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A thermal method using differential scanning calorimeter has been applied to aqueous solutions of a series of poly(tetraalkylammonium ethenesulfonates) (R4NPES). It was found that only the salts withR=n-C4H9 andR=i-C5H11 could form stable hydrates having large hydration numbers. The melting point and hydration numbers of these two hydrates were 12.0°C and 30±1 for the (n-C4H9)4NPES hydrate and 16.0°C and 53±2 for the (i-C5H11)4NPES hydrate, respectively. It was concluded that these hydrates were clathrate-like essentially similar to such hydrates as (n-C4H9)4NF·30H2O and (i-C5H11)4NF·40H2O.  相似文献   
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Simultaneous measurement system of DSC-Raman spectroscopy and its analysis method are developed. The developed method was applied to the melting of Indium and the optimum laser irradiation condition was determined. The obtained result of the heat flow is similar to the modulated DSC and the precise melting temperature and the heat of fusion can be obtained from the analyzed DSC. DSC-Raman spectroscopy is also applied to PLLA. Analyzed data indicate the existence of the recrystallization behavior in addition to T g and T m. Corresponding to these transitions, Raman peak shifts, intensities, and widths varied. From those results, it is proved that DSC-Raman spectroscopy is useful for the analysis of thermal property of the polymer in connection with the polymer structure.  相似文献   
4.
Transformation of plant-origin 7,14-dihydroxy-ent-kaurenes to ent-abietanes having a cis-fused α-methylene γ-lactones was accomplished efficiently under the Mitsunobu reaction conditions. The yields of the desired products were apparently influenced by the steric hindrance at C-1. The cytotoxic activity on P388 murine leukemia cells of the ent-abietanes having cis-fused α-methylene γ-lactones produced were assayed.  相似文献   
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An enantioselective total synthesis of sacrolide A, an antimicrobial and cytotoxic fourteen-membered macrolactonic oxylipin isolated from an edible freshwater cyanobacterium, has been accomplished from a known carboxylic acid in 20% overall yield by a concise ten-step sequence. The key transformations include chiral oxazolidinone-based diastereoselective installation of two hydroxy-bearing stereocenters, the Horner–Wadsworth–Emmons olefination to construct the full carbon skeleton, and the Shiina macrolactonization to establish the fourteen-membered macrolide structure.  相似文献   
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An attempt was made to calculate 13C NMR chemical shifts of poly(β-benzyl L-aspartate) having the right-handed α-helix (αR-helix) and left-handed α-helix (αL-helix) forms by a tight-binding MO sum-over-states theory within the extended Hückel framework, in order to examine whether or not the conformation-dependent 13C chemical shifts previously determined by the cross polarization-magic angle spinning technique are reproduced by a change of electronic structure of the polymer. It is found that the relative displacements of the observed Cα, Cβ and carbonyl 13C chemical shifts between the αR- and αL-helices are reproduced qualitatively by the calculation.  相似文献   
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The proposed structure for a moss-produced acetylenic oxylipin (10-keto-type structure) was synthesized from a known glycidol derivative by an 11-step sequence involving epoxide ring opening with a terminal acetylene and enzymatic hydrolysis of a methyl ester intermediate. The NMR spectra of the proposed structure was, however, different from those of the natural oxylipin, which prompted us to synthesize its 9-epi-isomer and two diastereomeric 12-keto-type positional isomers. Comparison of the NMR spectra of the three isomers with those of the natural oxylipin indicated that the natural oxylipin was actually a mixture of the two diastereomeric positional isomers.  相似文献   
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The conjugate of bacterial cytosine deaminase (bCD) and poly-l-lysine (PLL) that was functionalized with biotin, rhodamine, and Gd3+-DOTA was synthesized and characterized. It demonstrated high relaxivity, improved enzymatic specificity to prodrug 5-fluorocytosine, low cytotoxicity, efficient cell uptake, and high enzymatic stability in fresh mouse serum and human breast cancer cell culture.  相似文献   
10.
A method for conducting enantioselective bromolactonization reactions of trisubstituted alkenoic acids, using the C(3)-symmetric trisimidazoline 1 and 1,3-dibromo-5,5-dimethyl hydantoin as a bromine source, has been developed. The process generates chiral δ-lactones that contain a quaternary carbon. The results of studies probing geometrically different olefins show that (Z)-olefins rather than (E)-olefins are favorable substrates for the process. The method is not only applicable to acyclic olefin reactants but can also be employed to transform cyclic trisubstituted olefins into chiral spirocyclic lactones. Finally, the synthetic utility of the newly developed process is demonstrated by its application to a concise synthesis of tanikolide, an antifungal marine natural product.  相似文献   
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