全文获取类型
收费全文 | 1157篇 |
免费 | 88篇 |
国内免费 | 13篇 |
专业分类
化学 | 881篇 |
晶体学 | 13篇 |
力学 | 50篇 |
数学 | 131篇 |
物理学 | 183篇 |
出版年
2023年 | 4篇 |
2022年 | 9篇 |
2021年 | 20篇 |
2020年 | 24篇 |
2019年 | 29篇 |
2018年 | 15篇 |
2017年 | 12篇 |
2016年 | 41篇 |
2015年 | 42篇 |
2014年 | 59篇 |
2013年 | 80篇 |
2012年 | 77篇 |
2011年 | 78篇 |
2010年 | 72篇 |
2009年 | 81篇 |
2008年 | 70篇 |
2007年 | 67篇 |
2006年 | 53篇 |
2005年 | 55篇 |
2004年 | 59篇 |
2003年 | 39篇 |
2002年 | 43篇 |
2001年 | 22篇 |
2000年 | 29篇 |
1999年 | 15篇 |
1998年 | 13篇 |
1997年 | 9篇 |
1996年 | 8篇 |
1995年 | 11篇 |
1994年 | 10篇 |
1993年 | 20篇 |
1992年 | 12篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 4篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 7篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1936年 | 2篇 |
排序方式: 共有1258条查询结果,搜索用时 21 毫秒
991.
Hsin‐Yu Huang Huey‐Min Wang Rei‐Sheu Hou Hui‐Ting Cheng Ling‐Ching Chen 《中国化学会会志》2008,55(6):1204-1207
The task‐specific ionic liquid (TSIL) and 1‐n‐butyl‐3‐methylimidazolium thiocynanate, ([bmim]SCN) were used as the medium as well as the reactant for the synthesis of α‐thiocynanatoketones by the reaction with α‐sulfonyloxy aryl ketones. Significant rate enhancements and improved yields have been observed. 相似文献
992.
Chia‐Ching Liaw Yao‐Haur Kuo Tsong‐Long Hwang Ya‐Ching Shen 《Helvetica chimica acta》2008,91(11):2115-2121
Phytochemical investigation of Eupatorium chinense var. tozanense has resulted in the isolation of three new germacranolides, designated as eupatozansins A–C ( 1 – 3 ), along with five known compounds, (5S,6R,7R,8R)‐8‐angeloyloxy‐2‐oxoguaia‐1(10),3,11(13)‐trien‐12,6‐olide ( 4 ), costunolide ( 5 ), leptocarpin ( 6 ), 2α‐hydroxyeupatolide 8‐O‐angelate ( 7 ), and quercetin ( 8 ). The structures of the new compounds were identified by 1D and 2D NMR experiments, as well as high‐resolution mass spectrometry. The in vitro cytotoxic activities of compounds 1 – 8 were evaluated. 相似文献
993.
Protocols for highly enantioselective carbonyl allylation from the alcohol or aldehyde oxidation level are described based upon transfer hydrogenative C-C coupling. Exposure of allyl acetate to benzylic alcohols 1a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (R)-BINAP delivers products of C-allylation 2a-i. Employing isopropanol as terminal reductant, exposure of allyl acetate to aryl aldehydes 3a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (-)-TMBTP delivers identical products of C-allylation 2a-i. In all cases examined, exception levels of enantioselectivity are observed. Thus, enantioselective carbonyl allylation is achieved from the alcohol or aldehyde oxidation level in the absence of any preformed allylmetal reagents. These studies define a departure from preformed organometallic reagents in carbonyl additions that transcend the boundaries of oxidation level. 相似文献
994.
Two new approaches to reduce false positive interferences commonly observed with explosives and drugs detection in the field were reported for ion mobility spectrometry (IMS). One of the approaches involved the rapid preseparation of potential interferences prior to detection by IMS. Firstly, it was found that the introduction of a short column packed with adsorption packing material before an IMS could help to reduce the false positive rates. Secondly, the retention time at which the most intense response occurred over the analysis time period could be utilized to separate false positive responses from target analytes with the same drift times. Rapid preseparation of potential interferences provided a greater degree of confidence for the detection (in less than 30 s) of drugs, explosives and chemical warfare agents (CWAs). Detection limits as low as 10 pg of TNT with a sensitivity of 12 A g−1 were reported. Successful development of this technique may lead to the construction of a simple interface fitted with a short column of adsorption packing material to enhance either initial separation or to hold-back interferences mixed with explosive and drug responses in the field. 相似文献
995.
We generalize the matrix Kronecker product to tensors and propose the tensor Kronecker product singular value decomposition that decomposes a real k‐way tensor into a linear combination of tensor Kronecker products with an arbitrary number of d factors. We show how to construct , where each factor is also a k‐way tensor, thus including matrices (k=2) as a special case. This problem is readily solved by reshaping and permuting into a d‐way tensor, followed by a orthogonal polyadic decomposition. Moreover, we introduce the new notion of general symmetric tensors (encompassing symmetric, persymmetric, centrosymmetric, Toeplitz and Hankel tensors, etc.) and prove that when is structured then its factors will also inherit this structure. 相似文献
996.
