全文获取类型
收费全文 | 6211篇 |
免费 | 238篇 |
国内免费 | 26篇 |
专业分类
化学 | 4388篇 |
晶体学 | 39篇 |
力学 | 176篇 |
数学 | 965篇 |
物理学 | 907篇 |
出版年
2024年 | 4篇 |
2023年 | 49篇 |
2022年 | 126篇 |
2021年 | 201篇 |
2020年 | 163篇 |
2019年 | 157篇 |
2018年 | 114篇 |
2017年 | 116篇 |
2016年 | 253篇 |
2015年 | 213篇 |
2014年 | 223篇 |
2013年 | 331篇 |
2012年 | 398篇 |
2011年 | 494篇 |
2010年 | 280篇 |
2009年 | 259篇 |
2008年 | 388篇 |
2007年 | 362篇 |
2006年 | 364篇 |
2005年 | 335篇 |
2004年 | 312篇 |
2003年 | 246篇 |
2002年 | 208篇 |
2001年 | 78篇 |
2000年 | 73篇 |
1999年 | 76篇 |
1998年 | 48篇 |
1997年 | 52篇 |
1996年 | 77篇 |
1995年 | 49篇 |
1994年 | 47篇 |
1993年 | 39篇 |
1992年 | 49篇 |
1991年 | 39篇 |
1990年 | 23篇 |
1989年 | 22篇 |
1988年 | 13篇 |
1987年 | 16篇 |
1986年 | 18篇 |
1985年 | 24篇 |
1984年 | 21篇 |
1983年 | 22篇 |
1982年 | 16篇 |
1981年 | 12篇 |
1980年 | 14篇 |
1979年 | 17篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1906年 | 2篇 |
排序方式: 共有6475条查询结果,搜索用时 15 毫秒
111.
The low-temperature NMR spectra of 1,4-bis(mesitoyl)durene, 1, and of 1,4-bis(mesitylethenyl)durene, 2, reveal the presence of syn and anti rotamers at the equilibrium, their relative proportions depending on the dielectric constant of the solvent. In solution the more stable rotamer of 1 is the anti whereas, in the case of 2, the more stable is the syn. Depending on the crystallization solvent employed the more (anti) and the less stable (syn) rotamers were both observed (X-ray diffraction) in the solid state of 1. On the other hand, only the less stable rotamer (anti) was found to be present in the solid state of 2. As shown by MM calculations, the syn-to-anti interconversion occurs via a correlated process (cogwheel pathway) involving the mesityl-C and durene-C bond rotations: the dynamic NMR technique yields an experimental barrier of 8.2 kcal mol(-)(1) for 1 and 13.1 kcal mol(-)(1) for 2. In the case of derivative 2 a second barrier, due to a second type of correlated rotation process (torsion), was also determined (8.6 kcal mol(-)(1)). As a consequence of the restriction of this second torsional motion the anti rotamer of 2 displays two distinguishable NMR spectra at -133 degrees C, corresponding to a pair of conformers with different symmetry (anti C(i)() and anti C(2)). 相似文献
112.
Multielemental analysis of food and agricultural matrixes by inductively coupled plasma-mass spectrometry 总被引:1,自引:0,他引:1
The suitability of quadrupole inductively coupled plasma-mass spectrometry (ICP-MS) for multielemental analysis of food following microwave closed vessel digestion of samples was evaluated in relation to analytical challenges presented by some major food and agricultural matrixes. Fifteen key analytes (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) were determined in 9 reference materials representative of 3 major groups of staple foods (cereals, seafood, and meat). For all measurements, the method of external calibration was used and Rh was selected as internal standard. Matrix-induced interferences were evaluated for each material, and suitable methods to overcome them were applied. Spectral interferences caused by C, Cl, and Ca content of digestates were quantitated and corrected by entering a simple system of mathematical correction equations into the instrument software before each analytical run. Full mastering of interferences together with adoption of a series of measures to control the reliability of analytical measurements produced accurate results for all the analytes. A standard analytical protocol is outlined for the benefit of both research and routine high-throughput laboratories that perform ICP-MS analyses of food. 相似文献
113.
Arduini A Brindani E Giorgi G Pochini A Secchi A 《The Journal of organic chemistry》2002,67(17):6188-6194
A novel heteroditopic receptor (5) based on a rigid calix[4]arene cavity bearing at the upper rim four arylsulfonamido binding sites has been synthesized. The binding abilities of this new host have been investigated in apolar solvents toward a series of tetramethylammonium salts (tosylate, chloride, acetate, trifluoroacetate, and picrate) and compared with those of monotopic and heteroditopic calix[4]arene-bis(crown-3)-based receptors 1 and 2 in order to evaluate the role of the anion on ion-pair recognition. While monotopic host 1 shows an efficiency order toward the different salts that increases when the anion is less interactive (Hofmeister trend), an opposite role of the counteranion on the recognition process was observed with host 5 (anti-Hofmeister trend). A more complex behavior is experienced by host 2, which shows a high and leveled efficiency for all the anions tested. The results obtained were explained on the basis of the different types of ion pairs present in the recognition process. Further information on the role of the anion were obtained by the "dual host" strategy utilizing the tri-n-butylthioureido derivative of tren 7, which forms a stable complex with chloride anion. The very high efficiency shown by these heteroditopic hosts opens new routes in supramolecular projects and is a very interesting tool in the molecular recognition of ion-pairs and its applications. 相似文献
114.
