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841.
    
Kinetic study on the cleavage of N‐phenylphthalimide (NPhPT) in the presence of 0.05 M NH2NH2 and mixed H2O‐CH3CN solvents reveals the occurrence of reaction scheme where A, B, C, C1, An, E, and F represent NPhPT, o‐CO?2C6H4CONHC6H5, o‐CONHNH2C6H4‐ CONHC6H5, N‐aminophthalimide, aniline, o‐CO?2C6H4CONHNH2, and o‐CONHNH2C6H4‐CONHNH2, respectively. But, in the presence of either nonbuffered ?0.20 M NH2NH2 hydrazine buffer of pH ~7.30–8.26 with total buffer concentration ([Buf]T) of >0.02 M, further conversion of F to 2,3‐dihydrophthalazine‐1,4‐dione (DHPD) has been detected depending upon the length of the reaction time (t), the values of [Buf]T, and pH. It has been shown that the rate of conversion of C1 to F is much faster than that of C to C1 which is much faster than that of F to DHPD. The reaction step A → C involves general base (GB) catalysis, while step C → C1 seems to involve specific base–general acid (GA) and GB‐GB catalysis. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 147–161, 2005  相似文献   
842.
    
The viability of using composite membranes of heteropolyacid (HPA)/polysulfone (PSF), HPA/sulfonated polysulfone (SPSF) for use in proton exchange membrane fuel cells (PEMFC) was investigated. PSF and its sulfonated polymer, SPSF was solution‐blended with phosphotungstic acid, a commercially available HPA. Fourier transform infrared (FTIR) spectroscopy of the HPA–40/SPSF composite exhibited band shifts showing a possibility of intermolecular hydrogen bonding interaction between the HPA additive and the sulfonated polymer. The composite membranes exhibited improved mechanical strength and low water uptake. The conductivity of the composite membrane, HPA–40/SPSF, consisting of 40 wt % HPA and 60 wt % SPSF [with a degree of Sulfonation (DS) of 40%] exhibited a conductivity 0.089 S/cm at room temperature that linearly increased upto 0.14 S/cm at 120 °C, whereas the widely used commercial membrane Nafion 117, exhibited a room temperature conductivity of 0.1 S/cm that increased to only 0.12 S/cm at 120 °C. In contrast, the composite of HPA–40/PSF exhibited a proton conductivity of 0.02 S/cm at room temperature that increased only to 0.07 S/cm at a temperature of 100 °C. The incorporation of HPA into SPSF not only rendered the membranes suitable for elevated temperature operation of PEMFC but also provides an inexpensive alternative compared to Nafion. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1538–1547, 2005  相似文献   
843.
    
Influence of pretreatments, i.e., demineralization and pre‐soaking in some solvents on the yields of liquefied products obtained from hydro‐depolymerization of Pakistani coal in a pool of hydrogen has been discussed. Results of hydrogenation experiments demonstrated that demineralizing the coal sample prior to liquefaction caused the yields to decrease compared with the virgin coal samples. The contribution of mineral matter of coal has been evaluated by comparing the yields of liquid products of virgin and leached samples. Increase in the yields obtained from the hydrogenation experiments of swollen coal samples was not satisfactorily significant.  相似文献   
844.
    
Chemical and thermal stabilities of isotypic metal-organic frameworks (MOFs) like Al-BDC (Al-benzenedicarboxylate called MIL-53-Al), Cr-BDC (MIL-53-Cr) and V-BDC (MIL-47-V), after purification to remove uncoordinated organic linkers, have been compared to understand the effect of the central metal ions on the stabilities of the porous MOF-type materials. Chemical stability to acids, bases, and water decreases in the order of Cr-BDC>Al-BDC>V-BDC, suggesting stability increases with increasing inertness of the central metal ions. However, thermal stability decreases in the order of Al-BDC>Cr-BDC> V-BDC, and this tendency may be explained by the strength of the metal-oxygen bond in common oxides like Al(2)O(3), Cr(2)O(3), and V(2)O(5). In order to evaluate precisely the stability of a MOF, it is necessary to remove uncoordinated organic linkers that are located in the pores of the MOF, because a filled MOF may be more stable than the same MOF after purification.  相似文献   
845.
    
