan; Long, Jeffrey R

2014-02-12

166

Surface etching of methacrylic microparticles via basic hydrolysis and introduction of functional groups for click chemistry.  

PubMed

Controlled basic hydrolysis of poly(methyl methacrylate-co-ethylene glycol dimethacrylate) P(MMA-co-EGDMA) microparticles with a diameter d50=6 ?m led to high densities of carboxylic groups at the particles' surface of up to 1.288 ?eq g(-1) (equivalent to 1.277 ?mol m(-2)). The microparticles' core has not been altered by this surface activation procedure as seen by fluorescent staining. The kinetics of the hydrolysis reaction was investigated via electrophoretic light scattering and particle charge detection employing polycation titration under shear condition. The activated microparticle's surface was subsequently exploited in carbodiimide-mediated coupling reactions using a variety of molecular reactants, that is, 11-azido-3,6,9-trioxaundecan-1-amine, cysteamine, propargylamine, and fluoresceinamine, thus enabling the introduction of chemically reactive moieties such as azides, thiols, and alkynes. Fluorescent staining of the particles' surface successfully demonstrated the versatile applications of surface functionalized microparticles via copper-catalyzed huisgen cycloaddition. Carrying on this two-step procedure in a controlled manner provides an excellent way for relatively simple but highly effective surface functionalization. PMID:23481515

Speyerer, Christian; Borchers, Kirsten; Hirth, Thomas; Tovar, Günter E M; Weber, Achim

2013-05-01

167

Activation of carboxylic acids in asymmetric organocatalysis.  

PubMed

Organocatalysis, catalysis using small organic molecules, has recently evolved into a general approach for asymmetric synthesis, complementing both metal catalysis and biocatalysis. Its success relies to a large extent upon the introduction of novel and generic activation modes. Remarkably though, while carboxylic acids have been used as catalyst directing groups in supramolecular transition-metal catalysis, a general and well-defined activation mode for this useful and abundant substance class is still lacking. Herein we propose the heterodimeric association of carboxylic acids with chiral phosphoric acid catalysts as a new activation principle for organocatalysis. This self-assembly increases both the acidity of the phosphoric acid catalyst and the reactivity of the carboxylic acid. To illustrate this principle, we apply our concept in a general and highly enantioselective catalytic aziridine-opening reaction with carboxylic acids as nucleophiles. PMID:24888674

Monaco, Mattia Riccardo; Poladura, Belén; Diaz de Los Bernardos, Miriam; Leutzsch, Markus; Goddard, Richard; List, Benjamin

2014-07-01

168

Influence of functional groups on desorption of organic compounds from carbon nanotubes into water: insight into desorption hysteresis.  

PubMed

Adsorption-desorption of nitrobenzenes, phenols, and anilines on five multiwalled carbon nanotubes (MWCNTs) with different degrees of surface oxidation were investigated to examine the influence of functional groups of both organic chemicals and CNTs on desorption hysteresis. Desorption hysteresis was not observed for nitrobenzenes, phenols, and 4-nitroaniline from all MWCNTs. Significant desorption hysteresis was observed for aniline and 4-methylaniline on surface-oxidized MWCNTs but not on unoxidized MWCNTs. Formation of an irreversible amide bond (i.e.,-CONH-) by amidation reaction of amino group of anilines with oxygen-containing groups (i.e., carboxyl or lactonic groups) on MWCNTs was observed. We proposed that desorption hysteresis could be attributed to the immobilization of organic compounds on the surface of CNTs resulting from the irreversible chemical reaction/binding. The irreversible chemical immobilization is compound functional group selective and dependent on the surface oxygen-containing groups of CNTs. Hysteresis index (HI) values of aniline or 4-methylaniline on MWCNTs increased with the amounts of oxygen-containing groups on MWCNTs. Moreover, HI values of anilines on a given oxidized MWCNT followed an order of 4-nitroaniline < 4-chloroaniline < aniline < 4-methylaniline. PMID:23848495

Wu, Wenhao; Jiang, Wei; Zhang, Weidie; Lin, Daohui; Yang, Kun

2013-08-01

169

Functional grouping in residential homes for people with intellectual disabilities  

Microsoft Academic Search

The effects of functional grouping of people with intellectual disabilities on care practices in small residential homes in the community were investigated. A group comparison and a matched-pairs comparison were carried out in settings where less than or more than 75% residents were non-verbal, non-ambulant, had severe challenging behaviour, severe social impairment or were verbal and ambulant. Further analysis, focused

Jim Mansell; Julie Beadle-Brown; Susan Macdonald; Bev Ashman

2003-01-01

170

Species, functional groups, and thresholds in ecological resilience  

USGS Publications Warehouse

The cross-scale resilience model states that ecological resilience is generated in part from the distribution of functions within and across scales in a system. Resilience is a measure of a system's ability to remain organized around a particular set of mutually reinforcing processes and structures, known as a regime. We define scale as the geographic extent over which a process operates and the frequency with which a process occurs. Species can be categorized into functional groups that are a link between ecosystem processes and structures and ecological resilience. We applied the cross-scale resilience model to avian species in a grassland ecosystem. A species’ morphology is shaped in part by its interaction with ecological structure and pattern, so animal body mass reflects the spatial and temporal distribution of resources. We used the log-transformed rank-ordered body masses of breeding birds associated with grasslands to identify aggregations and discontinuities in the distribution of those body masses. We assessed cross-scale resilience on the basis of 3 metrics: overall number of functional groups, number of functional groups within an aggregation, and the redundancy of functional groups across aggregations. We assessed how the loss of threatened species would affect cross-scale resilience by removing threatened species from the data set and recalculating values of the 3 metrics. We also determined whether more function was retained than expected after the loss of threatened species by comparing observed loss with simulated random loss in a Monte Carlo process. The observed distribution of function compared with the random simulated loss of function indicated that more functionality in the observed data set was retained than expected. On the basis of our results, we believe an ecosystem with a full complement of species can sustain considerable species losses without affecting the distribution of functions within and across aggregations, although ecological resilience is reduced. We propose that the mechanisms responsible for shaping discontinuous distributions of body mass and the nonrandom distribution of functions may also shape species losses such that local extinctions will be nonrandom with respect to the retention and distribution of functions and that the distribution of function within and across aggregations will be conserved despite extinctions.

Sundstrom, Shana M.; Allen, Craig R.; Barichievy, Chris

2012-01-01

171

MICROBIAL TRANSFORMATION OF ESTERS OF CHLORINATED CARBOXYLIC ACIDS  

EPA Science Inventory

Two groups of compounds were selected for microbial transformation studies. In the first group were carboxylic acid esters having a fixed aromatic moiety and an increasing length of the alkyl component. Ethyl esters of chlorine-substituted carboxylic acids were in the second grou...

172

Langmuir monolayers from functionalized amphiphiles with epoxy terminal groups  

E-print Network

Langmuir monolayers from functionalized amphiphiles with epoxy terminal groups Kirsten L. Gensona June 2005 Abstract We studied Langmuir and Langmuir­Blodgett monolayers from amphiphiles applications [1­4]. Among them, photo- responsive amphiphiles possess the possibility of forming ordered, two

Vakni, David

173

“ Nafion”-functionalized mesoporous MCM-41 silica shows high activity and selectivity for carboxylic acid esterification and Friedel–Crafts acylation reactions  

Microsoft Academic Search

Hybrid organic–inorganic MCM-41 silicas functionalized with perfluoroalkylsulfonic acid groups analogous to that of Nafion were prepared in a simple single step by a condensation reaction between surface silanol groups of the mesoporous silicas and 1,2,2-trifluoro-2-hydroxy-1-trifluoromethyl-ethane sulfonic acid Beta-sultone. The catalysts showed very high activity for the esterification of long-chain fatty acids with ethanol and high-molecular-weight alcohols with essentially complete selectivity

Mercedes Alvaro; Avelino Corma; Debasish Das; Vicente Fornés; Hermenegildo García

2005-01-01

174

XPS of nitrogen-containing functional groups on activated carbon  

Microsoft Academic Search

XPS is used to study the binding energy of the Cls, Nls and Ols photoelectrons of surface groups on several nitrogen-containing activated carbons. Specific binding energies are assigned to amide (399.9 eV). lactam and imidc (399.7 eV). pyridine (398.7 eV), pyrrole (400.7 eV), alkylamine. secondary amide and N-alkylimide (399.9 eV) and trialkylaminc (399.7 cV) functional groups on activated carbon. Supporting

R. J. J. Jansen; H. van Bekkum

1995-01-01

175

High Lipophilicty of Perfluoroalkyl Carboxylate and Sulfonate  

PubMed Central

Here we report on remarkably high lipophilicity of perfluoroalkyl carboxylate and sulfonate. A lipophilic nature of this emerging class of organic pollutants has been hypothesized as an origin of their bioaccumulation and toxicity. Both carboxylate and sulfonate, however, are considered hydrophilic while perfluroalkyl groups are not only hydrophobic but also oleophobic. Partition coefficients of homologous series of perfluoroalkyl and alkyl carboxylates between water and n-octanol were determined as a measure of their lipophilicity by ion-transfer cyclic voltammetry. Very similar lipophilicity of perfluoroalkyl and alkyl chains with the same length is demonstrated experimentally for the first time by fragment analysis of the partition coefficients. This finding is important for pharmaceutical and biomedical applications of perfluoroalkyl compounds. Interestingly, ?2 orders of magnitude higher lipophilicity of a perfluoroalkyl carboxylate or sulfonate in comparison to its alkyl counterpart is ascribed nearly exclusively to their oxoanion groups. The higher lipophilicity originates from a strong electron-withdrawing effect of the perfluoroalkyl group on the adjacent oxoanion group, which is weakly hydrated to decrease its hydrophilicity. In fact, the inductive effect is dramatically reduced for a fluorotelomer with an ethylene spacer between perfluorohexyl and carboxylate groups, which is only as lipophilic as its alkyl counterpart, nonanoate, and is 400 times less lipophilic than perfluorononanoate. The high lipophilicity of perfluoroalkyl carboxylate and sulfonate implies that their permeation across such a thin lipophilic membrane as a bilayer lipid membrane is limited by their transfer at a membrane/water interface. The limiting permeability is lower and less dependent on their lipophilicity than the permeability controlled by their diffusion in the membrane interior as assumed in the classical solubility-diffusion model. PMID:19170492

Jing, Ping; Rodgers, Patrick J.; Amemiya, Shigeru

2009-01-01

176

Positive-definite functions on infinite-dimensional groups  

Microsoft Academic Search

This paper concerns positive-definite functions $$\\\\phi$$ on infinite-dimensional groups G. Our main results are as follows: first, we claim that if G has a ?-finite measure ? on the Borel field $$\\\\frak{B}(G)$$ whose right admissible shifts form a dense subgroup G\\u000a 0, a unique (up to equivalence) unitary representation (H, T) with a cyclic vector corresponds to $$\\\\phi$$ through a method

Hiroaki Shimomura

2008-01-01

177

Improved synthesis of DCDHF fluorophores with maleimide functional groups  

PubMed Central

A group of dicyanodihydrofuran (DCDHF) fluorophores with thiol-reactive maleimide functionality has been synthesized. One of the methods involves aromatic nucleophilic substitution reaction between an arylfluoride containing DCDHF and an amine containing protected maleimide. An alternative and generally useful method involves combination of the Mitsunobu reaction of a DCDHF-OH with a furan or 2-methylfuran protected maleimide and then subsequent retro Diels–Alder reaction. PMID:18584068

Lu, Zhikuan; Weber, Ryan; Twieg, Robert J.

2008-01-01

178

Water-enhanced solubility of carboxylic acids in organic solvents and its applications to extraction processes  

SciTech Connect

The solubilities of carboxylic acids in certain organic solvents increase remarkably with an increasing amount of water in the organic phase. This phenomenon leads to a novel extract regeneration process in which the co-extracted water is selectively removed from an extract, and the carboxylic acid precipitates. This approach is potentially advantageous compared to other regeneration processes because it removes a minor component of the extract in order to achieve a large recovery of acid from the extract. Carboxylic acids of interest include adipic acid, fumaric acid, and succinic acid because of their low to moderate solubilities in organic solvents. Solvents were screened for an increase in acid solubility with increased water concentration in the organic phase. Most Lewis-base solvents were found to exhibit this increased solubility phenomena. Solvents that have a carbonyl functional group showed a very large increase in acid solubility. 71 refs., 52 figs., 38 tabs.

Starr, J.N.; King, C.J.

1991-11-01

179

Biogenic oxidized organic functional groups in aerosol particles from a mountain forest site and their similarities to laboratory chamber products  

NASA Astrophysics Data System (ADS)

Submicron particles collected at Whistler, British Columbia, at 1020 m a.s.l. during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR) and X-ray fluorescence (XRF) techniques for organic functional groups (OFG) and elemental composition. Organic mass (OM) concentrations ranged from less than 0.5 to 3.1 ?g m-3, with a project mean and standard deviation of 1.3±1.0 ?g m-3 and 0.21±0.16 ?g m-3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and <1% of the average organic aerosol composition, respectively. Measurements of volatile organic compounds (VOC), including isoprene and monoterpenes from biogenic VOC (BVOC) emissions and their oxidation products (methyl-vinylketone / methacrolein, MVK/MACR), were made using co-located proton transfer reaction mass spectrometry (PTR-MS). We present chemically-specific evidence of OFG associated with BVOC emissions. Positive matrix factorization (PMF) analysis attributed 65% of the campaign OM to biogenic sources, based on the correlations of one factor to monoterpenes and MVK/MACR. The remaining fraction was attributed to anthropogenic sources based on a correlation to sulfate. The functional group composition of the biogenic factor (consisting of 32% alkane, 25% carboxylic acid, 21% organic hydroxyl, 16% ketone, and 6% amine groups) was similar to that of secondary organic aerosol (SOA) reported from the oxidation of BVOCs in laboratory chamber studies, providing evidence that the magnitude and chemical composition of biogenic SOA simulated in the laboratory is similar to that found in actual atmospheric conditions. The biogenic factor OM is also correlated to dust elements, indicating that dust may act as a non-acidic SOA sink. This role is supported by the organic functional group composition and morphology of single particles, which were analyzed by scanning transmission X-ray microscopy near edge X-ray absorption fine structure (STXM-NEXAFS).

Schwartz, R. E.; Russell, L. M.; Sjostedt, S. J.; Vlasenko, A.; Slowik, J. G.; Abbatt, J. P. D.; MacDonald, A. M.; Li, S. M.; Liggio, J.; Toom-Sauntry, D.; Leaitch, W. R.

2010-06-01

180

Biogenic oxidized organic functional groups in aerosol particles from a mountain forest site and their similarities to laboratory chamber products  

NASA Astrophysics Data System (ADS)

Submicron particles collected at Whistler, British Columbia, at 1020 masl during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR) and X-ray fluorescence (XRF) techniques for organic functional groups (OFG) and elemental composition. Organic mass (OM) ranged from less than 0.5 to 3.1?g m-3, with a project mean and standard deviation of 1.3±1.0 ?g m-3 and 0.21±0.16 ?g m-3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and <1% of the average organic aerosol composition, respectively. Measurements of volatile organic compounds (VOC), including isoprene and monoterpenes from biogenic VOC (BVOC) emissions and their oxidation products (methyl-vinylketone/methacrolein, MVK/MACR), were made using co-located proton transfer reaction mass spectrometry (PTR-MS). We present chemically-specific evidence of OFG associated with BVOC emissions. Positive matrix factorization (PMF) analysis attributed 65% of the campaign OM to biogenic sources, based on the correlations of one factor to monoterpenes and MVK/MACR. The remaining fraction was attributed to anthropogenic sources based on a correlation to sulfate. The functional group composition of the biogenic factor (consisting of 32% alkane, 25% carboxylic acid, 2% organic hydroxyl, 16% ketone, and 6% amine groups) was similar to that of secondary organic aerosol (SOA) reported from the oxidation of BVOCs in laboratory chamber studies, providing evidence that the magnitude and chemical composition of biogenic SOA simulated in the laboratory is similar to that found in actual atmospheric conditions. The biogenic factor OM is also correlated to dust elements, indicating that dust may act as a non-acidic SOA sink. This role is supported by the organic functional group composition and morphology of single particles, which were analyzed by scanning transmission X-ray microscopy near edge X-ray absorption fine structure (STXM-NEXAFS).

Schwartz, R. E.; Russell, L. M.; Sjosted, S. J.; Vlasenko, A.; Slowik, J. G.; Abbatt, J. P. D.; MacDonald, A. M.; Li, S. M.; Liggio, J.; Toom-Sauntry, D.; Leaitch, W. R.

2010-02-01

181

Characterization of Sea Lettuce Surface Functional Groups by Potentiometric Titrations  

NASA Astrophysics Data System (ADS)

In pursuit of our ultimate goal to better understand the prodigious capacity of the marine macroalga Ulva lactuca (sea lettuce) for adsorbing a broad range of dissolved trace metals from seawater, we performed an initial characterization of its surface functional groups. Specifically, the number of distinct functional groups as well as their individual bulk concentrations and acid dissociation constants (pKas) were determined by potentiometric titrations in NaCl solutions of various ionic strengths (I = 0.01-5.0 M), under inert nitrogen atmosphere at 25°C. Depending on the ionic strength, Ulva samples were manually titrated down to pH 2 or 3 with 1 N HCl and then up to pH 10 with 1 N NaOH in steps of 0.1-0.2 units, continuously monitoring pH with a glass combination electrode. Titrations of a dehydrated Ulva standard reference material (BCR-279) were compared with fresh Ulva tissue cultured in our laboratory. A titration in filtered natural seawater was also compared with one in an NaCl solution of equal ionic strength. Equilibrium constants for the ionization of water in NaCl solutions as a function of ionic strength were obtained from the literature. Fits to the titration data ([H]T vs. pH) were performed with the FITEQL4.0 computer code using non-electrostatic 3-, 4-, and 5-site models, either by fixing ionic strength at its experimental value or by allowing it to be extrapolated to zero, while considering all functional group pKas and bulk concentrations as adjustable parameters. Since pKas and bulk concentrations were found to be strongly correlated, the latter were also fixed in some cases to further constrain the pKas. Whereas these calculations are currently ongoing, preliminary results point to three, possibly four, functional groups with pKas of about 4.1, 6.3, and 9.5 at I = 0. Bulk concentrations of the three groups are very similar, about 5-6×10-4 mol/g based on dry weight, which suggests that all are homogeneously distributed over the surface and probably part of a single macromolecular scaffold. Fresh Ulva tissue appears to contain the same three functional groups but at lower concentrations, based on wet weight. The titration in natural seawater was largely dominated by the non-carbonate alkalinity of the solution and could not be robustly modeled. Results of fits with ionic strengths fixed at their experimental values indicate that the pKas of all three groups display prominent Debije-Hückel-type behavior, hence that these acid dissociation reactions involve a different mechanism than metal-proton exchange reactions on mineral surfaces, whose distribution coefficients (i.e., equilibrium constants) generally show a weak ionic strength dependence.

Ebling, A. M.; Schijf, J.

2008-12-01

182

Functional group diversity of bee pollinators increases crop yield  

PubMed Central

Niche complementarity is a commonly invoked mechanism underlying the positive relationship between biodiversity and ecosystem functioning, but little empirical evidence exists for complementarity among pollinator species. This study related differences in three functional traits of pollinating bees (flower height preference, daily time of flower visitation and within-flower behaviour) to the seed set of the obligate cross-pollinated pumpkin Cucurbita moschata Duch. ex Poir. across a land-use intensity gradient from tropical rainforest and agroforests to grassland in Indonesia. Bee richness and abundance changed with habitat variables and we used this natural variation to test whether complementary resource use by the diverse pollinator community enhanced final yield. We found that pollinator diversity, but not abundance, was positively related to seed set of pumpkins. Bees showed species-specific spatial and temporal variation in flower visitation traits and within-flower behaviour, allowing for classification into functional guilds. Diversity of functional groups explained even more of the variance in seed set (r2=45%) than did species richness (r2=32%) highlighting the role of functional complementarity. Even though we do not provide experimental, but rather correlative evidence, we can link spatial and temporal complementarity in highly diverse pollinator communities to pollination success in the field, leading to enhanced crop yield without any managed honeybees. PMID:18595841

Hoehn, Patrick; Tscharntke, Teja; Tylianakis, Jason M; Steffan-Dewenter, Ingolf

2008-01-01

183

Modeling the antisymmetric and symmetric stretching vibrational modes of aqueous carboxylate anions.  

PubMed

The infrared spectra of six aqueous carboxylate anions have been calculated at the M05-2X/cc-pVTZ level of theory with the SMD solvent model, and validated against experimental data from the literature over the region of 1700 cm(-1) to 1250 cm(-1); this region corresponds to the stretching modes of the carboxylate group, and is often interrogated when probing bonding of carboxylates to other species and surfaces. The anions studied here were formate, acetate, oxalate, succinate, glutarate and citrate. For the lowest energy conformer of each anion, the carboxylate moiety antisymmetric stretching peak was predicted with a mean signed error of only 4 cm(-1) using the SMD solvent model, while the symmetric peak was slightly overestimated. Performing calculations in vacuum and scaling was found to generally over-predict the antisymmetric vibrational frequencies and under predict the symmetric peak. Different conformers of the same anion were found to have only slightly different spectra in the studied region and the inclusion of explicit water molecules was not found to significantly change the calculated spectra when the implicit solvent model is used. Overall, the use of density functional theory in conjunction with an implicit solvent model was found to result in infra-red spectra that are the best reproduction of the features found experimentally for the aqueous carboxylate ions in the important 1700 cm(-1) to 1250 cm(-1) region. The development of validated model chemistries for simulating the stretching modes of aqueous carboxylate ions will be valuable for future studies that investigate how carboxylate anions complex with multivalent metal cations and related species in solution. PMID:25048288

Sutton, Catherine C R; Franks, George V; da Silva, Gabriel

2015-01-01

184

Carboxylic acid sorption regeneration process  

DOEpatents

Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine.

King, C. Judson (Kensington, CA); Poole, Loree J. (Baton Rouge, LA)

1995-01-01

185

Carboxylic acid sorption regeneration process  

DOEpatents

Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine. 10 figs.

King, C.J.; Poole, L.J.

1995-05-02

186

Functional renormalization group study of nuclear and neutron matter  

E-print Network

A chiral model based on nucleons interacting via boson exchange is investigated. Fluctuation effects are included consistently beyond the mean-field approximation in the framework of the functional renormalization group. The liquid-gas phase transition of symmetric nuclear matter is studied in detail. No sign of a chiral restoration transition is found up to temperatures of about 100 MeV and densities of at least three times the density of normal nuclear matter. Moreover, the model is extended to asymmetric nuclear matter and the constraints from neutron star observations are discussed.

Drews, Matthias

2014-01-01

187

Functional renormalization group study of nuclear and neutron matter  

E-print Network

A chiral model based on nucleons interacting via boson exchange is investigated. Fluctuation effects are included consistently beyond the mean-field approximation in the framework of the functional renormalization group. The liquid-gas phase transition of symmetric nuclear matter is studied in detail. No sign of a chiral restoration transition is found up to temperatures of about 100 MeV and densities of at least three times the density of normal nuclear matter. Moreover, the model is extended to asymmetric nuclear matter and the constraints from neutron star observations are discussed.

Matthias Drews; Wolfram Weise

2014-10-31

188

Characterization of functional groups of airborne particulate matter  

NASA Astrophysics Data System (ADS)

Particulate matter of organic combustibles burning consists of various hydrocarbons and radicals, which may cause harmful impact to human health. In this study solid particulate matter were collected on the filters from burning of various combustibles in a burning chamber and from atmosphere of city of Riga by dichotomous impactor. FTIR spectra were obtained before and after samples' treatment. Absorptions associated with aliphatic and aromatic hydrocarbons and alcohol functional groups were observed in the FTIR spectra. Free radicals of particulate matter were detected by electron paramagnetic resonance (EPR).

Baitimirova, M.; Katkevics, J.; Baumane, L.; Bakis, E.; Viksna, A.

2013-12-01

189

A Group Theoretical Approach to Graviton Two-Point Function  

E-print Network

From the group theoretical point of view, it is proved that the theory of linear conformal gravity should be written in terms of a tensor field of rank-3 and mixed symmetry \\cite{binegar}. Such field equation was obtained in de Sitter space \\cite{takook}. In this paper, a proper solution to the physical sector of this field equation in de Sitter ambient space is written as a product of a generalized polarization tensor and a massless minimally coupled scalar field. Similar to the minimally coupled scalar field, the Krein space quantization has been exploited to quantize this sector. We have calculated the physical part of the linear graviton two-point function. This two-point function is simultaneously de Sitter invariant and free of any pathological large-distance behavior.

S. Rahbardehghan; H. Pejhan; M. Elmizadeh

2014-06-17

190

A Group Theoretical Approach to Graviton Two-Point Function  

E-print Network

From the group theoretical point of view, it is proved that the theory of linear conformal gravity should be written in terms of a tensor field of rank-3 and mixed symmetry \\cite{binegar}. Such field equation was obtained in de Sitter space \\cite{takook}. In this paper, a proper solution to the physical sector of this field equation in de Sitter ambient space is written as a product of a generalized polarization tensor and a massless minimally coupled scalar field. Similar to the minimally coupled scalar field, the Krein space quantization has been exploited to quantize this sector. We have calculated the physical part of the linear graviton two-point function. This two-point function is simultaneously de Sitter invariant and free of any pathological large-distance behavior.

Rahbardehghan, S; Elmizadeh, M

2014-01-01

191

Plant Functional Group Composition Modifies the Effects of Precipitation Change on Grassland Ecosystem Function  

PubMed Central

Temperate grassland ecosystems face a future of precipitation change, which can alter community composition and ecosystem functions through reduced soil moisture and waterlogging. There is evidence that functionally diverse plant communities contain a wider range of water use and resource capture strategies, resulting in greater resistance of ecosystem function to precipitation change. To investigate this interaction between composition and precipitation change we performed a field experiment for three years in successional grassland in southern England. This consisted of two treatments. The first, precipitation change, simulated end of century predictions, and consisted of a summer drought phase alongside winter rainfall addition. The second, functional group identity, divided the plant community into three groups based on their functional traits- broadly described as perennials, caespitose grasses and annuals- and removed these groups in a factorial design. Ecosystem functions related to C, N and water cycling were measured regularly. Effects of functional groupidentity were apparent, with the dominant trend being that process rates were higher under control conditions where a range of perennial species were present. E.g. litter decomposition rates were significantly higher in plots containing several perennial species, the group with the highest average leaf N content. Process rates were also very strongly affected by the precipitation change treatmentwhen perennial plant species were dominant, but not where the community contained a high abundance of annual species and caespitose grasses. This contrasting response could be attributable to differing rooting patterns (shallower structures under annual plants, and deeper roots under perennials) and faster nutrient uptake in annuals compared to perennials. Our results indicate that precipitation change will have a smaller effect on key process rates in grasslandscontaining a range of perennial and annual species, and that maintaining the presence of key functional groups should be a crucial consideration in future grassland management. PMID:23437300

Fry, Ellen L.; Manning, Pete; Allen, David G. P.; Hurst, Alex; Everwand, Georg; Rimmler, Martin; Power, Sally A.

