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61.
A simple and efficient method for the dimerization of primary thioamides into 1,2,4-thiadiazoles using tert-butyl nitrite is described. The optimized condition was also found to be suitable for the dimerization of benzoselenoamides into 1,2,4-selenadiazoles. All the reactions proceed smoothly at room temperature and gave the desired products in excellent yields in a short span of time.  相似文献   
62.
N‐heterocyclic carbene (NHC) catalysis has emerged as a powerful strategy in organic synthesis. In recent years a number of reviews have been published on NHC‐catalyzed transformations involving Breslow intermediates, acyl azoliums, α,β‐unsaturated acyl azoliums, homoenolate equivalents, and azolium enolates. However, the azolium dienolate intermediates generated by NHCs have been employed in asymmetric synthesis only very recently, especially in cycloadditions dealing with remote functionalization. This Minireview highlights all the developments and the new advances in NHC‐catalyzed asymmetric cycloaddition reactions involving azolium dienolate intermediates.  相似文献   
63.
The influence of the presence of BaO impurity on the optical absorption, radiation hardness and thermally stimulated luminescence of BaF2 has been investigated. The presence of oxygen impurity gives rise to three absorption bands in the UV region, peaking around 220, 280 and 335 nm. Further, the impurity is found to be detrimental to crystal hardness against ionizing radiations. The thermally stimulated luminescence (TSL) has been studied from gamma-irradiated crystals containing different fractions of BaO impurity. Four prominent glow peaks around 100°C (peak I), 150°C (peak II), 220°C (peak III) and 290°C (peak IV) are observed for crystals containing BaO impurity concentrations lower than 0.5% (by wt). For crystals containing higher impurity concentrations, two additional peaks around 75°C and 260°C are also observed. The kinetics of TSL emission is observed to be of first order, implying that the absorption and the emission centers responsible for TSL are the same. The normalized TSL output for peak I is found to vary linearly with the concentration of oxide impurity. This fact can be utilized to detect the presence of minute amounts of oxygen in BaF2 lattice, which is crucial to the growth of crystals exhibiting high radiation hardness.  相似文献   
64.
Electrophoretic migration of proteins in semidilute polymer solutions   总被引:1,自引:0,他引:1  
We present a systematic study of the electrophoretic migration of 10-200 kDa protein fragments in dilute-polymer solutions using microfluidic chips. The electrophoretic mobility and dispersion of protein samples were measured in a series of monodisperse polydimethylacrylamide (PDMA) polymers of different molecular masses (243, 443, and 764 kDa, polydispersivity index <2) of varying concentration. The polymer solutions were characterized using rheometry. Prior to loading onto the microchip, the polymer solution was mixed with known concentrations of SDS (SDS) surfactant and a staining dye. SDS-denatured protein samples were electrokinetically injected, separated, and detected in the microchip using electric fields ranging from 100 to 300 V/cm. Our results show that the electrophoretic mobility of protein fragments decreases exponentially with the concentration c of the polymer solution. The mobility was found to decrease logarithmically with the molecular weight of the protein fragment. In addition, the mobility was found to be independent of the electric field in the separation channel. The dispersion is relatively independent of polymer concentration and it first increases with protein size and then decreases with a maximum at about 45 kDa. The resolution power of the device decreases with concentration of the PDMA solution but it is always better than 10% of the protein size. The protein migration does not seem to correspond to the Ogston or the reptation models. A semiempirical expression for mobility given by van Winkle fits the data very well.  相似文献   
65.
Surfactants are commonly incorporated into hydrogels to increase solute loading and attenuate the release rates. In this paper we focus on understanding and modeling the mechanisms of both surfactant and drug transport in hydrogels. Specifically, we focus on Brij 98 as the surfactant, Cyclosporine A (CyA) as the hydrophobic drug, and poly-hydroxy ethyl methacrylate (p-HEMA) as the polymer. The models developed here are validated by experiments conducted with gels of different thicknesses and surfactant loadings. Also the model is compared with prior experimental studies in literature. The model predicts that the percentage surfactant as well as drug release scales as 1/(surfactant loading)(0.5), and thus a four fold increase in surfactant loading leads to a two fold reduction in percentage release for both drug and surfactant at a given time. The models for the surfactant and drug release are fitted to the experimental data to obtain values of 1.44 x 10(-14) m(2)/s for CyA diffusivity and 414.4 for the partition coefficient between drug concentration inside the micelle and that in the gel. These models can be very helpful in tuning the drug release rates from hydrogels by controlling the surfactant concentration. The results also show that Brij 98 loaded p-HEMA exhibit an extended release of CyA and so contact lenses made with this material can be used for extended ocular delivery of CyA, which is an immunosuppressant drug commonly used for treatment of various ocular ailments.  相似文献   
66.