Atom transfer radical polymerization (ATRP) catalyzed by high oxidation state metal salts of FeX3 is developed for the first time in the absence of both external initiator and reducing agent. Methyl methacrylate (MMA) and styrene are polymerized successfully using FeX3/Phosphorous ligands with well‐controlled molecular weight distributions (=1.5). The molecular weight of the polymers increases with monomer consumption with the progress of time and the polymerization behaviors show a decent ATRP trend. Activators and initiators are suggested to generate in situ by the addition reaction of MMA and one equivalent of FeX3. The PMMA synthesized from without‐initiator system is characterized by 1H, 13C and DEPT (distortionless enhancement by polarization transfer nuclear magnetic resonance) nuclear magnetic resonance spectroscopy. Chain extension and copolymerization experiments prove the livingness of the obtained polymer.

  相似文献   

846.
    
An unusual oleanane triterpene(1) was isolated from aerial parts of Rhododendron campanulatum.The compound had shown prominent antibacterial and immunomodulatory activities.The structure of the compound was determined by spectroscopic data including 1D and 2D NMR spectral analysis.  相似文献   
847.
    
An expedient three‐step procedure for the synthesis of trichlorophenol derivatives based on the acid‐catalyzed rearrangement of the bicyclic ketone precursors 6ae in high overall yield is described. The bicyclic ketone precursors 6ae were obtained from Diels–Alder cycloadducts of β‐substituted vinyl acetates with tetrachloro‐5,5‐dimethoxycyclopentadiene in two steps.  相似文献   
848.
The antedrug approach for corticosteroids has been described as a fundamentally sound approach for the development of safer anti‐inflammatory and anti‐asthmatic therapy. However, the derivatization of prednisolone and its congeners have been considered to be major pitfalls, because their syntheses are complicated by the presence of numerous carboxylate esters and hydroxyl functions in the steroid nucleus. A simple and direct synthesis of 21‐thioalkylether derivatives of methyl 16‐prednisolonecarboxylates is described. The 21‐mesylate of the methyl 16‐prednisolonecarboxylate and 9‐fluoro‐17‐dehydro methyl 16‐prednisolonecarboxylate were reacted with Na‐thioalkoxides to furnish the desired thioethers in good yields. A previously published method for the methanolysis of 16‐cyanoprednisolone to methylcarboxylate has been reexamined, and the conditions are explained clearly. The reaction conditions for all these reactions were critical.  相似文献   
849.
    
A simple and efficient method for the convenient synthesis of 2-arylbenzimidazole has been described on reaction with o-phenylenediamine and various aromatic aldehydes using cobalt(II) chloride hexahydrate as a catalyst. The method is cost-effective, high-yielding, clean, and selective.  相似文献   
850.
    
The synthetic polycations are ideal candidates as antimicrobial agents, because they resemble natural antimicrobial peptides, but to render hemocompatibility to these materials is a great challenge. Herein, we used 2‐(tert‐butyl‐aminoethyl) methacrylate (TBAEMA), to synthesize its homopolymer and pegylated random and diblock copolymers with polyethyleneglycol methacrylate (PEGMA, Mn = 360 Da) by single‐electron transfer–living radical polymerization (SET‐LRP). In the second step, the secondary amino groups in the precursor polymers were quaternized with iodomethane and bromohexane, to obtain three series of quaternized polymers. The antimicrobial properties of these quaternized polymers were evaluated against Escherichia coli (E. coli), by studying the minimum inhibitory concentrations (MICs) which ranged between 32 and 200 mg L?1 and showed higher values for the quaternized random than the diblock copolymers. In addition to, we have also demonstrated the grafting of these polycations onto polycarbonate urethane film surfaces, which showed good killing efficacy against E. coli. Furthermore, the hemolysis of these materials was investigated against human red blood cells, which indicated that except the quaternized homopolymers that showed highest hemolysis, all other amphiphilic polycations exhibited very low hemolytic activity. Therefore, our designed materials with controlled structures and functionality, synthesized from cheaply available resources could serve as useful agents in the field of biomedicines and implantable materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3166–3176  相似文献   
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