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991.
The reaction of titanocene dichloride,Cp
2TiCl2 (Cp=5-C5H5), with one or two equivalents of sodium cyanodithioformate affords the new mono- or bis(dithiocarboxylato) derivativesCp
2TiCl(S2CCN) (1) andCp
2Ti(S2CCN)2 (2). Elimination of sulfur converts2 into the metallacyclicCp
2TiS2C2(CN)2 (3), which does not react with the diene isoprene, but can be reconverted into the appropriate titanocene dihalides by chlorine or bromine. 相似文献
992.
In solid-state NMR, deuteron (2H) spectroscopy can be performed in full analogy to1H spectroscopy, including2H chemical-shift resolution and2H-X dipolar correlation schemes, when the NMR experiments are conducted in a “rotor-synchronized” fashion under fast magic-angle
spinning. Here, 2H-X NMR experiments of this type, including2H-15N and2H-1H chemical-shift correlations and distance measurements, are introduced and demonstrated on cytosine monohydrate, whose acidic
protons can readily be replaced by deuterons by recrystallization from D2O. In this way,2H NMR spectroscopy provides information complementary to1H NMR data, which is particularly useful for studying hydrogen bonds in supra- or biomolecular systems.
Electronic supplementary material Supplementary material is available in the online versionof this article atand is accessible for authorized users. 相似文献
993.
V. Yu. Buz’ko I. V. Sukhno V. T. Panyushkin D. N. Ramazanova 《Journal of Structural Chemistry》2005,46(4):596-602
The structure and relative stability of 1,4-dioxane-water, (Diox)n·(H2O )m (n = 1, 2, m = 1–6), molecular complexes have been calculated by semiempirical MNDO/PM3 method. A considerable variety of (Diox)n·(H2O )m isomeric structures was stated. The mean energy of ODiox…HW-OW hydrogen bond in (Diox)n·(H2O)m complexes formed by 1,4-dioxane molecules in the chair conformation amounts to ?2.293 ± 0.210 kcal/mol with the average bond length 2.797 0.015 Å. 相似文献
994.
The proton affinity on each of the possible sites in the antitumor 2‐(4‐aminophenyl)benzazoles has been calculated at the B3LYP/6‐311G** level of theory in the gas phase and in solution. The N3‐site of protonation is found to be strongly favored over the NH2‐site for the studied compounds both in gas phase and in solution. The stability of N3‐protonated species is explained by the resonance interaction of the NH2‐group with the heterocyclic ring. The potential energy surface (PES) for the protonation process was studied at the density functional theory (DFT)/B3LYP/6‐311++G** level of theory. Solvent effects on the PES were also examined using two models: Onsager self‐consistent field and polarizable continuum model (PCM). © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
995.
IntroductionConsiderableattelltionisno\vbeillgpaidtotheCO7refonningof.etha..llto]forseveralreasonst(l)withthedevelopmentofindustrics.moreandnlorcCOZIsabettedintotheatmosphere,leadingto"greenhouseeffect",whichhasbroughtaboutgreatilltcreslallovertheworld.Th… 相似文献
996.
介绍了非均匀相催化剂的MOVS制备方法,以该法制得的MoO3催化剂在甲醇选择氧化制甲醛、CO加氢制高级和喹啉加氢脱氮中均显示出常规催化剂更为优异的催化性能,并探讨了MOVS催化剂的内在特性与催化性能的关系。 相似文献
997.
The influence of hydrothermal modification on the structure and hydrodenitrogenation (HDN) activity of NiMo/γ-Al2O3catalyst was studied in the range 140~180 ℃. The experimental results indicated that the hydrodenitrogenation reaction rate of pyridine was accelerated using the NiMo/γ-Al2O3catalyst synthesized via hydrothermal route due to the change of the structure, the increase of the amount of Mo and Ni and the rise of the specific surface area. The change of the structure of catalysts was enhanced at higher hydrothermal temperature, producing NiMo/γ-Al2O3catalyst with better HDN activity. 相似文献
998.
S. V. Shishkina T. G. Drushlyak L. A. Kutulya N. S. Pivnenko O. V. Shishkin 《Journal of Structural Chemistry》2004,45(5):889-895
X-ray analysis was carried out to study the molecular structure of β-hydroxyketone, which is one of the minor products of selective aldol condensation of (−)-menthone with 4-carbomethoxybenzaldehyde. The cyclohexanone ring of the compound has a practically undistorted chair conformation with an axial orientation of the 1-methyl group and the bulkiest 2-[1′-hydroxy-1′ -(4-carbomethoxyphenyl)]methyl substituent and the equatorial orientation of the isopropyl group in the 4 position. The stereochemical configuration was found to be (1R,2R,4 R, 1′ S), supporting that the compound belongs to the group of (+)-isomenthones; i.e., the starting (-)-menthone undergoes (to a certain extent) epimerization under the reaction conditions used. In crystal, there is intermolecular hydrogen bonding >C=O...HO- (the -O...H- bond length is 2.15 Å). The molecular conformation in hydroxyketone crystals differs from the one which prevails in solutions (according to previous NMR data) and which is characterized by an inverted cyclohexanone ring and intramolecular hydrogen bonding >C=O...HO.Original Russian Text Copyright © 2004 by S. V. Shishkina, T. G. Drushlyak, L. A. Kutulya, N. S. Pivnenko, and O. V. Shishkin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 933–940, September–October, 2004. 相似文献
999.
金负载量对低温水煤气变换Au/α-Fe2O3催化剂结构和性能的影响 总被引:5,自引:3,他引:5
采用共沉淀法制备了低温水煤气变换Au/α-Fe2O3催化剂。通过正交实验优化催化剂的还原活化条件,考察了金负载量对催化剂性能的影响。采用BET、XRD、UV-VIS、XRF、H2-TPR和O2-TPO等表征手段对催化剂的结构进行分析,并与其催化性能进行关联。结果表明,(1)采用10%-H2/N2还原气将催化剂在150 ℃原位还原9 h,其催化活性最高;(2)金的最佳负载量为8.00%,此时在催化剂制备过程中金的流失量较少,金粒子较小,也有利于抑制催化剂在反应过程中烧结;(3)TPR-TPO结果表明,金的负载量为8.00%时,Au/α-Fe2O3催化剂具有较易被还原、不易被氧化的性质,从而显示出最高催化活性。(4)Au/α-Fe2O3催化剂中的金以单质金(Au0)形式存在;其高活性与Au0-Fe3O4间的协同作用有关。 相似文献
1000.
手性5-l-(艹孟)氧基丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物的合成 总被引:2,自引:0,他引:2
研究了手性元5-(R)-(l-(艹孟)氧基)-2(5H)-呋喃酮与取代苯甲醛肟以次氯酸钙作为氧化剂进行的区域选择性原位1,3-偶极环加成反应,同步生成两个新的手性中心,得到了一系列光学纯丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物;应用波谱学手段及X射线单晶衍射法确证了产物的绝对构型,并对产物的核磁共振氢谱规律性加以总结. 相似文献