2013-01-01

192

Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes  

SciTech Connect

Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because of the speculation of improved water selectivity of the carboxylate pendant chain. During the first phase of these investigations the effort was focused on generating a thin, solution cast perfluoro carboxylate ionomer film, to evaluate the general, chemical and physical characteristics of the polymer, and to assess the material's aqueous transport performance (flux and nitrate separation efficiencies) in pervaporation and high-pressure environments. Results demonstrated that generating robust solution-cast films was difficult yet a number of membranes survived high trans-membrane pressures up to 700 psig. General characterization of the solution cast product showed reduced ion exchange capacities when compared with thicker, ''as received'' perfluoro carboxylate and similar sulfonate films. Small angle x-ray scattering analysis results suggested that the solution cast carboxylate films contained a small fraction of sulfonate terminated side-chains. Aqueous transport experimentation showed that permeate fluxes for both pure water and nitric acid were approximately two orders of magnitude smaller for the carboxylate solution cast membranes when compared to their sulfonate counterparts of similar thickness (Nafion{trademark} 111). Additionally, nitric acid separation efficiencies ({alpha}) were approximately one order of magnitude higher for the carboxylate solution cast films when compared to Nafion{trademark} 111. The second phase of our work included the generation of thin carboxylate films made by the chemical synthesis perfluoro sulfonate and mixed sulfonate/carboxylate polymers from a perfluoro sulfonyl fluoride precursor, the characterization of the newly generated material, and a study of the transport characteristics of these membranes. Transport studies consisted of the dehydration of nitric acid feeds by pervaporation. In addition, the initial hypothesis was expanded to include demonstration that transmembrane flux and separation efficiencies are a function of the ratio between sulfonate and carboxylate terminated side chains of the perfluoro ionomer. Investigations demonstrated the ability to generate in- house films with varying sulfonate/carboxylate concentrations from commercially available perfluoro sulfonyl fluoride material, and showed that the converted films could be characterized using Fourier transform infrared (FTIR) and x-ray fluorescence (XRF) spectroscopy. Finally, the mixed films where subjected to nitric acid dehydration transport tests and a relationship was found to exist between sulfonate/carboxylate pendant chain ratio and both flux and water separation capability. In summary, experimental results confirmed that, when compared to Nafion 111{trademark}, the mixed film's bulk fluxes decrease by approximately three orders of magnitude and the water separation factor increases by as much as two orders of magnitude as the carboxylate side-chain content was increased from 0 (pure sulfonate film) to 53 mole%, supporting the hypothesis given for this effort. It was observed that the water selectivity improved for both the solution cast perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films when judged against similar perfluoro sulfonate materials. Of great benefit was that during the investigation a number of research tools w

R.L. Ames

2004-09-01

193

Water Mediated Ligand Functional Group Cooperativity: The Contribution of a Methyl Group to Binding Affinity is Enhanced by a COO? Group Through Changes in the Structure and Thermo dynamics of the Hydration Waters of Ligand-Thermolysin Complexes  

PubMed Central

Ligand functional groups can modulate the contributions of one another to the ligand-protein binding thermodynamics, producing either positive or negative cooperativity. Data presented for four thermolysin phosphonamidate inhibitors demonstrate that the differential binding free energy and enthalpy caused by replacement of a H with a Me group, which binds in the well-hydrated S2? pocket, are more favorable in presence of a ligand carboxylate. The differential entropy is however less favorable. Dissection of these differential thermodynamic parameters, X-ray crystallography, and density-functional theory calculations suggest that these cooperativities are caused by variations in the thermodynamics of the complex hydration shell changes accompanying the H?Me replacement. Specifically, the COO? reduces both the enthalpic penalty and the entropic advantage of displacing water molecules from the S2? pocket, and causes a subsequent acquisition of a more enthalpically, less entropically, favorable water network. This study contributes to understanding the important role water plays in ligand-protein binding. PMID:22894131

Nasief, Nader N; Tan, Hongwei; Kong, Jing; Hangauer, David

2012-01-01

194

Group utility functions: learning equilibria between groups of agents in computer games by modifying the reinforcement signal  

Microsoft Academic Search

Group utility functions are an expansion of the well known team utility function for providing multiple agents with a common reinforcement learning signal for learning collective behaviour. In this paper we describe what group utility functions are and use them with reinforcement learning to learn non-player character behaviours in a simple computer game. As yet, reinforcement learning techniques have rarely

Jay Bradley; Gillian Hayes

2005-01-01

195

Changes in Bird Functional Diversity across Multiple Land Uses: Interpretations of Functional Redundancy Depend on Functional Group Identity  

PubMed Central

Examinations of the impact of land-use change on functional diversity link changes in ecological community structure driven by land modification with the consequences for ecosystem function. Yet, most studies have been small-scale, experimental analyses and primarily focussed on plants. There is a lack of research on fauna communities and at large-scales across multiple land uses. We assessed changes in the functional diversity of bird communities across 24 land uses aligned along an intensification gradient. We tested the hypothesis that functional diversity is higher in less intensively used landscapes, documented changes in diversity using four diversity metrics, and examined how functional diversity varied with species richness to identify levels of functional redundancy. Functional diversity, measured using a dendogram-based metric, increased from high to low intensity land uses, but observed values did not differ significantly from randomly-generated expected values. Values for functional evenness and functional divergence did not vary consistently with land-use intensification, although higher than expected values were mostly recorded in high intensity land uses. A total of 16 land uses had lower than expected values for functional dispersion and these were mostly low intensity native vegetation sites. Relations between functional diversity and bird species richness yielded strikingly different patterns for the entire bird community vs. particular functional groups. For all birds and insectivores, functional evenness, divergence and dispersion showed a linear decline with increasing species richness suggesting substantial functional redundancy across communities. However, for nectarivores, frugivores and carnivores, there was a significant hump-shaped or non-significant positive linear relationship between these functional measures and species richness indicating less redundancy. Hump-shaped relationships signify that the most functionally diverse communities occur at intermediate levels of species richness. Interpretations of redundancy thus vary for different functional groups and related ecosystem functions (e.g. pollination), and can be substantially different to relationships involving entire ecological communities. PMID:23696844

Luck, Gary W.; Carter, Andrew; Smallbone, Lisa

2013-01-01

196

Observations of Adolescent Peer Group Interactions as a Function of Within- and Between-Group Centrality Status  

ERIC Educational Resources Information Center

Observations of adolescent (n = 258; M age = 15.45) peer group triads (n = 86) were analyzed to identify conversation and interaction styles as a function of within-group and between-group centrality status. Group members' discussions about hypothetical dilemmas were coded for agreements, disagreements, commands, and opinions. Interactions during…

Ellis, Wendy E.; Dumas, Tara M.; Mahdy, Jasmine C.; Wolfe, David A.

2012-01-01

197

A conceptual basis to encode and detect organic functional groups in XML.  

PubMed

A conceptual basis to define and detect organic functional groups is developed. The basic model of a functional group is termed as a primary functional group and is characterized by a group center composed of one or more group center atoms bonded to terminal atoms and skeletal carbon atoms. The generic group center patterns are identified from the structures of known functional groups. Accordingly, a chemical ontology 'Font' is developed to organize the existing functional groups as well as the new ones to be defined by the chemists. The basic model is extended to accommodate various combinations of primary functional groups as functional group assemblies. A concept of skeletal group is proposed to define the characteristic groups composed of only carbon atoms to be regarded as equivalent to functional groups. The combination of primary functional groups with skeletal groups is categorized as skeletal group assembly. In order to make the model suitable for reaction modeling purpose, a Graphical User Interface (GUI) is developed to define the functional groups and to encode in XML format appropriate to detect them in chemical structures. The system is capable of detecting multiple instances of primary functional groups as well as the overlapping poly-functional groups as the respective assemblies. PMID:23666030

Sankar, Punnaivanam; Krief, Alain; Vijayasarathi, Durairaj

2013-06-01

198

The size of hydroxyl groups in solution and the changes in size associated with the ionization of phenolic, carboxylic and amino groups in phenolic quaternary ammonium salts, nicotine and some amino acids: possible implications for drug-water and drug-receptor interactions.  

PubMed Central

Size in solution can be expressed either as the apparent molal volume at infinite dilution (phi 0v) amd the concentration parameter (j) or as the partial molal volume of the solute at infinite dilution (V0(2)) and the concentration parameter for the solute or solvent (qs or qw). Although calculated differently, these are derived from the same results and are equivalent. From measurement with phenolic quaternary ammonium salts, including compounds with high nicotine-like activity, the apparent size of the hydroxyl group in water is small and variable. Phenolic groups are slightly larger than alcoholic groups, which should be better hydrogen donors. By measuring the volume change associated with ionisation it is possible to measure the size of charged groups such as phenate and carboxylate; these are much smaller than phenolic and carboxyl. Ammonium groups, however, are only slightly smaller than the corresponding amines. The zwitterion forms of amino acids are associated with a minimum in volume but the volume changes increase with chain length from glycine to gamma-aminobutyric acid. Groups separated by less than this distance interact in their effects on water. Decreases in volume or unexpectedly small increments in apparent molal volume represent decreases in entropy which must be taken into account in drug-water-receptor interactions. Although they may be offset by enthalpy changes, they should favour binding because there is more scope for an increase in entropy. This might explain the association of the small apparent size in water of the hydroxyl group in many compounds with its effects of their affinity for receptors. PMID:7470734

Barlow, R. B.

1980-01-01

199

Synthesis of Silver Nanoclusters and Functionalization with Glucosamine for Glyconanoparticles  

Microsoft Academic Search

Functionalized nanoparticles are promising candidates for the construction of new nanomaterials. In this paper, glucosamine was covalently functionalized on the surface of silver nanoparticles to fabricate glyconanoparticles. Silver nanoclusters obtained by liquid-solid-solution (LSS) strategy under hydrothermal condition were first functionalized by carboxyl-terminated alkanethiol and the terminal carboxyl group was subsequently bonded with side-chain amino group of glucosamine surface through EDC\\/NHS

Murugan Veerapandian; Kyusik Yun

2010-01-01

200

The SLC13 gene family of sodium sulphate\\/carboxylate cotransporters  

Microsoft Academic Search

The SLC13 gene family consist of five sequence-related members that have been identified in a variety of animals, plants, yeast and bacteria. Proteins encoded by these genes are divided into two functionally unrelated groups: the Na +-sulphate (NaS) cotransporters and the Na +-carboxylate (NaC) cotransporters. Members of this family include the renal Na +-dependent inorganic sulphate transporter-1 (NaSi-1, SLC13A1), the

Daniel Markovich; Heini Murer

2004-01-01

201

Plant Species and Functional Group Combinations Affect Green Roof Ecosystem Functions  

PubMed Central

Background Green roofs perform ecosystem services such as summer roof temperature reduction and stormwater capture that directly contribute to lower building energy use and potential economic savings. These services are in turn related to ecosystem functions performed by the vegetation layer such as radiation reflection and transpiration, but little work has examined the role of plant species composition and diversity in improving these functions. Methodology/Principal Findings We used a replicated modular extensive (shallow growing- medium) green roof system planted with monocultures or mixtures containing one, three or five life-forms, to quantify two ecosystem services: summer roof cooling and water capture. We also measured the related ecosystem properties/processes of albedo, evapotranspiration, and the mean and temporal variability of aboveground biomass over four months. Mixtures containing three or five life-form groups, simultaneously optimized several green roof ecosystem functions, outperforming monocultures and single life-form groups, but there was much variation in performance depending on which life-forms were present in the three life-form mixtures. Some mixtures outperformed the best monocultures for water capture, evapotranspiration, and an index combining both water capture and temperature reductions. Combinations of tall forbs, grasses and succulents simultaneously optimized a range of ecosystem performance measures, thus the main benefit of including all three groups was not to maximize any single process but to perform a variety of functions well. Conclusions/Significance Ecosystem services from green roofs can be improved by planting certain life-form groups in combination, directly contributing to climate change mitigation and adaptation strategies. The strong performance by certain mixtures of life-forms, especially tall forbs, grasses and succulents, warrants further investigation into niche complementarity or facilitation as mechanisms governing biodiversity-ecosystem functioning relationships in green roof ecosystems. PMID:20300196

Lundholm, Jeremy; MacIvor, J. Scott; MacDougall, Zachary; Ranalli, Melissa

2010-01-01

202

Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes  

NASA Astrophysics Data System (ADS)

The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

Li, Yang; Tu, Xingchen; Wang, Minglang; Wang, Hao; Sanvito, Stefano; Hou, Shimin

2014-11-01

203

Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes.  

PubMed

The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds. PMID:25381533

Li, Yang; Tu, Xingchen; Wang, Minglang; Wang, Hao; Sanvito, Stefano; Hou, Shimin

2014-11-01

204

The influence of oxygen-containing functional groups on the dispersion of single-walled carbon nanotubes in amide solvents  

NASA Astrophysics Data System (ADS)

Surface composition plays an important role in carbon nanotube dispersibility in different environments. Indeed, it determines the choice of dispersion medium. In this paper the effect of oxidation on the dispersion of HiPCO single-walled carbon nanotubes (SWNTs) in N-methyl-pyrrolidinone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), N-dodecyl-pyrrolidinone (N12P) and cyclohexyl-pyrrolidinone (CHP) was systematically studied. During the oxidation process, similar amounts of carboxylic acid and phenolic groups were introduced to mostly already existing defects. For each solvent the dispersion limits and the absorption coefficients were estimated by optical absorption analysis over a range of SWNT concentrations. The presence of acid oxygenated groups increased SWNT dispersibility in NMP, DMF and DMA, but decreased in N12P and CHP. The absorption coefficients, however, decreased for all solvents after oxidation, reflecting the weakening of the effective transition dipole of the ?-? transition with even limited extension functionalization and solvent interaction. The analysis of the results in terms of Hansen and Flory-Huggins solubility parameters evidenced the influence of dipolar interactions and hydrogen bonding on the dispersibility of oxidized SWNTs.

Brandão, S. D. F.; Andrada, D.; Mesquita, A. F.; Santos, A. P.; Gorgulho, H. F.; Paniago, R.; Pimenta, M. A.; Fantini, C.; Furtado, C. A.

2010-08-01

205

Adsorption of chromium (VI) ion from aqueous solution by succinylated mercerized cellulose functionalized with quaternary ammonium groups.  

PubMed

Succinylated mercerized cellulose (cell 1) was used to synthesize an anion exchange resin. Cell 1, containing carboxylic acid groups was reacted with triethylenetetramine to introduce amine functionality to this material to obtain cell 2. Cell 2 was reacted with methyl-iodide to quaternize the amine groups from this material to obtain cell 3. Cells 2 and 3 were characterized by mass percent gain, degree of amination and quaternization, FTIR and CHN. Cells 2 and 3 showed degrees of amination and quaternization of 2.8 and 0.9 mmol/g and nitrogen content of 6.07% and 2.13%, respectively. Cell 3 was used for Cr (VI) adsorption studies. Adsorption equilibrium time and optimum pH for Cr (VI) adsorption were found to be 300 min and 3.1, respectively. The Langmuir isotherm was used to model adsorption equilibrium data. The adsorption capacity of cell 3 was found to be 0.829 mmol/g. Kinetic studies showed that the rate of adsorption of Cr (VI) on cell 3 obeyed a pseudo-second-order kinetic model. PMID:19297152

Gurgel, Leandro Vinícius Alves; Perin de Melo, Júlio César; de Lena, Jorge Carvalho; Gil, Laurent Frédéric

2009-07-01

206

Perceived In-Group Homogeneity as a Function of Group Membership Salience and Stereotype Threat.  

ERIC Educational Resources Information Center

Considers two determinants--one cognitive and the other motivational--of perceptual fluctuations of in-group variation. Results indicate that when motivation to protect social or personal identity from threat is absent, priming the in-group social category promotes a homogeneous and cohesive view of the in-group. (RJM)

Lee, Yueh-Ting; Ottati, Victor

1995-01-01

207

Infrared-chemical derivatization method for determination of total hydroxyls and carboxyls in petroleum and syncrudes  

SciTech Connect

Oxygen-containing functional group (hydroxyl and carboxyl) in fuels or crude oils, or fractions thereof, are determined by RI spectroscopy. The approach is based on chemical derivatization followed by measurement of RI bands of the corresponding derivatives. The chemical derivatization procedure involves two steps: (1) esterification of carboxylic acids with 2,2,2-trifluoroethanol and (2) acylation of alcoholic and phenolic hydroxyls with trifluoroacetyl chloride. The aryl trifluoroacetates absorb at 1800 cm/sup /minus/1/; the 2,2,2-trifluoroethyl esters absorb in the region 1760-1740 cm/sup /minus/1/. Variation of molar absorptivity of the derivatives as a function of structure is determined using pure compounds and well defined fractions from actual fuel samples. The overall accuracy, precision, sensitivity, and range of applicability to petroleum and related sample types are discussed. 52 refs., 3 figs., 9 tabs.

Yu, S.K-T; Green, J.B.

1988-09-01

208

Modeling the active sites of non-heme diiron metalloproteins with sterically hindered carboxylates and syn N-Donor ligands  

E-print Network

Chapter 1. Different Synthetic Approaches to Modeling the Active Sites of Carboxylate-Bridged Non-Heme Diiron Enzymes Carboxylate-bridged non-heme diiron enzymes activate dioxygen to perform a variety of biological functions. ...

Friedle, Simone, 1976-

2009-01-01

209

Hydrolysis of organonitrate functional groups in aerosol particles  

SciTech Connect

Organonitrate (ON) groups are important substituents in secondary organic aerosols. Model simulations and laboratory studies indicate a large fraction of ON groups in aerosol particles, but much lower quantities are observed in the atmosphere. Hydrolysis of ON groups in aerosol particles has been proposed recently. To test this hypothesis, we simulated formation of ON molecules in a reaction chamber under a wide range of relative humidity (0% to 90%). The mass fraction of ON groups (5% to 20% for high-NOx experiments) consistently decreased with increasing relative humidity, which was best explained by hydrolysis of ON groups at a rate of 4 day-1 (lifetime of 6 hours) for reactions under relative humidity greater than 20%. In addition, we found that secondary nitrogen-containing molecules absorb light, with greater absorption under dry and high-NOx conditions. This work provides the first evidence for particle-phase hydrolysis of ON groups, a process that could substantially reduce ON group concentration in the atmosphere.

Liu, Shang; Shilling, John E.; Song, Chen; Hiranuma, Naruki; Zaveri, Rahul A.; Russell, Lynn M.

2012-10-19

210

Special functions and group theory in theoretical physics  

SciTech Connect

The subject of special functions, even where restricted to the narrower subject of special functions in theoretical physics, is far too broad for one to attempt any meaningfully complete survey. We attempt to review the important main themes in the subject and then show how recent advances broadened and extended these themes.

Biedenharn, L.C.; Gustafson, R.A.; Lohe, M.A.; Louck, J.D.; Milne, S.C.

1983-01-01

211

Enhancing the enzymatic hydrolysis of lignocellulosic biomass by increasing the carboxylic acid content of the associated lignin.  

PubMed

To assess the effects that the physical and chemical properties of lignin might have on the enzymatic hydrolysis of pretreated lignocellulosic substrates, protease treated lignin (PTL) and cellulolytic enzyme lignin (CEL) fractions, isolated from steam and organosolv pretreated corn stover, poplar, and lodgepole pine, were prepared and characterized. The adsorption of cellulases to the isolated lignin preparations corresponded to a Langmuir adsorption isotherm. It was apparent that, rather than the physical properties of the isolated lignin, the carboxylic acid functionality of the isolated lignin, as determined by FTIR and NMR spectroscopy, had much more of an influence when lignin was added to typical hydrolysis of pure cellulose (Avicel). An increase in the carboxylic content of the lignin preparation resulted in an increased hydrolysis yield. These results suggested that the carboxylic acids within the lignin partially alleviate non-productive binding of cellulases to lignin. To try to confirm this possible mechanism, dehydrogenative polymers (DHP) of monolignols were synthesized from coniferyl alcohol (CA) and ferulic acid (FA), and these model compounds were added to a typical enzymatic hydrolysis of Avicel. The DHP from FA, which was enriched in carboxylic acid groups compared with the DHP from CA, adsorbed a lower mount of cellulases and did not decrease hydrolysis yields when compared to the DHP from CA, which decreased the hydrolysis of Avicel by 8.4%. Thus, increasing the carboxylic acid content of the lignin seemed to significantly decrease the non-productive binding of cellulases and consequently increased the enzymatic hydrolysis of the cellulose. PMID:21246506

Nakagame, Seiji; Chandra, Richard P; Kadla, John F; Saddler, Jack N

2011-03-01

212

The Nonenzymatic Reactivity of the Acyl-Linked Metabolites of Mefenamic Acid toward Amino and Thiol Functional Group Bionucleophiles  

PubMed Central

Mefenamic acid (MFA), a carboxylic acid–containing nonsteroidal anti-inflammatory drug, is metabolized into the chemically-reactive MFA-1-O-acyl-glucuronide (MFA-1-O-G), MFA-acyl-adenylate (MFA-AMP), and the MFA-S-acyl-coenzyme A (MFA-CoA), all of which are electrophilic and capable of acylating nucleophilic sites on biomolecules. In this study, we investigate the nonenzymatic ability of each MFA acyl-linked metabolite to transacylate amino and thiol functional groups on the acceptor biomolecules Gly, Tau, l-glutathione (GSH), and N-acetylcysteine (NAC). In vitro incubations with each of the MFA acyl-linked metabolites (1 ?M) in buffer under physiologic conditions with Gly, Tau, GSH, or NAC (10 mM) revealed that MFA-CoA was 11.5- and 19.5-fold more reactive than MFA-AMP toward the acylation of cysteine-sulfhydryl groups of GSH and NAC, respectively. However, MFA-AMP was more reactive toward both Gly and Tau, 17.5-fold more reactive toward the N-acyl-amidation of taurine than its corresponding CoA thioester, while MFA-CoA displayed little reactivity toward glycine. Additionally, mefenamic acid-S-acyl-glutathione (MFA-GSH) was 5.6- and 108-fold more reactive toward NAC than MFA-CoA and MFA-AMP, respectively. In comparison with MFA-AMP and MFA-CoA, MFA-1-O-G was not significantly reactive toward all four bionucleophiles. MFA-AMP, MFA-CoA, MFA-1-O-G, MFA-GSH, and mefenamic acid-taurine were also detected in rat in vitro hepatocyte MFA (100 ?M) incubations, while mefenamic acid-glycine was not. These results demonstrate that MFA-AMP selectively reacts with the amino functional groups of glycine and lysine nonenzymatically, MFA-CoA selectively reacts nonenzymatically with the thiol functional groups of GSH and NAC, and MFA-GSH reacts with the thiol functional group of GSH nonenzymatically, all of which may potentially elicit an idiosyncratic toxicity in vivo. PMID:23975029

Horng, Howard

2013-01-01

213

Structure, function, and regulation of Group V phospholipase A 2  

Microsoft Academic Search

The hydrolysis of membrane phospholipid by phospholipase A2 (PLA2) is a key step in the production of inflammatory eicosanoids. Recent cell studies have shown that secretory group V PLA2 (gVPLA2) is involved in agonist-induced eicosanoid biosynthesis in mouse P388D1 cell line, mast cells, and transfected HEK 293 cells. gVPLA2 is homologous to other group II PLA2 family members but has

Wonhwa Cho

2000-01-01

214

Cloning and Functional Characterization of Novel Variants and Tissue-Specific Expression of Alternative Amino and Carboxyl Termini of Products of Slc4a10  

PubMed Central

Previous studies have shown that the electroneutral Na+/HCO3? cotransporter NBCn2 (SLC4A10) is predominantly expressed in the central nervous system (CNS). The physiological and pathological significances of NBCn2 have been well recognized. However, little is known about the tissue specificity of expression of different NBCn2 variants. Moreover, little is known about the expression of NBCn2 proteins in systems other than CNS. Here, we identified a set of novel Slc4a10 variants differing from the originally described ones by containing a distinct 5? untranslated region encoding a new extreme amino-terminus (Nt). Electrophysiology measurements showed that both NBCn2 variants with alternative Nt contain typical electroneutral Na+-coupled HCO3? transport activity in Xenopus oocytes. Luciferase reporter assay showed that Slc4a10 contains two alternative promoters responsible for expression of the two types of NBCn2 with distinct extreme Nt. Western blotting showed that NBCn2 proteins with the original Nt are primarily expressed in CNS, whereas those with the novel Nt are predominantly expressed in the kidney and to a lesser extent in the small intestine. Due to alternative splicing, the known NBCn2 variants contain two types of carboxyl-termini (CT) differing in the optional inclusion of a PDZ-binding motif. cDNA cloning showed that virtually all NBCn2 variants expressed in epithelial tissues contain, but the vast majority of those from the neural tissues lack the PDZ-binding motif. We conclude that alternative transcription and splicing of Slc4a10 products are regulated in a tissue-specific manner. Our findings provide critical insights that will greatly influence the study of the physiology of NBCn2. PMID:23409100

Qin, Xue; Xie, Zhang-Dong; Wang, Qing K.; Liu, Mugen; Chen, Li-Ming

2013-01-01

215

Application of a multiple endpoint bacterial reporter assay to evaluate toxicological relevant endpoints of perfluorinated compounds with different functional groups and varying chain length.  

PubMed

Perfluorinated compounds are widely distributed in the environment; good knowledge about the toxic mode of action of these compounds can contribute to improved molecular design and risk assessment. The studied compounds were evaluated with a bacterial multiple endpoint reporter assay for responses in four different mode of action classes (oxidative damage, DNA damage, general cell lesions and membrane damage). The results of our study clearly demonstrate that inductions of stress responsive genes occur for the different compounds and confirm some of the known mechanisms of work for well studied compounds like PFOA and PFOS, and in addition provide new information for less studied compounds. Few inductions were observed after exposure to the low carbon number carboxylic acids, PFBtA (CF(3)(CF(2))(2)C(O)O(-)), PFPtA (CF(3)(CF(2))(3)C(O)O(-)), PFHxA (CF(3)(CF(2))(4)C(O)O(-)) and PFHpA (CF(3)(CF(2))(5)C(O)O(-)) at equimolar concentrations (0.0156-1 mM). The induction of membrane damage markers (MicF and OsmY) is prominently present after exposure to PFOS (CF(3)(CF(2))(7)SO(3)(-)) and even more after exposure to PFNA (CF(3)(CF(2))(7)C(O)O(-)). This is the first report describing the mode of action of carboxylic acids with 11 and 12 carbon atoms; they are equally potent inducers relative to PFOS and PFNA. Overall, the effects seen at the level of gene expression were higher for the sulfonic acids than for the carboxylic acids, but the effect of the chain length is more important than the effect of the functional group. PMID:20619337

Nobels, Ingrid; Dardenne, Freddy; De Coen, Wim; Blust, Ronny

2010-09-01

216

Reactivity of End-functionalized Polymers Containing Diels-Alder Functional Groups  

NASA Astrophysics Data System (ADS)

Incorporation of reversible covalent bond into macromolecular systems has proven useful in engineering novel responsive architectures, and Diels-Alder bonding in this context is now well established. However, efficient synthesis of end-functionalized polymers is a major obstacle hindering further development of responsive and modular polymer architectures. In this current research, two immiscible polymers, poly(methyl methacrylate) (PMMA) and poly(benzyl methacrylate) (PBzMA) with controlled molecular weight, bearing terminal furan-maleimide groups, are prepared via Reversible Addition-Fragmentation chain transfer (RAFT) polymerization. The reactivity of such end-functionalized polymers is explored to expose the relationship between chain composition and their ability to undergo modular cross-coupling to form monodisperse block copolymers. To elucidate how reaction conditions affect the efficiency of the Diels-Alder reaction, Hydrogen Nuclear Magnetic Resonance (H-NMR) and Size Exclusion Chromatography (SEC) techniques are actively applied. Experimental results will be interpreted on the basis of dissimilarity between interaction energies of polymer segments and the concentration of reactive groups.

Meng, Yuan; Zhang, Yuan; Anthamatten, Mitchell

2013-03-01

217

Carboxylic Acid Unknowns and Titration 90 CARBOXYLIC ACID UNKNOWN  

E-print Network

Carboxylic Acid Unknowns and Titration 90 CARBOXYLIC ACID UNKNOWN A. Solubility Tests: Water, NaHCO3, and NaOH Test the solubility of your acid first in neutral water, in NaOH/H2O, and in NaHCO3 to 30 drops. Swirl/mix well. Use of small stir bar helps. · Water Test: Only acids with small numbers

Jasperse, Craig P.

218

4-methylene-2-octyl-5-oxotetrahydrofuran-3-carboxylic acid (C75), an inhibitor of fatty-acid synthase, suppresses the mitochondrial fatty acid synthesis pathway and impairs mitochondrial function.  

PubMed

4-Methylene-2-octyl-5-oxotetrahydrofuran-3-carboxylic acid (C75) is a synthetic fatty-acid synthase (FASN) inhibitor with potential therapeutic effects in several cancer models. Human mitochondrial ?-ketoacyl-acyl carrier protein synthase (HsmtKAS) is a key enzyme in the newly discovered mitochondrial fatty acid synthesis pathway that can produce the substrate for lipoic acid (LA) synthesis. HsmtKAS shares conserved catalytic domains with FASN, which are responsible for binding to C75. In our study, we explored the possible effect of C75 on HsmtKAS and mitochondrial function. C75 treatment decreased LA content, impaired mitochondrial function, increased reactive oxygen species content, and reduced cell viability. HsmtKAS but not FASN knockdown had an effect that was similar to C75 treatment. In addition, an LA supplement efficiently inhibited C75-induced mitochondrial dysfunction and oxidative stress. Overexpression of HsmtKAS showed cellular protection against low dose C75 addition, whereas there was no protective effect upon high dose C75 addition. In summary, the mitochondrial fatty acid synthesis pathway has a vital role in mitochondrial function. Besides FASN, C75 might also inhibit HsmtKAS, thereby reducing LA production, impairing mitochondrial function, and potentially having toxic effects. LA supplements sufficiently ameliorated the toxicity of C75, showing that a combination of C75 and LA may be a reliable cancer treatment. PMID:24784139

Chen, Cong; Han, Xiao; Zou, Xuan; Li, Yuan; Yang, Liang; Cao, Ke; Xu, Jie; Long, Jiangang; Liu, Jiankang; Feng, Zhihui

2014-06-13

219

Effects of sugar functional groups, hydrophobicity, and fluorination on carbohydrate-DNA stacking interactions in water.  

PubMed

Carbohydrate-aromatic interactions are highly relevant for many biological processes. Nevertheless, experimental data in aqueous solution relating structure and energetics for sugar-arene stacking interactions are very scarce. Here, we evaluate how structural variations in a monosaccharide including carboxyl, N-acetyl, fluorine, and methyl groups affect stacking interactions with aromatic DNA bases. We find small differences on stacking interaction among the natural carbohydrates examined. The presence of fluorine atoms within the pyranose ring slightly increases the interaction with the C-G DNA base pair. Carbohydrate hydrophobicity is the most determinant factor. However, gradual increase in hydrophobicity of the carbohydrate does not translate directly into a steady growth in stacking interaction. The energetics correlates better with the amount of apolar surface buried upon sugar stacking on top of the aromatic DNA base pair. PMID:24552250

Lucas, Ricardo; Peñalver, Pablo; Gómez-Pinto, Irene; Vengut-Climent, Empar; Mtashobya, Lewis; Cousin, Jonathan; Maldonado, Olivia S; Perez, Violaine; Reynes, Virginie; Aviñó, Anna; Eritja, Ramón; González, Carlos; Linclau, Bruno; Morales, Juan C

2014-03-21

220

Appendix 31 Disturbance Processes and Functions of Habitat Groups  

E-print Network

stands and grasslands. The nature and impact of the light severity fires varied from underburning that essentially left the forest structure intact, to areas burned that reduced vegetation in a function burned through light surface fuels, creating a mosaic of fuel conditions. The fuel loadings varied at any

221

Discriminant Function Analysis of Inventoried Interests Among Selected Engineering Groups.  

ERIC Educational Resources Information Center

The utility of multiple discriminant function analysis (MDFA) to differentiate among the interest patterns of engineers was examined. Subjects were 229 engineers who were administered the Strong Vocational Interest Blank (SVIB) in 1935 as college freshmen (1935 FR) and again in 1966, and 210 freshmen who completed the SVIB in 1966 and had…

Clemens, Bryan; Linden, James

222

Functional gene groups are concentrated within chromosomes, among chromosomes and in the nuclear space  

E-print Network

1 Functional gene groups are concentrated within chromosomes, among chromosomes and in the nuclear:+972-3-6405384 Keywords: chromosomes organization, gene function, chromosome conformation, spatial;2 Functional gene groups are concentrated within chromosomes, among chromosomes and in the nuclear space

Shamir, Ron

223

Influence of functional groups on charge transport in molecular junctions D. J. Mowbray,a  

E-print Network

or parent molecule may be altered in a consistent manner by the attachment of functional groups.9 Further general trends across molecular species.6­8 It is well known that the chemistry of a functional parent, the influence of a particular functional group on a parent molecule's chem- istry may be predicted qualitatively

Thygesen, Kristian

224

An experimental test of the effect of plant functional group diversity on arthropod diversity  

Microsoft Academic Search

Characteristics used to categorize plant species into functional groups for their effects on ecosystem functioning may also be relevant to higher trophic levels. In addition, plant and consumer diversity should be positively related because more diverse plant communities offer a greater variety of resources for the consumers. Thus, the functional group composition and richness of a plant community may affect

Amy J. Symstad; Evan Siemann; John Haarstad

2000-01-01

225

Surface charge regulation of carboxyl terminated polystyrene latex particles and their interactions at the oil/water interface.  

