全文获取类型
收费全文 | 12902篇 |
免费 | 2204篇 |
国内免费 | 1909篇 |
专业分类
化学 | 9767篇 |
晶体学 | 249篇 |
力学 | 713篇 |
综合类 | 148篇 |
数学 | 1219篇 |
物理学 | 4919篇 |
出版年
2024年 | 16篇 |
2023年 | 195篇 |
2022年 | 322篇 |
2021年 | 441篇 |
2020年 | 495篇 |
2019年 | 488篇 |
2018年 | 413篇 |
2017年 | 430篇 |
2016年 | 625篇 |
2015年 | 654篇 |
2014年 | 778篇 |
2013年 | 1004篇 |
2012年 | 1306篇 |
2011年 | 1374篇 |
2010年 | 964篇 |
2009年 | 948篇 |
2008年 | 998篇 |
2007年 | 873篇 |
2006年 | 847篇 |
2005年 | 737篇 |
2004年 | 559篇 |
2003年 | 379篇 |
2002年 | 415篇 |
2001年 | 330篇 |
2000年 | 253篇 |
1999年 | 223篇 |
1998年 | 182篇 |
1997年 | 137篇 |
1996年 | 102篇 |
1995年 | 90篇 |
1994年 | 81篇 |
1993年 | 66篇 |
1992年 | 57篇 |
1991年 | 55篇 |
1990年 | 40篇 |
1989年 | 20篇 |
1988年 | 16篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 9篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
采用量子化学的密度泛函B3LYP和二阶微扰MP2(full)方法对C4H4Y(Y=O,S,Se)与BX3(X=H,F,Cl)形成的电子授受型复合物进行了研究,所得18个复合物的构型包括BX3位于C=C双键上方的π-p作用型和B与O,S,Se直接作用的n-p作用型.体系C4H4Y-BH3以n-p作用型较为稳定,体系C4H4Y-BF3,C4H4Y-BCl3的π-p和n-p作用型复合物稳定性相当.对各复合物的几何构型、振动频率和自然键轨道分析表明,复合物的形成过程中均存在几何构型的改变、电荷的转移和振动频率的变化,它们的变化规律与复合物稳定性的变化规律基本一致,即按H,F,Cl的顺序依次降低. 相似文献
992.
Jae Yoon Chung Hwan Won Chung Seung Joo Cho Jung-Mi Hah Art E. Cho 《Journal of computer-aided molecular design》2010,24(5):385-397
Three dimensional (3D) quantitative structure-activity relationship studies of 37 B-Raf inhibitors, pyrazole-based derivatives,
were performed. Based on the co-crystallized compound (PDB ID: 3D4Q), several alignment methods were utilized to derive reliable
comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) models. Receptor-guided
alignment with quantum mechanics/molecular mechanics (QM/MM) minimization led to the best CoMFA model (q
2 = 0.624, r
2 = 0.959). With the same alignment, a statistically reliable CoMSIA model with steric, H-bond acceptor, and hydrophobic fields
was also derived (q
2 = 0.590, r
2 = 0.922). Both models were validated with an external test set, which gave satisfactory predictive r
2 values of 0.926 and 0.878, respectively. Contour maps from CoMFA and CoMSIA models revealed important structural features
responsible for increasing biological activity within the active site and explained the correlation between biological activity
and receptor-ligand interactions. New fragments were identified as building blocks which can replace R1-3 groups through combinatorial
screening methods. By combining these fragments a compound with a high bioactivity level prediction was found. These results
can offer useful information for the design of new B-Raf inhibitors. 相似文献
993.
