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Copper Causes Regiospecific Formation of C4F8‐Containing Six‐Membered Rings and their Defluorination/Aromatization to C4F4‐Containing Rings in Triphenylene/1,4‐C4F8I2 Reactions 下载免费PDF全文
Kerry C. Rippy Dr. Eric V. Bukovsky Dr. Tyler T. Clikeman Dr. Yu‐Sheng Chen Dr. Gao‐Lei Hou Dr. Xue‐Bin Wang Dr. Alexey A. Popov Dr. Olga V. Boltalina Prof. Steven H. Strauss 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):874-877
The presence of Cu in reactions of triphenylene (TRPH) and 1,4‐C4F8I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4F8‐containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive‐defluorination/aromatization (RD/A) to form C4F4‐containing aromatic rings. Without Cu, the reactions of TRPH and 1,4‐C4F8I2 were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cu‐promoted 1) regiospecific perfluoroannulation, 2) preparative C?F activation, and 3) RD/A. HPLC‐purified products were characterized by X‐ray diffraction, low‐temperature PES, and 1H/19F NMR. 相似文献
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Fangzhong Hu Xinxin Cheng Zixia Niu Xiaobing Yang Dan Li Lei Wan Junxiao Li Bin Liu Xiaomao Zou Huazheng Yang Bin Li 《Journal of heterocyclic chemistry》2015,52(3):793-801
A series of 3‐phenyl benzo[d][1,2,3]triazin‐4(3H)‐one derivatives were synthesized through the condensation of phenol E and alkyl (alkenyl, alkynyl) chlorides (bromides, iodide) or alkyl chloroacetates or N‐alkyl chloroacetamides using K2CO3 as the acid acceptor in N,N‐dimethylformamide. Phenol E was prepared from starting material, 5‐amino‐2‐chloro‐4‐fluorophenyl ethyl carbonate, in four steps involving in amidation, reduction, diazotization, and deprotecting‐group reaction. The herbicidal activities of the title compounds were tested against two dicotyledonous plants and two monocotyledonous plants, in which some of them exhibited high herbicidal activities against two dicotyledonous plants in preemergence and postemergence treatments. Moreover, when the dosage was decreased to 180 and 90 g/ha, compounds F1 , F8 , and F9 showed highly selective inhibitory activities against amaranth pigweed, alfalfa, asteraceae, field sowthistle, morning glory, purslane, and velvetleaf in postemergence treatment but had no herbicidal efficacy on rape except F1 , suggesting that it be possible to find a kind of herbicides to inhibit dicotyledonous weeds in the field of dicotyledonous crops with the same genus as aforementioned weeds. 相似文献
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Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells
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Xin‐Xing Zhan Xin Zhang Si‐Min Dai Shu‐Hui Li Xu‐Zhai Lu Dr. Lin‐Long Deng Prof. Su‐Yuan Xie Prof. Rong‐Bin Huang Prof. Lan‐Sun Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18709-18713
Despite being widely used as electron acceptor in polymer solar cells, commercially available PC71BM (phenyl‐C71‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC71BM has been isolated into three typical isomers, α‐, β1‐ and β2‐PC71BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β1‐ and β2‐PC71BM. Mixing the isomers in a ratio of α/β1/β2=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC71BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC71BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC71BM isomers in the otherwise same polymer solar cells. 相似文献
69.
Shi Qiu Wen-zhi Yang Xiao-jian Shi Chang-liang YaoMin Yang Xuan LiuBao-hong Jiang Wan-ying Wu De-an Guo 《Analytica chimica acta》2015
Exploration of new natural compounds is of vital significance for drug discovery and development. The conventional approaches by systematic phytochemical isolation are low-efficiency and consume masses of organic solvent. This study presents an integrated strategy that combines offline comprehensive two-dimensional liquid chromatography, hybrid linear ion-trap/Orbitrap mass spectrometry, and NMR analysis (2D LC/LTQ-Orbitrap-MS/NMR), aimed to establish a green protocol for the efficient discovery of new natural molecules. A comprehensive chemical analysis of the total ginsenosides of stems and leaves of Panax ginseng (SLP), a cardiovascular disease medicine, was performed following this strategy. An offline 2D LC system was constructed with an orthogonality of 0.79 and a practical peak capacity of 11,000. The much greener UHPLC separation and LTQ-Orbitrap-MS detection by data-dependent high-energy C-trap dissociation (HCD)/dynamic exclusion were employed for separation and characterization of ginsenosides from thirteen fractionated SLP samples. Consequently, a total of 646 ginsenosides were characterized, and 427 have not been isolated from the genus of Panax L. The ginsenosides identified from SLP exhibited distinct sapogenin diversity and molecular isomerism. NMR analysis was finally employed to verify and offer complementary structural information to MS-oriented characterization. The established 2D LC/LTQ-Orbitrap-MS/NMR approach outperforms the conventional approaches in respect of significantly improved efficiency, much less use of drug materials and organic solvent. The integrated strategy enables a deep investigation on the therapeutic basis of an herbal medicine, and facilitates new compounds discovery in an efficient and environmentally friendly manner as well. 相似文献
70.
Gold‐Catalyzed Fluorination–Hydration: Synthesis of α‐Fluorobenzofuranones from 2‐Alkynylphenol Derivatives 下载免费PDF全文
Qiang Wang Yu Jiang Run Sun Prof. Dr. Xiang‐Ying Tang Prof. Dr. Min Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14739-14745
The AuI‐catalyzed fluorination–hydration of 2‐alkynylphenol derivatives in the presence of Selectfluor [1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo‐[2.2.2]octane bis(tetrafluoroborate)] has been developed. This method provides straightforward access to α‐fluorobenzofuranones with the construction of C?O, C=O, and C?F bonds in a single step on the basis of an AuI/AuIII redox catalytic cycle. Several control experiments, including the asymmetric variant of this reaction, were also conducted to gain insight into the reaction mechanism. 相似文献