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991.
Momčilović N Clark PG Boydston AJ Grubbs RH 《Journal of the American Chemical Society》2011,133(47):19087-19089
A one-pot synthesis of polyrotaxanes has been developed. The method employs a supramolecular monomer comprising a polymerizable ammonium salt and crown ether, in combination with dynamic ADMet polymerization. Ultimately, highly efficient complexation, polymerization, and end-capping were accomplished in a single operation to yield polyrotaxanes with M(w) up to 19.3 kDa and >80% of the repeat units being complexed. 相似文献
992.
Mecinović J Snyder PW Mirica KA Bai S Mack ET Kwant RL Moustakas DT Héroux A Whitesides GM 《Journal of the American Chemical Society》2011,133(35):14017-14026
The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H(2)NSO(2)C(6)H(4)-CONHCH(2)(CX(2))(n)CX(3), n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and entropic contributions to the hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions). 相似文献
993.
Structure and dynamics of highly PEG-ylated sterically stabilized micelles in aqueous media 总被引:1,自引:0,他引:1
Vuković L Khatib FA Drake SP Madriaga A Brandenburg KS Král P Onyuksel H 《Journal of the American Chemical Society》2011,133(34):13481-13488
Molecular assemblies of highly PEG-ylated phospholipids are important in many biomedical applications. We have studied sterically stabilized micelles (SSMs) of self-assembled DSPE–PEG2000 in pure water and isotonic HEPES-buffered saline solution. The observed SSM sizes of 2–15 nm largely depend on the solvent and the lipid concentration used. The critical micelle concentration of DSPE–PEG2000 is 10 times higher in water than in buffer, and the viscosity of the dispersion dramatically increases with the lipid concentration. To explain the experimentally observed results, we performed atomistic molecular dynamics simulations of solvated SSMs. Our modeling revealed that the observed assemblies have very different aggregation numbers (N(agg) ≈ 90 in saline solution and N(agg) < 8 in water) because of very different screening of their charged PO4(–) groups. We also demonstrate that the micelle cores can inflate and their coronas can fluctuate strongly, thus allowing storage and delivery of molecules with different chemistries. 相似文献
994.
Ben Issa N Rajaković-Ognjanović VN Marinković AD Rajaković LV 《Analytica chimica acta》2011,(1):191-198
A simple and efficient method for separation and determination of inorganic arsenic (iAs) and organic arsenic (oAs) in drinking, natural and wastewater was developed. If arsenic is present in water prevailing forms are inorganic acids of As(III) and As(V). oAs can be found in traces as monomethylarsenic acid, MMA(V), and dimethylarsenic acid, DMAs(V). Three types of resins: a strong base anion exchange (SBAE) and two hybrid (HY) resins: HY-Fe and HY-AgCl, based on the activity of hydrated iron oxides and a silver chloride were investigated. It was found that the sorption processes (ion exchange, adsorption and chemisorptions) of arsenic species on SBAE (ion exchange) and HY resins depend on pH values of water. The quantitative separation of molecular and ionic forms of iAs and oAs was achieved by SBAE and pH adjustment, the molecular form of As(III) that exists in the water at pH <8.0 was not bonded with SBAE, which was convenient for direct determination of As(III) concentration in the effluent. HY-Fe resin retained all arsenic species except DMAs(V), which makes possible direct measurements of this specie in the effluent. HY-AgCl resin retained all iAs which was convenient for direct determination of oAs species concentration in the effluent. The selective bonding of arsenic species on three types of resins makes possible the development of the procedure for measuring and calculation of all arsenic species in water. In order to determine capacity of resins the preliminary investigations were performed in batch system and fixed bed flow system. Resin capacities were calculated according to breakthrough points in a fixed bed flow system which is the first step in designing of solid phase extraction (SPE) module for arsenic speciation separation and determination. Arsenic adsorption behavior in the presence of impurities showed tolerance with the respect to potential interference of anionic compounds commonly found in natural water. Proposed method was established performing standard procedures: with external standard, certified reference material and standard addition method. Two analytical techniques: the inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectroscopy-hydride generation (AAS-GH) were comparatively applied for the determination of arsenic in all arsenic species in water. ICP-MS detection limit was 0.2 μg L−1 and relative standard deviation (RSD) of all arsenic species investigated was between 3.5 and 5.1%. 相似文献
995.