Zhen Wang Yongmei Xu Bo Yang Gopinath Tiruchinapally Bin Sun Renpeng Liu Steven Dulaney Jian Liu Xuefei Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(28):8365-8375
Heparin (HP) and heparan sulfate (HS) play important roles in many biological events. Increasing evidence has shown that the biological functions of HP and HS can be critically dependent upon their precise structures, including the position of the iduronic acids and sulfation patterns. However, unraveling the HP code has been extremely challenging due to the enormous structural variations. To overcome this hurdle, we investigated the possibility of assembling a library of HP/HS oligosaccharides using a preactivation‐based, one‐pot glycosylation method. A major challenge in HP/HS oligosaccharide synthesis is stereoselectivity in the formation of the cis‐1,4‐linkages between glucosamine and the uronic acid. Through screening, suitable protective groups were identified on the matching glycosyl donor and acceptor, leading to stereospecific formation of both the cis‐1,4‐ and trans‐1,4‐linkages present in HP. The protective group chemistry designed was also very flexible. From two advanced thioglycosyl disaccharide intermediates, all of the required disaccharide modules for library preparation could be generated in a divergent manner, which greatly simplified building‐block preparation. Furthermore, the reactivity‐independent nature of the preactivation‐based, one‐pot approach enabled us to mix the building blocks. This allowed rapid assembly of twelve HP/HS hexasaccharides with systematically varied and precisely controlled backbone structures in a combinatorial fashion. The speed and the high yields achieved in glycoassembly without the need to use a large excess of building blocks highlighted the advantages of our approach, which can be of general use to facilitate the study of HP/HS biology. As a proof of principle, this panel of hexasaccharides was used to probe the effect of backbone sequence on binding with the fibroblast growth factor‐2 (FGF‐2). A trisaccharide sequence of 2‐O‐sulfated iduronic acid flanked by N‐sulfated glucosamines was identified to be the minimum binding motif and N‐sulfation was found to be critical. This provides useful information for further development of more potent compounds towards FGF‐2 binding, which can have potential applications in wound healing and anticancer therapy. 相似文献
994.
Three new caged prenylxanthones (xanthone=9H‐xanthen‐9‐one), named neobractatin ( 1 ), 3‐O‐methylneobractatin ( 2 ), and 3‐O‐methylbractatin ( 3 ), along with eight known compounds, were isolated from the twig of Garcinia bracteata. The structures of the new compounds were elucidated on the basis of 1D‐ and 2D‐NMR experiments, including HMBC, HSQC, 1H,1H‐COSY, and ROESY, as well as HR‐MS analysis. 相似文献
995.
Jiun‐Yang Chang Mohamed H. Abd El‐Razek Yu‐Hui Chen Yuan‐Bin Cheng Shun‐Ying Chen Ching‐Te Chien Yao‐Haur Kuo Ya‐Ching Shen 《Helvetica chimica acta》2010,93(1):123-132
A phytochemical investigation of the MeOH extract of Illicium arborescens yielded the two new phytoquinoid epimers, 2,3‐didehydro‐5‐O‐methyl‐11‐epiillifunone E ( 1 ) and 2,3‐didehydro‐5‐O‐methylillifunone E ( 2 ), as well as five new sesquiterpene lactones (8,9‐secoprezizaane‐type sesquiterpenes). Two of them, i.e., 3 and 4 , were minwanensin‐type sesquiterpenes, the other two, i.e., 5 and 6 , had the anisatin‐type (or floridanolide type) skeleton, and the fifth, i.e., 7 , was a dunnianin‐type sesquiterpene. Their structures were established by analyses of 1D‐ and 2D‐NMR, HR‐MS, and chemical evidence. The in vitro cytotoxic activity of compounds 1 – 7 was tested against four human tumor cell lines, including HeLa (cervical epitheloid), WiDr (colon), Daoy (medulloblastoma), and Hep2 (liver carcinoma) human‐tumor cells. 相似文献
996.
Liu JQ Liu B Wang YY Liu P Yang GP Liu RT Shi QZ Batten SR 《Inorganic chemistry》2010,49(22):10422-10426
A fascinating 3D entangled metal-organic framework, namely, {[Co(2)(bcp)(2)]·3H(2)O}(n) (1), was obtained through the solvothermal generation of flexible and long dicarboxylate (bcp) and metal salt. The crystal structure contains a 1D metal chain with bcp ligands wrapped around it in a wavy line and features an unusual entangled topological net. Furthermore, the magnetic behavior of 1 was also studied and indicated the existence of ferromagnetic interaction and long-range ordering character. 相似文献
997.