PubMed

We study electrostatic interactions of polystyrene particles at an oil/water interface controlled by a chemical reaction of carboxylate surface functional groups. By replacing the carboxyl functional groups with hydrocarbon chains using the well-known EDC (1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide) coupling reaction, the surface charge density decreases while the hydrophobicity of the colloid surface increases. Direct visualization of the particle-laden interface reveals that, depending on the extent of hydrocarbon coupling, the strength of the electrostatic repulsion can be regulated: the repulsive interaction increases with the reaction, removing aggregates, but rapidly decreases if the reaction proceeds too much, forming a large aggregation. This simple reaction, thus, dramatically changes the structures of the colloidal monolayers at the oil/water interface. We conclude that such structural change is the result of change of the repulsive interactions from the oil phase, although interactions in the water phase are also changed slightly. PMID:25226338

Kim, KyuHan; Park, Kyuheong; Kim, Gahee; Kim, Hyunjung; Choi, Myung Chul; Choi, Siyoung Q

2014-10-21

226

Vibrational spectra, electronic absorption, nonlinear optical properties, evaluation of bonding, chemical reactivity and thermodynamic properties of ethyl 4-(1-(2-(hydrazinecarbonothioyl)hydrazono)ethyl)-3,5-dimethyl-1H-pyrrole-2-carboxylate molecule by ab initio HF and density functional methods.  

PubMed

In this work, detailed vibrational spectral analysis of ethyl 4-(1-(2-(hydrazinecarbonothioyl)hydrazono)ethyl)-3,5-dimethyl-1H-pyrrole-2-carboxylate (EHCHEDPC) molecule has been carried out using FT-IR spectroscopy and potential energy distribution (PED). Theoretical calculations were performed by ab initio RHF and density functional theory (DFT) method, using 6-31G(d,p) and 6-311+G(d,p) basis sets. The other carried outwork cover: structural, thermodynamic properties, electronic transitions, bonding, multiple interaction, chemical reactivity and hyperpolarizability analysis. The results of the calculation were applied to the simulated spectra of (EHCHEDPC), which show excellent agreement with observed spectra. The vibrational analysis shows red shift in both group, the proton donor (pyrrole N-H) and proton acceptor (C=O of ester) indicating the presence of intermolecular hydrogen bonding. Time dependent density functional theory (TD-DFT) has been used to find electronic excitations and their nature. The results of natural bond orbital (NBOs) analysis show the charges transfer and delocalization in various intra- and intermolecular interactions. The binding energy of intermolecular multiple interactions is calculated to be 12.54 kcal mol(-1) using QTAIM calculation. The electronic descriptors analyses reveal the investigated molecule used as precursor for heterocyclic derivatives synthesis. First hyperpolarizability (?0) has been computed to evaluate non-linear optical (NLO) response. PMID:25168004

Singh, R N; Rawat, Poonam; Sahu, Sangeeta

2015-01-25

227

Synthesis of functional poly(ester-andydride)s based on succinic acid  

Microsoft Academic Search

This paper describes the three-step synthesis and characteristics of succinic acid based functional poly(ester-anhydride)s bearing allyl groups in side chains. Firstly, carboxyl terminated functional oligoesters with molecular weight in the range of 300–1000 were obtained by melt condensation of allyl glycidyl ether with an excess of succinic acid. Secondly, carboxyl end groups of the macromer obtained were converted to mixed

Katarzyna Jaszcz; Jan ?ukaszczyk; Monika ?miga-Matuszowicz

2008-01-01

228

Can descriptors of the electron density distribution help to distinguish functional groups?  

PubMed

Our study is aimed at understanding the characteristics of functional group descriptors based on peaks of the electronic density distribution rho(->r) . The descriptors calculated are the rho(->r) value at peak location, volume, ellipticity, curvatures of rho ( r) , and the peak-functional group distance. By the implementation of an automated and global process for large-scale calculation of the descriptors, we generated a statistically meaningful data set focusing on the association between peaks and 77 types of functional groups extracted from 62,936 organic molecules issued from the Cambridge Structural Database. Statistical analyses demonstrated that selected descriptors are capable of discriminating subtypes of functional groups. A projection in a principal component space coupled to a hierarchical clustering confirmed the suitability of the descriptors to provide an appropriate description of the functional groups. The results indicated that functional similarity or dissimilarity could be quantified based on electron density descriptors. PMID:18831545

Burton, Julien; Meurice, Nathalie; Leherte, Laurence; Vercauteren, Daniel P

2008-10-01

229

Red electroluminescence of ruthenium sensitizer functionalized by sulfonate anchoring groups.  

PubMed

We have synthesized five novel Ru(ii) phenanthroline complexes with an additional aryl sulfonate ligating substituent at the 5-position [Ru(L)(bpy)2](BF4)2 (1), [Ru(L)(bpy)(SCN)2] (2), [Ru(L)3](BF4)2 (3), [Ru(L)2(bpy)](BF4)2 (4) and [Ru(L)(BPhen)(SCN)2] (5) (where L = 6-one-[1,10]phenanthroline-5-ylamino)-3-hydroxynaphthalene 1-sulfonic, bpy = 2,2'-bipyridine, BPhen = 4,7-diphenyl-1,10-phenanthroline), as both photosensitizers for oxide semiconductor solar cells (DSSCs) and light emitting diodes (LEDs). The absorption and emission maxima of these complexes red shifted upon extending the conjugation of the phenanthroline ligand. Ru phenanthroline complexes exhibit broad metal to ligand charge transfer-centered electroluminescence (EL) with a maximum near 580 nm. Our results indicated that a particular structure (2) can be considered as both DSSC and OLED devices. The efficiency of the LED performance can be tuned by using a range of ligands. Device (2) has a luminance of 550 cd m(-2) and maximum efficiency of 0.9 cd A(-1) at 18 V, which are the highest values among the five devices. The turn-on voltage of this device is approximately 5 V. The role of auxiliary ligands in the photophysical properties of Ru complexes was investigated by DFT calculation. We have also studied photovoltaic properties of dye-sensitized nanocrystalline semiconductor solar cells based on Ru phenanthroline complexes and an iodine redox electrolyte. A solar energy to electricity conversion efficiency (?) of 0.67% was obtained for Ru complex (2) under standard AM 1.5 irradiation with a short-circuit photocurrent density (Jsc) of 2.46 mA cm(-2), an open-circuit photovoltage (Voc) of 0.6 V, and a fill factor (ff) of 40%, which are all among the highest values for ruthenium sulfonated anchoring groups reported so far. Monochromatic incident photon to current conversion efficiency was 23% at 475 nm. Photovoltaic studies clearly indicated dyes with two SCN substituents yielded a higher Jsc for the cell than dyes with a tris-homoleptic anchor substituent. PMID:24818219

Shahroosvand, Hashem; Abbasi, Parisa; Mohajerani, Ezeddin; Janghouri, Mohammad

2014-06-28

230

Functional Groups Based on Leaf Physiology: Are they Spatially and Temporally Robust?  

NASA Technical Reports Server (NTRS)

The functional grouping hypothesis, which suggests that complexity in function can be simplified by grouping species with similar responses, was tested in the Florida scrub habitat. Functional groups were identified based on how species in fire maintained FL scrub function in terms of carbon, water and nitrogen dynamics. The suite of physiologic parameters measured to determine function included both instantaneous gas exchange measurements obtained from photosynthetic light response curves and integrated measures of function. Using cluster analysis, five distinct physiologically-based functional groups were identified. Using non-parametric multivariate analyses, it was determined that these five groupings were not altered by plot differences or by the three different management regimes; prescribed burn, mechanically treated and burn, and fire-suppressed. The physiological groupings also remained robust between the two years 1999 and 2000. In order for these groupings to be of use for scaling ecosystem processes, there needs to be an easy-to-measure morphological indicator of function. Life form classifications were able to depict the physiological groupings more adequately than either specific leaf area or leaf thickness. THe ability of life forms to depict the groupings was improved by separating the parasitic Ximenia americana from the shrub category.

Foster, Tammy E.; Brooks, J. Renee; Quincy, Charles (Technical Monitor)

2002-01-01

231

Carboxylic Acid Esters as Substrates of Cholinesterases  

NASA Astrophysics Data System (ADS)

Data on the kinetics of the hydrolysis of various carboxylic acid esters by two main types of cholinesterases — acetylcholinesterase from human erythrocytes and butyrylcholinesterase from horse blood serum — are surveyed. It is shown that the rate of enzyme hydrolysis depends significantly on the structure of the acyl part of the ester molecule, the nature of the ester heteroatom, the structure of the alcohol component, and particularly the structure of the onium group. Esters based on natural products are of special interest as specific substrates of these enzymes. The role of the productive and non-productive sorption of the substrates in enzyme catalysis is demonstrated. The bibliography includes 81 references.

Brestkin, A. P.; Rozengart, E. V.; Abduvakhabov, A. A.; Sadykov, A. A.

1983-10-01

232

The interaction of carboxylic acids with aluminium oxides: journeying from a basic understanding of alumina nanoparticles to water treatment for industrial and humanitarian applications.  

PubMed

Carboxylic acids are found to react with aluminium oxides via a topotactic reaction such that the carboxylate acts as a bridging ligand. This reaction allows for carboxylate-functionalized alumina nanoparticles to be prepared directly from boehmite (AlOOH). Understanding the structural relationship between molecular and surface species allows for the rationalization/prediction of suitable alternative ligands as well as alternative oxide surfaces. The identity of the carboxylate substituent controls the pH stability of a nanoparticle as well as the porosity and processability of ceramics prepared by thermolysis. Through the choice of functional groups on the carboxylic acid the properties of the alumina surface or alumina nanoparticle can be tailored. For example, the solubility/miscibility of nanoparticles can be tuned to the solvent/matrix, and the wettability to be varied from hydrophobic to super hydrophilic. The choice Zwitter ionic substituents on alumina micro-/ultra-filtration membranes are found to enhance the flux and limit fouling while allowing for the facile separation of organic compounds from water. Examples are presented of purification of frac and flow-back water from oil well production as well as providing drinking water from contaminated sources in underdeveloped regions. PMID:24728503

Barron, Andrew R

2014-06-14

233

Partial androgen insensitivity with phenotypic variation caused by androgen receptor mutations that disrupt activation function 2 and the NH 2- and carboxyl-terminal interaction  

Microsoft Academic Search

Partial androgen insensitivity with sex phenotype variation in two unrelated families was associated with missense mutations in the androgen receptor (AR) gene that disrupted the AR NH2-terminal\\/carboxy terminal interaction. Each mutation caused a single amino acid change within the region of the ligand-binding domain that forms activation function 2 (AF2). In one family, the mutation I737T was in alpha helix

Charmian A. Quigley; Jiann-an Tan; Bin He; Zhong-xun Zhou; Farida Mebarki; Yves Morel; Maguelone G. Forest; Pierre Chatelain; E. Martin Ritzén; Frank S. French; Elizabeth M. Wilson

2004-01-01

234

Effect of saline iontophoresis on skin barrier function and cutaneous irritation in four ethnic groups  

Microsoft Academic Search

The effect of saline iontophoresis on skin barrier function and irritation was investigated in four ethnic groups (Caucasians, Hispanics, Blacks and Asians). Forty healthy human volunteers were recruited according to specific entry criteria. Ten subjects, five males and five females, were assigned to each ethnic group. Skin barrier function was examined after 4 hours of saline iontophoresis at a current

J Singh; M Gross; B Sage; H. T Davis; H. I Maibach

2000-01-01

235

Detection of low concentration oxygen containing functional groups on activated carbon fiber surfaces through fluorescent labeling  

E-print Network

carbon, activated carbon fibers and carbon nano- tubes, are based on the presence of oxygen containingDetection of low concentration oxygen containing functional groups on activated carbon fiber of surface functional groups (OH, COOH and CHO) on activated carbon fiber surfaces. The chromophores were

Borguet, Eric

236

Nylon surface modification. Part 1. Targeting the amide groups for selective introduction of reactive functionalities  

Microsoft Academic Search

Nylon is a widely used synthetic polymer because it has a combination of strength, flexibility, toughness, and abrasion resistance. For a variety of applications, however, it is necessary to impart desired surface properties by introducing specific functional groups in specific locations and densities. Several chemical modification methods were developed for the introduction of functional groups to nylon surfaces using amide-selective

Xinqiao Jia; Margarita Herrera-Alonso; Thomas J. McCarthy

2006-01-01

237

Psychosocial functioning in patients with treatment-resistant depression after group cognitive behavioral therapy  

Microsoft Academic Search

BACKGROUND: Although patients with Treatment Resistant Depression (TRD) often have impaired social functioning, few studies have investigated the effectiveness of psychosocial treatment for these patients. We examined whether adding group cognitive behavioral therapy (group-CBT) to medication would improve both the depressive symptoms and the social functioning of patient with mild TRD, and whether any improvements would be maintained over one

Miki Matsunaga; Yasumasa Okamoto; Shin-ichi Suzuki; Akiko Kinoshita; Shinpei Yoshimura; Atsuo Yoshino; Yoshihiko Kunisato; Shigeto Yamawaki

2010-01-01

238

Functionalization of poly-SNS-anchored carboxylic acid with Lys and PAMAM: surface modifications for biomolecule immobilization/stabilization and bio-sensing applications.  

PubMed

Poly(2-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl) (SNS) acetic acid) was electrochemically deposited on graphite electrodes and functionalized with lysine (Lys) amino acid and poly(amidoamine) derivatives (PAMAM G2 and PAMAM G4) to investigate their matrix properties for biosensor applications. Glucose oxidase (GOx) was immobilized onto the modified surface as the model enzyme. X-Ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to report the surface properties of the matrices in each step of the biosensor construction. The biosensors were characterized in terms of their operational and storage stabilities and the kinetic parameters (K(app)(m) and I(max)). Three new glucose biosensors revealed good stability, featuring low detection limits (19.0 ?M, 3.47 ?M and 2.93 ?M for lysine-, PAMAM G2- and PAMAM G4-functionalized electrodes, respectively) and prolonged the shelf lives (4, 5, and 6 weeks for Lys-, PAMAM G2- and PAMAM G4-modified electrodes, respectively). The proposed biosensors were tested for glucose detection on real human blood serum samples. PMID:22832474

Demirci, Sema; Emre, Fatma Bilge; Ekiz, Fulya; O?uzkaya, Funda; Timur, Suna; Tanyeli, Cihangir; Toppare, Levent

2012-09-21

239

Tetra-methyl anthracene-2,3,6,7-tetra-carboxyl-ate-tetra-methyl 9,10-dihydro-9,10-dioxoanthracene-2,3,6,7-tetra-carboxyl-ate (1/1).  

PubMed

In the title co-crystal, C(22)H(16)O(10)·C(22)H(18)O(8), the independent tetra-methyl 9,10-dihydro-9,10-dioxoanthracene-2,3,6,7-tetra-carboxyl-ate, (I), and tetra-methyl anthracene-2,3,6,7-tetra-carboxyl-ate, (II), components occupy separate crystallographic inversion centers. In (II), the dihedral angles between the mean aromatic plane and the two independent carboxyl-ate planes are 41.32?(10) and -38.35?(10)°. The methyl-carboxyl-ate groups of (I) are disordered, with each resolvable into two groups. In the least disordered carboxyl-ate, the apparent angles between the mean aromatic plane and the two partial carboxyl-ate planes [site occupations = 0.510?(3) and 0.490?(3)] are 16.8?(3) and 23.3?(3)°. In the highly disordered group, the apparent angles between the mean aromatic plane and the two partial carboxyl-ate planes [site occupations = 0.510?(3) and 0.490?(3)] are 78.3?(3) and -74.1?(3)°. In addition, this extreme disorder leads to an artificially elongated C(aromatic)-C(carbox-yl) bond. PMID:22904973

Drake, Brenton L; Morris, J Larry; McLaughlin, Mark L; Fronczek, Frank R; Watkins, Steven F

2012-08-01

240

A CRM Domain Protein Functions Dually in Group I and Group II Intron Splicing in Land Plant Chloroplasts[W  

PubMed Central

The CRM domain is a recently recognized RNA binding domain found in three group II intron splicing factors in chloroplasts, in a bacterial protein that associates with ribosome precursors, and in a family of uncharacterized proteins in plants. To elucidate the functional repertoire of proteins with CRM domains, we studied CFM2 (for CRM Family Member 2), which harbors four CRM domains. RNA coimmunoprecipitation assays showed that CFM2 in maize (Zea mays) chloroplasts is associated with the group I intron in pre-trnL-UAA and group II introns in the ndhA and ycf3 pre-mRNAs. T-DNA insertions in the Arabidopsis thaliana ortholog condition a defective-seed phenotype (strong allele) or chlorophyll-deficient seedlings with impaired splicing of the trnL group I intron and the ndhA, ycf3-int1, and clpP-int2 group II introns (weak alleles). CFM2 and two previously described CRM proteins are bound simultaneously to the ndhA and ycf3-int1 introns and act in a nonredundant fashion to promote their splicing. With these findings, CRM domain proteins are implicated in the activities of three classes of catalytic RNA: group I introns, group II introns, and 23S rRNA. PMID:18065687

Asakura, Yukari; Barkan, Alice

2007-01-01

241

A CRM domain protein functions dually in group I and group II intron splicing in land plant chloroplasts.  

PubMed

The CRM domain is a recently recognized RNA binding domain found in three group II intron splicing factors in chloroplasts, in a bacterial protein that associates with ribosome precursors, and in a family of uncharacterized proteins in plants. To elucidate the functional repertoire of proteins with CRM domains, we studied CFM2 (for CRM Family Member 2), which harbors four CRM domains. RNA coimmunoprecipitation assays showed that CFM2 in maize (Zea mays) chloroplasts is associated with the group I intron in pre-trnL-UAA and group II introns in the ndhA and ycf3 pre-mRNAs. T-DNA insertions in the Arabidopsis thaliana ortholog condition a defective-seed phenotype (strong allele) or chlorophyll-deficient seedlings with impaired splicing of the trnL group I intron and the ndhA, ycf3-int1, and clpP-int2 group II introns (weak alleles). CFM2 and two previously described CRM proteins are bound simultaneously to the ndhA and ycf3-int1 introns and act in a nonredundant fashion to promote their splicing. With these findings, CRM domain proteins are implicated in the activities of three classes of catalytic RNA: group I introns, group II introns, and 23S rRNA. PMID:18065687

Asakura, Yukari; Barkan, Alice

2007-12-01

242

Using protein-semantic network metrics to evaluate functional coherence of protein groups.  

PubMed

Modern bioinformatics analyses of high throughput experiments often produce groups of proteins or genes of interest. Many metrics have been developed to evaluate the enrichment of proteins sharing similar functions within such groups. Commonly used evaluation using information of the Gene Ontology annotation has limitations. In this poster, we present the results of a research project to directly utilize the semantic information of biomedical literature for evaluating the functional coherence of protein groups. PMID:18694270

Zheng, Bin; Lu, Xinghua

2007-01-01

243

Unitary representations of three dimensional Lie groups revisited: An approach via harmonic functions  

E-print Network

Harmonic functions of the three dimensional Lie groups defined on certain manifolds related to the Lie groups themselves and carrying all their unitary representations are explicitly constructed. The realisations of these Lie groups are shown to be related with each other by either natural operations as real forms or In\\"on\\"u-Wigner contractions.

R. Campoamor-Stursberg; M. Rausch de Traubenberg

2014-04-18

244

Functional wild-type and carboxyl-terminal-tagged rat substance P receptors expressed in baculovirus-infected insect Sf9 cells.  

PubMed

The rat substance P (SP) receptor (SPR) was expressed in insect Sf9 cells by infection with recombinant baculovirus. The receptor bound SP with high affinity (KD = 360 pM) and had a rank order of affinity of SP > neurokinin A > neurokinin B. Ligand activation of the receptor resulted in an increase in both inositol lipid hydrolysis and intracellular Ca2+ concentration ([Ca2+]i). However, high-level expression of the receptor, in the absence of ligand, was correlated with increased basal turnover of inositol lipids and an elevated rate of Ca2+ influx. These results demonstrate that the Sf9 cells provide a suitable environment for the high-level expression of a functionally active SPR. Two carboxy-terminal epitope-tagged receptors (SPR-KT3 = SPR-TPPPEPET, COOH; SPR-Glu = SPR-EEEEYMPME, COOH) were also expressed. The affinity of the KT3-tagged receptor for ligand was similar to that of the wild-type receptor (KD = 405 pM), and that of the Glu-tagged receptor was slightly lower (KD = 1,082 pM). The high-affinity SP binding site of all three receptors was sensitive to guanosine 5'-O-(3-thiotriphosphate) pretreatment. The maximal signal-transducing ability of the epitope-tagged receptors was comparable to that of the wild-type receptor ([Ca2+]i rise as a percentage of wild-type: SPR-KT3, 80-100%; SPR-Glu, 88-100%). These data show that heterologous expression in the baculovirus system results in high expression of functional wild-type and tagged receptors. PMID:7891090

Schreurs, J; Yamamoto, R; Lyons, J; Munemitsu, S; Conroy, L; Clark, R; Takeda, Y; Krause, J E; Innis, M

1995-04-01

245

Activity groupings reflecting functional characteristics required in daily life in institutionalized dependent females in the old old elderly group  

Microsoft Academic Search

Objectives  This study aimed to determine the activity groupings reflecting functional characteristics required in daily life for the\\u000a institutionalized dependent females in the old-old elderly group, by examining the interrelationships of activities based\\u000a on actual achievement characteristics.\\u000a \\u000a \\u000a \\u000a Methods  The participants were 697 dependent elderly living at welfare institutions in Japan and 344 old-old females were used for\\u000a analysis. Factor analysis, based on

Shinichi Demura; Susumu Sato; Masaki Minami; Kohsho Kasuga

2003-01-01

246

Social disinterest attitudes and group cognitive-behavioral social skills training for functional disability in schizophrenia.  

PubMed

The majority of clinical trials of cognitive-behavioral therapy (CBT) for schizophrenia have used individual therapy to target positive symptoms. Promising results have been found, however, for group CBT interventions and other treatment targets like psychosocial functioning. CBT for functioning in schizophrenia is based on a cognitive model of functional outcome in schizophrenia that incorporates dysfunctional attitudes (eg, social disinterest, defeatist performance beliefs) as mediators between neurocognitive impairment and functional outcome. In this report, 18 clinical trials of CBT for schizophrenia that included measures of psychosocial functioning were reviewed, and two-thirds showed improvements in functioning in CBT. The cognitive model of functional outcome was also tested by examining the relationship between social disinterest attitudes and functional outcome in 79 people with schizophrenia randomized to either group cognitive-behavioral social skills training or a goal-focused supportive contact intervention. Consistent with the cognitive model, lower social disinterest attitudes at baseline and greater reduction in social disinterest during group therapy predicted better functional outcome at end of treatment for both groups. However, the groups did not differ significantly with regard to overall change in social disinterest attitudes during treatment, suggesting that nonspecific social interactions during group therapy can lead to changes in social disinterest, regardless of whether these attitudes are directly targeted by cognitive therapy interventions. PMID:19628761

Granholm, Eric; Ben-Zeev, Dror; Link, Peter C

2009-09-01

247

Galloylglucoses of low molecular weight as mordant in electron microscopy. II. The moiety and functional groups possibly involved in the mordanting effect  

PubMed Central

Synthetic pentamonogalloylglucose applied to fixed tissues acts as a mordant, inducing high and diversified contrast similar to that obtained with natural gallotannins of low molecular weight (LMGG). By the separate use of each of the two moieties of the galloylglucose molecule, it was found that gallic acid is the mordanting agent. Glucose may contribute, however, to the effect by increasing the solubility and cross-linking potential of the compound, since the mordanting induced by gallic acid alone is weaker than that produced by its hexose esters. As suggested by results obtained with various phenolics and benzoic acid derivatives, the functional groups required for the mordanting effect of such agents are the carboxyl group, and at least one hydroxyl group concomitantly present on the benzene ring. In the case of galloylglucoses, it is assumed that the effect is due to hydrolysis products (gallic, digallic, or trigallic acids) or to the multiple hydroxyl groups of the intact molecule. Esters of gallic acid (propyl- and methylgallate), as well as pyrogallol, produce a "reversed staining" of all membranes, except for those of communicating (gap) junctions. PMID:783173

1976-01-01

248

Heat capacity, saturation vapor pressure, and thermodynamic functions of ethyl esters of C3-C5 and C18 carboxylic acids  

NASA Astrophysics Data System (ADS)

The heat capacities of ethyl propanoate (EPr), ethyl n-pentanoate (EPen), and ethyl n-octadecanoate (ethyl stearate, ESt) were measured by vacuum adiabatic calorimetry in the temperature range of 6 to 373 K. Triple point temperatures, fusion enthalpies and entropies, and purity of the samples of the sub-stances under study were determined. The saturation vapor pressures for EPr and EPen were determined by comparative ebulliometry in an atmospheric pressure range of 4.0 to 101.7 kPa. The normal boiling points and vaporization enthalpies vs. temperature were obtained. The standard thermodynamic functions ( S, H, and G) were calculated for the condensed and ideal gas states on the basis of the experimental data. The vapor pressures of the atmospheric range were extrapolated to entire ranges of the liquid phases of EPr and EPen using the principle of corresponding states and the combined processing of pT parameters and low-temperature differences in the heat capacities of an ideal gas and liquid.

Agafonova, L. E.; Varushchenko, R. M.; Druzhinina, A. I.; Polyakova, O. V.; Kolesov, Yu. S.

2011-09-01

249

A substrate-driven approach to determine reactivities of ?,?-unsaturated carboxylic esters towards asymmetric bioreduction.  

PubMed

The degree of C=C bond activation in the asymmetric bioreduction of ?,?-unsaturated carboxylic esters by ene-reductases was studied, and general recommendations to render these "borderline-substrates" more reactive towards enzymatic reduction are proposed. The concept of "supported substrate activation" was developed. In general, an additional ?-halogenated substituent proved to be beneficial for enzymatic activity, whereas ?-alkyl or ?-aryl substituents were detrimental for the reactivity of nonhalogenated substrates, and ?-cyano groups showed little effect. The alcohol moiety of the ester functionality was found to have a strong influence on the reaction rate. Overall, activities were determined by both steric and electronic effects. PMID:22736443

Tasnádi, Gábor; Winkler, Christoph K; Clay, Dorina; Sultana, Nargis; Fabian, Walter M F; Hall, Mélanie; Ditrich, Klaus; Faber, Kurt

2012-08-13

250

Functional assignments for the carboxyl-terminal domains of the ferrochelatase from Synechocystis PCC 6803: the CAB domain plays a regulatory role, and region II is essential for catalysis.  

PubMed

Ferrochelatase (FeCH) catalyzes the insertion of Fe(2+) into protoporphyrin, forming protoheme. In photosynthetic organisms, FeCH and magnesium chelatase lie at a biosynthetic branch point where partitioning down the heme and chlorophyll (Chl) pathways occurs. Unlike their mammalian, yeast, and other bacterial counterparts, cyanobacterial and algal FeCHs as well as FeCH2 isoform from plants possess a carboxyl-terminal Chl a/b-binding (CAB) domain with a conserved Chl-binding motif. The CAB domain is connected to the FeCH catalytic core by a proline-rich linker sequence (region II). In order to dissect the regulatory, catalytic, and structural roles of the region II and CAB domains, we analyzed a FeCH ?H347 mutant that retains region II but lacks the CAB domain and compared it with the ?H324-FeCH mutant that lacks both these domains. We found that the CAB domain is not required for catalytic activity but is essential for dimerization of FeCH; its absence causes aberrant accumulation of Chl-protein complexes under high light accompanied by high levels of the Chl precursor chlorophyllide. Thus, the CAB domain appears to serve mainly a regulatory function, possibly in balancing Chl biosynthesis with the synthesis of cognate apoproteins. Region II is essential for the catalytic function of the plastid-type FeCH enzyme, although the low residual activity of the ?H324-FeCH is more than sufficient to furnish the cellular demand for heme. We propose that the apparent surplus of FeCH activity in the wild type is critical for cell viability under high light due to a regulatory role of FeCH in the distribution of Chl into apoproteins. PMID:21081693

Sobotka, Roman; Tichy, Martin; Wilde, Annegret; Hunter, C Neil

2011-04-01

251

Molecular Structure of Cyclopropane carboxylic acid  

NSDL National Science Digital Library

Cyclopropane carboxylic acid is a clear liquid used as an intermediate for agrochemicals, pharmaceuticals, and other organic synthesis such as for the applications of electronics, chemicals, polymer additives, coatings, adhesives, surfactants, and other applications. Also, derivatives of cyclopropane-carboxylic acid are used against parasites in plants and animals. For example, the alkynyl esters of cyclopropane-carboxylic acid are used as pesticides. Similarly, cyclopropane carboxylic acid esters containing a polyhalogenated substituent are used as fungicides.

2003-04-11

252

Preparation of sulfonic-functionalized graphene oxide as ion-exchange material and its application into electrochemiluminescence analysis  

Microsoft Academic Search

Graphene oxide (GO) obtained from chemical oxidation of flake graphite was derivatized with sulfonic groups to form sulfonic-functionalized GO (GO–SO3?) through four sulfonation routes: through amide formation between the carboxylic group of GO and amine of sulfanilic acid (AA–GO–SO3?), aryl diazonium reaction of sulfanilic acid (AD–GO–SO3?), amide formation between the carboxylic group of GO and amine of cysteamine and oxidation

Guifen Chen; Shengyong Zhai; Yanling Zhai; Ke Zhang; Qiaoli Yue; Lei Wang; Jinsheng Zhao; Huaisheng Wang; Jifeng Liu; Jianbo Jia

2011-01-01

253

Simple coupling chemistry linking carboxyl-containing organic molecules to silicon oxide surfaces under acidic conditions.  