A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described. Treatment of 1-O-acyl-glycoses 1 , 7 , 13 , and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2 , 4 , 8 , 10 , 14 , 16 , 20 , and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3 , 5 , 9 , 11 , 15 , 17 , 21 , and 23 as the minor anomers. The 1,2-cis-configurated phosphonates 4 , 10 , 16 , and 22 were deprotected to give the (β-D -glucopyranosyl)phosphonate 6 , the (β-D -mannopyranosyl)phosphonate 12 , the (β-D -ribofuranosyl)phosphonate 18 , and the (β-D -arabinofuranosyl)phosphonate 24 , respectively, in high yields. The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26 ) and a stabilization of the cis-configurated salts through formation of a pentacoordinated species (such as 28 ). 相似文献
115.
A two-step protocol for the first chemoselective cleavage of 2-hydroxy acid amides has been developed. Mesylation of the model substrate 2-(hydroxypropionylamino)-4-methylpentanoic acid methyl ester (11) followed by treatment with N-ethylthiourea (13) allows cleavage of 2-hydroxy acid amides under smooth conditions. Successful application of this methodology to the open-chain transesterification product 15 (methylester) of the cyclic heptadepsipeptide HUN-7293, a potent inhibitor of inducible cell adhesion molecule expression, delivered the corresponding hexapeptide 18 with unprotected N-terminus in 70-75% yield. This result demonstrates that the protocol developed even works in the presence of an ester and several methylated and unmethylated amide bonds. Finally, a sequence of ligation of methyl D-dehydroglutaminate (20) to the C-terminus of the saponification product 21, followed by the degradation protocol and ring closure, allowed chemical "point mutation" at the DGCN site affording the aza analogue of HUN-7293 (24) in 15% overall yield. To the best of our knowledge this is the first report on chemoselective cleavage of 2-hydroxy acid amides. 相似文献
116.
Giuliana Gervasio Domenica Marabello Andrea Secco 《Journal of organometallic chemistry》2004,689(1):35-42
The reaction of Ru3(CO)12 with but-2-yn-1,4-diol (HOCH2CCCH2OH, BUD) in CH3OH/KOH followed by acidification with HCl leads to four products, one of which has been identified as the title complex (μ-Cl)Ru3(CO)9[μ3-η4-H2CCC(H)CH2]. This is an open cluster containing a bridging Cl atom on the open side and a C4H5 moiety bound to all the metals. The structure of the complex has been determined by X-ray analysis.The thermal reaction of Ru3(CO)12 with BUD has been revisited for a comparison with the results in alkaline solution. The main product is the allylic derivative HRu3(CO)9[HCCHCCHO]. 相似文献
117.
Cacciapaglia R Casnati A Mandolini L Reinhoudt DN Salvio R Sartori A Ungaro R 《The Journal of organic chemistry》2005,70(2):624-630
The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst-substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal > 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism. 相似文献
118.
Chichak KS Peters AJ Cantrill SJ Stoddart JF 《The Journal of organic chemistry》2005,70(20):7956-7962
[Structure: See text] In addition to a parent zinc(II) Borromean ring (BR) complex, the preparation and characterization of two hexasubstituted BR complexes with either 4-acetoxymethylphenyl or 4-methylthiophenyl substituents associated in turn with all six pyridyl rings has been achieved convergently in good yields by appealing to the dynamic features of the reactions between primary amino groups in a preformed acyclic ligand and 2,6-diformylpyridine. Two molecules of the acyclic ligands react with two molecules of 2,6-diformylpyridine to form a cyclic [2 + 2] tetraimine in the presence of Zn(II) ions as templates in 2-propanol at 70 degrees C. The successful preparation of the two derivatives by convergent template-directed syntheses opens up opportunities to self-assemble, under equilibrium control, numerous nanoscale metallo-organic particles with potentially useful properties. 相似文献
119.
Densities and excess molar volumes for binary mixtures of N,N-dimethylformamide+ 1,2-dimethoxyethane
Fulvio Corradini Gian Carlo Franchini Andrea Marchetti Mara Tagliazucchi Lorenzo Tassi Giuseppe Tosi 《Journal of solution chemistry》1994,23(7):777-785
Densities are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from –10 to 80°C. The experimental density data have been fitted by empirical relations and the excess volumes by a Redlich-Kister equation. The 11 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made. 相似文献
120.
Favero G Campanella L Cavallo S D'Annibale A Perrella M Mattei E Ferri T 《Journal of the American Chemical Society》2005,127(22):8103-8111
The realization of a reliable receptor biosensor requires stable, long-lasting, reconstituted biomembranes able to supply a suitable biomimetic environment where the receptor can properly work after incorporation. To this end, we developed a new method for preparing stable biological membranes that couple the biomimetic properties of BLMs (bilayer lipid membranes) with the high stability of HBMs (hybrid bilayer membranes); this gives rise to an innovative assembly, named MHBLM (mixed hybrid bilayer lipid membrane). The present work deals with the characterization of biosensors achieved by embedding an ionotropic glutamate receptor (GluR) on MHBLM. Thanks to signal (transmembrane current) amplification, which is typical of natural receptors, the biosensor here produced detects glutamate at a level of nmol L(-1). The transmembrane current changes linearly vs glutamate up to 100 nmol L(-1), while the limit of detection is 1 nmol L(-1). In addition, the biosensor response can be modulated both by receptor agonists (glycine) and antagonists (Mg(2+)) as well, and by exploiting the biosensor response, the distribution of different kinds of ionotropic GluR present in the purified sample, and embedded in MHBLM, was also evaluated. Finally, one of the most important aspects of this investigation is represented by the high stability of the biomimetic system, which allows the use of biosensor under flowing conditions, where the solutions flow on both biomembrane faces. 相似文献