Solvothermally synthesized cobalt sulphide/reduced graphene oxide (CoS/rGO) was used to fabricate an electrochemical sensor for detection of artemisinin. Microscopic techniques were used to characterize CoS/rGO nanocomposite. The electrochemical sensor was fabricated by modifying the surface of glassy carbon electrode with CoS/rGO nanocomposite. [Fe(CN)6]3−/4− was used as a mediator to aid oxidation of artemisinin. Differential pulse voltammetric technique was used for the detection of artemisinin. A linear range of 30–100 μM was used. Experimentally, a detection limit of 0.5 μM was obtained. Therefore, the developed sensor can be used for quality control of artemisinin.  相似文献   
67.
We study the influence of polymer pore interactions and focus on the role played by the concentration gradient of salt in the translocation of polyelectrolytes (PE) through nanopores explicitly using coarse-grained Langevin dynamics simulations. The mean translocation time is calculated by varying the applied voltage, the pH, and the salt concentration gradient. Changing the pH can alter the electrostatic interaction between the protein pore and the polyelectrolyte chain. The polymer pore interaction is weakened by the increase in the strength of the externally applied electric field that drives translocation. Additionally, the screening effect of the salt can reduce the strong charge-charge repulsion between the PE beads which can make translocation faster. The simulation results show there can be antagonistic or synergistic coupling between the salt concentration-induced screening effect and the drift force originating from the salt concentration gradient thereby affecting the translocation time. Our simulation results are explained qualitatively with free energy calculations.  相似文献   
68.
One chalcone-ester homologous series of mesogens α-4-[4/-n-alkoxybenzoyloxy phenyl β-4//methoxy benzoyl ethylenes (A) and one azo-ester homologous series of mesogens p-(p/-n-alkoxybenzoyloxy) phenyl azo-p//-methoxy benzene (B) being structurally similar are discussed. Both series (A) and (B) differ in respect of central bridges linking two phenyl rings. Mesomorphic properties start from 6th and 1st member of series (A) and (B) respectively. In series (A), 6th to 12th members show both smectogenic and nematogenic properties, and the 14th and 16th members show only nematogenic property. While in series (B), 1st to 10th members show nematogenic properties, 11th member shows both smectogenic and nematogenic properties, while 12th member shows only smectogenic property. Thermal stability of series (A) is relatively high as compared to series (B). Transition temperatures are observed through hot stage polarizing microscope by the miscibility method. Analytical data support the structure of molecules. Textures of series (A) in nematic are threaded and Schlieren in SmecticSmectic A type, while that of series (B) in nematic are threaded in SmecticSmectic A and smectic C.  相似文献   
69.
Novel stannoxane type dinuclear tin complex C16H13N4O2Sn2Cl7 (1) and its modulated macrocyclic complexes [C24H36N10O3Sn2CuCl7] ClO4 (2) and [C24H34N10O2Sn2NiCl7] ClO4 (3) were synthesized and characterized by elemental analysis and various spectroscopic techniques (IR, 1H, 13C, 119Sn NMR, ESI-MS, EPR and UV-Vis). 119Sn NMR shows the presence of two tin metal centers in different environment. The proposed pseudo-octahedral geometry of copper in complex 2 and square pyramidal geometry of nickel in complex 3 were established by the analysis of spectroscopic data. Absorption and fluorescence spectral studies and viscosity measurements have been carried out to assess the comparative binding of dinuclear stannoxane complex 1 and its modulated copper complex 2 with calf thymus DNA. The intrinsic binding constants Kb of the complex 1 and 2 were determined as 4.4 × 104 M−1 and 7.5 × 104 M−1, respectively. Cyclic voltammetric studies have also been employed to ascertain the binding of complex 2 with CTDNA. The results suggest that the complex 2 binds to CTDNA twice in the order of magnitude compared to complex 1. Interaction studies of complex 2 with guanosine 5′-monophosphate further confirm the binding via N7 position of guanine and phosphate moiety.  相似文献   
70.
The structural and electronic properties of berberine and berberrubine have been studied extensively using density functional theory (DFT) employing B3LYP exchange correlation. The geometries of these molecules have been fully optimized at the B3LYP/6-311G** level. The chemical shift of 1H and 13C resonances in NMR spectra of these molecules have been calculated using the gauge invariant atomic model (GIAO) method as implemented in Gaussian 98. One- and two-dimensional HSQC (1H-13C), HMBC (1H-13C) and ROESY (1H-1H) spectra were recorded at 500 MHz for the berberine molecule in D(2)O solution. All proton and carbon resonances were unambiguously assigned, and inter-proton distances obtained from ten observed NOE contacts. A restrained molecular dynamics (RMD) approach was used to get the optimized solution structure of berberine. The structure of berberine and berberrubine molecules was also obtained using the ROESY data available in literature. Comparison of the calculated NMR chemical shifts with the experimental values revealed that DFT methods produce very good results for both proton and carbon chemical shifts. The importance of the basis sets to the calculated NMR parameters is discussed. It has been found that calculated structure and chemical shifts in the gas phase predicted with B3LYP/6-311G** are in very good agreement with the present experimental data and the measured values reported earlier.  相似文献   
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