PubMed

The coupling chemistry of carboxymethylated amylose with organo-silanized silicon oxide surfaces at pH 7.4 and 2.0 was investigated using atomic force microscopy (AFM) based single-molecule force spectroscopy. At close to neutral pH, carbodiimide activation of a carboxylic acid affords formation of an amide bond with an amino surface linker. At pH 2.0, no activation with carbodiimide was required to anchor carboxymethylated amylose between an AFM tip and a glass substrate. At the same time, the mean bond rupture force f(r) dropped from 1.65 ± 0.37 nN at pH 7.4 to 1.39 ± 0.30 nN at pH 2.0 without carbodiimide, indicating that a different link to the surface can be formed at low pH. The coupling mechanism at pH 2.0 was elucidated by a series of experiments, in which the surface was functionalized with four different organosilanes, each containing characteristic functional groups. The results are rationalized with an acid-catalyzed ester condensation between a carboxyl group and a free, unreacted silanol group in the surface anchor or on the surface. PMID:20822126

Schmidt, Sebastian W; Christ, Timo; Glockner, Christian; Beyer, Martin K; Clausen-Schaumann, Hauke

2010-10-01

254

The unramified principal series of p-adic groups : the Bessel function  

E-print Network

Let G be a connected reductive group with a split maximal torus defined over a nonarchimedean local field. I evaluate a matrix coefficient of the unramified principal series of G known as the "Bessel function" at torus ...

DeFranco, Mario A. (Mario Anthony)

2014-01-01

255

Chemical imaging of functional group distributions in living biofilms using infrared microspectroscopy  

E-print Network

Chemical imaging of functional group distributions in living biofilms using infrared Kingdom INTRODUCTION Bacteria predominantly grow as biofilms attached to liquid or solid interfaces. Biofilms are complex structures that contain bacterial cells interwoven in an extracellular polysaccharide

256

Synthesis and small molecule chemistry of the niobaziridine-hydride functional group  

E-print Network

Chapter 1. Synthesis and Divergent Reactivity of the Niobaziridine-Hydride Functional Group The synthesis, characterization and reactivity of the niobaziridine-hydride complex Nb(H)([eta]²-t- ]Bu(H)C=NAr)(N[Np]Ar)? (la-H; ...

Figueroa, Joshua S

2005-01-01

257

Organic functional groups in aerosol particles from burning and non-burning forest emissions at a high-elevation mountain site  

NASA Astrophysics Data System (ADS)

Ambient particles collected on teflon filters at the Peak of Whistler Mountain, British Columbia (2182 m a.s.l.) during spring and summer 2009 were measured by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFG). The project mean and standard deviation of organic aerosol mass concentrations (OM) for all samples was 3.2±3.3 (?g m-3). The OM was dominated by regional forest sources, burning, and non-burning that occurred mostly during June-September. On average, organic hydroxyl, alkane, carboxylic acid, ketone, and amine, groups represented 31%±11%, 34%±9%, 23%±6%, 6%±7%, and 6%±3% of OM, respectively. Ketone groups were associated with the forest aerosols and represented up to 27% of the OM in these aerosols. Additional measurements of aerosol mass fragments, size, and number concentrations were used to separate fossil-fuel combustion and burning and non-burning forest sources of the measured organic aerosol. The OM concentrations observed at Whistler Peak during this campaign were higher than those measured during a shorter period in the spring of 2008 at a site in Whistler valley, over one km lower than the peak location. The 2009 campaign was largely influenced by the wildfire emissions that were absent during the 2008 campaign.

Takahama, S.; Schwartz, R. E.; Russell, L. M.; MacDonald, A. M.; Sharma, S.; Leaitch, W. R.

2011-01-01

258

Few-body hierarchy in non-relativistic functional renormalization group equations and a decoupling theorem  

NASA Astrophysics Data System (ADS)

For non-relativistic quantum field theory in the few-body limit with instantaneous interactions it is shown within the functional renormalization group formalism that propagators are not renormalized and that the renormalization group equations of one-particle irreducible vertex functions are governed by a hierarchical structure. This hierarchy allows to solve the equations in the n-body sector without knowledge or assumptions about the m-body sectors where m>n.

Floerchinger, Stefan

2014-07-01

259

Anatomic and Functional Variability: The Effects of Filter Size in Group fMRI Data Analysis  

Microsoft Academic Search

In the analysis of group fMRI scans, an optimal spatial filter should be large enough to accurately blend functionally homologous anatomic regions, yet small enough not to blur the functionally distinct regions. Hanning filters varying from 0.0 to 18.0 mm were evaluated in a group analysis of six healthy controls performing a simple finger-tapping paradigm. Test–retest reliability and Talairach-based measurements

Tonya White; Daniel O'Leary; Vincent Magnotta; Stephan Arndt; Michael Flaum; Nancy C. Andreasen

2001-01-01

260

The use of heterogeneous chemistry for the characterization of functional groups at the gas/particle interface of soot and TiO2 nanoparticles.  

PubMed

Six gases [N(CH(3))(3), NH(2)OH, CF(3)COOH, HCl, NO(2) and O(3)] were selected to probe the surface of seven different types of combustion aerosol samples (amorphous carbon, flame soot) and three types of TiO(2) nanoparticles using heterogeneous, i.e. gas-surface reactions. The gas uptake to saturation of the probes was measured under molecular flow conditions in a Knudsen flow reactor and expressed as a density of surface functional groups on a particular aerosol, namely acidic (carboxylic) and basic (conjugated oxides such as pyrone, N-heterocycle and amine) sites, carbonyl (R(1)-C(O)-R(2)) and oxidizable (olefinic, -OH) groups. The limit of detection was generally well below 1% of a formal monolayer of adsorbed probe gas. With few exceptions most investigated aerosol samples interacted with all probe gases to various extents which points to the coexistence of different functional groups on the same aerosol surface such as acidic and basic groups. Generally, the carbonaceous particles displayed significant differences in surface group density: Printex 60 amorphous carbon had the lowest density of surface functional groups throughout, whereas Diesel soot recovered from a Diesel particulate filter had the largest. The presence of basic oxides on carbonaceous aerosol particles was inferred from the ratio of uptakes of CF(3)COOH and HCl owing to the larger stability of the acetate compared to the chloride counterion in the resulting pyrylium salt. Both soots generated from a rich and a lean hexane diffusion flame had a large density of oxidizable groups similar to amorphous carbon FS 101. TiO(2) 15 had the lowest density of functional groups studied for all probe gases among the three TiO(2) nanoparticles despite the smallest size of its primary particles. The technique used enabled the measurement of the uptake probability of the probe gases on the various supported aerosol samples. The initial uptake probability, gamma(0), of the probe gas onto the supported nanoparticles differed significantly among the various investigated aerosol samples but was roughly correlated with the density of surface groups, as expected. PMID:19606331

Setyan, A; Sauvain, J-J; Rossi, M J

2009-08-01

261

A functional renormalization group approach to zero-dimensional interacting systems  

NASA Astrophysics Data System (ADS)

We apply the functional renormalization group method to the calculation of dynamical properties of zero-dimensional interacting quantum systems. We discuss as case studies the anharmonic oscillator and the single-impurity Anderson model. We truncate the hierarchy of flow equations such that the results are at least correct up to second-order perturbation theory in the coupling. For the anharmonic oscillator, energies and spectra obtained within two different functional renormalization group schemes are compared to numerically exact results, perturbation theory results, and the mean field approximation. Even at large coupling, the results obtained using the functional renormalization group agree quite well with the numerical exact solution. The better of the two schemes is used to calculate spectra of the single-impurity Anderson model, which are then compared to the results from perturbation theory and the numerical renormalization group ones. For small to intermediate couplings the functional renormalization group gives results which are close to the ones obtained using the very accurate numerical renormalization group method. In particular, the low energy scale (Kondo temperature) extracted from the functional renormalization group results shows the expected behaviour.

Hedden, R.; Meden, V.; Pruschke, Th; Schönhammer, K.

2004-07-01

262

Oxidation of Thiol Anchor Groups in Molecular Junction Devices: A Density Functional Theory Study  

E-print Network

Oxidation of Thiol Anchor Groups in Molecular Junction Devices: A Density Functional Theory Study of these devices under oxidizing conditions may lead to oxidation of the thiolate anchor groups. Herein we theory calculations on various oxide derivatives of ethanethiolate on gold clusters (EtSOn/Au13; n ) 0

Goddard III, William A.

263

Characteristics of Interactional Management Functions in Group Oral by Japanese Learners of English  

ERIC Educational Resources Information Center

This study attempted to investigate the characteristics of interaction dynamics in a group oral interaction carried out by Japanese learners of English. The relationship between the participants' language development and interactional management functions (IMFs) was also explored. Oral performance tests in a paired or a small group have recently…

Negishi, Junko

2010-01-01

264

Aggressive and Prosocial Peer Group Functioning: Effects on Children's Social, School, and Psychological Adjustment  

ERIC Educational Resources Information Center

This study examined the effects of aggressive and prosocial contexts of peer groups on children's socioemotional and school adjustment. Data on informal peer groups, social functioning, and different aspects of adjustment were collected from multiple sources in a sample of elementary school children (149 boys, 181 girls; M age = 10 years).…

Chung-Hall, Janet; Chen, Xinyin

2010-01-01

265

Perceptions of popularity among a group of high-functioning adults with autism  

Microsoft Academic Search

The purpose of this study was to determine how a group of adults with autism perceived one another's interpersonal attributes and popularity. Five female and 11 male high-functioning autistic adults, 18–45 years old, participated in a social skills group together for several years. A sociogram and a questionnaire designed to determine perceptions of best looking, most athletic, and most humorous

Gary B. Mesibov; Janet Stephens

1990-01-01

266

Holomorphic Functions and the Heat Kernel Measure on an Infinite Dimensional Complex Orthogonal Group  

Microsoft Academic Search

The heat kernel measure µt is constructed on an infinite dimensional complex group using a diffusion in a Hilbert space. Then it is proved that holomorphic polynomials on the group are square integrable with respect to the heat kernel measure. The closure of these polynomials, H L2(S OH S, µt), is one of two spaces of holomorphic functions we consider.

Maria Gordina

2000-01-01

267

Computations for Group Sequential Boundaries Using the Lan-DeMets Spending Function Method  

Microsoft Academic Search

We describe an interactive Fortran program which performs computations related to the design and analysis of group sequential clinical trials using Lan-DeMets spending functions. Many clinical trials include interim analyses of accumulating data and rely on group sequential methods to avoid consequent inflation of the type I error rate. The computations are appropriate for interim test statistics whose distribution or

David M. Reboussin; David L. DeMets; KyungMann Kim; K. K. Gordon Lan

2000-01-01

268

Functional Groups Based on Leaf Physiology: Are they Spatially and Temporally Robust?  

NASA Technical Reports Server (NTRS)

The functional grouping hypothesis, which suggests that complexity in ecosystem function can be simplified by grouping species with similar responses, was tested in the Florida scrub habitat. Functional groups were identified based on how species in fire maintained Florida scrub regulate exchange of carbon and water with the atmosphere as indicated by both instantaneous gas exchange measurements and integrated measures of function (%N, delta C-13, delta N-15, C-N ratio). Using cluster analysis, five distinct physiologically-based functional groups were identified in the fire maintained scrub. These functional groups were tested to determine if they were robust spatially, temporally, and with management regime. Analysis of Similarities (ANOSIM), a non-parametric multivariate analysis, indicated that these five physiologically-based groupings were not altered by plot differences (R = -0.115, p = 0.893) or by the three different management regimes; prescribed burn, mechanically treated and burn, and fire-suppressed (R = 0.018, p = 0.349). The physiological groupings also remained robust between the two climatically different years 1999 and 2000 (R = -0.027, p = 0.725). Easy-to-measure morphological characteristics indicating functional groups would be more practical for scaling and modeling ecosystem processes than detailed gas-exchange measurements, therefore we tested a variety of morphological characteristics as functional indicators. A combination of non-parametric multivariate techniques (Hierarchical cluster analysis, non-metric Multi-Dimensional Scaling, and ANOSIM) were used to compare the ability of life form, leaf thickness, and specific leaf area classifications to identify the physiologically-based functional groups. Life form classifications (ANOSIM; R = 0.629, p 0.001) were able to depict the physiological groupings more adequately than either specific leaf area (ANOSIM; R = 0.426, p = 0.001) or leaf thickness (ANOSIM; R 0.344, p 0.001). The ability of life forms to depict the physiological groupings was improved by separating the parasitic Ximenia americana from the shrub category (ANOSIM; R = 0.794, p = 0.001). Therefore, a life form classification including parasites was determined to be a good indicator of the physiological processes of scrub species, and would be a useful method of grouping for scaling physiological processes to the ecosystem level.

Foster, Tammy E.; Brooks, J. Renee

2004-01-01

269

The Properties of Poor Groups of Galaxies. III. The Galaxy Luminosity Function  

Microsoft Academic Search

The form of the galaxy luminosity function (GLF) in poor groups-regions of intermediate galaxy density that are common environments for galaxies-is not well understood. Multiobject spectroscopy and wide-field CCD imaging now allow us to measure the GLF of bound group members directly (i.e., without statistical background subtraction) and to compare the group GLF with the GLFs of the field and

Ann I. Zabludoff; John S. Mulchaey

2000-01-01

270

First principles investigations on the electronic structure of anchor groups on ZnO nanowires and surfaces  

NASA Astrophysics Data System (ADS)

We report on density functional theory investigations of the electronic properties of monofunctional ligands adsorbed on ZnO-(1010) surfaces and ZnO nanowires using semi-local and hybrid exchange-correlation functionals. We consider three anchor groups, namely thiol, amino, and carboxyl groups. Our results indicate that neither the carboxyl nor the amino group modify the transport and conductivity properties of ZnO. In contrast, the modification of the ZnO surface and nanostructure with thiol leads to insertion of molecular states in the band gap, thus suggesting that functionalization with this moiety may customize the optical properties of ZnO nanomaterials.

Dominguez, A.; Lorke, M.; Schoenhalz, A. L.; Rosa, A. L.; Frauenheim, Th.; Rocha, A. R.; Dalpian, G. M.

2014-05-01

271

Plant Species and Functional Group Combinations Affect Green Roof Ecosystem Functions  

Microsoft Academic Search

BackgroundGreen roofs perform ecosystem services such as summer roof temperature reduction and stormwater capture that directly contribute to lower building energy use and potential economic savings. These services are in turn related to ecosystem functions performed by the vegetation layer such as radiation reflection and transpiration, but little work has examined the role of plant species composition and diversity in

Jeremy Lundholm; J. Scott Macivor; Zachary MacDougall; Melissa Ranalli; Hans Henrik Bruun

2010-01-01

272

Group B Streptococcal b-Hemolysin/Cytolysin Directly Impairs Cardiomyocyte Viability and Function  

E-print Network

Group B Streptococcal b-Hemolysin/Cytolysin Directly Impairs Cardiomyocyte Viability and Function the effects of the GBS pore-forming b-hemolysin/cytolysin (Bh/c) exotoxin on cardiomyocyte viability for viability by trypan blue exclusion and for apoptosis by TUNEL staining. Functionality of exposed

Nizet, Victor

273

Quantitative analysis of sulfur functional groups in natural organic matter by XANES spectroscopy  

E-print Network

Quantitative analysis of sulfur functional groups in natural organic matter by XANES spectroscopy sulfur functionalities in natural organic matter from S K-edge XANES spectroscopy are presented-induced errors, inherent to the choice of a particular curve, are typically lower than 5% of total sulfur

274

Tuning the photoluminescence of graphene quantum dots through the charge transfer effect of functional groups.  

PubMed

The band gap properties of graphene quantum dots (GQDs) arise from quantum confinement effects and differ from those in semimetallic graphene sheets. Tailoring the size of the band gap and understanding the band gap tuning mechanism are essential for the applications of GQDs in opto-electronics. In this study, we observe that the photoluminescence (PL) of the GQDs shifts due to charge transfers between functional groups and GQDs. GQDs that are functionalized with amine groups and are 1-3 layers thick and less than 5 nm in diameter were successfully fabricated using a two-step cutting process from graphene oxides (GOs). The functionalized GQDs exhibit a redshift of PL emission (ca. 30 nm) compared to the unfunctionalized GQDs. Furthermore, the PL emissions of the GQDs and the amine-functionalized GQDs were also shifted by changes in the pH due to the protonation or deprotonation of the functional groups. The PL shifts resulted from charge transfers between the functional groups and GQDs, which can tune the band gap of the GQDs. Calculations from density functional theory (DFT) are in good agreement with our proposed mechanism for band gap tuning in the GQDs through the use of functionalization. PMID:23272894

Jin, Sung Hwan; Kim, Da Hye; Jun, Gwang Hoon; Hong, Soon Hyung; Jeon, Seokwoo

2013-02-26

275

Sub-grouping and sub-functionalization of the RIFIN multi-copy protein family  

PubMed Central

Background Parasitic protozoans possess many multicopy gene families which have central roles in parasite survival and virulence. The number and variability of members of these gene families often make it difficult to predict possible functions of the encoded proteins. The families of extra-cellular proteins that are exposed to a host immune response have been driven via immune selection to become antigenically variant, and thereby avoid immune recognition while maintaining protein function to establish a chronic infection. Results We have combined phylogenetic and function shift analyses to study the evolution of the RIFIN proteins, which are antigenically variant and are encoded by the largest multicopy gene family in Plasmodium falciparum. We show that this family can be subdivided into two major groups that we named A- and B-RIFIN proteins. This suggested sub-grouping is supported by a recently published study that showed that, despite the presence of the Plasmodium export (PEXEL) motif in all RIFIN variants, proteins from each group have different cellular localizations during the intraerythrocytic life cycle of the parasite. In the present study we show that function shift analysis, a novel technique to predict functional divergence between sub-groups of a protein family, indicates that RIFINs have undergone neo- or sub-functionalization. Conclusion These results question the general trend of clustering large antigenically variant protein groups into homogenous families. Assigning functions to protein families requires their subdivision into meaningful groups such as we have shown for the RIFIN protein family. Using phylogenetic and function shift analysis methods, we identify new directions for the investigation of this broad and complex group of proteins. PMID:18197962

Joannin, Nicolas; Abhiman, Saraswathi; Sonnhammer, Erik L; Wahlgren, Mats

2008-01-01

276

Alkali-catalyzed low temperature wet crosslinking of plant proteins using carboxylic acids.  

PubMed

We report the development of a new method of alkali-catalyzed low temperature wet crosslinking of plant proteins to improve their breaking tenacity without using high temperatures or phosphorus-containing catalysts used in conventional poly(carboxylic acid) crosslinking of cellulose and proteins. Carboxylic acids are preferred over aldehyde-containing crosslinkers for crosslinking proteins and cellulose because of their low toxicity and cost and ability to improve the desired properties of the materials. However, current knowledge in carboxylic acid crosslinking of proteins and cellulose requires the use of carboxylic acids with at least three carboxylic groups, toxic phosphorous-containing catalysts and curing at high temperatures (150-185 degrees C). The use of high temperatures and low pH in conventional carboxylic acid crosslinking has been reported to cause substantial strength loss and/or undesired changes in the properties of the crosslinked materials. In this research, gliadin, soy protein, and zein fibers have been crosslinked with malic acid, citric acid, and butanetetracarboxylic acid to improve the tenacity of the fibers without using high temperatures and phosphorus-containing catalysts. The new method of wet crosslinking using carboxylic acids containing two or more carboxylic groups will be useful to crosslink proteins for various industrial applications. PMID:19224570

Reddy, Narendra; Li, Ying; Yang, Yiqi

2009-01-01

277

Clickable SBA-15 to screen functional groups for adsorption of antibiotics.  

PubMed

Pharmaceutical antibiotics, as emerging contaminants, are usually composed of several functional groups that endow them with the ability to interact with adsorbents through different interactions. This makes the preparation of adsorbents tedious and time-consuming to screen appropriate functionalized materials. Herein, we describe the synthesis of clickable SBA-15 and demonstrate its feasibility as a screening material for the adsorption of antibiotics based on similar adsorption trends on materials with similar functional groups obtained by a click reaction and cocondensation/grafting methods. PMID:24265185

Gao, Jinsuo; Zhang, Xueying; Xu, Shutao; Liu, Jian; Tan, Feng; Li, Xinyong; Qu, Zhenping; Zhang, Yaobin; Quan, Xie

2014-03-01

278

MATERIALS-19 Incorporating Amphoteric Groups in Ion Track-etched Single Conical Nanochannels  

E-print Network

Nanochannels fabricated in polymer membranes have a great range of applications in biotechnology, where they are suitable for sensing biomolecules 1, and act as stimuliresponsive devices 2 and molecular filters of high selectivity. 3 The surface of ion track-etched nanochannels in polymer membranes bear carboxyl (-COOH) groups which were chemically reacted with a variety of different molecules having variable size and polarity. Previously, gold coated nanochannels were used for the incorporation of amphoteric groups into the nanochannels via the chemisorption of cysteine molecules. 4 Here, we report a facile and straight-forward approach to incorporate amphoteric groups inside the single conical nanochannels. This was realized by direct chemical modification of the surface carboxyl groups with L-lysine chains whose positive and negative charges are very sensitive to the external pH. The chemically functionalised channels were characterized both theoretically and experimentally. The single nanochannel constitutes a universal nanofluidic diode in the sense that the amphoteric chains attached at its surface allow for a broad set of rectification properties. Briefly, the selective functionalization of lysine with surface carboxyl groups was accomplished by blocking the amino group and carboxyl group bonded to the ?-carbon with Cu 2+ ion to form a copper-chelate complex. This process leaves an unprotected ?-amino group which was covalently attached with the carboxyl group created during track-etching via EDC/PFP coupling chemistry. 5 COOH

unknown authors

279

The electrokinetic characterization of gold nanoparticles, functionalized with cationic functional groups, and its' interaction with DNA.  

PubMed

Gold nanoparticles have attracted strong biomedical interest for drug delivery due to their low toxic nature, surface plasmon resonance and capability of increasing the stability of the payload. However, gene transfection represents another important biological application. Considering that cellular barriers keep enclosed their secret to deliver genes using nanoparticles, an important step can be achieved by studying the functionalization of nanoparticles with DNA. In the present contribution the synthesis of nanoparticles consisting of a gold core coated with one or more layers of amino acid (l-lysine), and cationic polyelectrolytes (poly-ethyleneimine and poly-l-lysine) is reported. All nanoparticles were subjected to dynamic light scattering, electrophoretic mobility measurements, UV-vis optical spectrophotometry analysis and transmission electron microscopy imaging. In addition, the adsorption of DNA plasmid (pSGS) with linear and supercoiled configurations was studied for those gold nanoparticles under the most suitable surface modifications. Preliminary results showed that the gold nanoparticles functionalized with poly-ethyleneimine and poly-l-lysine, respectively, and bound to linear DNA configurations, present in absolute value a higher electrophoretic mobility irrespective of the pH of the media, compared to the supercoiled and nicked configuration. The findings from this study suggest that poly-ethyleneimine and poly-l-lysine functionalized gold nanoparticles are biocompatible and may be promising in the chemical design and future optimization of nanostructures for biomedical applications such as gene and drug delivery. PMID:25009100

Lazarus, Geraldine Genevive; Revaprasadu, Neerish; López-Viota, Julián; Singh, Moganavelli

2014-09-01

280

Hydration of carboxylate anions: infrared spectroscopy of aqueous solutions.  

PubMed

Hydration of carboxylate ions was studied in aqueous solutions of sodium salts by means of FTIR spectroscopy using the HDO molecule as a probe. The quantitative version of the difference spectra method has been applied to determine the solute-affected water spectra. They display two-component bands of affected HDO at ca. 2550 and 2420 cm(-1). These bands are attributed to the -COO(-) group of the R-COO(-) ion (R = H, CH(3), C(2)H(5)), because water molecules surrounding the substituent R behave roughly as molecules in the bulk phase. For the studied carboxylates the net water structure making effect is observed, which increases with electron-donor ability of R, by means of changing the relative intensity of solute-affected HDO component bands. The observed splitting of the carboxylate-ion-affected HDO band is unique for these anions. The experimental results were confronted with DFT-calculated structures of small gas-phase and polarizable continuum model (PCM) solvated aqueous clusters to establish the structural and energetic states of carboxylate ions hydrates. This was achieved by comparison of the calculated optimal geometries with the interatomic distances derived from HDO band positions. Different possibilities have been considered to explain the peculiar spectral results. The plausible explanation assumes symmetry breaking of the carboxylate ion induced by interaction with water solvent: C-O bond lengths of RCOO(-) and electric charge localization become unequal. It is demonstrated by nonequivalent interaction of oxygen atoms of the RCOO(-) anion with water molecules. Taking into account only the energetic effect, the phenomenon is explained by the anticooperative H-bond formation of the carboxylate group with water molecules, which increases with the electron-donor ability of the substituent R. In this interaction two water molecules play an important part, as appears from the calculated clusters. They interact with oxygen atoms of the RCOO(-) ion, forming a cooperative system, within which solvent molecules are nonequivalent with respect to H-bond formation with both proton-accepting sites of the solute. This additionally enhances solvent-induced symmetry breaking of carboxylate anion. Strongly hydrogen-bonded solvent is more effective in inducing symmetry breaking; thus, increasing the temperature decreases the splitting of the carboxylate-ion-affected water, as experimentally observed. PMID:19438223

Goj?o, Emilia; Smiechowski, Maciej; Panuszko, Aneta; Stangret, Janusz

2009-06-11

281

Aqueous and nonaqueous chemical approaches to elucidating structure and function in proteins  

E-print Network

]NMR techniques. Reacting ethoxyformic anhydride or acetic anhydride with protein functional groups afforded acyl groups and their corresponding amino acid residues in protein was facilitated by the observation derivatives of N and N-amino groups and mixed anhydrides of side-chain carboxyl groups. These mixed anhydrides

Taralp, Alpay

282

Di-?-aqua-bis­[aqua­(5-carboxyl­ato-1H-1,2,3-triazole-4-carb­oxy­lic acid-?2 N 3,O 4)lithium  

PubMed Central

The crystal structure of the title compound, [Li2(C4H2N3O4)2(H2O)4], contains centrosymmetric dinuclear mol­ecules in which two LiI ions are bridged by two water O atoms. The metal ion is coordinated by one N,O-bidentate ligand and three water O atoms (one of them is symmetry generated), with one of the bridging water O atoms in the apical position of a distorted square pyramid. The carboxyl­ate group that participates in coordination to the metal ion remains protonated; the other is deprotonated and coordination inactive. An intra­molecular O—H?O hydrogen bond between carboxyl­ate groups is observed. In the crystal, dimers are linked by O—H?O, O—H?N and N—H?O hydrogen bonds, generating a three-dimensional network. PMID:24427005

Starosta, Wojciech; Leciejewicz, Janusz

2013-01-01

283

Organic functional groups in aerosol particles from burning and non-burning forest emissions at a high-elevation mountain site  

NASA Astrophysics Data System (ADS)

Ambient particles collected on teflon filters at the Peak of Whistler Mountain, British Columbia (2182 m a.s.l.) during spring and summer 2009 were measured by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFG). The project mean and standard deviation of organic aerosol mass concentrations (OM) for all samples was 3.2±3.3 (?g m-3). Measurements of aerosol mass fragments, size, and number concentrations were used to separate fossil-fuel combustion and burning and non-burning forest sources of the measured organic aerosol. The OM was composed of the same anthropogenic and non-burning forest components observed at Whistler mid-valley in the spring of 2008; during the 2009 campaign, biomass burning aerosol was additionally observed from fire episodes occurring between June and September. On average, organic hydroxyl, alkane, carboxylic acid, ketone, and primary amine groups represented 31 %±11 %, 34 %±9 %, 23 %±6 %, 6 %±7 %, and 6 %±3 % of OM, respectively. Ketones in aerosols were associated with burning and non-burning forest origins, and represented up to 27 % of the OM. The organic aerosol fraction resided almost entirely in the submicron fraction without significant diurnal variations. OM/OC mass ratios ranged mostly between 2.0 and 2.2 and O/C atomic ratios between 0.57 and 0.76, indicating that the organic aerosol reaching the site was highly aged and possibly formed through secondary formation processes.

Takahama, S.; Schwartz, R. E.; Russell, L. M.; MacDonald, A. M.; Sharma, S.; Leaitch, W. R.

2011-07-01

284

Zwitterionic metal carboxylate complexes: In solid state  

NASA Astrophysics Data System (ADS)

A flexible dicarboxylic acid having composition [(CH(o-C5H4N)(p-C6H4OCH2CO2H)2] derived from corresponding bis-phenol reacts with various metal(II) acetates such as manganese(II), cobalt(II) and nickel(II) acetate leads to zwtterionic complexes with compositions [CH(o-C5H4N)(p-C6H4OCH2CO2){p-C6H4OCH2CO2M(H2O)5}].6H2O (where M = Mn, Co, Ni). The complexes are characterised by X-ray crystallography. These complexes have chiral center due to unsymmetric structure conferred to the ligand through coordination at only one carboxylate group of the ligand. In solid state these complexes are racemic.

Nath, Bhaskar; Kalita, Dipjyoti; Baruah, Jubaraj B.

2012-07-01

285

Evolution of the galaxy luminosity function in progenitors of fossil groups  

E-print Network

Using the semi-analytic models based on the Millennium simulation, we trace back the evolution of the luminosity function of galaxies residing in progenitors of groups classified by the magnitude gap at redshift zero. We determine the luminosity function of galaxies within $ 0.25R_{200}, 0.5R_{200} $, and $R_{200}$ for galaxy groups/clusters. The bright end of the galaxy luminosity function of fossil groups shows a significant evolution with redshift, with changes in $M^*$ by $\\sim$ 1-2 mag between $z\\sim0.5$ and $z=0$ (for the central $0.5R_{200}$), suggesting that the formation of the most luminous galaxy in a fossil group has had a significant impact on the $M^{*}$ galaxies e.g. it is formed as a result of multiple mergers of the $ M^{*} $ galaxies within the last $\\sim5$ Gyr. In contrast, the slope of the faint end, $\\alpha$, of the luminosity function shows no considerable redshift evolution and the number of dwarf galaxies in the fossil groups exhibits no evolution, unlike in non-fossil groups where it ...

