Browsing by Subject "Solvents"
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Item Open Access Elucidating solvent contributions to solution reactions with ab initio QM/MM methods.(J Phys Chem B, 2010-03-04) Hu, Hao; Yang, WeitaoComputer simulations of reaction processes in solution in general rely on the definition of a reaction coordinate and the determination of the thermodynamic changes of the system along the reaction coordinate. The reaction coordinate often is constituted of characteristic geometrical properties of the reactive solute species, while the contributions of solvent molecules are implicitly included in the thermodynamics of the solute degrees of freedoms. However, solvent dynamics can provide the driving force for the reaction process, and in such cases explicit description of the solvent contribution in the free energy of the reaction process becomes necessary. We report here a method that can be used to analyze the solvent contributions to the reaction activation free energies from the combined QM/MM minimum free-energy path simulations. The method was applied to the self-exchange S(N)2 reaction of CH(3)Cl + Cl(-), showing that the importance of solvent-solute interactions to the reaction process. The results were further discussed in the context of coupling between solvent and solute molecules in reaction processes.Item Open Access Inhalant use among incarcerated adolescents in the United States: prevalence, characteristics, and correlates of use.(Drug and alcohol dependence, 2008-03) Howard, Matthew O; Balster, Robert L; Cottler, Linda B; Wu, Li-Tzy; Vaughn, Michael GOBJECTIVE: To characterize patterns and correlates of inhalant use among incarcerated youth. METHOD: Residents (N=723) of 27 Missouri Division of Youth Services facilities completed interviews assessing substance use, psychiatric symptoms, antisocial traits, trauma, suicidality, and criminality. RESULTS: Participants averaged 15.5 (S.D.=1.2) years of age, were ethnically diverse, and predominantly male. More than one-third (36.9%) reported lifetime inhalant use; 47.9% of users had tried four or more inhalant products. Comparatively high rates of use were observed for Hispanic and small town/rural youth. Commonly abused agents included gasoline (22%), permanent markers (15%), computer "air duster," (15%) and spray paint (12%). Inhalant users evidenced significantly higher levels of criminal behavior, antisocial attitudes, current psychiatric symptoms, earlier onset of offending and substance use, and more extensive histories of head injury, kidney disease, hormonal problems, mental illness, suicidality, trauma, and substance-related problems than nonusers. In multiple logistic regression models, race/ethnicity, geographic area of residence, fearlessness, suicidality, and polydrug use distinguished inhalant users and nonusers. Measures of cognitive impairment, impulsivity, fearlessness, blame externalization, polydrug use, and substance-related problems were positively associated with lifetime frequency of inhalant use. CONCLUSIONS: Inhalant use was widespread in this sample and associated with serious physical and mental health impairments.Item Open Access Short-lived alpha-helical intermediates in the folding of beta-sheet proteins.(Biochemistry, 2010-07-06) Chen, E; Everett, ML; Holzknecht, ZE; Holzknecht, RA; Lin, SS; Bowles, DE; Parker, WSeveral lines of evidence point strongly toward the importance of highly alpha-helical intermediates in the folding of all globular proteins, regardless of their native structure. However, experimental refolding studies demonstrate no observable alpha-helical intermediate during refolding of some beta-sheet proteins and have dampened enthusiasm for this model of protein folding. In this study, beta-sheet proteins were hypothesized to have potential to form amphiphilic helices at a period of <3.6 residues/turn that matches or exceeds the potential at 3.6 residues/turn. Hypothetically, such potential is the basis for an effective and unidirectional mechanism by which highly alpha-helical intermediates might be rapidly disassembled during folding and potentially accounts for the difficulty in detecting highly alpha-helical intermediates during the folding of some proteins. The presence of this potential was confirmed, indicating that a model entailing ubiquitous formation of