全文获取类型
收费全文 | 79295篇 |
免费 | 16706篇 |
国内免费 | 8792篇 |
专业分类
化学 | 72530篇 |
晶体学 | 1164篇 |
力学 | 3179篇 |
综合类 | 658篇 |
数学 | 7658篇 |
物理学 | 19604篇 |
出版年
2024年 | 99篇 |
2023年 | 800篇 |
2022年 | 1415篇 |
2021年 | 1733篇 |
2020年 | 2899篇 |
2019年 | 4162篇 |
2018年 | 2559篇 |
2017年 | 2349篇 |
2016年 | 5314篇 |
2015年 | 5633篇 |
2014年 | 5992篇 |
2013年 | 7364篇 |
2012年 | 7046篇 |
2011年 | 6506篇 |
2010年 | 6094篇 |
2009年 | 5998篇 |
2008年 | 5680篇 |
2007年 | 4846篇 |
2006年 | 4368篇 |
2005年 | 3947篇 |
2004年 | 3206篇 |
2003年 | 2751篇 |
2002年 | 3507篇 |
2001年 | 2648篇 |
2000年 | 2332篇 |
1999年 | 1265篇 |
1998年 | 649篇 |
1997年 | 546篇 |
1996年 | 455篇 |
1995年 | 432篇 |
1994年 | 370篇 |
1993年 | 310篇 |
1992年 | 228篇 |
1991年 | 216篇 |
1990年 | 192篇 |
1989年 | 149篇 |
1988年 | 136篇 |
1987年 | 85篇 |
1986年 | 97篇 |
1985年 | 79篇 |
1984年 | 35篇 |
1983年 | 36篇 |
1982年 | 34篇 |
1981年 | 17篇 |
1980年 | 23篇 |
1979年 | 26篇 |
1978年 | 23篇 |
1973年 | 10篇 |
1971年 | 12篇 |
1936年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Shyh‐Jong Chen Cheng Chen Yaw‐Shun Hong 《International journal of quantum chemistry》2005,103(2):198-214
This investigation conducted reaction channels of weakly bound complexes CO2…HF, CO2…HF…NH3, CO2…HF…NH2CH3, CO2…HF…NH(CH3)2, and CO2…HF…N(CH3)3 systems, using the Gaussian 98 package at the B3LYP/6‐311++G(3df,2pd) level. The syn‐fluoroformic acid or syn‐fluoroformic acid plus NH3 or amine conformers are more stable than the related anti‐fluoroformic acid or anti‐fluoroformic acid plus NH3 or amine conformers. However, the above‐mentioned weakly bound complexes are more stable than both the related syn‐ and anti‐type fluoroformic acid or acid plus NH3 or amine conformers and their related decomposed into CO2 + HF or CO2 + NHR3F (R?H, CH3) combined molecular systems. Five reaction channels of the weakly bound complexes exist. Each channel includes weakly bound complexes and their related above‐mentioned systems. Moreover, each reaction channel contains two transition states. The transition state between the weakly bound complex and anti‐fluoroformic acid type structure (T13) is significantly higher than that of internal rotation (T23) between syn‐ and anti‐FCO2H (or FCO2H…NR3) structures. However, the above‐mentioned T13 can significantly decrease its energy by adding the third molecule NH3 or NR3 (R?H or CH3). The more CH3 that is substituted in NR3 of the reaction channel, the lower the activation energy of the transition state in the system is affected. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
992.
993.
Fourier transform infrared reflection-absorption spectroscopy (FT-IRAS) has been used to study the orientation and coordination of glycine, L-phenylalanine and L-histidine on gold and copper surfaces. It was found that glycine and L-histidine were weakly adsorbed (physisorbed) in the zwitterionic form on gold. The surface chemical bonding of L-histidine and L-phenylalanine to copper were chemical rather than physical by nature. Conclusive evidence was obtained for coordination to copper through both the amino-nitrogen and carboxylate-oxygen atoms. 相似文献
994.
Thermodynamics and crystallization kinetics of the hydrothermal synthesis of Na4Ti4Si3O10 (NaTS) were systemically studied by both experiments and model simulation. Experimental results showed that the curve of
crystallinity with time was a characteristic signmoid in the shape that indicated the crystallization of Na4Ti4Si3O10 was a typical spontaneous nucleation process on the laboratory scale. Crystallization of NaTS belongs to the liquid-liquid
transformation mechanism and the reaction is endothermic (ΔH = 15.3 kJ/mol). A mathematic model of crystallization kinetics was developed to simulate the synthesis of NaTS. Runge-Kutta
and simplex methods were adopted to solve the partial differential equations. Model results fitted well with the experimental
data and showed that the synthesis process belongs to spontaneous nucleation and crystal growth. Moreover, the very small
crystal growth constant (5.6·10−7) and gel dissolution constant (7.0·10−7) indicate they are the rate-limiting steps of the whole synthesis process. 相似文献
995.
Binyuan Liu Yang Li Boo-gyo Shin Li Zhang Weidong Yan 《Polymer Degradation and Stability》2007,92(5):868-875
The thermal properties and degradation behaviors of poly(norbornene-2,3-dicarboxylic acid dialkyl esters) (PNB-dialkyl esters) (alkyl = Me (PNB-Me), Et (PNB-Et), Pr (PNB-Pr), and Bu (PNB-Bu)) were investigated by thermogravimetric analysis (TGA) in dynamic conditions and by infrared (IR) spectroscopy. The PNB-dialkyl esters show good thermal stability up to 350 °C, and the thermal stability decreases in the order Me > Et > Pr > Bu with the increase in size of side chain. The effect of side-chain size on the thermal degradation behaviors of PNB-dialkyl esters is evidenced by one-step thermal degradation profile for PNB-Me while two-step thermal degradation profile for PNB-Et, PNB-Pr, and PNB-Bu. Transformation is deduced to undergo β-hydrogen elimination and formation of anhydride group in the first stage of thermal degradation reaction according to TGA and IR results for PNB-Et, PNB-Pr, and PNB-Bu. The apparent activation energy and thermal degradation model of PNB-dialkyl esters are estimated by means of Ozawa-Flynn-wall method and Phadnis-Deshpande method, respectively. 相似文献
996.