Gozaliasl, G; Dariush, A A; Finoguenov, A; Jassur, D M Z; Molaeinajad, A

2014-01-01

286

Evolution of the galaxy luminosity function in progenitors of fossil groups  

NASA Astrophysics Data System (ADS)

Using the semi-analytic models based on the Millennium simulation, we trace back the evolution of the luminosity function of galaxies residing in progenitors of groups classified by the magnitude gap at redshift zero. We determine the luminosity function of galaxies within 0.25 R200, 0.5 R200, and R200 for galaxy groups/clusters. The bright end of the galaxy luminosity function of fossil groups shows a significant evolution with redshift, with changes in M? by ~1-2 mag between z ~ 0.5 and z = 0 (for the central 0.5 R200), suggesting that the formation of the most luminous galaxy in a fossil group has had a significant impact on the M? galaxies e.g. it is formed as a result of multiple mergers of M? galaxies within the last 5 Gyr. In contrast, the slope of the faint end, ?, of the luminosity function shows no considerable redshift evolution and the number of dwarf galaxies in the fossil groups exhibits no evolution, unlike in non-fossil groups where it grows by ~ 25-42% towards low redshifts. In agreement with previous studies, we also show that fossil groups accumulate most of their halo mass earlier than non-fossil groups. Selecting the fossils at a redshift of 1 and tracing them to a redshift 0, we show that 80% of the fossil groups (1013 M?h-1 < M200 < 1014 M?h-1) will lose their large magnitude gap. However, about 40% of fossil clusters (M200 > 1014 M?h-1) will retain their large gaps.

Gozaliasl, G.; Khosroshahi, H. G.; Dariush, A. A.; Finoguenov, A.; Jassur, D. M. Z.; Molaeinezhad, A.

2014-11-01

287

Grouping  

NSDL National Science Digital Library

This interactive Flash applet models the measurement interpretation of division. A child or teacher chooses a total number of objects and a divisor representing the size of equal groups. The applet allows the user to move the objects into equal groups and links the process to jumps on a number line. The applet can be used to introduce children to remainders and to reinforce the language and notation of division. It works well on an interactive white board or projector. A teacher's guide to this collection of applets is cataloged separately.

2006-01-01

288

Polymerization process for carboxyl containing polymers utilizing oil soluble ionic surface active agents  

SciTech Connect

This patent describes a method for polymerizing olefinically unsaturated carboxylic acid monomers containing at least one activated carbon to carbon olefinic double bond and at least one carboxyl group. The monomers are polymerized in an organic media consisting essentially of organic liquids, in the presence of free radical forming catalysts and at least one oil soluble ionic surface active agent selected from the group consisting of: (a) anionic surface active agents; (b) cationic surface active agents; and (c) amphoteric surface active agents.

Uebele, C.E.; Ball, L.E.; Jorkasky, R.J. II; Wardlow, E. Jr.

1987-09-08

289

How surface functional groups influence fracturation in nanofluid droplet dry-outs.  

PubMed

In this study of drying water-based nanofluid droplets, we report the influence of surface functional groups and substrate surface energies on crack formation and dry-out shape. These two key parameters are investigated by allowing nanofluids with several functional groups grafted on polystyrene nanoparticle surfaces to dry on various substrates. These experiments result in a variety of regular crack patterns with identical nanoparticle diameter, material, concentration, and drying conditions. We demonstrate that, despite the various patterns observed, the crack spacing/deposit height ratio is constant for similar substrate surface energies and linearly increases with this parameter. Moreover, this study shows that the crack shape is strongly influenced by surface functional groups as a result of particle interactions (depending on the particle surface potentials) and compaction during solvent evaporation. PMID:23902151

Carle, Florian; Brutin, David

2013-08-13

290

pKA values of carboxyl groups in the native and denatured states of barnase: the pKA values of the denatured state are on average 0.4 units lower than those of model compounds.  

PubMed

We have determined the pKA values of the 12 carboxyl residues in the native and denatured state of barnase by a combination of thermodynamic measurements on mutants of charged residues and NMR titration data. The pKA values of the 11 residues titrating under folding conditions (above pH 2.2) were determined by two-dimensional 1H NMR. The pKA value of the remaining residue, Asp 93 which forms a salt link with Arg 69 and titrates at much lower pH values, was determined by changes in the pH dependence of the stability of the protein upon mutation to Asn: pKAsp93A at low ionic strength (50 mM) and pKAsp93A at high ionic strength (600 mM). The overall titration of the native state is nonideal, and the protein retains fractionally ionized residues other than Asp 93 throughout the experimental pH range of 0.2-6.3. Protonation events taking place at pH values below 2 were further characterized by the pH dependence of the unfolding kinetics of wild-type and charge-mutant proteins. By comparing the observed pH dependence of the protein stability with that calculated from the pKA values for the native protein, we demonstrate that the pKA values of the denatured state are significantly lower than those reported for model compounds: the pKA values of the denatured state appear on average 0.4 units lower than previous estimates in the presence of chemical denaturant. The results have direct implications for calculations of the energetics of proton equilibria and suggest that the acid/thermally denatured state is not an extended coil where the residues are isolated from one another by the intervening solvent but is compact and involves intramolecular charge repulsion. PMID:7626612

Oliveberg, M; Arcus, V L; Fersht, A R

1995-07-25

291

Standard partial molar volumes of some aqueous alkanolamines and alkoxyamines at temperatures up to 325 degrees C: functional group additivity in polar organic solutes under hydrothermal conditions.  

PubMed

Apparent molar volumes of dilute aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), N,N-dimethylethanolamine (DMEA), ethylethanolamine (EAE), 2-diethylethanolamine (2-DEEA), and 3-methoxypropylamine (3-MPA) and their salts were measured at temperatures from 150 to 325 degrees C and pressures as high as 15 MPa. The results were corrected for the ionization and used to obtain the standard partial molar volumes, Vo2. A three-parameter equation of state was used to describe the temperature and pressure dependence of the standard partial molar volumes. The fitting parameters were successfully divided into functional group contributions at all temperatures to obtain the standard partial molar volume contributions. Including literature results for alcohols, carboxylic acids, and hydroxycarboxylic acids yielded the standard partial molar volume contributions of the functional groups >CH-, >CH2, -CH3, -OH, -COOH, -O-, -->N, >NH, -NH2, -COO-Na+, -NH3+Cl-, >NH2+Cl-, and -->NH+Cl- over the range (150 degrees C groups at temperatures up to approximately 310 degrees C and pressures of 10-20 MPa to within a precision of +/-5 cm3 x mol(-1). The model could not be extended to higher temperatures because of uncertainties caused by thermal decomposition. At temperatures above approximately 250 degrees C, the order of the group contributions to Vo2 changes from that observed at 25 degrees C, to become increasingly consistent with the polarity of each functional group. The effect of the dipole moment of each molecule on the contribution to Vo2 from long-range solvent polarization was calculated from the multipole expansion of the Born equation using dipole moments estimated from restricted Hartree-Fock calculations with Gaussian 03 (Gaussian, Inc., Wallingford, CT) and the Onsager reaction-field approximation for solvent effects. Below 325 degrees C, the dipole contribution was found to be less than 2 cm3 x mol(-1) for all the solute molecules studied. At higher temperatures and pressures near steam saturation, the effect is much larger and may explain anomalies in functional group additivity observed in small, very polar solutes. PMID:18412415

Bulemela, E; Tremaine, Peter R

2008-05-01

292

Functional groups of marine ciliated protozoa and their relationships to water quality.  

PubMed

Ciliated protozoa (ciliates) play important ecological roles in coastal waters, especially regarding their interaction with environmental parameters. In order to increase our knowledge and understanding on the functional structure of ciliate communities and their relationships to environmental conditions in marine ecosystems, a 12-month study was carried out in a semi-enclosed bay in northern China. Samples were collected biweekly at five sampling stations with differing levels of pollution/eutrophication, giving a total of 120 samples. Thirteen functional groups of ciliates (A-M) were defined based on their specific spatio-temporal distribution and relationships to physico-chemical parameters. Six of these groups (H-M) were the primary contributors to the ciliate communities in the polluted/eutrophic areas, whereas the other seven groups (A-G) dominated the communities in less polluted areas. Six groups (A, D, G, H, I and K) dominated during the warm seasons (summer and autumn), with the other seven (B, C, E, F, J, L and M) dominating in the cold seasons (spring and winter). Of these, groups B (mainly aloricate ciliates), I (aloricate ciliates) and L (mainly loricate tintinnids) were the primary contributors to the communities. It was also shown that aloricate ciliates and tintinnids represented different roles in structuring and functioning of the communities. The results suggest that the ciliate communities may be constructed by several functional groups in response to the environmental conditions. Thus, we conclude that these functional groups might be potentially useful bioindicators for bioassessment and conservation in marine habitats. PMID:23381800

Jiang, Yong; Xu, Henglong; Hu, Xiaozhong; Warren, Alan; Song, Weibo

2013-08-01

293

1,3-dimethylimidazolium-2-carboxylate: the unexpected synthesis of an ionic liquid precursor and carbene-CO2 adduct.  

PubMed

1,3-Dimethylimidazolium-2-carboxylate is formed in good yield, rather than the anticipated organic salt, 1,3-dimethylimidazolium methyl carbonate, as the reaction product resulting from both N-alkylation and C-carboxylation of 1-methylimidazole with dimethyl carbonate; the crystal structure of the zwitterion exhibits pi-stacked rings and two-dimensional sheets constructed by hydrogen-bonds from imidazolium-ring hydrogens to the carboxylate group. PMID:12610949

Holbrey, John D; Reichert, W Matthew; Tkatchenko, Igor; Bouajila, Ezzedine; Walter, Olaf; Tommasi, Immacolata; Rogers, Robin D

2003-01-01

294

EFFECTS OF GRAZING ON MICROBIAL FUNCTIONAL GROUPS INVOLVED IN SOIL N DYNAMICS  

Microsoft Academic Search

6 UMR1229 Microbiologie et geochimie des Sols (INRA), 17 rue Sully—B.P. 86510, 21065 Dijon, France Abstract. Enhancement of soil nitrogen (N) cycling by grazing has been observed in many grassland ecosystems. However, whether grazing affects the activity only of the key microbial functional groups driving soil N dynamics or also affects the size (cell number) and\\/or composition of these groups

A. K. Patra; L. Abbadie; A. Clays-Josserand; V. Degrange; S. J. Grayston; P. Loiseau; F. Louault; S. Mahmood; S. Nazaret; L. Philippot; F. Poly; J. I. Prosser; A. Richaume; X. Le Roux

2005-01-01

295

Group 3 late embryogenesis abundant protein in Arabidopsis : structure, regulation, and function  

Microsoft Academic Search

Group 3 late embryogenesis abundant proteins accumulate in maturing seeds, in which their expression correlates with desiccation\\u000a tolerance. Group 3 proteins are also strongly associated with tolerance for abiotic stresses, such as high salinity, drought,\\u000a cold, and osmotic stress in vegetative tissues. However, the precise function of these proteins remained obscure for more\\u000a than 20 years. In this study, the structure

PengShan ZhaoFei; Fei Liu; GuoChang Zheng; Heng Liu

2011-01-01

296

Functional group substitutions as probes of hydrogen bonding between GA mismatches in RNA internal loops  

Microsoft Academic Search

The contribution of hydrogen bonding to the stability of GA mismatches in RNA is investigated by making functional group substitutions. Such substitutions are made possible by the chemical synthesis of RNA; chemical incorporation of purine riboside and 2-aminopurine riboside into oligoribonucleotides is reported. In particular, replacing the 6-amino groups of internal loop adenosines with hydrogen atoms in (rGC-GCG)*, ( rGGCGAGCC)2,

John SantaLucia; Ryszard Kierzek; Douglas H. Turner

1991-01-01

297

Cellular distribution and cytotoxicity of graphene quantum dots with different functional groups  

PubMed Central

Graphene quantum dots (GQDs) have been developed as promising optical probes for bioimaging due to their excellent photoluminescent properties. Additionally, the fluorescence spectrum and quantum yield of GQDs are highly dependent on the surface functional groups on the carbon sheets. However, the distribution and cytotoxicity of GQDs functionalized with different chemical groups have not been specifically investigated. Herein, the cytotoxicity of three kinds of GQDs with different modified groups (NH2, COOH, and CO-N (CH3)2, respectively) in human A549 lung carcinoma cells and human neural glioma C6 cells was investigated using thiazoyl blue colorimetric (MTT) assay and trypan blue assay. The cellular apoptosis or necrosis was then evaluated by flow cytometry analysis. It was demonstrated that the three modified GQDs showed good biocompatibility even when the concentration reached 200 ?g/mL. The Raman spectra of cells treated with GQDs with different functional groups also showed no distinct changes, affording molecular level evidence for the biocompatibility of the three kinds of GQDs. The cellular distribution of the three modified GQDs was observed using a fluorescence microscope. The data revealed that GQDs randomly dispersed in the cytoplasm but not diffused into nucleus. Therefore, GQDs with different functional groups have low cytotoxicity and excellent biocompatibility regardless of chemical modification, offering good prospects for bioimaging and other biomedical applications. PMID:24597852

2014-01-01

298

Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems  

NASA Astrophysics Data System (ADS)

This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (-COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and 13C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

Dutta, Saikat; Kao, Hsien-Ming; Wu, Kevin C.-W.

2014-11-01

299

Direct conversion of carboxylate salts to carboxylic acids via reactive extraction  

E-print Network

-molecular-weight tertiary amine and carbon dioxide to precipitate calcium carbonate. In a distillation column, the Biomass Acid Springing Route 2 Mixed Carboxylic Acids Pretreatment Fermentation Dewater Reactive Extraction Carboxylate Salts Solution Thermal... makes it possible to extract carboxylic acids from the aqueous phase into high-molecular-weight tertiary amine (tri- n-octylamine). Through the physical solubility of the solute in the extractant phase, the carboxylic acids form acid-amine complexes...

Xu, Xin

2008-10-10

300

Solvent extraction of rare-earth metals by carboxylic acids  

SciTech Connect

The solvent extraction of the trivalent lanthanides and yttrium from nitrate media by solutions of carboxylic acids in xylene has been studied. Commercially available carboxylic acids such as Versatic 10 and naphthenic acids were used, as well as model compounds of known structure, such as 2-ethylhexanoic and 3-cyclohexylpropanoic acids. In a few cases, extraction of the metals from sulphate and chloride solutions was also investigated. The dependence of the extraction properties of the carboxylic acids on the atomic number of the lanthanide shows a definite relationship to the steric bulk of the carboxylic acid molecule quantified by means of the steric parameter, E{sub s}{prime} of the substituent alkyl group. The stoichiometries of the extracted complexes for representative light (La), middle (Gd) and heavy (Lu) rare-earth metals were investigated by the slope-analysis technique for a sterically hindered acid (Versatic 10 acid; -E{prime}{sub s} = 3.83) and an acid with low steric hindrance (3-cyclohexylpropanoic acid; -E{prime}{sub s} = 0.28). 14 refs., 13 figs., 3 tabs.

Preez, A.C. du; Preston, J.S. [Mintek, Randburg (South Africa)

1992-04-01

301

Isolation and Characterization of Functional Tripartite Group II Introns Using a Tn5-Based Genetic Screen  

PubMed Central

Background Group II introns are RNA enzymes that splice themselves from pre-mRNA transcripts. Most bacterial group II introns harbour an open reading frame (ORF), coding for a protein with reverse transcriptase, maturase and occasionally DNA binding and endonuclease activities. Some ORF-containing group II introns were shown to be mobile retroelements that invade new DNA target sites. From an evolutionary perspective, group II introns are hypothesized to be the ancestors of the spliceosome-dependent nuclear introns and the small nuclear RNAs (snRNAs – U1, U2, U4, U5 and U6) that are important functional elements of the spliceosome machinery. The ability of some group II introns fragmented in two or three pieces to assemble and undergo splicing in trans supports the theory that spliceosomal snRNAs evolved from portions of group II introns. Methodology/Principal Findings We used a transposon-based genetic screen to explore the ability of the Ll.LtrB group II intron from the Gram-positive bacterium Lactococcus lactis to be fragmented into three pieces in vivo. Trans-splicing tripartite variants of Ll.LtrB were selected using a highly efficient and sensitive trans-splicing/conjugation screen. We report that numerous fragmentation sites located throughout Ll.LtrB support tripartite trans-splicing, showing that this intron is remarkably tolerant to fragmentation. Conclusions/Significance This work unveils the great versatility of group II intron fragments to assemble and accurately trans-splice their flanking exons in vivo. The selected introns represent the first evidence of functional tripartite group II introns in bacteria and provide experimental support for the proposed evolutionary relationship between group II introns and snRNAs. PMID:22876289

Ritlop, Christine; Monat, Caroline; Cousineau, Benoit

2012-01-01

302

Amine- and carboxyl- quantum dots affect membrane integrity of bacterium Cupriavidus metallidurans CH34.  

PubMed

The present study examines the interaction of amine- and carboxyl- PEG core/shell quantum dots (QDs) with metal resistant bacterium Cupriavidus metallidurans CH34. The evolution of the number of QDs, their hydrodynamic radius, diffusion coefficients, and single particle fluorescence were characterized before and during the contact with bacterium by fluorescence correlation spectroscopy (FCS). The obtained results showed that at nanomolar concentrations the amine- and carboxyl-PEG-QDs with average hydrodynamic radiuses of 16.4 and 13.5 nm, form stable dispersions in the absence and presence of 15 mgC L(-1) HA. The decrease of the number of fluorescent particles in the bacterial medium, determined by FCS, together with the increase of the fluorescence of bacterial cells over the background, found by flow cytometry (FCM), demonstrated the association of QDs to C. metallidurans. Furthermore, QDs enhanced the level of the reactive oxygen species in the bacterial cells and augmented the percentage of the cells with damaged and leaky membranes as probed by FCM in combination with 5-(and-6)-carboxy-27'-dichlorodihydrofluorescein diacetate and propidium iodide stains. No difference in the behavior of amine- and carboxyl-PEG-QDs was found, suggesting that different functional groups in the surface coating have no effect on bacterium-QD interactions under the studied conditions. The presence of HA does not affect the hydrodynamic characteristics of the functionalized QDs, but prevented the damage to the bacterial membrane. The slight decrease in the bacterial growth found after exposure of C. metallidurans to these QDs was attributed to the nanoparticles themselves rather the cadmium, zinc, or selenium ions released from the QDs. PMID:19673316

Slaveykova, Vera I; Startchev, Konstantin; Roberts, Joanna

2009-07-01

303

Speciation of functional groups formed on the surface of ammoxidised carbonaceous materials by XPS method  

NASA Astrophysics Data System (ADS)

X-ray photoelectron spectroscopy (XPS) has been used to investigate the fate of nitrogen functional groups present in carbonaceous materials obtained from European plum ( Prunus domestica) stones and modified by ammonia-air mixture at 250 or 300 °C. Peaks have been found in the XPS patterns, corresponding to different nitrogen functional forms i.e. pyrrolic, pyridinic, pyridone, amine and chemisorbed nitrogen oxides. It has been found that the distribution of nitrogen functional forms changes as a result of the modification processes.

Wachowski, Leszek; Sobczak, Janusz W.; Hofman, Magdalena

2007-02-01

304

Neuropsychological Functioning in Specific Learning Disorders--Reading, Writing and Mixed Groups  

ERIC Educational Resources Information Center

Aim: The study compared the pattern of deficits, intelligence and neuropsychological functioning in subcategories of learning disorders. Methods: Forty-six children (16 with reading disorders, 11 with writing disorders and 19 with both reading and writing disorders--mixed group) in the age range of 7-14 years were assessed using the NIMHANS Index…

Kohli, Adarsh; Kaur, Manreet; Mohanty, Manju; Malhotra, Savita

2006-01-01

305

Group Social Skills Instruction for Adolescents with High-Functioning Autism Spectrum Disorders  

ERIC Educational Resources Information Center

Given the increased recognition of autism spectrum disorders (ASD) and the chronic and pervasive nature of associated deficits, there is a pressing need for effective treatments. The feasibility and preliminary efficacy of a structured, group social skills training program for high-functioning youth with ASD was examined in this study. Fifteen…

White, Susan W.; Koenig, Kathleen; Scahill, Lawrence

2010-01-01

306

Functionally Distinct Groups of Interneurons Identified During Rhythmic Carbachol Oscillations in Hippocampus In Vitro  

Microsoft Academic Search

During distinct behavioral states, the hippocampus exhibits characteristic rhythmic electrical activity. Evidence in vivo sug- gests that both principal pyramidal cells and GABAergic inter- neurons participate in generating oscillations. We found that during rhythmic oscillations in area CA3, functionally distinct classes of interneurons could be identified, although all re- corded interneurons had similar dendritic and axonal arbors. One group of

Lori L. McMahon; John H. Williams; Julie A. Kauer

1998-01-01

307

Impacts of chronic nitrogen additions vary seasonally and by microbial functional group in tundra soils  

E-print Network

Impacts of chronic nitrogen additions vary seasonally and by microbial functional group in tundra, Tundra soils Abstract. Previous studies have shown that fertilization with nitrogen depresses overall nitrogen addi- tions in alpine tundra soils. We measured soil enzyme activities, mineralization kinetics

Schmidt, Steven K.

308

A FUNCTIONAL GROUP CHARACTERIZATION OF ORGANIC PM 2.5 EXPOSURE: RESULTS FROM THE RIOPA STUDY  

EPA Science Inventory

The functional group (FG) composition of urban residential outdoor, indoor, and personal fine particle (PM2.5) samples is presented and used to provide insights relevant to organic PM2.5 exposure. PM2.5 samples (48 h) were collected during the Rel...

309

Measuring the complexity of interaction webs using vertical links between functional groups  

Microsoft Academic Search

Ecological insights into the usually high complexity of interaction webs demand a simplification of their structure to concentrate on the most important interactions within a community. One way to achieve this goal is to use functional groups (FGs). Using simple and partial Mantel tests the vertical interactions between FGs from different trophic levels were studied both at a disturbed grassland

Jörg Perner; Winfried Voigt

2007-01-01

310

Biocidal Siloxane Coating Material Containing N-Halogenated Amine and Amide Functional Groups.  

National Technical Information Service (NTIS)

N-halamine compounds which contain hindered amine and amide functional groups. Compounds include 1 wherein X, X(feet), and X(inches) independently are H, Cl, or Br, wherein no more than two of X, X(feet), and X(inches) are H and 2 wherein R, R(feet), and ...

S. D. Worley, Y. Chen, J. Liang, R. Wu K. Barnes

2004-01-01

311

Complexation of cadmium to sulfur and oxygen functional groups in an organic soil  

Microsoft Academic Search

Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd)

Torbjörn Karlsson; Kristin Elgh-Dalgren; Erik Björn; Ulf Skyllberg

2007-01-01

312

Detecting Native Language Group Differences at the Subskills Level of Reading: A Differential Skill Functioning Approach  

ERIC Educational Resources Information Center

Differential skill functioning (DSF) exists when examinees from different groups have different probabilities of successful performance in a certain subskill underlying the measured construct, given that they have the same ability on the overall construct. Using a DSF approach, this study examined the differences between two native language…

Li, Hongli; Suen, Hoi K.

2013-01-01

313

Department and function: Institute for Virology; Group leader (Cell & Virus Genetics)  

E-print Network

Department and function: Institute for Virology; Group leader (Cell & Virus Genetics) Education: 2002 PhD in Biology (Virology), University Heidelberg Positions: 2003-2006: Postdoc at the department for Virology Major research interests: Retroviral gene expression on the RNA level Mutations in cellular genes

Manstein, Dietmar J.

314

Large Sample Group Independent Component Analysis of Functional Magnetic Resonance Imaging Using Anatomical  

E-print Network

from noise. The traditional approach to fMRI data analysis is explicitly model driven, usingLarge Sample Group Independent Component Analysis of Functional Magnetic Resonance Imaging Using, Los Angeles, CA Abstract Independent component analysis (ICA) is a popular method for the analysis

Yuille, Alan L.

315

Study of Hand Function in a Group of Shoe Factory Workers Engaged in Repetitive Work  

Microsoft Academic Search

Background: Work related hand and wrist musculoskeletal disorders are well known. The contributing factors could be repetitive movements, forceful work and awkward posture. It is not known how these movements affect grip or pinch strength and other functional aspects of the hand. Aims: To study a group of shoe factory workers doing repetitive thumb and wrist movements for prevalence of

Anupam Datta Gupta; Dilip Mahalanabis

2006-01-01

316

Urinary Cortisol Circadian Rhythm in a Group of High-Functioning Children with Autism.  

ERIC Educational Resources Information Center

This study found no evidence for abnormal temporal placement of the basal urinary cortisol circadian rhythm in a group of 18 high-functioning children (ages 4-14) with autism. There was a tendency toward cortisol hypersecretion during the day, predominantly in autistic children who were integrated into the normal school system. (Author/JDD)

Richdale, Amanda L.; Prior, Margot R.

1992-01-01

317

Variation in tropical forest growth rates: combined effects of functional group composition and resource availability  

Microsoft Academic Search

Rates of tree growth in tropical forests reflect variation in life history strategies, contribute to the determination of species' distributional limits, set limits to timber harvesting and control the carbon balance of the stands. Here, we review the resources that limit tree growth at different temporal and spatial scales, and the different growth rates and responses of functional groups defined

Timothy R. Baker; Michael D. Swaine; David F. R. P. Burslem

2003-01-01

318

Cosmological constraints from the virial mass function of nearby galaxy groups and clusters  

E-print Network

In this thesis, I present a new determination of the cluster mass function in a volume ~107 h-03 70 Mpc3 using the ROSAT-2MASS-FAST Group Survey (R2FGS). R2FGS is an X-ray-selected sample of systems from the ROSAT All-Sky ...

Hill, James Colin

2008-01-01

319

Species and functional group diversity independently influence biomass accumulation and its response  

E-print Network

independently influ- ence biomass accumulation and its response to elevated CO2 and N. Biodiversity canSpecies and functional group diversity independently influence biomass accumulation and its , Joseph Craine*, David Wedin**, and Jared Trost* Departments of *Forest Resources and Ecology, Evolution

Minnesota, University of

320

Class-Wide Function-Related Intervention Teams: Effects of Group Contingency Programs in Urban Classrooms  

ERIC Educational Resources Information Center

The purpose of the study was to determine the effectiveness of the Class-Wide Function-related Intervention Teams (CW-FIT) program, a group contingency intervention for whole classes, and for students with disruptive behaviors who are at risk for emotional/behavioral disorders (EBD). The CW-FIT program includes four elements designed from…

Kamps, Debra; Wills, Howard P.; Heitzman-Powell, Linda; Laylin, Jeff; Szoke, Carolyn; Petrillo, Tai; Culey, Amy

2011-01-01

321

IMPORTANCE OF ACTIVATED CARBON'S OXYGEN SURFACE FUNCTIONAL GROUPS ON ELEMENTAL MERCURY ADSORPTION  

EPA Science Inventory

The effect of varying physical and chemical properties of activated carbons on adsorption of elemental mercury [Hg(0)] was studied by treating two activated carbons to modify their surface functional groups and pore structures. Heat treatment (1200 K) in nitrogen (N2), air oxidat...

322

Impacts of chronic nitrogen additions vary seasonally and by microbial functional group in tundra soils  

Microsoft Academic Search

Previous studies have shown that fertilization with nitrogen depresses overall microbial biomass and activity in soil. In the present study we broaden our understanding of this phenomenon by studying the seasonality of responses of specific microbial functional groups to chronic nitrogen additions in alpine tundra soils. We measured soil enzyme activities, mineralization kinetics for 8 substrates, biomass of 8 microbial

S. K. Schmidt; D. A. Lipson; R. E. Ley; M. C. Fisk; A. E. West

2004-01-01

323

Organic functional group transformations in water at elevated temperature and pressure: Reversibility, reactivity, and mechanisms  

NASA Astrophysics Data System (ADS)

Many transformation reactions involving hydrocarbons occur in the presence of H2O in hydrothermal systems and deep sedimentary systems. We investigate these reactions using laboratory-based organic chemistry experiments at high temperature and pressure (300 °C and 100 MPa). Organic functional group transformation reactions using model organic compounds based on cyclohexane with one or two methyl groups provided regio- and stereochemical markers that yield information about reversibility and reaction mechanisms. We found rapidly reversible interconversion between alkanes, alkenes, dienes, alcohols, ketones, and enones. The alkane-to-ketone reactions were not only completely reversible, but also exhibited such extensive reversibility that any of the functional groups along the reaction path (alcohol, ketone, and even the diene) could be used as the reactant and form all the other groups as products. There was also a propensity for these ring-based structures to dehydrogenate; presumably from the alkene, through a diene, to an aromatic ring. The product suites provide strong evidence that water behaved as a reactant and the various functional groups showed differing degrees of reactivity. Mechanistically-revealing products indicated reaction mechanisms that involve carbon-centered cation intermediates. This work therefore demonstrates that a wide range of organic compound types can be generated by abiotic reactions at hydrothermal conditions.

Shipp, Jessie; Gould, Ian R.; Herckes, Pierre; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.

2013-03-01

324

Health and role functioning: the use of focus groups in the development of an item bank  

PubMed Central

Background Role functioning is an important part of health-related quality of life. However, assessment of role functioning is complicated by the wide definition of roles and by fluctuations in role participation across the life-span. The aim of this study is to explore variations in role functioning across the lifespan using qualitative approaches, to inform the development of a role functioning item bank and to pilot test sample items from the bank. Methods Eight focus groups were conducted with a convenience sample of 38 English-speaking adults recruited in Rhode Island. Participants were stratified by gender and four age groups. Focus groups were taped, transcribed, and analyzed for thematic content. Results Participants of all ages identified family roles as the most important. There was age variation in the importance of social life roles, with younger and older adults rating them as more important. Occupational roles were identified as important by younger and middle-aged participants. The potential of health problems to affect role participation was recognized. Participants found the sample items easy to understand, response options identical in meaning and preferred five response choices. Conclusions Participants identified key aspects of role functioning and provided insights on their perception of the impact of health on their role participation. These results will inform item bank generation. PMID:20047086

Bjorner, Jakob B.

