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961.
B3LYP/6-31++G** method was applied to investigate the mechanism of alanine isomerization.12 minima and 22 transition states were obtained after optimization and several paths of isomerization were found.It is found that intramolecular single-bond rotation and proton transfer might lead to isomerization.The energy barrier of C–N bond rotation was lower than 2.52 kcal·mol 1,while the energy barrier ranges of the rotation of C–C and C–O were separately 0.43~ 7.01 and 4.69~12.19 kcal·mol 1,and the minimum energy barrier of proton transfer was 30.76 kcal·mol 1.The most probable isomerization path and mechanism for the two most stable conformations was discussed to find that the highest energy barrier to be crossed in this path was 11.87 kcal·mol 1.In order to understand the microscopic nature why only 4 conformations were detected in the experiment,thermodynamic properties of all conformations at the experimental temperature of 391 K was calculated.It is found that conformations XII,XI,X and IX can only unidirectionally convert into conformations rapidly with low energy and vanish immediately.The other conformations were distributed according to Maxwell-Boltzman's law,and the distribution probabilities of conformations I,II,III,IV,V,VI,VII and VIII were respectively 27.2%,26.5%,25.8%,6.4%,5.2%,4.8%,2.5% and 1.6%.Conformations I,II and III with bigger probability and stronger absorption peak were easy to detect in the experiment.Conformation IV had a relatively smaller probability(6.4%) and weak absorption peak which,however,could also be identified.The other conformations had too small probability to identify in the spectrum. 相似文献
962.
YE Hong-De HU Jiu-Rong ZHENG Da-Gui PENG Hua-Nan YE Qing ZOU Ru-Yi YAN Hong 《结构化学》2013,(10):1517-1522
A new compound [CpCo(Se2C2BIoH9)CH2C(O)C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P21/c with a = 10.9481(10), b = 24.6600(12), c = 25.7430(14) A, β = 100.863(3)°, C42H57B30Co306Se6"CH2C12"0.25H20, Mr = 1722.16, V = 6825.6(8) A3, Dc= 1.676 g/cm3, Z = 1 and F(000) = 3346. The molecular structure shows a 1:1 ratio product of the two reactants of 16e half-sandwich complex CpCo(Se2C2B10H10) and alkyne 1-(2-furyl)-2-propyn-l-one. The hydrogen atom in the B(3) position of CpCo(Se2C2B10HIo) has been activated and migrated to the terminal carbon of 1-(2-furyl)- 2-propyn-l-one to form the B-CH2 unit. The title compound molecules are linked and extended further into a one-dimensional chain through atypical hydrogen bonds. 相似文献
963.
The title compound, neogeodin hydrate (C17H14C1208, CAS: 94540-50-8), was derived from marine fungus Aspergilhts terreus CRIM301. It was unequivocally characterized by IR, NMR spectroscopies, and single-crystal X-ray crystallography and tested for various biological activities. Neogeodin hydrate crystallizes in the triclinic space group P1 with a = 8.1159(5) A, b = 8.2472(4) A, c= 14.1278(7) A, a = 81.448(2)°, β = 84.860(2)°, γ= 70.400(2)°, V = 880.13(8) A3; Z = 2. It comprises a diphenyl ether, asterric acid skeleton and dichloro substituents. The methoxyphenoxy rings of the inversely related molecules form a ribbon-like structure that is stabilized by O-H...O hydrogen bonds through the doubly disordered carboxyl groups and by C-H...O interactions, generating the same R22(8) ring motif. The chlorinated methylbenzoate rings, making mostly a right angle, link the parallel upper and lower ribbons via bifurcated O-H...O and C-H...O hydrogen bonds, yielding endless channels. The channels formed are further sustained by C-H...O and π...π interactions Neogeodin hydrate exhibits inhibition against superoxide anion radical formation in the xanthine/xanthine oxidase (XXO) assay, but has no aromatase inhibitory activity. 相似文献
964.