Antonio Doménech María Teresa Doménech‐Carbó Howell G. M. Edwards 《Electroanalysis》2007,19(18):1890-1900
Multivariate chemometric methods are applied for identifying earth pigments from square‐wave voltammetric measurements performed at pigment‐modified paraffin‐impregnated graphite electrodes allowing for a separation between hematite‐based earths, French ochres, Spanish ochres, siennas, umbers and green earths. This methodology is applied to the identification of the pigments in samples from the ceiling frescoes of Antonio Palomino (dated 1707) in the vaulted nave of the Sant Joan del Mercat church in Valencia (Spain). These frescoes suffered considerable damage by fire during the Spanish Civil War in 1936, resulting in severe chemical and chromatic alterations. Electrochemical data, supported by scanning electron microscopy/energy dispersive X‐ray microanalysis and Raman spectroscopy, indicate that thermal stress induced the transformation of goethite‐based yellow ochres into hematite and magnetite. 相似文献
997.
Adam Bange Jian Tu Xiaoshan Zhu Chong Ahn H. Brian Halsall William R. Heineman 《Electroanalysis》2007,19(21):2202-2207
A microbead based sandwich immunoassay for MS2 bacteriophage was developed using an interdigitated array (IDA) electrode with nanoscale dimensions (220 nm electrode width, 620 nm gap). The IDA was fabricated using an electron beam lithographic lift‐off technique. After an antibody‐assisted capture of MS2 using paramagnetic microbeads, a β‐galactosidase labeled secondary antibody was used to convert p‐aminophenyl‐β‐D ‐galactopyranoside (PAPG) into the redox active p‐aminophenol (PAP). Amperometric detection of PAP with IDA electrodes at +300 and ?200 mV vs. a Ag/AgCl reference electrode was used to measure the result, detecting MS2 concentrations as low as 10 ng/mL. 相似文献
998.
Intracellular delivery of enzymes is essential for protein-based diagnostic and therapeutic applications. Protein-spherical nucleic acids (ProSNAs) defined by protein core and dense shell of oligonucleotides have been demonstrated as a promising vehicle-free enzyme delivery platform. In this work, we reported a crosslinking strategy to vastly improve both delivery efficiency and intracellular sensor performance of ProSNA. By assembling individual ProSNA with lactate oxidase (LOX) core into a nanoscale particle, termed as crosslinked SNA (X-SNA), the enzyme delivery efficiency increased up to 5–6 times higher. The LOX X-SNA was later demonstrated as a ratiometric probe for quantitative detection of lactate in living cells. More importantly, X-SNA probe showed significantly improved sensor performance with signal-to-noise ratio 4 times as high as ProSNA when detecting intracellular lactate.By crosslinking protein spherical nucleic acid (SNA) into a supramolecular architecture X-SNA, the intracellular enzyme delivery efficiency was significantly enhanced, showing 3–4 times higher signal-to-noise ratio in detecting intracellular lactate. 相似文献
999.
Peng Chen Xiaojun Luo Guanqi Dai Yuchuan Jiang Yue Luo Shuang Peng Hao Wang Penghui Xie Chen Qu Wenyu Lin Jian Hong Xue Ning Aimin Li 《Experimental & molecular medicine》2020,52(7):1062
Dexmedetomidine (DEX) is an anesthetic that is widely used in the clinic, and it has been reported to exhibit paradoxical effects in the progression of multiple solid tumors. In this study, we sought to explore the mechanism by which DEX regulates hepatocellular carcinoma (HCC) progression underlying liver fibrosis. We determined the effects of DEX on tumor progression in an orthotopic HCC mouse model of fibrotic liver. A coculture system and a subcutaneous xenograft model involving coimplantation of mouse hepatoma cells (H22) and primary activated hepatic stellate cells (aHSCs) were used to study the effects of DEX on HCC progression. We found that in the preclinical mouse model of liver fibrosis, DEX treatment significantly shortened median survival time and promoted tumor growth, intrahepatic metastasis and pulmonary metastasis. The DEX receptor (ADRA2A) was mainly expressed in aHSCs but was barely detected in HCC cells. DEX dramatically reinforced HCC malignant behaviors in the presence of aHSCs in both the coculture system and the coimplantation mouse model, but DEX alone exerted no significant effects on the malignancy of HCC. Mechanistically, DEX induced IL-6 secretion from aHSCs and promoted HCC progression via STAT3 activation. Our findings provide evidence that the clinical application of DEX may cause undesirable side effects in HCC patients with liver fibrosis.Subject terms: Cancer microenvironment, Cell growth 相似文献
1000.
The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS). Key innovations in this synthesis consist of (1) a highly efficient electro-oxidative dearomatization; (2) an unprecedented bisoxirane-directed intermolecular aldol reaction from the sterically hindered face of the ketone and (3) the diastereoselective one-step Meerwein–Eschenmoser–Claisen rearrangement enabling the construction of vicinal quaternary stereocenters. Related family members e.g. penicimutanolone (3) and penicimutatin (5) have also been synthesized alongside, elucidating their absolute configurations, hence the absolute configuration of 1.The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS). 相似文献