2013-01-01

325

Quantification of protein group coherence and pathway assignment using functional association  

PubMed Central

Background Genomics and proteomics experiments produce a large amount of data that are awaiting functional elucidation. An important step in analyzing such data is to identify functional units, which consist of proteins that play coherent roles to carry out the function. Importantly, functional coherence is not identical with functional similarity. For example, proteins in the same pathway may not share the same Gene Ontology (GO) terms, but they work in a coordinated fashion so that the aimed function can be performed. Thus, simply applying existing functional similarity measures might not be the best solution to identify functional units in omics data. Results We have designed two scores for quantifying the functional coherence by considering association of GO terms observed in two biological contexts, co-occurrences in protein annotations and co-mentions in literature in the PubMed database. The counted co-occurrences of GO terms were normalized in a similar fashion as the statistical amino acid contact potential is computed in the protein structure prediction field. We demonstrate that the developed scores can identify functionally coherent protein sets, i.e. proteins in the same pathways, co-localized proteins, and protein complexes, with statistically significant score values showing a better accuracy than existing functional similarity scores. The scores are also capable of detecting protein pairs that interact with each other. It is further shown that the functional coherence scores can accurately assign proteins to their respective pathways. Conclusion We have developed two scores which quantify the functional coherence of sets of proteins. The scores reflect the actual associations of GO terms observed either in protein annotations or in literature. It has been shown that they have the ability to accurately distinguish biologically relevant groups of proteins from random ones as well as a good discriminative power for detecting interacting pairs of proteins. The scores were further successfully applied for assigning proteins to pathways. PMID:21929787

2011-01-01

326

Recovery of carboxylic acids produced by fermentation.  

PubMed

Carboxylic acids such as citric, lactic, succinic and itaconic acids are useful products and are obtained on large scale by fermentation. This review describes the options for recovering these and other fermentative carboxylic acids. After cell removal, often a primary recovery step is performed, using liquid-liquid extraction, adsorption, precipitation or conventional electrodialysis. If the carboxylate is formed rather than the carboxylic acid, the recovery process involves a step for removing the cation of the formed carboxylate. Then, bipolar electrodialysis and thermal methods for salt splitting can prevent that waste inorganic salts are co-produced. Final carboxylic acid purification requires either distillation or crystallization, usually involving evaporation of water. Process steps can often be combined synergistically. In-situ removal of carboxylic acid by extraction during fermentation is the most popular approach. Recovery of the extractant can easily lead to waste inorganic salt formation, which counteracts the advantage of the in-situ removal. For industrial production, various recovery principles and configurations are used, because the fermentation conditions and physical properties of specific carboxylic acids differ. PMID:24751382

López-Garzón, Camilo S; Straathof, Adrie J J

2014-01-01

327

Wetting properties of model interphases coated with defined organic functional groups  

NASA Astrophysics Data System (ADS)

Surface properties of soil particles are of particular interest regarding transport of water and sorption of solutes, especially hazardous xenobiotic species. Wetting properties (e.g. determined by contact angle, CA), governed by the functional groups exposed, are crucial to understand sorption processes in water repellent soils as well as for the geometry of water films sustaining microbial processes on the pore scale. Natural soil particle surfaces are characterized by a wide variety of mineralogical and chemical compounds. Their composition is almost impossible to identify in full. Hence, in order to get a better understanding about surface properties, an option is the usage of defined model surfaces, whereas the created surface should be comparable to natural soil interphases. We exposed smooth glass surfaces to different silane compounds, resulting in a coating covalently bound to the surface and exhibiting defined organic functional groups towards the pore space. The wetting properties as evaluated by CA and the surface free energy (SFE), calculated according to the Acid-Base Theory, were found to be a function of the specific functional group. Specifically, the treated surfaces showed a large variation of CA and SFE as function of chain length and polarity of the organic functional group. The study of wetting properties was accompanied by XPS analysis for selective detection of chemical compounds of the interphase. As the reaction mechanism of the coating process is known, the resulting interphase structure can be modeled based on energetic considerations. A next step is to use same coatings for the defined modification of the pore surfaces of porous media to study transport and sorption processes in complex three phase systems.

Woche, Susanne K.; Goebel, Marc-O.; Guggenberger, Georg; Tunega, Daniel; Bachmann, Joerg

2013-04-01

328

Functionalization of carbon nanotubes with -CHn, -NHn fragments, -COOH and -OH groups  

NASA Astrophysics Data System (ADS)

We present results of extensive theoretical studies concerning stability, morphology, and band structure of single wall carbon nanotubes (CNTs) covalently functionalized by -CHn (for n = 2,3,4), -NHn (for n = 1,2,3,4), -COOH, and -OH groups. These studies are based on ab initio calculations in the framework of the density functional theory. For functionalized systems, we determine the dependence of the binding energies on the concentration of the adsorbed molecules, critical densities of adsorbed molecules, global and local changes in the morphology, and electronic structure paying particular attention to the functionalization induced changes of the band gaps. These studies reveal physical mechanisms that determine stability and electronic structure of functionalized systems and also provide valuable theoretical predictions relevant for application. In particular, we observe that functionalization of CNTs causes generally their elongation and locally sp2 to sp3 rehybridization in the neighborhood of chemisorbed molecules. For adsorbants making particularly strong covalent bonds with the CNTs, such as the -CH2 fragments, we observe formation of the characteristic pentagon/heptagon (5/7) defects. In systems functionalized with the -CH2, -NH4, and -OH groups, we determine critical density of molecules that could be covalently bound to the lateral surface of CNTs. Our studies show that functionalization of CNTs can be utilized for band gap engineering. Functionalization of CNTs can also lead to changes in their metallic/semiconductor character. In semiconducting CNTs, functionalizing molecules such as -CH3, -NH2, -OH, -COOH, and both -OH and -COOH, introduce ``impurity'' bands in the band gap of pristine CNTs. In the case of -CH3, -NH2 molecules, the induced band gaps are typically smaller than in the pure CNT and depend strongly on the concentration of adsorbants. However, functionalization of semiconducting CNTs with hydroxyl groups leads to the metallization of CNTs. On the other hand, the functionalization of semi-metallic (9,0) CNT with -CH2 molecules causes the increase of the band gap and induces semi-metall to semiconductor transition.

Milowska, Karolina Z.; Majewski, Jacek A.

2013-05-01

329

Matrix Intensification Alters Avian Functional Group Composition in Adjacent Rainforest Fragments  

PubMed Central

Conversion of farmland land-use matrices to surface mining is an increasing threat to the habitat quality of forest remnants and their constituent biota, with consequences for ecosystem functionality. We evaluated the effects of matrix type on bird community composition and the abundance and evenness within avian functional groups in south-west Ghana. We hypothesized that surface mining near remnants may result in a shift in functional composition of avifaunal communities, potentially disrupting ecological processes within tropical forest ecosystems. Matrix intensification and proximity to the remnant edge strongly influenced the abundance of members of several functional guilds. Obligate frugivores, strict terrestrial insectivores, lower and upper strata birds, and insect gleaners were most negatively affected by adjacent mining matrices, suggesting certain ecosystem processes such as seed dispersal may be disrupted by landscape change in this region. Evenness of these functional guilds was also lower in remnants adjacent to surface mining, regardless of the distance from remnant edge, with the exception of strict terrestrial insectivores. These shifts suggest matrix intensification can influence avian functional group composition and related ecosystem-level processes in adjacent forest remnants. The management of matrix habitat quality near and within mine concessions is important for improving efforts to preserveavian biodiversity in landscapes undergoing intensification such as through increased surface mining. PMID:24058634

Deikumah, Justus P.; McAlpine, Clive A.; Maron, Martine

2013-01-01

330

Tumor-suppressor effects of chemical functional groups in an in vitro co-culture system  

NASA Astrophysics Data System (ADS)

Liver normal cells and cancer cells co-cultured on surfaces modified by different chemical functional groups, including mercapto (-SH), hydroxyl (-OH) and methyl (-CH3) groups. The results showed that different cells exhibited changes in response to different surfaces. Normal cells on -SH surface exhibited the smallest contact area with mostly rounded morphology, which led to the death of cancer cells, while cancer cells could not grow on -CH3 groups, which also died. In the co-culture system, the -CH3 group exhibited its unique effect that could trigger the death of cancer cells and had no effects on normal cells. Our findings provide useful information on strategies for the design of efficient and safe regenerative medicine materials.

Xu, Su-Ju; Cui, Fu-Zhai; Kong, Xiang-Dong

2014-06-01

331

Mechanism of isoprenylcysteine carboxyl methylation from the crystal structure of the integral membrane methyltransferase ICMT.  

PubMed

The posttranslational modification of C-terminal CAAX motifs in proteins such as Ras, most Rho GTPases, and G protein ? subunits, plays an essential role in determining their subcellular localization and correct biological function. An integral membrane methyltransferase, isoprenylcysteine carboxyl methyltransferase (ICMT), catalyzes the final step of CAAX processing after prenylation of the cysteine residue and endoproteolysis of the -AAX motif. We have determined the crystal structure of a prokaryotic ICMT ortholog, revealing a markedly different architecture from conventional methyltransferases that utilize S-adenosyl-L-methionine (SAM) as a cofactor. ICMT comprises a core of five transmembrane ? helices and a cofactor-binding pocket enclosed within a highly conserved C-terminal catalytic subdomain. A tunnel linking the reactive methyl group of SAM to the inner membrane provides access for the prenyl lipid substrate. This study explains how an integral membrane methyltransferase achieves recognition of both a hydrophilic cofactor and a lipophilic prenyl group attached to a polar protein substrate. PMID:22195972

Yang, Jing; Kulkarni, Kiran; Manolaridis, Ioannis; Zhang, Ziguo; Dodd, Roger B; Mas-Droux, Corine; Barford, David

2011-12-23

332

Adsorption of volatile sulphur compounds onto modified activated carbons: effect of oxygen functional groups.  

PubMed

The effect of physical and chemical properties of activated carbon (AC) on the adsorption of ethyl mercaptan, dimethyl sulphide and dimethyl disulphide was investigated by treating a commercial AC with nitric acid and ozone. The chemical properties of ACs were characterised by temperature programme desorption and X-ray photoelectron spectroscopy. AC treated with nitric acid presented a larger amount of oxygen functional groups than materials oxidised with ozone. This enrichment allowed a significant improvement on adsorption capacities for ethyl mercaptan and dimethyl sulphide but not for dimethyl disulphide. In order to gain a deeper knowledge on the effect of the surface chemistry of AC on the adsorption of volatile sulphur compounds, the quantum-chemical COSMO-RS method was used to simulate the interactions between AC surface groups and the studied volatile sulphur compounds. In agreement with experimental data, this model predicted a greater affinity of dimethyl disulphide towards AC, unaffected by the incorporation of oxygen functional groups in the surface. Moreover, the model pointed out to an increase of the adsorption capacity of AC by the incorporation of hydroxyl functional groups in the case of ethyl mercaptan and dimethyl sulphide due to the hydrogen bond interactions. PMID:23708449

Vega, Esther; Lemus, Jesús; Anfruns, Alba; Gonzalez-Olmos, Rafael; Palomar, José; Martin, María J

2013-08-15

333

Dual catalysis. Merging photoredox with nickel catalysis: coupling of ?-carboxyl sp³-carbons with aryl halides.  

PubMed

Over the past 40 years, transition metal catalysis has enabled bond formation between aryl and olefinic (sp(2)) carbons in a selective and predictable manner with high functional group tolerance. Couplings involving alkyl (sp(3)) carbons have proven more challenging. Here, we demonstrate that the synergistic combination of photoredox catalysis and nickel catalysis provides an alternative cross-coupling paradigm, in which simple and readily available organic molecules can be systematically used as coupling partners. By using this photoredox-metal catalysis approach, we have achieved a direct decarboxylative sp(3)-sp(2) cross-coupling of amino acids, as well as ?-O- or phenyl-substituted carboxylic acids, with aryl halides. Moreover, this mode of catalysis can be applied to direct cross-coupling of C(sp³)-H in dimethylaniline with aryl halides via C-H functionalization. PMID:24903563

Zuo, Zhiwei; Ahneman, Derek T; Chu, Lingling; Terrett, Jack A; Doyle, Abigail G; MacMillan, David W C

2014-07-25

334

Nanomechanical characterization of chemical interaction between gold nanoparticles and chemical functional groups.  

PubMed

We report on how to quantify the binding affinity between a nanoparticle and chemical functional group using various experimental methods such as cantilever assay, PeakForce quantitative nanomechanical property mapping, and lateral force microscopy. For the immobilization of Au nanoparticles (AuNPs) onto a microscale silicon substrate, we have considered two different chemical functional molecules of amine and catecholamine (here, dopamine was used). It is found that catecholamine-modified surface is more effective for the functionalization of AuNPs onto the surface than the amine-modified surface, which has been shown from our various experiments. The dimensionless parameter (i.e., ratio of binding affinity) introduced in this work from such experiments is useful in quantitatively depicting such binding affinity, indicating that the binding affinity and stability between AuNPs and catecholamine is approximately 1.5 times stronger than that between amine and AuNPs. Our study sheds light on the experiment-based quantitative characterization of the binding affinity between nanomaterial and chemical groups, which will eventually provide an insight into how to effectively design the functional material using chemical groups. PMID:23113991

Lee, Gyudo; Lee, Hyungbeen; Nam, Kihwan; Han, Jae-Hee; Yang, Jaemoon; Lee, Sang Woo; Yoon, Dae Sung; Eom, Kilho; Kwon, Taeyun

2012-01-01

335

Linking avian communities and avian influenza ecology in southern Africa using epidemiological functional groups  

PubMed Central

The ecology of pathogens, and particularly their emergence in multi-host systems, is complex. New approaches are needed to reduce superficial complexities to a level that still allows scientists to analyse underlying and more fundamental processes. One promising approach for simplification is to use an epidemiological-function classification to describe ecological diversity in a way that relates directly to pathogen dynamics. In this article, we develop and apply the epidemiological functional group (EFG) concept to explore the relationships between wild bird communities and avian influenza virus (AIV) in three ecosystems in southern Africa. Using a two year dataset that combined bird counts and bimonthly sampling for AIV, we allocated each bird species to a set of EFGs that captured two overarching epidemiological functions: the capacity of species to maintain AIV in the system, and their potential to introduce the virus. Comparing AIV prevalence between EFGs suggested that the hypothesis that anseriforms (ducks) and charadriiforms (waders) drive AIV epidemiology cannot entirely explain the high prevalence observed in some EFGs. If anseriforms do play an important role in AIV dynamics in each of the three ecosystems, the role of other species in the local maintenance of AIV cannot be ruled out. The EFG concept thus helped us to identify gaps in knowledge and to highlight understudied bird groups that might play a role in AIV epidemiology. In general, the use of EFGs has potential for generating a range of valuable insights in epidemiology, just as functional group approaches have done in ecology. PMID:23101696

2012-01-01

336

Visual target modulation of functional connectivity networks revealed by self-organizing group ICA.  

PubMed

We applied a data-driven analysis based on self-organizing group independent component analysis (sogICA) to fMRI data from a three-stimulus visual oddball task. SogICA is particularly suited to the investigation of the underlying functional connectivity and does not rely on a predefined model of the experiment, which overcomes some of the limitations of hypothesis-driven analysis. Unlike most previous applications of ICA in functional imaging, our approach allows the analysis of the data at the group level, which is of particular interest in high order cognitive studies. SogICA is based on the hierarchical clustering of spatially similar independent components, derived from single subject decompositions. We identified four main clusters of components, centered on the posterior cingulate, bilateral insula, bilateral prefrontal cortex, and right posterior parietal and prefrontal cortex, consistently across all participants. Post hoc comparison of time courses revealed that insula, prefrontal cortex and right fronto-parietal components showed higher activity for targets than for distractors. Activation for distractors was higher in the posterior cingulate cortex, where deactivation was observed for targets. While our results conform to previous neuroimaging studies, they also complement conventional results by showing functional connectivity networks with unique contributions to the task that were consistent across subjects. SogICA can thus be used to probe functional networks of active cognitive tasks at the group-level and can provide additional insights to generate new hypotheses for further study. PMID:17990304

van de Ven, Vincent; Bledowski, Christoph; Prvulovic, David; Goebel, Rainer; Formisano, Elia; Di Salle, Francesco; Linden, David E J; Esposito, Fabrizio

2008-12-01

337

Nanomechanical characterization of chemical interaction between gold nanoparticles and chemical functional groups  

NASA Astrophysics Data System (ADS)

We report on how to quantify the binding affinity between a nanoparticle and chemical functional group using various experimental methods such as cantilever assay, PeakForce quantitative nanomechanical property mapping, and lateral force microscopy. For the immobilization of Au nanoparticles (AuNPs) onto a microscale silicon substrate, we have considered two different chemical functional molecules of amine and catecholamine (here, dopamine was used). It is found that catecholamine-modified surface is more effective for the functionalization of AuNPs onto the surface than the amine-modified surface, which has been shown from our various experiments. The dimensionless parameter (i.e., ratio of binding affinity) introduced in this work from such experiments is useful in quantitatively depicting such binding affinity, indicating that the binding affinity and stability between AuNPs and catecholamine is approximately 1.5 times stronger than that between amine and AuNPs. Our study sheds light on the experiment-based quantitative characterization of the binding affinity between nanomaterial and chemical groups, which will eventually provide an insight into how to effectively design the functional material using chemical groups.

Lee, Gyudo; Lee, Hyungbeen; Nam, Kihwan; Han, Jae-Hee; Yang, Jaemoon; Lee, Sang Woo; Yoon, Dae Sung; Eom, Kilho; Kwon, Taeyun

2012-10-01

338

Wetland macroinvertebrates of Prentiss Bay, Lake Huron, Michigan: diversity and functional group composition  

USGS Publications Warehouse

The Great Lakes support many fish and waterbirds that depend directly or indirectly on coastal wetlands during some portion of their life cycle. It is known that macroinvertebrates make up an important part of wetland food webs and ecosystem function; however, our understanding of species distribution within and among wetlands has only recently received attention. We investigated the macroinvertebrates of a freshwater marsh (Prentiss Bay) in the Les Chenaux Island Area of Northern Lake Huron, Michigan. Macroinvertebrate taxa diversity and functional feeding group composition were compared between two habitats. A shallow depositional habitat with higher vegetation diversity and little wave action was compared to a deeper erosional habitat with fewer plant species and more wave action. A total of 83 taxa were collected over the summer of 1996, representing two phyla (Arthropoda and Mollusca) and five classes (Arachnida, Bivalvia, Malacostraca, Gastropoda and Insecta). A total of 79 genera were identified, with 92% being insects (39 families composed of at least 73 genera). Of the total, 42 insect genera were common to both habitats,while relatively fewer were collected exclusively from the erosional compared the depositional habitat. When habitats were pooled, predators comprised about 50% of the functional group taxa, while gathering collectors and shredders each were about 20%. Filtering collectors and scrapers each represented < 10%. When comparing habitats, there was a relatively higher percentage of predators and shredders in the depositional habitat, while all other functional groups were lower. These data suggest that vegetation diversity, depth and wave action affect taxa composition and functional group organization of the Prentiss Bay marsh.

Merritt, R. W.; Benbow, M. E.; Hudson, P. L.

2002-01-01

339

Direct carboxylation of simple arenes with CO2 through a rhodium-catalyzed C-H bond activation.  

PubMed

Direct carboxylation of simple arenes under atmospheric pressure of CO2 is achieved through a rhodium-catalyzed C-H bond activation without the assistance of a directing group. Various arenes such as benzene, toluene, xylene, electron-rich or electron-deficient benzene derivatives, and heteroaromatics are directly carboxylated with high TONs. PMID:25296263

Suga, Takuya; Mizuno, Hajime; Takaya, Jun; Iwasawa, Nobuharu

2014-10-23

340

Azidothymidine: crystal structure and possible functional role of the azido group.  

PubMed

The crystal and molecular structures of the anti-acquired immunodeficiency syndrome agent 3'-azido-3'-deoxythymidine (AZT) have been determined by x-ray diffraction. There are two crystallographically independent AZT molecules in the crystal asymmetric unit; they have similar conformations and differ primarily in the glycosyl torsion angle. Comparisons with a hydrated thymidylate structure indicate that the azido group does not significantly affect the gross conformational preference of the molecule. The comparisons also suggest possible functional roles for the azido group in enzyme binding. PMID:2446321

Camerman, A; Mastropaolo, D; Camerman, N

1987-12-01

341

Azidothymidine: crystal structure and possible functional role of the azido group.  

PubMed Central

The crystal and molecular structures of the anti-acquired immunodeficiency syndrome agent 3'-azido-3'-deoxythymidine (AZT) have been determined by x-ray diffraction. There are two crystallographically independent AZT molecules in the crystal asymmetric unit; they have similar conformations and differ primarily in the glycosyl torsion angle. Comparisons with a hydrated thymidylate structure indicate that the azido group does not significantly affect the gross conformational preference of the molecule. The comparisons also suggest possible functional roles for the azido group in enzyme binding. PMID:2446321

Camerman, A; Mastropaolo, D; Camerman, N

1987-01-01

342

The two-point correlation function for groups of galaxies in the Center for Astrophysics redshift survey  

NASA Technical Reports Server (NTRS)

The large-scale distribution of groups of galaxies selected from complete slices of the CfA redshift survey extension is examined. The survey is used to reexamine the contribution of group members to the galaxy correlation function. The relationship between the correlation function for groups and those calculated for rich clusters is discussed, and the results for groups are examined as an extension of the relation between correlation function amplitude and richness. The group correlation function indicates that groups and individual galaxies are equivalent tracers of the large-scale matter distribution. The distribution of group centers is equivalent to random sampling of the galaxy distribution. The amplitude of the correlation function for groups is consistent with an extrapolation of the amplitude-richness relation for clusters. The amplitude scaled by the mean intersystem separation is also consistent with results for richer clusters.

Ramella, Massimo; Geller, Margaret J.; Huchra, John P.

1990-01-01

343

Closed equations of the two-point functions for tensorial group field theory  

NASA Astrophysics Data System (ADS)

In this paper, we provide the closed equations that satisfy two-point correlation functions of rank 3 and 4 tensorial group field theory. The formulation of the current problem extends the method used by Grosse and Wulkenhaar (2009 arXiv:0909.1389) to the tensor case. Ward-Takahashi identities and Schwinger-Dyson equations are combined to establish a nonlinear integral equation for the two-point functions. In the three-dimensional case, the solution of this equation is given perturbatively at the second order of the coupling constant.

Ousmane Samary, Dine

2014-09-01

344

Synthesis of crambescin B carboxylic acid, a potent inhibitor of voltage-gated sodium channels.  

PubMed

The stereocontrolled synthesis of a racemic carboxylic acid of crambescin B, a marine alkaloid, is described. The synthesis features two highly stereoselective reactions: (I) palladium-catalyzed hydroxymethylation of an alkynyl aziridine having an N-guanidino group and (II) cascade bromocyclization providing a spiro-hemiaminal structure. The cell-based colorimetric assay showed that the synthesized carboxylic acid exhibited a potent inhibitory activity on voltage-gated sodium channels. PMID:24216693

Nakazaki, Atsuo; Ishikawa, Yuki; Sawayama, Yusuke; Yotsu-Yamashita, Mari; Nishikawa, Toshio

2014-01-01

345

Assemblage patterns of fish functional groups relative to habitat connectivity and conditions in floodplain lakes  

USGS Publications Warehouse

We evaluated the influences of habitat connectivity and local environmental factors on the distribution and abundance patterns of fish functional groups in 17 floodplain lakes in the Yazoo River Basin, USA. The results of univariate and multivariate analyses showed that species-environmental relationships varied with the functional groups. Species richness and assemblage structure of periodic strategists showed strong and positive correlations with habitat connectivity. Densities of most equilibrium and opportunistic strategists decreased with habitat connectivity. Densities of certain equilibrium and opportunistic strategists increased with turbidity. Forested wetlands around the lakes were positively related to the densities of periodic and equilibrium strategists. These results suggest that decreases in habitat connectivity, forested wetland buffers and water quality resulting from environmental manipulations may cause local extinction of certain fish taxa and accelerate the dominance of tolerant fishes in floodplain lakes. ?? 2010 John Wiley & Sons A/S.

Miyazono, S.; Aycock, J.N.; Miranda, L.E.; Tietjen, T.E.

2010-01-01

346

Functional Group Selective Derivatization and Gas-Phase Fragmentation Reactions of Plasmalogen Glycerophospholipids  

PubMed Central

A reaction strategy involving functional group selective modification of the O-alkenyl-ether double bond within plasmenyl ether containing lipids using iodine and methanol, in conjunction with functional group selective derivatization of amine-containing lipids using a novel 13C1-S,S?-dimethylthiobutanoylhydroxysuccinimide ester (13C1-DMBNHS) reagent, is shown to improve the capabilities of ‘shotgun’ high resolution/accurate mass spectrometry for comprehensive lipidome analysis. Importantly, the characteristic mass shifts introduced as a result of these derivatization reactions enables the resolution and unambiguous identification of isobaric mass plasmenyl- and plasmanyl-ether containing lipid species from within crude complex lipid extracts, without need for chromatographic fractionation or additional lipid extraction steps prior to analysis. Additionally, the positive ionization mode tandem mass spectrometry fragmentation behavior of the derivatized plasmenyl ether containing glycerophosphocholine and glycerophosphoethanolamine lipids are shown to yield abundant characteristic product ions that directly enable the assignment of their molecular lipid identities. PMID:24349934

Fhaner, Cassie J.; Liu, Sichang; Zhou, Xiao; Reid, Gavin E.

2013-01-01

347

Self-consistent, nonorthogonal group function approximation for polyatomic systems. II. Analysis of noncovalent interactions  

Microsoft Academic Search

The self-consistent nonorthogonal group function (NOGF) approximation has been reformulated for the calculation and analysis of noncovalent interactions. With the help of perturbation theory it is shown that the present analysis differs from previous decompositions in the polarization interaction, and the source of this difference is exhibited. The method is applied to several H-bonded dimers and one non-H-bonded complex, and

Ernest L. Mehler

1981-01-01

348

Finding Landmarks in the Functional Brain: Detection and Use for Group Characterization  

Microsoft Academic Search

\\u000a FMRI group studies are usually based on stereotactic spatial normalization and present voxel by voxel average activity across\\u000a subjects. This technique does not in general adequately model the inter subject spatial variability. In this work, we propose\\u000a to identify functional landmarks that are reliable across subjects with subject specific Talairach coordinates that are similar\\u000a -but not exactly identical- between subjects.

Bertrand Thirion; Philippe Pinel; Jean-baptiste Poline

2005-01-01

349

One-loop functional renormalization group flow of scalar theories with electroweak symmetry  

NASA Astrophysics Data System (ADS)

Using functional renormalization methods, we study the one-loop renormalization group evolution of theories with four scalars, at second order in the derivative expansion, in which electroweak symmetry is nonlinearly realized. In this framework we study the stability of O(4) symmetry and find the O(4)-violating eigenperturbations and their corresponding eigenspectrum around three different geometries of the target space, namely those of the flat space, cylinder, and sphere.

Safari, Mahmoud

2014-09-01

350

Response of arthropod species richness and functional groups to urban habitat structure and management  

Microsoft Academic Search

Urban areas are a particular landscape matrix characterized by a fine-grained spatial arrangement of very diverse habitats\\u000a (urban mosaic). We investigated arthropods to analyse biodiversity-habitat associations along five environmental gradients\\u000a (age, impervious area, management, configuration, composition) in three Swiss cities (96 study sites). We considered total\\u000a species richness and species richness within different functional groups (zoophagous, phytophagous, pollinator, low mobility,

T. Sattler; P. Duelli; M. K. Obrist; R. Arlettaz; M. Moretti

2010-01-01

351

?-Diversity of Functional Groups of Woody Plants in a Tropical Dry Forest in Yucatan  

PubMed Central

Two main theories have attempted to explain variation in plant species composition (?-diversity). Niche theory proposes that most of the variation is related to environment (environmental filtering), whereas neutral theory posits that dispersal limitation is the main driver of ?-diversity. In this study, we first explored how ?- and ?-diversity of plant functional groups defined by growth form (trees, shrubs and lianas, which represent different strategies of resource partitioning), and dispersal syndrome (autochory, anemochory and zoochory, which represent differences in dispersal limitation) vary with successional age and topographic position in a tropical dry forest. Second, we examined the effects of environmental, spatial, and spatially-structured environmental factors on ?-diversity of functional groups; we used the spatial structure of sampling sites as a proxy for dispersal limitation, and elevation, soil properties and forest stand age as indicators of environmental filtering. We recorded 200 species and 22,245 individuals in 276 plots; 120 species were trees, 41 shrubs and 39 lianas. We found that ?-diversity was highest for shrubs, intermediate for lianas and lowest for trees, and was slightly higher for zoochorous than for autochorous and anemochorous species. All three dispersal syndromes, trees and shrubs varied in composition among vegetation classes (successional age and topographic position), whilst lianas did not. ?-diversity was influenced mostly by proxies of environmental filtering, except for shrubs, for which the influence of dispersal limitation was more important. Stand age and topography significantly influenced ?-diversity across functional groups, but showed a low influence on ?-diversity –possibly due to the counterbalancing effect of resprouting on plant distribution and composition. Our results show that considering different plant functional groups reveals important differences in both ?- and ?-diversity patterns and correlates that are not apparent when focusing on overall woody plant diversity, and that have important implications for ecological theory and biodiversity conservation. PMID:24040014

Lopez-Martinez, Jorge Omar; Sanaphre-Villanueva, Lucia; Dupuy, Juan Manuel; Hernandez-Stefanoni, Jose Luis; Meave, Jorge Arturo; Gallardo-Cruz, Jose Alberto

2013-01-01

352

Generalized Green functions and unipotent classes for finite reductive groups, I  

Microsoft Academic Search

The algorithm of computing generalized Green functions of a finite reductive group contains some unkonwn scalars occuring from the F_q structure of irreducible local systems on unipotent classes on G. In this paper, we determine such scalars in the case where G = SL_n with Frobenius map F of split or non-split type. In the case where F is of

Toshiaki Shoji

2005-01-01

353

Organic Mass Fragments and Organic Functional Groups in Aged Biomass Burning and Fossil Fuel Combustion Aerosol  

Microsoft Academic Search

Organic functional group concentrations in submicron aerosol particles collected from 27 June to 17 September at the Scripps Pier in La Jolla, California as part of AeroSCOPE 2008 were quantified using Fourier Transform Infrared (FTIR) spectroscopy. Organic and inorganic non-refractory components in the same air masses were quantified using a Quadrupole Aerosol Mass Spectrometer (Q-AMS). Previous measurements at the Scripps

D. A. Day; L. N. Hawkins; L. M. Russell

2009-01-01

354

Effects of antagonistic Fusarium oxysporum on functional groups of indigenous bacteria in soil  

Microsoft Academic Search

Before planning the commercial use of microorganisms, genetically manipulated or not, in agricultural environments, their behavior and potential impact on soil ecosystems should be carefully studied as part of risk assessment. The influence of added inoculum of antagonistic Fusarium oxysporum strains, genetically manipulated (T26\\/6) or not (233\\/1) on nitrogen and carbon functional groups were evaluated in three soils from different

Monica Mezzalama; Raquel Ghini; Paola Ruffa; Roberto Arnbrosoli; Angelo Garibaldi

1997-01-01

355

Antiferromagnetic critical point on graphene's honeycomb lattice: A functional renormalization group approach  

E-print Network

Electrons on the half-filled honeycomb lattice are expected to undergo a direct continuous transition from the semimetallic into the antiferromagnetic insulating phase with increase of on-site Hubbard repulsion. We attempt to further quantify the critical behavior at this quantum phase transition by means of functional renormalization group (RG), within an effective Gross-Neveu-Yukawa theory for an SO(3) order parameter ("chiral Heisenberg universality class"). Our calculation yields an estimate of the critical exponents $\

Lukas Janssen; Igor F. Herbut

2014-02-25

356

EFFECTS OF DIETARY ESFENVALERATE EXPOSURES ON THREE AQUATIC INSECT SPECIES REPRESENTING DIFFERENT FUNCTIONAL FEEDING GROUPS  

Microsoft Academic Search

Given the chemical properties of synthetic pyrethroids, it is probable that compounds, including esfenvalerate, that enter surface waters may become incorporated into aquatic insect food sources. We examined the effect of dietary esfenvalerate uptake in aquatic insects representing different functional feeding groups. We used three field-collected aquatic insect species: A grazing scraper,Cinygmula reticulata McDunnough (Ephemeroptera: Heptageniidae); an omnivorous filter feeder,Brachycentrusamericanus

Katherine R. Palmquist; Jeffrey J. Jenkins; Paul C. Jepson

2008-01-01

357

Vibrational coupling in carboxylic acid dimers  

NASA Astrophysics Data System (ADS)

The vibrational level splitting in the ground electronic state of carboxylic acid dimers mediated by the doubly hydrogen-bonded networks are investigated using pure and mixed dimers of benzoic acid with formic acid as molecular prototypes. Within the 0-2000-cm-1 range, the frequencies for the fundamental and combination vibrations of the two dimers are experimentally measured by using dispersed fluorescence spectroscopy in a supersonic jet expansion. Density-functional-theory calculations predict that most of the dimer vibrations are essentially in-phase and out-of-phase combinations of the monomer modes, and many of such combinations show significantly large splitting in vibrational frequencies. The infrared spectrum of the jet-cooled benzoic acid dimer, reported recently by Bakker et al. [J. Chem. Phys. 119, 11180 (2003)], has been used along with the dispersed fluorescence spectra to analyze the coupled g-u vibrational levels. Assignments of the dispersed fluorescence spectra of the mixed dimer are suggested by comparing the vibronic features with those in the homodimer spectrum and the predictions of density-functional-theory calculation. The fluorescence spectra measured by excitations of the low-lying single vibronic levels of the mixed dimer reveal that the hydrogen-bond vibrations are extensively mixed with the ring modes in the S1 surface.