Hafner A Dürrigl M Pepić I Filipović-Grčić J 《Chemical & pharmaceutical bulletin》2011,59(9):1117-1123
The aim of this study was to establish a freeze-drying process for melatonin-loaded lecithin/chitosan nanoparticles (NPs) to preserve their chemical and physical stability for a longer time period that what is possible in an aqueous suspension. Glucose and trehalose were investigated as potential excipients during freeze-drying of NP suspensions. Lecithin/chitosan NPs were characterised by mean diameter and zeta potential, ranging between 117.4 and 328.5 nm and 6.7 and 30.2 mV, respectively, depending on the lecithin type and chitosan content in the preparation. Melatonin loadings were up to 7.1%. For all lecithin/chitosan NPs, no notable differences in the mean particle size, size distribution, zeta potential or melatonin content were observed before or immediately after the lyophilisation process or after 7 months of storage at 4 °C. The residual moisture contents of lyophilisates with glucose and trehalose immediately after the lyophilisation process varied between 4.0-4.8% and 2.4-3.0%, respectively. All lecithin/chitosan NPs had a fully amorphous nature after the freeze-drying process, as indicated by modulated differential scanning calorimetry. NP lyophilisates with glucose had a low glass transition temperature (ca. 5 °C), confirming that lyophilisation with glucose as a cryoprotectant was not appropriate. All lyophilisates with trehalose had a glass transition temperature above the room temperature, allowing formation of the cake without a collapse of the structure, which was capable of preserving its characteristics and appearance following 7 months of storage at 4 °C. 相似文献
996.
Cvijeta Jakobušić Brala Viktor Pilepić Ivana Sajenko Ana Karković Stanko Uršić 《Helvetica chimica acta》2011,94(9):1718-1731
The effects of charged species on proton‐coupled electron‐transfer (PCET) reaction should be of significance for understanding/application of important chemical and biological PCET systems. Such species can be found in proximity of activated complex in a PCET reaction, although they are not involved in the charge transfer process. Reported here is the first study of the above‐mentioned effects. Here, the effects of Na+, K+, Li+, Ca2+, Mg2+, and Me4N+ observed in PCET reaction of ascorbate monoanions with hexacyanoferrate(III) ions in H2O reveal that, in presence of ions, this over‐the‐barrier reaction entered into tunneling regime. The observations are: a) dependence of the rate constant on the cation concentration, where the rate constant is 71 (at I = 0.0023), and 821 (at 0.5M K+), 847 (at 1.0M Na+), and 438 M ?1 s?1 (at 0.011M Ca2+); b) changes of kinetic isotope effect (KIE) in the presence of ions, where kH/kD=4.6 (at I = 0.0023), and 3.4 (in the presence of 0.5M K+), 3.3 (at 1.0M Na+), 3.9 (at 0.001M Ca2+), and 3.9 (at 0.001M Mg2+), respectively; c) the isotope effects on Arrhenius pre‐factor where AH/AD=0.97 (0.15) in absence of ions, and 2.29 (0.60) (at 0.5M Na+), 1.77 (0.29) (at 1.0M Na+), 1.61 (0.25) (at 0.5M K+), 0.42 (0.16) (at 0.001M Ca2+) and 0.16 (0.19) (at 0.001M Mg2+); d) isotope differences in the enthalpies of activation in H2O and in D2O, where ΔΔH?(D,H)=3.9 (0.4) kJ mol?1 in the absence of cations, 1.3 (0.6) at 0.5M Na+, 1.8 (0.4) at 0.5M K+, 1.5 (0.4) at 1.0M Na+, 5.5 (0.9) (at 0.001M Ca2+), and 7.9 (2.8) (at 0.001M Mg2+) kJ mol?1; e) nonlinear proton inventory in reaction. In the H2O/dioxane 1 : 1, the observed KIE is 7.8 and 4.4 in the absence and in the presence of 0.1M K+, respectively, and AH/AD=0.14 (0.03). The changes when cations are present in the reaction are explained in terms of termolecular encounter complex consisting of redox partners, and the cation where the cation can be found in a near proximity of the reaction‐activated complex thus influencing the proton/electron double tunneling event in the PCET process. A molecule of H2O is involved in the transition state. The resulting ‘configuration’ is more ‘rigid’ and more appropriate for efficient tunneling with Na+ or K+ (extensive tunneling observed), i.e., there is more precise organized H transfer coordinate than in the case of Ca2+ and Mg2+ (moderate tunneling observed) in the reaction. 相似文献
997.
