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61.
Noncovalent interactions between an artificial molecular scaffold and a protein are interesting due to the possibility of reversible modulation of the activity of the protein. alpha-Chymotrypsin is a positively charged protein that has been shown to interact with negatively charged polymers. Here we show that positively charged polymers are also capable of electrostatically binding to this protein. The resulting experiments show that the ability of a polymer to bind a protein does not depend only on the pI of the protein. We also realized that the variations in charge density in the polymer backbone afford different selectivities of the enzyme toward charged substrates.  相似文献   
62.
In this paper we include the rearrangement correction (discussed in the preceding paper) in a coupled Hartree–Fock (CHF) calculation of atomic hyperpolarizabilities and other related properties. We have studied the effect of these corrections on properties like electric dipole hyperpolarizabilities, uniform electric field quadrupole polarizabilities and shielding factors in two-electron ions and have noticed significant changes in the computed values over the CHF results.  相似文献   
63.
CNDO molecular orbital calculations have been performed to analyze donor—acceptor interactions between molecular chlorine and benzene, toluene, mesitylene and hexamethylbenzene and the, as yet, unreported chlorine—hexafluorobenzene and carbon disulfide—benzene pairs. The stabilization energy and the dipole moment and its derivative (?p/?RCICI) calculated for the benzene—chlorine complex are in good agreement with the estimated experimental values. The trends in the experimental stabilization energies and the Cl-Cl vibrational frequencies with increasing methyl substitution appear to be well reproduced by the calculations. The charge transferred from the benzene donor is polarized toward the outer chlorine atom or sulfur atom. For hexafluorobenzene-chlorine the direction of electronic charge polarization is reversed from that of the benzene and methylbenzene complexes. The calculated results are discussed within the framework of Muliiken's simplified resonance theory for complexes.  相似文献   
64.
The double-T injector design employed in many microchip capillary electrophoresis devices allows for the formation of very small (50-500 pL) sample plugs for subsequent analysis on-chip. In this study, we show that sample plugs formed at the channel junction can be geometrically defined. The channel width and injector symmetry prove to be of great importance to good performance. A unique pushback of solvent into the side channels can be induced when the side channels have a very low resistance to flow, and this helps to better define the injected sample plug. Samples and running buffers of differing ionic strength (e.g., 10 mM KCl buffer and 20 mM KCl sample) can yield widely variable results in terms of plug shape and amount injected (variations of 1.5 to 10x). Applying bias voltages to all the intersecting channels aids in controlling the plug shape. However, when the ionic strengths of buffer and sample are not matched, the actual amount injected (up to 10x variations) can be inconsistent with the appearance of the plug formed in the injector (up to only 30 % variations). Operating at constant pH and ionic strength produced the most consistent results. This report examines the effects of altering the injector geometry and solution ionic strengths, and presents the results of using bias voltages to control plug formation. The observed results should provide a benchmark for modeling of the fluid dynamics in channel intersections.  相似文献   
65.
IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem. 73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the (1)H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating (13)C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice.  相似文献   
66.
Steady state and time-resolved fluorescence measurements compare the photophysical properties of Coumarin 152 (C152) and Coumarin 461 (C461) in bulk methanol solution and adsorbed to silica/vapor and silica/methanol interfaces. C152 and C461 share the same structure except for a -CF(3) (C152) or -CH(3) (C461) group at the molecule's 4-position. This modest structural difference leads to markedly different emission behavior in bulk solution and different organization when adsorbed to silica surfaces. Steady state emission spectra of C152 and C461 adsorbed to silica surfaces from bulk methanol solutions show that the two solutes have similar surface activities (ΔG(ads) of -29.0 kJ/mol and -30.8 kJ/mol for C152 and C461, respectively) and that the interface itself has a polarity similar to that of short chain alcohols. Both solutes appear to form multilayers at higher bulk concentrations given observed linear growth in fluorescence emission intensities. At higher C152 surface concentrations a second emissive state appears at longer wavelengths, whereas the emission of C461 remains dominated by a single feature. Time dependent emission of C152 and C461 adsorbed to the silica/methanol interface shows that the silica surface inhibits C152's fast, nonradiative pathway inferred from bulk solution measurements but the fluorescence lifetime of adsorbed C461 remains unchanged from bulk solution limits. These findings are discussed in terms of the interface's ability to restrict C152 isomerization into a nonradiative, twisted intramolecular charge-transfer (TICT) state, despite the fact that this conformation represents an energetic minimum in polar solvation environments.  相似文献   
67.
Useful procedures for preparing a novel tetraazacyclotetradecadiene and a pentaazacyclotetradecatriene are reported. J. Heterocyclic Chem., 14, 1097 (1977)  相似文献   
68.
Guanine-rich peptide nucleic acid probes hybridize to DNA G quadruplex targets with high affinity, forming PNA-DNA heteroquadruplexes. We report a surprising degree of kinetic discrimination for PNA heteroquadruplex formation with a series of DNA targets. The fastest hybridization is observed for targets folded into parallel morphologies.  相似文献   
69.
The reaction of [OsX2(HL)(L)] (1) {X = Cl or Br; HL = PhC(O)C(=NOH)Ph (HL1) or PhC(O)C(=NOH)Me (HL2)] with n-BuONO yields mononuclear [OsX(NO)(L1)2] (2) or binuclear [OsX2(NO)(L2)]22 (3) nitrosyls depending on L. The complexes are also obtained by reacting (1) with NaNO2 plus HCl. Molecular weight determinations are in agreement with mono- and binuclear formulations. The diamagnetic orange-red nitrosyls exhibit (NO) at ca. 1890 cm–1 indicating NO+ character of the bound nitrogen monoxide. In 1H-n.m.r. a single sharp L2 methyl signal is in line with the centrosymmetric geometry (4) of the binuclear nitrosyls. The complexes display both spin-allowed and -forbidden charge transfer transitions in the 1000–200 nm range. Both (2) and (3) are electroactive and reductions characteristic of mono- and binuclear compositions are observable on the negative side of s.c.e. They react smoothly with acetylacetone (acacH) in the presence of K2CO3 yielding K[Os(acamo)(L1)2] (5) and K[Os(acac)(acamo)(L2)] (6) [acamo = deprotonated MeC(O)C(=NOH)C(O)Me] respectively.  相似文献   
70.
S B Roy  P Chaddah 《Pramana》1999,53(4):659-684
Superconductivity in CeRu2 was discovered 40 years ago, and was extensively studied because alloying with magnetic elements showed the coexistence of superconductivity and magnetic order. The normal state of CeRu2 has been of interest because of its intermediate valuence character. The superconducting state has been studied extensively because of its paramagnetic nature and anomalous pinning properties. This review presents the present status of knowledge, and discusses the puzzling features of CeRu2.  相似文献   
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