Won Hee Kim Jin-Ah Kang Jin-Ah Kim Pusoon Chun Chong-Kyo Lee Hyung Ryong Moon 《Tetrahedron》2010,66(9):1706-5156
The first synthesis of 2′-oxabicyclo[3.1.0]hexyl nucleosides, a novel class of bicyclonucleosides, with a north conformation was successfully accomplished starting from (S)-epichlorohydrin via a tandem alkylation-lactonization, a less steric hindrance-dependent silylation in equilibrium and a coupling reaction with nucleobases under Vorbruggen conditions. Addition of acetic acid prevented a benzoyl group from migrating during desilylation with TBAF. 1H NMR and X-ray crystallographic analysis indicated that the anomeric effect worked on the β-2′-oxabicyclo[3.1.0]hexyl nucleosides. 相似文献
998.
利用重氮树脂(DR)中N2+的光解特性,通过罗丹明(B(RhB))对重氮树脂的接枝反应,得到了染料功能化的接枝聚合物DR-g-RhB,并由傅里叶红外光谱、1H-NMR、紫外-可见吸收光谱和荧光光谱等分析方法确认了产物结构。结果表明DR-g-RhB具有良好的热稳定性,失重5%所对应的温度超过360°C。通过溶液涂敷法形成的薄膜在不同酸碱度溶液中的UV-Vis吸收光谱会随浸入时间产生规律性变化:在pH=7.0的水中,吸光值基本不随时间变化;而在pH=12.0的肼水溶液中,吸光值随时间先下降、再增加;但在酸中则持续增加,而且对盐酸(pH=2.0)的响应比对醋酸(pH=2.3)更灵敏。 相似文献
999.
A sonochemical method has been successfully used to synthesize MnO2/MWNTs nanocomposites. The structure and nature of the resulting MnO2/MWNTs composite were characterized by scanning electron microscopy (SEM), energy‐dispersive X‐ray diffraction (EDX), X‐ray photoelectron spectroscopy (XPS).The results show that the sonochemically synthesized MnO2 nanoparticles were homogeneously dispersed on the modified MWNT surfaces. The performance of the MnO2/MWNTs nanocomposites modified electrode was characterized using cyclic voltammetry (CV) and Nyquist plots. The electrode exhibits efficient electron transfer ability and high electrochemical response towards hydrazine. This may be attributed to the small particle size, high dispersion of MnO2 particles. The fabricated hydrazine sensor showed a wide linear range of 5.0×10?7–1.0×10?3 M with a response time less than 5 s and a detection limit of 0.2 μM. Taking the advantage of the unique properties of both MWNTs and MnO2, it would greatly broaden the applications of MWNTs and MnO2. 相似文献
1000.
Rongxing Shen Xiangzi Li Guilin Lium Yulan Ji Guangfeng Wang Bin Fang 《Electroanalysis》2010,22(20):2383-2388
This work describes the electrochemical properties of glassy carbon electrodes (GCE) modified with chromium(III) hexacyanoferrate(II) (Crhf) nanoparticles attached multiwalled carbon nanotube (MWNTs). The morphological characterization of Crhf/MWNTs nanocomposites was examined by scanning electron microscopy (SEM), UV‐vis spectroscopy, and Fourier transform infrared spectrometry (FT‐IR). The electrocatalytic activity of these nanocomposites was investigated and showed a good electrocatalytic effect for oxidation of L ‐cysteine (L ‐Cys) in 0.1 M phosphate buffer solution (pH 3.0). Under optimum conditions linear calibration graphs were obtained over the L ‐Cys concentration range 5.0×10?7 to 6.0×10?5 M with a correlation coefficient of 0.9998 and a detection limit (signal‐to‐noise ratio was 3) of 1.0×10?8 M. The proposed method is simple and it also showed excellent sensitivity and stability. The excellent electrocatalytic ability of the modified electrode towards L ‐Cys manifests that the Crhf/MWNTs can provide a new platform for biosensors and other biology. 相似文献