Nandi, Chayan K.; Hazra, Montu K.; Chakraborty, Tapas

2005-09-01

358

Two group I ribozymes with different functions in a nuclear rDNA intron.  

PubMed Central

DiSSU1, a mobile intron in the nuclear rRNA gene of Didymium iridis, was previously reported to contain two independent catalytic RNA elements. We have found that both catalytic elements, renamed GIR1 and GIR2, are group I ribozymes, but with differing functionality. GIR2 carries out the several reactions associated with self-splicing. GIR1 carries out a hydrolysis reaction at an internal processing site (IPS-1). These conclusions are based on the catalytic properties of RNAs transcribed in vitro. Mutation of the P7 pairing segment of GIR2 abrogated self-splicing, while mutation of P7 in GIR1 abrogated hydrolysis at the IPS-1. Much of the P2 stem and all of the associated loop could be deleted without effect on self-splicing. These results are accounted for by a secondary structure model, in which a long P2 pairing segment brings the 5' splice site to the GIR2 catalytic core. GIR1 is the smallest natural group I ribozyme yet reported and is the first example of a group I ribozyme whose presumptive biological function is hydrolysis. We hypothesize that GIR1-mediated cleavage of the excised intron RNA functions in the generation and expression of the mRNA for the intron-encoded endonuclease I-DirI. Images PMID:7556099

Decatur, W A; Einvik, C; Johansen, S; Vogt, V M

1995-01-01

359

Interpersonal distance regulates functional grouping tendencies of agents in team sports.  

PubMed

The authors examined whether, similar to collective agent behaviors in complex, biological systems (e.g., schools of fish and colonies of ants), performers in team sports displayed functional coordination tendencies, based on local interaction rules during performance. To investigate this issue, they used videogrammetry and digitizing procedures to observe interpersonal interactions in common 4 versus 2 + 2 subphases of the team sport of rugby union, involving 16 participants aged between 16 and 17 years of age. They observed pattern-forming dynamics in attacking subunits (n = 4 players) attempting to penetrate 2 defensive lines (n = 2 players in each). Data showed that within each attacking subunit, the 4 players displayed emergent functional grouping tendencies that differed between the 2 defensive lines. Results confirmed that grouping tendencies in attacking subunits of team games are sensitive to different task constraints, such as relative positioning to nearest defenders. It was concluded that running correlations were particularly useful for measuring the level of interpersonal coordination in functional grouping tendencies within attacking subunits. PMID:21400329

Passos, Pedro; Milho, João; Fonseca, Sofia; Borges, João; Araújo, Duarte; Davids, Keith

2011-01-01

360

Identifying functional groups for response to disturbance in an abandoned pasture  

NASA Astrophysics Data System (ADS)

In an abandoned pasture in Brittany, we compared artificial small-scale disturbances to natural disturbances by wild boar and undisturbed vegetation. We developed a multivariate statistical approach which analyses how species biological attributes explain the response of community composition to disturbances. This technique, which reconciles the inductive and deductive approaches for functional classifications, identifies groups of species with similar responses to disturbance and characterizes their biological profiles. After 5 months of recolonization, artificial disturbances had a greater species richness than undisturbed vegetation as a result of recruitment of new species without the exclusion of pre-existing matrix species. Species morphology, described by canopy structure, canopy height and lateral spread, explained a large part (16 %) of community response to disturbance. Regeneration strategies, described by life history, seed mass, dispersal agent, dormancy and the existence of vegetative multiplication, explained a smaller part of community response to disturbance (8 %). Artificial disturbances were characterized by therophyte and compact rosettes with moderately dormant seeds, including a number of Asteraceae and other early successional species. Natural disturbances were colonized by leafy guerrilla species without seed dormancy. Few species were tightly related to undisturbed vegetation and were essentially grasses with a phalanx rosette morphology. The functional classification obtained is consistent with the classification of the community into fugitives, regenerators and persistors. These groups are structured according to Grubb's model for temperate grasslands, with regenerators and persistors in the matrix and fugitives taking advantage of gaps open by small-scale disturbances. The conjunction of functional diversity and species diversity within functional groups is the key to resilience to disturbance, an important ecosystem function.

Lavorel, Sandra; Touzard, Blaise; Lebreton, Jean-Dominique; Clément, Bernard

1998-06-01

361

Short-Chain Carboxylic-Acid-Stimulated, PMN-Mediated Gingival Inflammation  

Microsoft Academic Search

This communication reviews the effects of short-chain carboxylic acids on human cells of importance to the periodontium. The central hypothesis is that these acids can alter both cell function and gene expression, and thus contribute to the initiation and prolongation of gingival inflammation.Short-chain carboxylic acids [CH3-(CH2)x-COOH, x < 3] are metabolic intermediates with a broad range of apparently paradoxical biological

Richard Niederman; Jie Zhang; Shelby Kashket

1997-01-01

362

Functionalized quantum dots induce proinflammatory responses in vitro: the role of terminal functional group-associated endocytic pathways  

NASA Astrophysics Data System (ADS)

PEGylation has been applied as an effective strategy of surface functionalization to improve the stability and reduce non-specific binding of quantum dots (QDs). However, its effects on the proinflammatory properties of QDs and the underlying mechanism have not been well elucidated yet. Herein, the proinflammatory effects of PEGylated CdSe/ZnS QDs with an amphiphilic polymer coating (PEG-pQDs) were investigated in human pulmonary epithelial cells and macrophages by evaluating the cytokine/chemokine production. The results showed that the proinflammatory effects of PEG-pQDs were strongly associated with the functional groups (-COOH, -NH2, -OH, and -OCH3) at the end of PEG chain. COOH-PEG-pQDs demonstrated the most proinflammatory effects followed by NH2-PEG-pQDs and HO-PEG-pQDs with CH3O-PEG-pQDs exhibiting the least proinflammatory effects. The proinflammatory effects of PEG-pQDs relied on lipid raft- and class A scavenger receptor (SRA)-dependent endocytic pathways as well as the downstream NF-?B and MAPK signaling cascades. COOH-PEG-pQDs were selectively internalized by lipid raft- and SRA-mediated endocytosis, which consequently activated NF-?B signaling pathway. On the other hand, NH2-PEG-pQDs and HO-PEG-pQDs were mostly internalized via lipid raft-mediated endocytosis, thereby activating p38 MAPK/AP-1 signaling cascades. These data revealed a critical role of terminal functional group-associated endocytic pathways in the proinflammatory responses induced by PEGylated QDs in human pulmonary epithelial cells and macrophages.PEGylation has been applied as an effective strategy of surface functionalization to improve the stability and reduce non-specific binding of quantum dots (QDs). However, its effects on the proinflammatory properties of QDs and the underlying mechanism have not been well elucidated yet. Herein, the proinflammatory effects of PEGylated CdSe/ZnS QDs with an amphiphilic polymer coating (PEG-pQDs) were investigated in human pulmonary epithelial cells and macrophages by evaluating the cytokine/chemokine production. The results showed that the proinflammatory effects of PEG-pQDs were strongly associated with the functional groups (-COOH, -NH2, -OH, and -OCH3) at the end of PEG chain. COOH-PEG-pQDs demonstrated the most proinflammatory effects followed by NH2-PEG-pQDs and HO-PEG-pQDs with CH3O-PEG-pQDs exhibiting the least proinflammatory effects. The proinflammatory effects of PEG-pQDs relied on lipid raft- and class A scavenger receptor (SRA)-dependent endocytic pathways as well as the downstream NF-?B and MAPK signaling cascades. COOH-PEG-pQDs were selectively internalized by lipid raft- and SRA-mediated endocytosis, which consequently activated NF-?B signaling pathway. On the other hand, NH2-PEG-pQDs and HO-PEG-pQDs were mostly internalized via lipid raft-mediated endocytosis, thereby activating p38 MAPK/AP-1 signaling cascades. These data revealed a critical role of terminal functional group-associated endocytic pathways in the proinflammatory responses induced by PEGylated QDs in human pulmonary epithelial cells and macrophages. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr01653f

Zhang, Yijuan; Pan, Hong; Zhang, Pengfei; Gao, Ningning; Lin, Yi; Luo, Zichao; Li, Ping; Wang, Ce; Liu, Lanlan; Pang, Daiwen; Cai, Lintao; Ma, Yifan

2013-06-01

363

Evidence supporting the importance of microbial functional groups in decomposition models  

NASA Astrophysics Data System (ADS)

Microbial communities mediate organic carbon decomposition in both soil and marine environments. Decomposition depends on microbes that produce extracellular enzymes to degrade complex organic matter, as well as microbes that mineralize simple organic matter to CO2. Therefore microbes could be represented in Earth system models as functional groups based on the extracellular enzymes they produce. However, the importance of including the functional diversity of microbes in decomposition models has been unclear. In this study we simulated microbial functional diversity with two strains of Pseudomonas fluorescens bacteria, one of which secretes extracellular protease and one that does not. These two strains were competed on several carbon resources including casein-glucose, casamino acids-glucose and glucose over several days. We then fit a series of models to the resulting data: 1) an explicit model representing both biomass and substrate pools, 2) a simplified substrate pool model with two biomass pools and one substrate pool, 3) a simplified biomass pool model with one biomass and two substrate pools, 4) a simplified biomass/substrate pool model with one biomass and one substrate pool, and 5) a single carbon pool model. We found that the explicit model (#1) fit the laboratory data significantly better than the other models, suggesting that functional groups and substrate pools should be represented in global decomposition models with time steps on the order of hours.

Todd-Brown, K. E.; Lu, L.; Allison, S. D.

2010-12-01

364

Real-space dynamic renormalization group. III. Calculation of correlation functions  

SciTech Connect

The real-space dynamic renormalization group method developed in previous papers is applied to the kinetic Ising model defined on a square lattice. In particular we extend the formalism to the calculation of space- and time-dependent equilibrium averaged correlation functions. We find that conventional methods for implementing the real-space renormalization group via cumulant expansions in terms of the intercell coupling lead to correlation functions which decay algebraically in space at large distances in the disordered phase in qualitative disagreement with the known exponential decay. We indicate how one can develop new perturbation theory expansion methods which lead to the proper exponential decay at large distances and also lead to good quantitative results for other observable quantities like the magnetization, susceptibility, and single spin time autocorrelation function. As the result of a first-order calculation we obtain excellent results for the static critical exponents and a value of z=1.79 for the dynamic critical exponent. The critical exponents obtained from the correlation functions calculated using this method satisfy the proper static and dynamic scaling relations.

Mazenko, G.F.; Hirsch, J.E.; Nolan, M.J.; Valls, O.T.

1981-02-01

365

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids  

PubMed Central

Summary The near-unlimited availability of CO2 has stimulated a growing research effort in creating value-added products from this greenhouse gas. This paper presents the trends on the most important methods used in the electrochemical synthesis of carboxylic acids from carbon dioxide. An overview is given of different substrate groups which form carboxylic acids upon CO2 fixation, including mechanistic considerations. While most work focuses on the electrocarboxylation of substrates with sacrificial anodes, this review considers the possibilities and challenges of implementing other synthetic methodologies. In view of potential industrial application, the choice of reactor setup, electrode type and reaction pathway has a large influence on the sustainability and efficiency of the process. PMID:25383120

Matthessen, Roman; Fransaer, Jan; Binnemans, Koen

2014-01-01

366

Improving plant functional groups for dynamic models of biodiversity: at the crossroads between functional and community ecology  

PubMed Central

The pace of on-going climate change calls for reliable plant biodiversity scenarios. Traditional dynamic vegetation models use plant functional types that are summarized to such an extent that they become meaningless for biodiversity scenarios. Hybrid dynamic vegetation models of intermediate complexity (hybrid-DVMs) have recently been developed to address this issue. These models, at the crossroads between phenomenological and process-based models, are able to involve an intermediate number of well-chosen plant functional groups (PFGs). The challenge is to build meaningful PFGs that are representative of plant biodiversity, and consistent with the parameters and processes of hybrid-DVMs. Here, we propose and test a framework based on few selected traits to define a limited number of PFGs, which are both representative of the diversity (functional and taxonomic) of the flora in the Ecrins National Park, and adapted to hybrid-DVMs. This new classification scheme, together with recent advances in vegetation modeling, constitutes a step forward for mechanistic biodiversity modeling. PMID:24403847

Isabelle, Boulangeat; Pauline, Philippe; Sylvain, Abdulhak; Roland, Douzet; Luc, Garraud; Sebastien, Lavergne; Sandra, Lavorel; Jeremie, Van Es; Pascal, Vittoz; Wilfried, Thuiller

2013-01-01

367

Functional-Group Selective Ion/Molecule Reactions: Mass Spectrometric Identification of the Amido Functionality in Protonated Monofunctional Compounds  

PubMed Central

A mass spectrometric method was developed for the screening of the amido functionality in monofunctional protonated analytes. This method is based on selective gas-phase derivatization of protonated analytes by (N,N-diethylamino)dimethylborane in a Fourier transform ion cyclotron resonance (FT-ICR) and triple quadrupole mass spectrometer. Examination of a series of protonated analytes demonstrated that only the compounds containing the amido functionality react with the aminoborane by the derivatization reaction. The mechanism involves proton transfer from the protonated analyte to the borane, followed by addition of the amide to the boron center, which leads to the elimination of neutral diethylamine. The derivatized analytes are readily identified based on a shift of 40 m/z units relative to the m/z value of the protonated analyte and characteristic boron isotope patterns. Collision-activated dissociation was used to provide support for the structures assigned to the derivatized analytes. The structural information gained from this gas-phase derivatization method will aid in the functional group identification of unknown compounds in mixtures. PMID:17397220

Campbell, Karinna M.; Watkins, Michael A.; Li, Sen; Fiddler, Marc; Winger, Brian; Kenttamaa, Hilkka I.

2008-01-01

368

Transplacental Transfer of Oseltamivir Carboxylate  

PubMed Central

Objectives Determine the bidirectional transfer of oseltamivir carboxylate (OC) across term human placenta and its distribution between the tissue, maternal and fetal circuits. Methods The technique of dual perfusion of placental lobule (DPPL) in its recirculating mode was utilized to determine the transfer of the drug. OC (350 ng/ml) was co-perfused with its [3H]-isotope and the marker compound antipyrine (AP, 20 ?g/mL) together with its [14C]-isotope. The concentrations of OC and any of its metabolite(s) formed during perfusion were determined in the tissue, maternal and fetal circuits by liquid scintillation spectrometry following their separation by High Performance Liquid Chromatography (HPLC). Results The distribution of OC following its perfusion in the Maternal-to-Fetal direction for 4 hours was as follows: 21 ± 4% of the drug was transferred to the fetal circuit, 13 ± 5% was retained by the perfused lobule, and 66 ± 4% remained in the maternal circuit. The normalized transfer of OC to that of AP (Clearance index) in the Maternal-to-Fetal direction was (0.47 ± 0.11) and was not different from its transfer from the Fetal-to-Maternal direction (0.47 ± 0.06) suggesting that involvement of placental efflux transporters is unlikely. Conclusions OC crosses human placenta. Since the transfer rate of OC is 47% of the freely diffusible AP, it is likely that fetus could be exposed to OC during pregnancy. PMID:22590979

Nanovskaya, Tatiana N.; Patrikeeva, Svetlana; Zhan, Ying; Hankins, Gary D. V.; Ahmed, Mahmoud S.

2014-01-01

369

Functionalized multi-walled carbon nanotubes as affinity ligands  

Microsoft Academic Search

Functionalization of carbon nanotubes is very challenging for their applications. The paper here describes a new method to functionalize multi-walled carbon nanotubes (MWCNTs) as specific affinity adsorbents. MWCNTs were acid purified and pretreated with (3-aminopropyl)-triethoxysilane (APTES) in order to introduce abundant amino groups on the surface of MWCNTs. After the conversion of amino groups to carboxyl groups by succinic acid

L. Yu; C. M. Li; Q. Zhou; Y. Gan; Q. L. Bao

2007-01-01

370

Enhancing the efficiency of lithium intercalation in carbon nanotube bundles using surface functional groups.  

PubMed

The effect of surface functionalization on the ability and kinetics of lithium intercalation in carbon nanotube (CNT) bundles has been studied by comparing the dynamical behaviors of lithium (Li) ions in pristine and -NH2 functionalized CNTs via ab initio molecular dynamics simulations. It was observed that lithium intercalation has been achieved quickly for both the pristine and surface functionalized CNT bundle. Our calculations demonstrated for the first time that CNT functionalization improved the efficiency of lithium intercalation significantly at both low and high Li ion density. Moreover, we found that keeping the nanotubes apart with an appropriate distance and charging the battery at a rational rate were beneficial to achieve a high rate of lithium intercalation. Besides, the calculated adsorption energy curves indicated that the potential wells in the system of -NH2 functionalized CNT were deeper than that of the pristine CNT bundle by 0.74 eV, and a third energy minimum with a value of 2.64 eV existed at the midpoint of the central axis of the nanotube. Thus, it would be more difficult to remove Li ions from the nanotube interior after surface functionalization. The barrier for lithium diffusion in the interior of the nanotube is greatly decreased because of the surface functional groups. Based on these results, we would suggest to "damage" the nanotube by introducing defects at its sidewall in order to improve not only the capacity of surface functionalized CNTs but also the efficiency of lithium intercalation and deintercalation processes. Our results presented here are helpful in understanding the mechanism of lithium intercalation into nanotube bundles, which may potentially be applied in the development of CNT based electrodes. PMID:24963820

Xiao, Shiyan; Zhu, Hong; Wang, Lei; Chen, Liping; Liang, Haojun

2014-08-14

371

Manganese peroxidase degrades pristine but not surface-oxidized (carboxylated) single-walled carbon nanotubes.  

PubMed

The transformation of engineered nanomaterials in the environment can significantly affect their transport, fate, bioavailability, and toxicity. Little is known about the biotransformation potential of single-walled carbon nanotubes (SWNTs). In this study, we compared the enzymatic transformation of SWNTs and oxidized (carboxylated) SWNTs (O-SWNTs) using three ligninolytic enzymes: lignin peroxidase, manganese peroxidase (MnP), and laccase. Only MnP was capable of transforming SWNTs, as determined by Raman spectroscopy, near-infrared spectroscopy, and transmission electron microscopy. Interestingly, MnP degraded SWNTs but not O-SWNTs. The recalcitrance of O-SWNTs to enzymatic transformation is likely attributable to the binding of Mn2+ by their surface carboxyl groups at the enzyme binding site, which inhibits critical steps in the MnP catalytic cycle (i.e., Mn2+ oxidation and Mn3+ dissociation from the enzyme). Our results suggest that oxygen-containing surface functionalities do not necessarily facilitate the biodegradation of carbonaceous nanomaterials, as is commonly assumed. PMID:24988479

Zhang, Chengdong; Chen, Wei; Alvarez, Pedro J J

2014-07-15

372

Novel 5-substituted benzyloxy-2-arylbenzofuran-3-carboxylic acids as calcium activated chloride channel inhibitors.  

PubMed

Transmembrane protein 16A (TMEM16A) channels are recently discovered membrane proteins that functions as a calcium activated chloride channel (CaCC). CaCCs are major regulators of various physiological processes, such as sensory transduction, epithelial secretion, smooth muscle contraction and oocyte fertilization. Thirty novel 5-substituted benzyloxy-2-arylbenzofuran-3-carboxylic acids (B01-B30) were synthesized and evaluated for their TMEM16A inhibitory activity by using short circuit current measurements in Fischer rat thyroid (FRT) cells expressing human TMEM16A. IC(50) values were calculated using YFP fluorescence plate reader assay. Final compounds, having free carboxylic group displayed significant inhibition. Eight of the novel compounds B02, B13, B21, B23, B25, B27, B28, B29 exhibit excellent CaCCs inhibition with IC(50) value <6 ?M, with compound B25 exhibiting the lowest IC(50) value of 2.8 ± 1.3 ?M. None of the tested ester analogs of final benzofuran derivatives displayed TMEM16A/CaCCs inhibition. PMID:22739085

Kumar, Satish; Namkung, Wan; Verkman, A S; Sharma, Pawan K

2012-07-15

373

The bacteriorhodopsin carboxyl-terminus contributes to proton recruitment and protein stability.  

PubMed

We examined functional and structural roles for the bacteriorhodopsin (bR) carboxyl-terminus. The extramembranous and intracellular carboxyl-terminus was deleted by insertion of premature translation stop codons. Deletion of the carboxyl-terminus had no effect on purple membrane (PM) lattice dimensions, sheet size, or the electrogenic environment of the ground-state chromophore. Removal of the distal half of the carboxyl-terminus had no effect on light-activated proton pumping, however, truncation of the entire carboxyl-terminus accelerated the rates of M-state decay and proton uptake approximately 3.7-fold and severely distorted the kinetics of proton uptake. Differential scanning calorimetry (DSC) and SDS denaturation demonstrated that removal of the carboxyl-terminus decreased protein stability. The DSC melting temperature was lowered by 6 degrees C and the calorimetric enthalpy reduced by 50% following removal of the carboxyl-terminus. Over the time range of milliseconds to hours at least 3 phases were required to describe the SDS denaturation kinetics for each bR construction. The fastest phases were indistinguishable for all bR's, and reflected PM solubilization. At pH 7.4, 20 degrees C, and in 0.3% SDS (w/v) the half-times of bR denaturation were 19.2 min for the wild-type, 12.0 min for the half-truncation and 3.6 min for the full-truncation. Taken together the results of this study suggest that the bR ground state exhibits two "domains" of stability: (1) a core chromophore binding pocket domain that is insensitive to carboxyl-terminal interactions and (2) the surrounding helical bundle whose contributions to protein stability and proton pumping are influenced by long-range interactions with the extramembranous carboxyl-terminus. PMID:19140737

Turner, George J; Chittiboyina, Shirisha; Pohren, Lauren; Hines, Kirk G; Correia, John J; Mitchell, Drake C

2009-02-10

374

Sodium-sulfate/carboxylate cotransporters (SLC13).  

PubMed

The SLC13 gene family is comprised of five sequence related proteins that are found in animals, plants, yeast and bacteria. Proteins encoded by the SLC13 genes are divided into the following two groups of transporters with distinct anion specificities: the Na(+)-sulfate (NaS) cotransporters and the Na(+)-carboxylate (NaC) cotransporters. Members of this gene family (in ascending order) are: SLC13A1 (NaS1), SLC13A2 (NaC1), SLC13A3 (NaC3), SLC13A4 (NaS2) and SLC13A5 (NaC2). SLC13 proteins encode plasma membrane polypeptides with 8-13 putative transmembrane domains, and are expressed in a variety of tissues. They are all Na(+)-coupled symporters with strong cation preference for Na(+), and insensitive to the stilbene 4, 4'-diisothiocyanatostilbene-2, 2'-disulphonic acid (DIDS). Their Na(+):anion coupling ratio is 3:1, indicative of electrogenic properties. They have a substrate preference for divalent anions, which include tetra-oxyanions for the NaS cotransporters or Krebs cycle intermediates (including mono-, di- and tricarboxylates) for the NaC cotransporters. This review will describe the molecular and cellular mechanisms underlying the biochemical, physiological and structural properties of the SLC13 gene family. PMID:23177988

Markovich, Daniel

2012-01-01

375

Impact of dendrimer surface functional groups on the release of doxorubicin from dendrimer carriers.  

PubMed

Generation 5 (G5) poly(amidoamine) dendrimers with acetyl (G5.NHAc), glycidol hydroxyl (G5.NGlyOH), and succinamic acid (G5.SAH) terminal groups were used to physically encapsulate an anticancer drug doxorubicin (DOX). Both UV-vis spectroscopy and multiple NMR techniques including one-dimensional NMR and two-dimensional NMR were applied to investigate the interactions between different dendrimers and DOX. The influence of the surface functional groups of G5 dendrimers on the DOX encapsulation, release kinetics, and cancer cell inhibition effect was investigated. We show that all three types of dendrimers are able to effectively encapsulate DOX and display therapeutic inhibition effect to cancer cells, which is solely associated with the loaded DOX. The relatively stronger interactions of G5.NHAc or G5.NGlyOH dendrimers with DOX than that of G5.SAH dendrimers with DOX demonstrated by NMR techniques correlate well with the slow release rate of DOX from G5.NHAc/DOX or G5.NGlyOH/DOX complexes. In contrast, the demonstrated weak interaction between G5.SAH and DOX causes a fast release of DOX, suggesting that the G5.SAH/DOX complex may not be a proper option for further in vivo research. Our findings suggest that the dendrimer surface functional groups are crucial for further design of multifunctional dendrimer-based drug delivery systems for various biomedical applications. PMID:24467521

Zhang, Mengen; Guo, Rui; Kéri, Mónika; Bányai, István; Zheng, Yun; Cao, Mian; Cao, Xueyan; Shi, Xiangyang

2014-02-13

376

Stochastic geometric network models for groups of functional and structural connectomes.  

PubMed

Structural and functional connectomes are emerging as important instruments in the study of normal brain function and in the development of new biomarkers for a variety of brain disorders. In contrast to single-network studies that presently dominate the (non-connectome) network literature, connectome analyses typically examine groups of empirical networks and then compare these against standard (stochastic) network models. The current practice in connectome studies is to employ stochastic network models derived from social science and engineering contexts as the basis for the comparison. However, these are not necessarily best suited for the analysis of connectomes, which often contain groups of very closely related networks, such as occurs with a set of controls or a set of patients with a specific disorder. This paper studies important extensions of standard stochastic models that make them better adapted for analysis of connectomes, and develops new statistical fitting methodologies that account for inter-subject variations. The extensions explicitly incorporate geometric information about a network based on distances and inter/intra hemispherical asymmetries (to supplement ordinary degree-distribution information), and utilize a stochastic choice of network density levels (for fixed threshold networks) to better capture the variance in average connectivity among subjects. The new statistical tools introduced here allow one to compare groups of networks by matching both their average characteristics and the variations among them. A notable finding is that connectomes have high "smallworldness" beyond that arising from geometric and degree considerations alone. PMID:25067815

Friedman, Eric J; Landsberg, Adam S; Owen, Julia P; Li, Yi-Ou; Mukherjee, Pratik

2014-11-01

377

Carboxylic acid accelerated formation of diesters  

DOEpatents

This invention pertains to accelerating the rate of formation of 1,1-dicarboxylic esters from the reaction of an aldehyde with a carboxylic acid anhydride or a ketene in the presence of a non-iodide containing a strong Bronsted acid catalyst by the addition of a carboxylic acid at about one bar pressure and between about 0.degree. and 80.degree. C. in the substantial absence of a hydrogenation or carbonylation catalyst.

Tustin, Gerald Charles (Kingsport, TN); Dickson, Todd Jay (Kingsport, TN)

1998-01-01

378

pH feedback and phenotypic diversity within bacterial functional groups of the human gut.  