LUO Ya-Nan XU Xian-Zhua YU Xiao-Yang ZHU Guang-Shan QU Xiao-Shu ZHANG Xiao YU Li-Ying 《结构化学》2013,(11):1667-1672
A new coordination polymer, {[CdL(en)]'DMF}n (1, H2L = 4-[(8-hydroxy-5- quinolinyl)azo]-benzenesulfonic acid, en = ethylenediamine, DMF = N,N-dimethylformamide), has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffrac- tion, infrared (IR) spectra, elemental analysis, powder X-ray diffractions (PXRD) and thermo- gravimetric analysis (TGA). Compound 1 crystallizes in monoclinic, space group P2Jc with a = 14.6525(9), b = 13.3917(9), c = 11.8838(8) A, β = 101.2290(10)°, V = 2287.2(3) A3, Z = 4, C20H24CdN6OsS, Mr = 572.91, Dc. = 1.664 mg-mm-3, F(000) = 1160, p = 1.091 mm-1, R = 0.0232 and wR = 0.0587 for 3597 observed reflections (I 〉 2σ(I)). Compound 1 exhibits a one-dimensional (1D) double-chain structure which is further connected through hydrogen bonding and π-π interactions into a three-dimensional (3D) supramolecular network. In addition, it exhibits blue fluorescence at room temperature in the solid state. 相似文献
965.
取代γ-丁内酯是一类非常重要的精细化学品。N-杂环卡宾(NHC)催化α,β-不饱和醛发生共轭极性反转后,与芳香醛、三氟甲基酮、酮酸酯或邻二酮等发生环化反应可一步生成不同取代的γ-丁内酯化合物。该方法具有原子经济性高、路径简捷、反应条件温和等明显的优势。本文主要结合笔者课题组的研究方向,从不同催化剂前体和不同反应底物两方面进行分类,介绍近年来NHC催化合成取代γ-丁内酯的方法及其研究进展,归纳总结了不同催化体系的优缺点,并在此基础上展望了NHC催化合成取代γ-丁内酯反应的发展趋势和应用前景。 相似文献
966.
967.
968.
讨论了天然植物高分子药用胶囊的最新研究与发展,介绍了目前的主要研究成果并提出展望.不仅从化学结构、流变和相变等基础理论方面探讨了各类植物药用胶囊的特性和研制中所遇到的问题,同时对各种胶囊制备设备与工艺的发展及应用中的技术改进进行了综述分析.传统明胶胶囊生产工艺的应用已有160多年的历史,目前植物胶囊生产设备和工艺多是建立在传统明胶胶囊生产的基础上.研究植物胶囊材料的流变和凝胶性能以尽量满足传统明胶的设备与工艺是当今急需解决的难题之一.近年来,随着人们对淀粉结构和改性方法的深入研究(尤其是将淀粉基可生物降解材料的制备技术与传统食品科学的研究成果有效结合),应用高分子科学理论和方法提高淀粉基材料的加工性能,力学性能与稳定性的研究有了突破性进展,为淀粉胶囊的研制提供了理论和技术上的有力支持.使用传统塑料加工的挤出加工法制备植物胶囊,是植物胶囊研究中的重大突破和创新.从原材料来源的充足性和价格上考虑,淀粉是最有潜力替代传统胶囊的原料之一. 相似文献
969.
970.
采用超声辐射法制备了聚乙烯基吡咯烷酮(PVP)-多壁碳纳米管(MWCNT’s)复合材料(PVP-MWCNT’s),将该复合材料分散在N,N-二甲基甲酰胺(DMF)中并滴涂在玻碳电极表面,制备了聚乙烯基吡咯烷酮-多壁碳纳米管复合修饰玻碳电极(PVP-MWCNT’s/GCE)。研究发现:抗坏血酸在修饰电极上出现一对可逆的氧化还原峰,提出了用差分脉冲伏安法测定抗坏血酸的方法。还原峰电流与抗坏血酸的浓度在1.0×10-7~1.0×10-3 mol·L-1范围内呈线性关系。 相似文献