全文获取类型
收费全文 | 6675篇 |
免费 | 1112篇 |
国内免费 | 733篇 |
专业分类
化学 | 4647篇 |
晶体学 | 72篇 |
力学 | 390篇 |
综合类 | 38篇 |
数学 | 778篇 |
物理学 | 2595篇 |
出版年
2024年 | 24篇 |
2023年 | 135篇 |
2022年 | 247篇 |
2021年 | 234篇 |
2020年 | 240篇 |
2019年 | 273篇 |
2018年 | 214篇 |
2017年 | 207篇 |
2016年 | 299篇 |
2015年 | 334篇 |
2014年 | 361篇 |
2013年 | 435篇 |
2012年 | 585篇 |
2011年 | 626篇 |
2010年 | 390篇 |
2009年 | 336篇 |
2008年 | 395篇 |
2007年 | 369篇 |
2006年 | 371篇 |
2005年 | 290篇 |
2004年 | 227篇 |
2003年 | 207篇 |
2002年 | 153篇 |
2001年 | 153篇 |
2000年 | 155篇 |
1999年 | 175篇 |
1998年 | 144篇 |
1997年 | 129篇 |
1996年 | 122篇 |
1995年 | 116篇 |
1994年 | 110篇 |
1993年 | 74篇 |
1992年 | 75篇 |
1991年 | 85篇 |
1990年 | 55篇 |
1989年 | 34篇 |
1988年 | 33篇 |
1987年 | 30篇 |
1986年 | 19篇 |
1985年 | 19篇 |
1984年 | 9篇 |
1983年 | 19篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有8520条查询结果,搜索用时 10 毫秒
141.
A method of free energy calculation is proposed, which enables to cover a wide range of pressure and temperature. The free energies of proton-disordered hexagonal ice (ice Ih) and liquid water are calculated for the TIP4P [J. Chem. Phys. 79, 926 (1983)] model and the TIP5P [J. Chem. Phys. 112, 8910 (2000)] model. From the calculated free energy curves, we determine the melting point of the proton-disordered hexagonal ice at 0.1 MPa (atmospheric pressure), 50 MPa, 100 MPa, and 200 MPa. The melting temperatures at atmospheric pressure for the TIP4P ice and the TIP5P ice are found to be about T(m)=229 K and T(m)=268 K, respectively. The melting temperatures decrease as the pressure is increased, a feature consistent with the pressure dependence of the melting point for realistic proton-disordered hexagonal ice. We also calculate the thermal expansivity of the model ices. Negative thermal expansivity is observed at the low temperature region for the TIP4P ice, but not for the TIP5P ice at the ambient pressure. 相似文献
142.
Zeng X Sun H Chen L Leng X Xu F Li Q He X Zhang W Zhang ZZ 《Organic & biomolecular chemistry》2003,1(6):1073-1079
Two novel tweezer-like 25,27-dihydroxy-26,28-bis(phenylthiaethoxy)calix[4]arenes 6 and 7 were synthesized by the reaction of 25,27-dihydroxy-26,28-bis(bromoethoxy)calix[4]arenes 3 and 4 for the evaluation of their ion-selectivity in ion-selective electrodes (ISEs). X-ray structural analysis indicated that calix[4]arene 7 is in an interesting infinite linear aggregate via self-inclusion. For investigation of the influences of substitutes on the behavior of the ISEs, the halogen substituted aryl analogues of 25,27-dihydroxy-26,28-bis(arylthiaethoxy)calix[4]arenes 8-12 were also synthesized and their ISE performances were evaluated under the same conditions. ISEs based on 6-12 as neutral ionophores were prepared, and their selectivity coefficients for Ag+ (log KAg,M(pot)) were investigated against other alkali metal, alkaline-earth metal, lead, ammonium ions and some transition metal ions using the fixed interference method (FIM). These ISEs showed excellent Ag+ selectivity over most of the interfering cations examined, except for Hg2+ having relative smaller interference (log KAg,Hg(pot) < or = 2.1). The 19F NMR spectra of 9 and 9.AgClO4 were recorded for investigation the fluorine environments in the complex. The 19F NMR spectra strongly suggested that the fluorine atoms on ionophore 9 participated in ligation with silver cation. 相似文献
143.