Ching W. Chan 《Supramolecular chemistry》2017,29(10):688-695
AbstractAlthough buffer-specific effects on molecular recognition are known in biological science, they remain rare in supramolecular chemistry. The binding between a cationic dye, mallard blue (MalB) and polyanionic heparin in aqueous NaCl (150 mM) is studied in three commonly used buffers (Tris-HCl, HEPES, Phosphate, each 10 mM). Although MalB has a very similar UV–visible spectrum in each buffer, the sensory response towards heparin was different in each case. This can be ascribed to differences in the complex formed. In Tris-HCl which has the least competitive chloride counter-anions, MalB exhibits a hypsochromic shift of 25 nm, assigned to strong binding and aggregation of the dye on heparin. In more competitive HEPES, containing a sulfonate anion, there is weaker binding and less aggregation of MalB along the heparin; the hypsochromic shift is only 15 nm. In phosphate buffer, MalB can interact quite strongly with buffer phosphate anions; although heparin binding is still observed, the hypsochromic shift associated with dye aggregation is only 5 nm. As such, specific buffer interactions with the MalB–heparin complex mediate host–guest binding and sensing. Buffer choice must be made carefully in studies of molecular recognition – we would caution against using phosphate and sulfonate containing buffers when studying electrostatic binding. 相似文献
997.
Chi‐I Chang Yen‐Cheng Li Chang‐Syan Yang Che‐Yi Chao Yi‐Jen Li Hsun‐Shuo Chang Ching‐Jeng Huang Ching‐Chuan Kuo Yueh‐Hsiung Kuo 《Helvetica chimica acta》2015,98(1):123-127
Two new labdane‐type diterpene acids, (12S)‐12‐hydroxylabda‐8(17),13(16),14‐trien‐18‐oic acid ( 1 ) and (12R)‐12‐hydroxy‐15,16‐epoxylabda‐8(17),13‐dien‐18‐oic acid ( 2 ), along with a known labdane‐type diterpene, (11E)‐15,16‐bisnor‐13‐oxolabda‐8(17),11‐dien‐19‐oic acid ( 3 ), were isolated from the MeOH extract of the wood of Cunninghamia konishii. Their structures were determined by analysis of spectroscopic data and comparison with the data of known analogs. 相似文献
998.
Cheah Jue Lee Chew Sin Nah Chin Siew Teng Wee Wen Jun Muniyandy Saravanan 《Chemical Papers》2015,69(10):1325-1330
Arabinoxylan (AX) microspheres were formulated by ionotropic gelation for extended drug delivery. AX from Plantago ovata was tested for gelation with aluminium, barium, calcium, magnesium, and iron(III) chloride. Only calcium was found to lead to weak gelation with AX. The conventional needle extrusion produced fragile AX beads with calcium and hence the spray drying process was adopted for the preparation of metronidazole hydrochloride (MH) loaded AX microspheres. MH loading in AX microspheres was 30.8 mass %, 31.9 mass %, and 29.3 mass % in formulations gelled with 0.05 g, 0.1 g, and 0.15 g of calcium chloride per 100 mL of solution, respectively. Scanning electron microscopy revealed the crystallinity reduction of MH in microspheres. The surface of drug loaded calcium gelled AX microsphere was rougher than that of an ungelled one. Interactions of calcium with AX and the amorphous nature of the drug in the microspheres were evidenced by infrared spectroscopy and X-ray diffraction studies. Calcium-induced gelation can extend the drug release to over 90 min in 0.1 M HCl despite the hydrophilic nature of AX and the high solubility of metronidazole. 相似文献
999.
In this, the second part of a two part paper, results obtained by using the finite element (FE) method in conjunction with micromechanics to predict the effective elastic stiffness and strength of a carbon 2D triaxially braided composite (2DTBC), are presented. The 3D FE based micromechanics study was carried out on one representative unit cell (RUC) of the carbon 2DTBC (the “micromodel”). The FE models were first used to determine the macroscopic elastic orthotropic stiffnesses of the 2DTBC. The micromodel was deemed acceptable (in terms of the number of elements used in the mesh of the micromodel) if the elastic stiffnesses it displayed were within 5% of the elastic properties found experimentally. Subsequently, buckling eigenmodes were determined for the FE RUC under uniaxial and biaxial loading states, corresponding to the experimental investigation reported in part I of this two part paper. The lowest symmetric modes were identified and these mode shapes were used as imperfections to the FE model for a subsequent nonlinear response analysis using an arc-length method in conjunction with the ABAQUS commercial FE code. The magnitude of the imperfections was left as a parameter and its effect on the predicted response was quantified. The present micromechanics computational model provides a means to assess the compressive and compressive/tensile biaxial strength of the braided composites and its dependence on various microstructural parameters. It also serves as a tool to assess the most significant parameter that affects compressive strength. 相似文献
1000.
Mussel‐Inspired Modification of Nanofibers for REST siRNA Delivery: Understanding the Effects of Gene‐Silencing and Substrate Topography on Human Mesenchymal Stem Cell Neuronal Commitment 下载免费PDF全文