PubMed

Microbial diversity in the human colon is very high with apparently large functional redundancy such that within each bacterial functional group there are many coexisting strains. Modelling this mathematically is problematic since strains within a functional group are often competing for the same limited number of resources and therefore competitive exclusion theory predicts a loss of diversity over time. Here we investigate, through computer simulation, a fluctuation dependent mechanism for the promotion of diversity. A variable pH environment caused by acidic by-products of bacterial growth on a fluctuating substrate coupled with small differences in acid tolerance between strains promotes diversity under both equilibrium and far-from-equilibrium conditions. Under equilibrium conditions pH fluctuations and relative nonlinearity in pH limitation among strains combine to prevent complete competitive exclusion. Under far-from-equilibrium conditions, loss of diversity through extinctions is made more difficult because pH cycling leads to fluctuations in the competitive ranking of strains, thereby helping to equalise fitness. We assume a trade-off between acid tolerance and maximum growth rate so that our microbial system consists of strains ranging from specialists to generalists. By altering the magnitude of the effect of the system on its pH environment (e.g. the buffering capacity of the colon) and the pattern of incoming resource we explore the conditions that promote diversity. PMID:24211524

Kettle, Helen; Donnelly, Ruairi; Flint, Harry J; Marion, Glenn

2014-02-01

379

A finite-frequency functional renormalization group approach to the single impurity Anderson model  

NASA Astrophysics Data System (ADS)

We use the Matsubara functional renormalization group (FRG) to describe electronic correlations within the single impurity Anderson model. In contrast to standard FRG calculations, we account for the frequency dependence of the two-particle vertex in order to address finite-energy properties (e.g, spectral functions). By comparing with data obtained from the numerical renormalization group (NRG) framework, the FRG approximation is shown to work well for arbitrary parameters (particularly finite temperatures) provided that the electron-electron interaction U is not too large. We demonstrate that aspects of (large U) Kondo physics which are described well by a simpler frequency-independent truncation scheme are no longer captured by the 'higher-order' frequency-dependent approximation. In contrast, at small to intermediate U the results obtained by the more elaborate scheme agree better with NRG data. We suggest to parametrize the two-particle vertex not by three independent energy variables but by introducing three functions each of a single frequency. This considerably reduces the numerical effort to integrate the FRG flow equations.

Karrasch, C.; Hedden, R.; Peters, R.; Pruschke, Th; Schönhammer, K.; Meden, V.

2008-08-01

380

Telomere length kinetics assay (TELKA) sorts the telomere length maintenance (tlm) mutants into functional groups  

PubMed Central

Genome-wide systematic screens in yeast have uncovered a large gene network (the telomere length maintenance network or TLM), encompassing more than 400 genes, which acts coordinatively to maintain telomere length. Identifying the genes was an important first stage; the next challenge is to decipher their mechanism of action and to organize then into functional groups or pathways. Here we present a new telomere-length measuring program, TelQuant, and a novel assay, telomere length kinetics assay, and use them to organize tlm mutants into functional classes. Our results show that a mutant defective for the relatively unknown MET7 gene has the same telomeric kinetics as mutants defective for the ribonucleotide reductase subunit Rnr1, in charge of the limiting step in dNTP synthesis, or for the Ku heterodimer, a well-established telomere complex. We confirm the epistatic relationship between the mutants and show that physical interactions exist between Rnr1 and Met7. We also show that Met7 and the Ku heterodimer affect dNTP formation, and play a role in non-homologous end joining. Thus, our telomere kinetics assay uncovers new functional groups, as well as complex genetic interactions between tlm mutants. PMID:24728996

Rubinstein, Linda; Ungar, Lior; Harari, Yaniv; Babin, Vera; Ben-Aroya, Shay; Merenyi, Gabor; Marjavaara, Lisette; Chabes, Andrei; Kupiec, Martin

2014-01-01

381

Surface and aqueous properties of anionic gemini surfactants having dialkyl amide, carboxyl, and carboxylate groups  

Microsoft Academic Search

A systematic study of the equilibrium surface properties (in water and in the presence of 10?2 M NaCl) of a novel series of anionic gemini surfactants, (CH2)2[N(COCnH2n+1)CH(COOH)CH2COOH]·2NaOH (GA), where (n+1)=8, 10, 12, 14, and 16, was investigated. The responses of humans to closed patch tests with\\u000a (CH2)2[N(COC11H23)CH(COOH)?CH2COOH]2·2NaOH (GA-12) were also investigated. Premicellar self-aggregation (both in water and 10?2 M NaCl)

Kazuyuki Tsubone; Tomoyasu Ogawa; Kunio Mimura

2003-01-01

382

Population Group Differences in Cognitive Functioning in a National Sample of Israelis Fifty Years and Older  

PubMed Central

The study evaluates population group differences of Israelis 50 years and older in cognitive functioning. Groups were defined based on year of arrival and preferred language (e.g., veteran Jewish Israelis- n= 1,974; new immigrants from the former Soviet Union- n=187; and Arab Israelis- n=331). Using a cross-sectional analysis of the first wave of SHARE-Israel, we evaluate a representative sample of Israelis over the age of 50 stratified by population group. Cognitive screens assessed include time orientation, arithmetic, verbal learning, verbal recall, word fluency and subjective reading and writing abilities. To evaluate population group differences, we conducted multivariate analyses of each of the cognitive domains, controlling for age, gender, education, household income, and ever smoking. Relative to veteran Jewish Israelis, new immigrants from the former Soviet Unions were more likely to rate their reading ability as impaired (OR=2.47, 95% CI: 1.32-4.60). In addition, there was a significant interaction between population group and education on the arithmetic task (OR=.69, 95% CI: .58-.83). New immigrants from the former Soviet Union were less impaired than the other two groups especially at lower levels of education. New immigrants were more impaired on the verbal learning task (OR=2.65, 95% CI: 1.38-5.07). On the other hand, relative to veteran Israeli-Jews, Israeli-Arabs were significantly less likely to have impaired performance on the verbal recall task (OR=.31, 95% CI=.16-.60). The results demonstrate that overall, new immigrant from the Former Soviet Union exhibit greater difficulties on the verbal tasks, but not on the arithmetic task. The findings from the current study are somewhat in contrast with the international literature which tends to show that the majority culture outperforms relative to ethnic minorities. PMID:23308032

Ayalon, Liat; Heinik, Jeremia; Litwin, Howard

2012-01-01

383

Zinc carboxylating: a new conversion treatment of zinc  

Microsoft Academic Search

This study is devoted to a new surface treatment of zinc, called “carboxylating”, which could be an environmentally friendly alternative to the usual conversion treatments. Carboxylating requires use of both n-alkyl carboxylic acid and peroxoborate as oxidizing agent, in a water–ethanol mixture. As in the phosphating process, the carboxylating one is carried out in four steps: the activation step, oxidation

J. Peultier; E. Rocca; J. Steinmetz

2003-01-01

384

Social functions of individual vasopressin-oxytocin cell groups in vertebrates: what do we really know?  

PubMed

Vasopressin-oxytocin (VP-OT) nonapeptides modulate numerous social and stress-related behaviors, yet these peptides are made in multiple nuclei and brain regions (e.g., >20 in some mammals), and VP-OT cells in these areas often exhibit overlapping axonal projections. Furthermore, the magnocellular cell groups release peptide volumetrically from dendrites and soma, which gives rise to paracrine modulation in distal brain areas. Nonapeptide receptors also tend to be promiscuous. Hence, behavioral effects that are mediated by any given receptor type (e.g., the OT receptor) in a target brain region cannot be conclusively attributed to either VP or OT, nor to a specific cell group. We here review what is actually known about the social behavior functions of nonapeptide cell groups, with a focus on aggression, affiliation, bonding, social stress, and parental behavior, and discuss recent studies that demonstrate a diversity of sex-specific contributions of VP-OT cell groups to gregariousness and pair bonding. PMID:24813923

Kelly, Aubrey M; Goodson, James L

2014-10-01

385

Distinct roles of group I mGlu receptors in striatal function.  

PubMed

In the recent past, evidence accumulated in favour of a central role of group I metabotropic glutamate (mGlu) receptors, mGlu1 and mGlu5, in the modulation of cell excitability both of striatal medium spiny projection neurons (MSNs) and interneuronal population. Electrophysiological and pharmacological studies have clearly shown that activation of mGlu1 and mGlu5 receptors exerts distinct actions, depending on the neuronal subtype involved. MGlu5 receptor activation mediates the potentiation of NMDA responses in MSNs, and underlies the retrograde inhibitory signaling by endocannabinoids at corticostriatal synapses. Conversely, both group I mGlu receptors are involved in long-term synaptic plasticity of MSNs. Likewise, either mGlu1 or mGlu5 receptors are engaged in shaping the excitability of large cholinergic interneurons, playing different roles in the membrane responses. Differently, although GABAergic parvalbumin-positive, fast-spiking interneurons have been shown to express both group I receptors, only mGlu1 receptor seems to mediate membrane and synaptic responses. This review provides a brief survey of the cellular and synaptic actions of group I mGlu receptors, and discusses the potential relevance of these findings in neostriatal function and motor control. PMID:18602651

Bonsi, P; Platania, P; Martella, G; Madeo, G; Vita, D; Tassone, A; Bernardi, G; Pisani, A

2008-09-01

386

Hirshfeld partitioning of the electron density: atomic dipoles and their relation with functional group properties.  

PubMed

Atomic dipole moments, derived within the Hirshfeld partitioning of the molecular electron density, have been studied for compounds of the type H-X and Cl-X, for a series of functional groups X frequently encountered in organic molecules. In the case of the H-X compounds, the component of the atomic dipole moment on H along the axis connecting H with the central atom in X is found to be linearly correlated with the electronegativity of X, the hardness of X playing no significant role. In the case of the Cl-X compounds, the situation is less clear. However, evidence seems to point to the conclusion that for these compounds, also the group hardness plays an important role. PMID:12594789

De Proft, F; Vivas-Reyes, R; Peeters, A; Van Alsenoy, C; Geerlings, P

2003-03-01

387

Preparation of magnetic latexes functionalized with chloromethyl groups via emulsifier-free miniemulsion polymerization  

NASA Astrophysics Data System (ADS)

Functionalized crosslinked polystyrene-co-divinylbenzene-co-chloromethylstyrene magnetic latex particles were prepared via emulsifier-free miniemulsion polymerization using 2, 2' azobis (2-amidinopropane) dihydrochloride (V-50) as an initiator and in the presence of magnetite nanoparticles in the monomers. Transmission electron microscopy (TEM) proved the presence of magnetite nanoparticles in polymer particles. Differential scanning calorimetery (DSC) analysis of the product showed an exothermic signal due to crosslinking of chains through electrophilic aromatic substitution of phenyl groups with chloromethyl groups in the presence of the dispersed Fe 3O 4 as Lewis acid. This was proven by thermogravimetric analysis (TGA) via the loss of gaseous HCl. The results were also compared with those of magnetite-free miniemulsion polymerization using V-50.

Faridi-Majidi, Reza; Sharifi-Sanjani, Naser

2007-04-01

388

Algorithmic derivation of functional renormalization group equations and Dyson-Schwinger equations  

NASA Astrophysics Data System (ADS)

We present the Mathematica application DoFun which allows to derive Dyson-Schwinger equations and renormalization group flow equations for n-point functions in a simple manner. DoFun offers several tools which considerably simplify the derivation of these equations from a given physical action. We discuss the application of DoFun by means of two different types of quantum field theories, namely a bosonic O(N) theory and the Gross-Neveu model. Program summaryProgram title:DoFun Catalogue identifier: AELN_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AELN_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 35 506 No. of bytes in distributed program, including test data, etc.: 571 837 Distribution format: tar.gz Programming language: Mathematica 7 and higher Computer: PCs and workstations Operating system: All on which Mathematica is available (Windows, Unix, MacOS) Classification: 11.1, 11.4, 11.5, 11.6 Nature of problem: Derivation of functional renormalization group equations and Dyson-Schwinger equations from the action of a given theory. Solution method: Implementation of an algorithm to derive functional renormalization group and Dyson-Schwinger equations. Unusual features: The results can be plotted as Feynman diagrams in Mathematica. The output is compatible with the syntax of many other programs and is therefore suitable for further (algebraic) computations. Running time: Seconds to minutes

Huber, Markus Q.; Braun, Jens

2012-06-01

389

Pollinators of the Rocky Mountain columbine: temporal variation, functional groups and associations with floral traits  

PubMed Central

Background and Aims Pollinators together with other biotic and some abiotic factors can select for floral traits. However, variation in pollinator abundance over time and space can weaken such selection. In the present study, the variation in pollinator abundance over time and space was examined in populations of the Rocky Mountain columbine. The variation in three floral traits is described and correlations between pollinator type, functional pollinator groups or altitude and floral traits are examined. Methods Pollinator observations took place in six Aquilegia coerulea populations over 1–4 years and spur length, flower colour and sepal length were measured in 12 populations. Pollinator abundance, measured as visits per flower per hour, was compared among populations and years. Pollinators were grouped into two functional groups: pollen or nectar collectors. The following associations were examined: annual presence of hawkmoths and whiter flowers with longer spurs; the presence of Sphinx vashti and longer spurs; and higher altitudes and whiter flowers. The study looked at whether an increase in the proportion of hawkmoths in a population was associated with whiter and larger flowers with longer spurs. Key Results The abundance of different pollinator groups varied over time and space. Floral traits varied among populations. Higher altitude was correlated with bluer flowers. Whiter flowers were associated with the annual presence of hawkmoths. Populations visited by Sphinx vashti had longer spurs than populations visited only by Hyles lineata. Populations with greater percentage of nectar-collecting pollinators did not have whiter, larger flowers with longer spurs. Conclusions Despite the large variation in pollinator abundance over time and space, one species of bumble-bee or hawkmoth tended to predominate in each population each year. Future studies of Aquilegia coerulea should examine the specific influences of pollinators and the environment on flower colour and of hawkmoth species on spur length. PMID:19414518

Brunet, Johanne

2009-01-01

390

Correlation functions in the Non Perturbative Renormalization Group and field expansion  

NASA Astrophysics Data System (ADS)

The usual procedure of including a finite number of vertices in Non Perturbative Renormalization Group equations in order to obtain n-point correlation functions at finite momenta is analyzed. This is done by exploiting a general method recently introduced which includes simultaneously all vertices although approximating their momentum dependence. The study is performed using the self-energy of the tridimensional scalar model at criticality. At least in this example, low order truncations miss quantities as the critical exponent ? by as much as 60%. However, if one goes to high order truncations the procedure seems to converge rapidly.

Guerra, D.; Méndez-Galain, R.; Wschebor, N.

2007-10-01

391

Influence on hydrophobicity of silicone rubber surface by introducing fluorocarbon functional groups  

NASA Astrophysics Data System (ADS)

Hydrophobic modification on surface of silicone rubber (SIR) by CF4 radio frequency inductively coupled plasma is discussed. Static contact angle, atomic force microscopy and X-ray photoelectron spectroscopy were used in characterizing the hydrophobic property, surface appearance and chemical composition of the modified SIR. The results show that the improvement of surface hydrophobic property on modified SIR is attributed to the introduction of fluorocarbon functional groups (C-CF n , n = 1, 2, 3) and fluosilicic structures (Si-F and Si-F2) during the treatment.

Gao, Song-Hua; Gao, Li-Hua

2014-09-01

392

Functional Gene Group Analysis Indicates No Role for Heterotrimeric G Proteins in Cognitive Ability  

PubMed Central

Previous functional gene group analyses implicated common single nucleotide polymorphisms (SNPs) in heterotrimeric G protein coding genes as being associated with differences in human intelligence. Here, we sought to replicate this finding using five independent cohorts of older adults including current IQ and childhood IQ, and using both gene- and SNP-based analytic strategies. No significant associations were found between variation in heterotrimeric G protein genes and intelligence in any cohort at either of the two time points. These results indicate that, whereas G protein systems are important in cognition, common genetic variation in these genes is unlikely to be a substantial influence on human intelligence differences. PMID:24626473

Davies, Gail; Liewald, David Cherry McLachlan; Payton, Anthony; Craig, Leone C. A.; Whalley, Lawrence J.; Horan, Mike; Ollier, William; Starr, John M.; Pendleton, Neil; Posthuma, Danielle; Bates, Timothy C.; Deary, Ian J.

2014-01-01

393

Functional renormalization group approach to conventional theory of superfluidity and beyond  

E-print Network

Fermionic functional renormalization group (FRG) is applied to describe the superfluid phase transition of the two-component fermionic system with attractive contact interaction. Connection between the fermionic FRG approach and the Bardeen-Cooper-Schrieffer (BCS) theory with its Gorkov and Melik-Barkhudarov (GMB) correction is made clear, and the FRG flow of the fermion self-energy is also studied to go beyond the BCS+GMB theory. The superfluid transition temperature and the associated chemical potential are calculated in the region of the negative scattering length using fermionic FRG.

Yuya Tanizaki; Gergely Fej?s; Tetsuo Hatsuda

2013-11-17

394

Nonlinear optical properties of copolyesters containing azobenzene functionality and chiral groups  

NASA Astrophysics Data System (ADS)

The synthesis and characterization of a series of new copolyesters containing azo mesogenic groups and chiral building blocks are reported. The polyesters were prepared by the condensation of bis(4-hydroxyphenyl)azo 2,2'- dinitro(3,5,3',5'-tetramethyl)diphenylmethane, terephthaloyl chloride and 1,4;3,6-dianhydro-D-sorbitol. The polysters showed higher thermal and photochemical stability with high values of glass transition temperature. DSC studies showed liquid crystalline behavior over a wide range. High values of second order nonlinear susceptibilities were recorded as a function of the molar proportion of isosorbide units.

Bahulayan, D.; Thomas, Vinoy; Sreekumar, K.

1998-04-01

395

Effect of functional end groups of silane self assembled monolayer surfaces on apatite formation, fibronectin adsorption and osteoblast cell function  

PubMed Central

Bioactive glass (BG) can directly bond to living bone without fibrous tissue encapsulation. Key mechanistic steps of BG’s activity are attributed to calcium phosphate formation, surface hydroxylation and fibronectin (FN) adsorption. In the present study, self-assembled monolayers (SAMs) of alkanesilanes with different surface chemistry (OH, NH2, and COOH) were used as a model system to mimic BG’s surface activity. Calcium phosphate (Ca-P) was formed on SAMs by immersion in a solution which simulates the electrolyte content of physiological fluids. FN adsorption kinetics and monolayer coverage was determined on SAMs with or without Ca-P coating. The surface roughness was also examined on these substrates before and after FN adsorption. The effects of FN-adsorbed, Ca-P coated SAMs on the function of MC3T3-E1 were evaluated by cell growth, expression of alkaline phosphatase activity, and actin cytoskeleton formation. We demonstrate that, although the FN monolayer coverage and the rms roughness are similar on ?OH and ?COOH terminated SAMs with or without Ca-P coating, higher levels of ALP activity, more actin cytoskeleton formation and more cell growth are obtained on ?OH and ?COOH terminated SAMs with Ca-P coating. In addition, although the FN monolayer coverage is higher on Ca-P coated ?NH2 terminated SAMs and SiOx surfaces, higher levels of ALP activity and more cell growth are obtained on Ca-P coated ?OH and ?COOH terminated SAMs. Thus with same Ca-P coatings, different surface functional groups have different effects on the function of osteoblastic cells. These findings represent new insights into the mechanism of bioactivity of BG and, thereby, may lead to designing superior constructs for bone grafting. PMID:19012271

Toworfe, G.K.; Bhattacharyya, S.; Composto, R.J.; Adams, C.S.; Shapiro, I.M.; Ducheyne, P.

2008-01-01

396

Truncation Effects in the Functional Renormalization Group Study of Spontaneous Symmetry Breaking  

E-print Network

We study the occurrence of spontaneous symmetry breaking (SSB) for O(N) models using functional renormalization group techniques. We show that even the local potential approximation (LPA) when treated exactly is sufficient to give qualitatively correct results for systems with continuous symmetry, in agreement with the Mermin-Wagner theorem and its extension to systems with fractional dimensions. For general N (including the Ising model N=1) we study the solutions of the LPA equations for various truncations using a finite number of terms (and different regulators), showing that SSB always occurs even where it should not. The SSB is signalled by Wilson-Fisher fixed points which for any truncation are shown to stay on the line defined by vanishing mass beta functions.

Defenu, N; Marian, I G; Nandori, I; Trombettoni, A

2014-01-01

397

Stereoselective palladium-catalyzed carbocyclization of allenic allylic carboxylates.  

PubMed

Palladium(0)-catalyzed reaction of allene-substituted allylic carboxylates 3-8 employing 2-5 mol % of Pd(dba)(2) in refluxing toluene leads to the carbocyclization and elimination of carboxylic acid to give bicyclo[4.3.0]nonadiene and bicyclo[5.3.0]decadiene derivatives (12-17). The carbon-carbon bond formation is stereospecific, occurring syn with respect to the leaving group. Addition of maleic anhydride as a ligand to the above-mentioned procedures changed the outcome of the reaction, and under these conditions 3-5 afforded cycloisomerized products 21-23. The experimental results are consistent with a mechanism involving oxidative addition of the allylic carboxylate to Pd(0) to give an electron-deficient (pi-allyl)palladium intermediate, followed by nucleophilic attack by the allene on the face of the pi-allyl opposite to that of the palladium atom. Furthermore, it was found that the Pd(dba)(2)-catalyzed cyclization of the trans-cycloheptene derivative (trans-8) can be directed to give either the trans-fused (trans-17) or the cis-fused (cis-17) ring system by altering the solvent. The former reaction proceeds via a nucleophilic trans-allene attack on the (pi-allyl)palladium intermediate, whereas the latter involves a syn-allene insertion into the allyl-Pd bond of the same intermediate. The products from the carbocylization undergo stereoselective Diels-Alder reactions to give stereodefined polycyclic systems in high yields. PMID:14611252

Franzén, Johan; Löfstedt, Joakim; Falk, Jennica; Bäckvall, Jan-E

2003-11-19

398

Nitrogen niches revealed through species and functional group removal in a boreal shrub community.  

PubMed

Most theories attempting to explain the coexistence of species in local communities make fundamental assumptions regarding whether neighbors exhibit competitive, neutral, or positive resource-use interactions; however, few long-term data from naturally assembled plant communities exist to test these assumptions. We utilized a 13-year experiment consisting of factorial removal of three shrub species (Vaccinium myrtillus, V. vitis-idaea, and Empetrum hermaphroditum) and factorial removal of two functional groups (tree roots and feather mosses) to assess how neighbors affect N acquisition and growth of each of the three shrub species. The removal plots were established on each of 30 lake islands in northern Sweden that form a natural gradient of resource availability. We tested the hypotheses that: (1) the presence of functionally similar neighbors would reduce shrub N acquisition through competition for a shared N resource; (2) the removal of functional groups would affect shrub N acquisition by altering the breadth of their niches; and (3) soil fertility would influence the effects of neighbor removals. We found that the removal of functionally similar neighbors (i.e., other shrub species) usually resulted in higher biomass and biomass N, with the strength of these effects varying strongly with site fertility. Shrub species removals never resulted in altered stable N isotope ratios (delta(15)N), suggesting that the niche breadth of the three shrubs was unaffected by the presence of neighboring shrub species. In the functional group removal experiment, we found positive effects of feather moss removal on V. myrtillus biomass and biomass N, and negative effects on E. hermaphrotium N concentration and V. vitis-idaea biomass and biomass N. Tree root removal also caused a significant shift in foliar delta(15)N of V. myrtillus and altered the delta(15)N, biomass, and biomass N of E. hermaphroditum. Collectively, these results show that the resource acquisition and niche breadth of the three shrub species are often affected by neighbors, and further that both the identity of neighbors and site fertility strongly determine whether these interactions are positive, negative, or neutral. These findings have implications for understanding species coexistence and the reciprocal relationships between productivity and species diversity in this ecosystem. PMID:22919915

Gundale, Michael J; Hyodo, Fujio; Nilsson, Marie-Charlotte; Wardle, David A

2012-07-01

399

Chemical reactivity of the functional groups of insulin. Concentration-dependence studies.  

PubMed Central

A modification to the competitive labelling procedure of Duggleby and Kaplan [(1975) Biochemistry 14, 5168-5175] was used to study the reactivity of the N-termini, lysine, histidine and tyrosine groups of insulin over the concentration range 1 X 10(-3)-1 X 10(-7)M. Reactions were carried out with acetic anhydride and 1-fluoro-2,4-dinitrobenzene in 0.1 M-KCl at 37 degrees C using Pyrex glass, Tefzel and polystyrene reaction vessels. At high concentrations all groups had either normal or enhanced reactivity but at high dilution the reactivities of all functional groups became negligible. This behaviour is attributed to the adsorption of insulin to the reaction vessels. The histidine residues show a large decrease in reactivity in all reaction vessels in the concentration range 1 X 10(-3)-1 X 10(-5)M where there are no adsorption effects and where the reactivities of all other functional groups are independent of concentration. With polystyrene, where adsorption effects become significant only below 1 X 10(-6)M, the reactivity of the phenylalanine N-terminus also shows a decrease in reactivity between 1 X 10(-5) and 1 X 10(-6)M. In 1 M-KCl insulin does not absorb to Pyrex glass and under these conditions the histidine reactivity is concentration-dependent from 1 X 10(-3) to 5 X 10(-6)M and the B1 phenylalanine alpha-amino and the B29 lysine epsilon-amino reactivities from 5 X 10(-6) to 1 X 10(-7)M, whereas the reactivities of all other groups are constant. These alterations in reactivity on dilution are attributed to disruption of dimer-dimer interactions for histidine and to monomer-monomer interactions for the phenylalanine and lysine amino groups. It is concluded that the monomeric unit of insulin has essentially the same conformation in its free and associated states. PMID:6365082

Kaplan, H; Hefford, M A; Chan, A M; Oda, G

1984-01-01

400

A highly specific tetrazole-based chemosensor for fluoride ion: A new sensing functional group based on intramolecular proton transfer  

NASA Astrophysics Data System (ADS)

A simple but highly selective colorimetric and fluorescent chemosensor for fluoride ion has been prepared based on coumarin chromophore and 1H-tetrazole. Tetrazole functional group provided a novel sensing functional group containing the ESIPT structure for designing fluoride chemosensor.

Li, Ju-Ying; Zhou, Xin-Qi; Zhou, Yi; Fang, Yuan; Yao, Cheng

2013-02-01

401

Performing Grouping and Aggregate Functions in XML Huayu Wu, Tok Wang Ling, Liang Xu, and Zhifeng Bao  

E-print Network

in a query, how to efficiently compute grouping and aggregate functions over XML document is not well studiedPerforming Grouping and Aggregate Functions in XML Queries Huayu Wu, Tok Wang Ling, Liang Xu yet. In this paper, we extend our previous XML query processing algo- rithm, VERT, to efficiently

Ling, Tok Wang

402

THE DARK MATTER HALO CONCENTRATION AND STELLAR INITIAL MASS FUNCTION OF A CASSOWARY GROUP  

SciTech Connect

We exploit the group environment of the CAmbridge Sloan Survey Of Wide ARcs in the skY z = 0.3 lens J2158+0257 to measure the group dynamical mass as a complement to the central dynamical and lensing mass constraints. Follow-up spectroscopy of candidate group members is performed using VLT/FORS2. From the resulting N = 21 confirmed members, we measure the group dynamical mass by calibrating an analytic tracer mass estimator with cosmological simulations. The luminosity-weighted line-of-sight velocity dispersion and the Einstein radius of the lens are used as mass probes in the inner regions of the galaxy. Combining these three observational probes allows us to independently constrain the mass and concentration of the dark matter halo, in addition to the total stellar mass of the central galaxy. We find a dark matter halo in remarkably good agreement with simulations (log{sub 10} M{sub 200}/M{sub Sun} = 14.2 {+-} 0.2, c{sub 200}= 4.4{sup +1.6}{sub -1.4}) and a stellar mass-to-light ratio which favors a Salpeter initial mass function ((M/L)* = 5.7 {+-} 1.2). Our measurement of a normal halo concentration suggests that there is no discrepancy between simulations and observations at the group mass scale. This is in contrast to the cluster mass scale for which a number of studies have claimed over-concentrated halos. While the halo mass is robustly determined, and the halo concentration is not significantly affected by systematics, the resulting stellar mass-to-light ratio is sensitive to the choice of stellar parameters, such as density profile and velocity anisotropy.

Deason, A. J. [Department of Astronomy and Astrophysics, University of California Santa Cruz, Santa Cruz, CA 95064 (United States); Auger, M. W.; Belokurov, V.; Evans, N. W., E-mail: alis@ucolick.org [Institute of Astronomy, Madingley Rd, Cambridge, CB3 0HA (United Kingdom)

2013-08-10

403

In situ synchrotron IR study relating temperature and heating rate to surface functional group changes in biomass.  

PubMed

Three types of woody biomass were investigated under pyrolysis condition to observe the change in the surface functional groups by Fourier transform infrared (FTIR) technique with increasing temperature under two different (5 and 150°C/min) heating rates. The experiments were carried out in situ in the infrared microscopy beamline (IRM) of the Australian Synchrotron. The capability of the beamline made it possible to focus on single particles to obtain low noise measurements without mixing with KBr. At lower heating rate, the surface functional groups were completely removed by 550°C. In case of higher heating rate, a delay was observed in losing the functional groups. Even at a high temperature, significant number of functional groups was retained after the higher heating rate experiments. This implies that at considerably high heating rates typical of industrial reactors, more functional groups will remain on the surface. PMID:24189382

Kirtania, Kawnish; Tanner, Joanne; Kabir, Kazi Bayzid; Rajendran, Sharmen; Bhattacharya, Sankar

2014-01-01

404

Theoretical and experimental studies on the carbon-nanotube surface oxidation by nitric acid: interplay between functionalization and vacancy enlargement.  

PubMed

The nitric acid oxidation of multiwalled carbon nanotubes leading to surface carboxylic groups has been investigated both experimentally and theoretically. The experimental results show that such a reaction involves the initial rapid formation of carbonyl groups, which are then transformed into phenol or carboxylic groups. At room temperature, this reaction takes place on the most reactive carbon atoms. At higher temperatures a different mechanism would operate, as evidenced by the difference in activation energies. Experimental data can be partially related to first-principles calculations, showing a multistep functionalization mechanism. The theoretical aspects of the present article have led us to propose the most efficient pathway leading to carboxylic acid functional groups on the surface