A sensitive hydrophilic interaction liquid chromatography/electrospray ionization mass spectrometry (HILIC/ESI-MS/MS) method was developed for determination of selected aliphatic (i.e. malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, maleic, fumaric, glycolic and pyruvic acid), alicyclic (i.e. cis-pinonic and pinic acid) and aromatic (i.e. trimesic, phthalic acid and its isomers) carboxylic acids. Analytes were separated on an amide column using a gradient elution with a 10mM constant ionic strength mobile phase containing acetonitrile and aqueous ammonium acetate buffer (pH 5.0). The influence of the buffer type, pH, polar modifier and temperature on analyte retention under HILIC was studied. Static sonication-assisted solvent extraction was optimized for sample preparation prior to analysis. The recoveries obtained were higher than 90% for most analytes. The method was proven to be sensitive with limits of detection ranged from 0.03 to 16.0 μg/L in selected reaction monitoring mode (SRM). The repeatability and intermediate precision of the method, expressed as RSD (%) of the peak area ratio between analytes and their internal standards were generally lower than 5%. The method was successfully applied for determination of the studied acids in samples of ambient aerosol particles. A big advantage of the new method is also its ability to detect and separate the isobaric compounds of the selected carboxylic acids. Our results demonstrate that the method is specific and sensitive for the determination of a wider range of polar carboxylic acids at low concentrations in complex samples of aerosol particles. 相似文献
998.
We report results for the ground-state energy and structural properties of small (4)He-T↓ clusters consisting of up to four T↓ and eight (4)He atoms. These results have been obtained using very well-known (4)He-(4)He and T↓- T↓ interaction potentials and several models for the (4)He- T↓ interatomic potential. All the calculations have been performed with variational and diffusion Monte Carlo methods. It takes at least three atoms to form a mixed bound state. In particular, for small clusters the binding energies are significantly affected by the precise form of the (4)He- T↓ interatomic potential but the stability limits remain unchanged. The only exception is the (4)He(2)T↓ trimer whose stability in the case of the weakest (4)He- T↓ interaction potential is uncertain while it seems stable for other potentials. The mixed trimer (4)He(T↓)(2), a candidate for the Borromean state, is not bound. All other studied clusters are stable. Some of the weakest bound clusters can be classified as quantum halo as a consequence of having high probability of being in a classically forbidden region. 相似文献
999.
The aim of this study was to investigate the connection between the lipid/amphiphile monolayer structure at the interface and its macroscopic/rheological properties, in particular, to establish the link between the fractality of the monolayer structure and its compressibility modulus. To that purpose we have used fractal analysis of images obtained by Brewster angle microscopy to infer the fractal dimension of the monolayer structure and relate its change to the corresponding changes in compressibility derived from a simultaneously measured π-A isotherm. The results of the study confirmed the starting assumption based on theoretical considerations that the fractal dimension of an amphiphilic monolayer and its compressibility should be correlated. We have shown that there exists a strong correlation between the fractal dimension and the corresponding compressibility modulus of different amphiphilic materials. Thus, confirming the link between the short ordered structure on the molecular level and the macroscopic property-compressibility of the monolayer. The established correlation between the fractal dynamics and compressibility modulus of the monolayer enabled identification of onset of percolation-a second-order phase transition that is otherwise not easy and unambiguously detectable. We have found that the signature of percolation in a monolayer, regardless of its composition, is the occurrence of a sharp increase (a jump) of compressibility modulus (at macroscopic level) at the characteristic value of the corresponding fractal dimension D = 1.89. This is the result of the abrupt establishment of a connected structure on the molecular level, consequently involving a change in the elastic properties of the monolayer on a macroscopic scale. The results of this investigation provide means for unambiguous identification of the onset of percolation in the Langmuir layer and should facilitate a more efficient application of the percolation theory in further study of processes and structures at the interface during the monolayer compression. 相似文献
1000.
We report the synthesis of nine conjugated cruciform-shaped molecules based on the central benzo[1,2-d:4,5-d']bisoxazole nucleus, at which two conjugated currents intersect at a ~90° angle. Cruciforms' substituents were varied pairwise among the electron-neutral phenyl groups, electron-rich 4-(N,N-dimethylamino)phenyl substituents, and electron-poor pyridines. Hybrid density functional theory calculations revealed that the highest occupied molecular orbitals (HOMOs) are localized (24-99%) in all cruciforms, in contrast to the lowest unoccupied molecular orbitals (LUMOs) which are strongly dependent on the substitution and less localized (6-64%). Localization of frontier molecular orbitals (FMOs) along different axes of these cruciforms makes them promising as sensing platforms, since analyte binding to the cruciform should mandate a change in the HOMO-LUMO gap and the resultant optical properties. This prediction was verified using UV/vis absorption and emission spectroscopy: cruciforms' protonation results in hypsochromic and bathochromic shifts consistent with the preferential stabilization of HOMO and LUMO, respectively. In donor-acceptor-substituted systems, a two-step optical response to protonation was observed, wherein an initial bathochromic shift is followed by a hypsochromic one with continued acidification. X-ray diffraction studies of three selected cruciforms revealed the expected ~90° angle between the cruciform's substituents, and crystal packing patterns dominated by [π···π] stacking and edge-to-face [C-H···π] contacts. 相似文献