alpha-helical intermediates during the folding of globular proteins predicts previously unrecognized features of primary structure. Further, the folding of fatty acid binding protein, a predominantly beta-sheet protein that exhibits no apparent highly alpha-helical intermediate during folding, was dramatically accelerated by 2,2,2-trifluoroethanol, a solvent that stabilizes alpha-helical structure. This observation suggests that formation of an alpha-helix can be a rate-limiting step during folding of a predominantly beta-sheet protein and further supports the role of highly alpha-helical intermediates in the folding of all globular proteins.Item Open Access Stereocomplexed poly(lactic acid)-poly(ethylene glycol) nanoparticles with dual-emissive boron dyes for tumor accumulation.(ACS Nano, 2010-09-28) Kersey, Farrell R; Zhang, Guoqing; Palmer, Gregory M; Dewhirst, Mark W; Fraser, Cassandra LResponsive biomaterials play important roles in imaging, diagnostics, and therapeutics. Polymeric nanoparticles (NPs) containing hydrophobic and hydrophilic segments are one class of biomaterial utilized for these purposes. The incorporation of luminescent molecules into NPs adds optical imaging and sensing capability to these vectors. Here we report on the synthesis of dual-emissive, pegylated NPs with "stealth"-like properties, delivered intravenously (IV), for the study of tumor accumulation. The NPs were created by means of stereocomplexation using a methoxy-terminated polyethylene glycol and poly(D-lactide) (mPEG-PDLA) block copolymer combined with iodide-substituted difluoroboron dibenzoylmethane-poly(L-lactide) (BF2dbm(I)PLLA). Boron nanoparticles (BNPs) were fabricated in two different solvent compositions to study the effects on BNP size distribution. The physical and photoluminescent properties of the BNPs were studied in vitro over time to determine stability. Finally, preliminary in vivo results show that stereocomplexed BNPs injected IV are taken up by tumors, an important prerequisite to their use as hypoxia imaging agents in preclinical studies.Item Open Access The effect of hydrogen bonding on the diffusion of water in n-alkanes and n-alcohols measured with a novel single microdroplet method.(J Chem Phys, 2010-01-28) Su, Jonathan T; Duncan, P Brent; Momaya, Amit; Jutila, Arimatti; Needham, DavidWhile the Stokes-Einstein (SE) equation predicts that the diffusion coefficient of a solute will be inversely proportional to the viscosity of the solvent, this relation is commonly known to fail for solutes, which are the same size or smaller than the solvent. Multiple researchers have reported that for small solutes, the diffusion coefficient is inversely proportional to the viscosity to a fractional power, and that solutes actually diffuse faster than SE predicts. For other solvent systems, attractive solute-solvent interactions, such as hydrogen bonding, are known to retard the diffusion of a solute. Some researchers have interpreted the slower diffusion due to hydrogen bonding as resulting from the effective diffusion of a larger complex of a solute and solvent molecules. We have developed and used a novel micropipette technique, which can form and hold a single microdroplet of water while it dissolves in a diffusion controlled environment into the solvent. This method has been used to examine the diffusion of water in both n-alkanes and n-alcohols. It was found that the polar solute water, diffusing in a solvent with which it cannot hydrogen bond, closely resembles small nonpolar solutes such as xenon and krypton diffusing in n-alkanes, with diffusion coefficients ranging from 12.5x10(-5) cm(2)/s for water in n-pentane to 1.15x10(-5) cm(2)/s for water in hexadecane. Diffusion coefficients were found to be inversely proportional to viscosity to a fractional power, and diffusion coefficients were faster than SE predicts. For water diffusing in a solvent (n-alcohols) with which it can hydrogen bond, diffusion coefficient values ranged from 1.75x10(-5) cm(2)/s in n-methanol to 0.364x10(-5) cm(2)/s in n-octanol, and diffusion was slower than an alkane of corresponding viscosity. We find no evidence for solute-solvent complex diffusion. Rather, it is possible that the small solute water may be retarded by relatively longer residence times (compared to non-H-bonding solvents) as it moves through the liquid.