Caignan GA Deshmukh R Wilks A Zeng Y Huang HW Moënne-Loccoz P Bunce RA Eastman MA Rivera M 《Journal of the American Chemical Society》2002,124(50):14879-14892
The origin of the unusual regioselectivity of heme oxygenation, i.e. the oxidation of heme to delta-biliverdin (70%) and beta-biliverdin (30%), that is exhibited by heme oxygenase from Pseudomonas aeruginosa (pa-HO) has been studied by (1)H NMR, (13)C NMR, and resonance Raman spectroscopies. Whereas resonance Raman indicates that the heme-iron ligation in pa-HO is homologous to that observed in previously studied alpha-hydroxylating heme oxygenases, the NMR spectroscopic studies suggest that the heme in this enzyme is seated in a manner that is distinct from that observed for all other alpha-hydroxylating heme oxygenase enzymes for which a structure is known. In pa-HO, the heme is rotated in-plane approximately 110 degrees, so the delta-meso-carbon of the major orientational isomer is located within the HO-fold in the place where the alpha-hydroxylating enzymes typically place the alpha-meso-carbon. The unusual heme seating displayed by pa-HO places the heme propionates so that these groups point in the direction of the solvent-exposed heme edge and appears to originate in large part from the absence of stabilizing interactions between the polypeptide and the heme propionates, which are typically found in alpha-hydroxylating heme oxygenase enzymes. These interactions typically involve Lys-16 and Tyr-112, in Neisseriae meningitidis HO, and Lys-16 and Tyr-134, in human and rat HO-1. The corresponding residues in pa-HO are Asn-19 and Phe-117, respectively. In agreement with this hypothesis, we found that the Asn-19 Lys/Phe-117 Tyr double mutant of pa-HO exists as a mixture of molecules exhibiting two distinct heme seatings; one seating is identical to that exhibited by wild-type pa-HO, whereas the alternative seating is very similar to that typical of alpha-hydroxylating heme oxygenase enzymes and is related to the wild-type seating by approximately 110 degrees in-plane rotation of the heme. Furthermore, each of these heme seatings in the pa-HO double mutant gives rise to a subset of two heme isomeric orientations that are related to each other by 180 degrees rotation about the alpha-gamma-meso-axis. The coexistence of these molecules in solution, in the proportions suggested by the corresponding area under the peaks in the (1)H NMR spectrum, explains the unusual regioselectivity of heme oxygenation observed with the double mutant, which we found produces alpha- (55%), delta- (35%), and beta-biliverdin (10%). Alpha-biliverdin is obtained by oxidation of the heme seated similar to that of alpha-hydroxylating enzymes, whereas beta- and delta-biliverdin are formed from the oxidation of heme seated as in wild-type pa-HO. 相似文献
144.
145.
Jian-zhang?Li Bin?Xu Shen-Xin?Li Wei?Zeng Sheng-ying?QinEmail author 《Transition Metal Chemistry》2005,30(6):669-676
Four manganese(III) complexes (MnL1Cl, MnL2Cl, MnL42Cl, MnL52Cl) with a crowned salicylaldimine Schiff base ligand have been synthesized and employed as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (PNPP). The kinetics and mechanism of catalytic PNPP hydrolysis have been investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes has been proposed. The effects of the ligand structure and crown ether ring in complexes, and the reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results show that compared with the crown-free analogous MnL3Cl and MnL62Cl, the crowned Schiff base manganese(III) complexes, MnL1Cl, MnL2Cl, MnL42Cl and MnL52Cl, exhibit more high catalytic activity, which follow the order: MnL1Cl >MnL2Cl >MnL42Cl >MnL52Cl >MnL3Cl >MnL62Cl; the pseudo-first-order-rate (kobs) for the PNPP hydrolysis catalyzed by the complex MnL1Cl containing three crown ether rings is highest among six complexes and is 1.81 times that of MnL3Cl, 1.49 × 103 times that of spontaneous hydrolysis of PNPP, respectively, at pH = 7.00, [S] = 2.0 × 10−4 mol dm−3. 相似文献
146.
Electric-field-induced transient pore formation (electroporation) in synthetic unilamellar vesicles is utilized for the preparation of subnanometer size uncapped gold quantum dots. With the precursor AuCl4(-) placed in the aqueous bulk solution and the reducing agent BH4(-) originally entrapped in the vesicles' compartments, the redox reaction--that occurs in the bulk--is initiated by the opening of transient pores in the vesicles' bilayers. The absence of caps permits (i) continued growth of the Au clusters formed, (ii) the assessment of their true absorption spectra unaltered by stabilizing ligands, and (iii) the previously inaccessible live observation of the growth of the clusters in the molecular size regime. The normally rapid self-aggregation of Au atoms is slowed to the time scales of hour and week by their adsorption at the exterior surface of the vesicles. The UV spectra exhibit novel, time-dependent, oscillating red and blue shifts of the characteristic absorption band, which can be attributed to the evolution of cluster size transiently halting at magic aggregation numbers corresponding to Au2, Au8, Au20, and Au34. Subsequent growth is associated with a monotonic red shift of the absorption band up to the characteristic surface plasmon absorption at 520 nm. 相似文献
147.
148.
A hierarchy of Hamiltonian systems obtained from the Lax pair of KdV hierarchy under the constraint condition on potentialu = q, q is presented. The independent integrals for these Hamiltonian systems are constructed by using recursion operator and shown to be in involution. Thus this hierarchy of Hamiltonian systems is completely integrable in the sense of Liouville, and they commute with each other.This project is supported by the National Natural Science Foundation of China. 相似文献
149.
聚丙烯酰胺对石油磺酸盐/正丁醇混合胶束体系流变性的影响 总被引:1,自引:0,他引:1
研究了一定矿化度下,不同分子量、不同水解度的聚丙烯酰胺对石油磺酸盐/正丁醇混合胶事体系的流型、粘度等充变性质的影响。 相似文献
150.
Yu-Fen Zhao De-Qing Zhang Chu-Biao Xue Jia-Ning Zeng Gai-Jiao Ji 《Journal of mass spectrometry : JMS》1991,26(5):510-513
Positive ion fast atom bombardment mass spectrometry of N-diisopropyloxyphosphoryl dipeptides and tripeptides showed a novel cleavage pattern in that only the N-phosphoryl fragment ions gave intense peaks while the C-terminal series of ions was suppressed. The base peak was the N-phosphoryl imino ion responding to the N-terminal residue. These advantages are superior to those of other types of N-protecting groups. 相似文献