全文获取类型
收费全文 | 11039篇 |
免费 | 1609篇 |
国内免费 | 2107篇 |
专业分类
化学 | 9829篇 |
晶体学 | 115篇 |
力学 | 272篇 |
综合类 | 132篇 |
数学 | 112篇 |
物理学 | 4295篇 |
出版年
2024年 | 22篇 |
2023年 | 126篇 |
2022年 | 299篇 |
2021年 | 346篇 |
2020年 | 417篇 |
2019年 | 371篇 |
2018年 | 354篇 |
2017年 | 488篇 |
2016年 | 590篇 |
2015年 | 555篇 |
2014年 | 637篇 |
2013年 | 1086篇 |
2012年 | 806篇 |
2011年 | 683篇 |
2010年 | 556篇 |
2009年 | 675篇 |
2008年 | 647篇 |
2007年 | 685篇 |
2006年 | 690篇 |
2005年 | 585篇 |
2004年 | 584篇 |
2003年 | 492篇 |
2002年 | 472篇 |
2001年 | 324篇 |
2000年 | 320篇 |
1999年 | 284篇 |
1998年 | 212篇 |
1997年 | 208篇 |
1996年 | 171篇 |
1995年 | 166篇 |
1994年 | 130篇 |
1993年 | 125篇 |
1992年 | 118篇 |
1991年 | 79篇 |
1990年 | 62篇 |
1989年 | 58篇 |
1988年 | 68篇 |
1987年 | 38篇 |
1986年 | 32篇 |
1985年 | 23篇 |
1984年 | 21篇 |
1983年 | 17篇 |
1982年 | 24篇 |
1981年 | 11篇 |
1980年 | 16篇 |
1979年 | 16篇 |
1978年 | 16篇 |
1977年 | 12篇 |
1976年 | 18篇 |
1973年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
171.
W. Kunz J. Barthel L. Klein T. Cartailler P. Turq B. Reindl 《Journal of solution chemistry》1991,20(9):875-891
A variety of methods has been used for the study of lithium bromide solutions in acetonitrile yielding by their combination reliable information on different levels of approximation. Osmotic coefficients based on precise vapor pressure measurements are reproduced by CM (chemical model) and HNC (hypernetted chain) calculations and by BD (brownian dynamics) simulations. The results of neutron scattering experiments are treated with the help of HNC and BD methods. Hartree-Fock calculations on isolated LiBr pairs and solvated lithium ions yield reliable particle distances and reveal the geometry of the lithium solvation sphere. 相似文献
172.
《Mendeleev Communications》2020,30(5):679-682
- Download : Download high-res image (153KB)
- Download : Download full-size image
173.
Mark Salomon 《Journal of solution chemistry》1990,19(12):1225-1236
Conductivity data are used to determine thermodynamic complex formation constants for cases in which both the initial electrolyte and the complexed electrolyte form ion pairs. Using the method described in the text, the complex formation constants of Li+, Na+ and K+ with the crown ether 18-crown-6 and of Li+ with the ligand triphenylphosphine oxide in propylene carbonate have been evaluated from conductance data. The complexation of AgBr in propylene carbonate solutions of n-etrabutylammonium bromide has also been studied by the measurement of molar conductivities. The results of these studies indicate that ion pairing should not be neglected, even in high permittivity solvents such as propylene carbonate, and that the ion pair association constants correlate well with structural studies on cation-crown ether molecular conformations. 相似文献
174.
利用扫描电镜、热失重-红外、元素分析、低温氮吸附等技术和化学手段对聚羧酸基FFC-1离子交换纤维的结构与性能特点等进行了系统研究.结果表明:FFC-1离子交换纤维为含适量酰肼类交联键的聚羧酸(钠)型离子交换材料,外比表面积大和传质距离短是其反应动力学性能优异的主要原因,FFC-1纤维具有良好的化学与热稳定性。在5mol/L硫酸、硝酸、盐酸和2mol/L氢氧化钠溶液中浸泡,交换容量未见明显降低。但过氧化氢溶液对其功能基有明显破坏,CO2为FFC-1纤维在高温区间(300℃~350℃)的主要分解产物。 相似文献
175.
176.
Studies of the vibrational spectra of matrix-isolated M+NO
3
–
ion pairs have been extended to glassy aprotic solvents. The deuterated form of the solvents DMSO, THF, and ACN have windows through the 7- nitrate ionv
3(e) mode infrared region, so it was possible to clearly observe the splitting of the degeneracy of this mode,v
3, produced by the contacting, but solvated, alkali metal cation. Primary attention has been directed to the extent to which this splitting is reduced relative to the argon matrix values. This reduction, which reflects electron-density transfer from the solvating molecules to the ion pairs, is comparable to that observed for H2O and NH3 matrices as the splitting is reduced to 20–35% of the argon-matrix values. The extent of reduction ofv
3 for the different solvents has been related to Gutmann's donicity number scale with the correlation holding well for solvent molecules of comparable size, DMSO, THF and DMF, but breaking down for the smaller linear ACN, apparently because of more molecules in the cation solvation sphere. The matrix data have also been used, through comparison with spectra for saturated liquid solutions of Li+NO
3
–
, to show that the contact ion pair is the dominant species in liquid THF and ACN, whereas the ions are largely solvent separated in DMSO. 相似文献
177.
Gary W. Schnuelle S. Swaminathan David L. Beveridge 《Theoretical chemistry accounts》1978,48(1):17-27
A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li+, Na+, K+, F– and Cl– each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties. 相似文献
178.
Ionization of esters of carboxylic acids RCOOR' (R = H, alkyl; R' = alkyl) within the air plasma of the Atmospheric Pressure Chemical Ionization (APCI) source occurs largely via H(+)-transfer and, to a minor extent, via NO(+) association. The protonated ester MH(+) is normally observed as M(2)H(+) and as higher aggregates (M(3)H(+), M(3)H(+)(H(2)O)) also at high source temperature. The behavior of M(2)H(+) upon collisional activation is consistent with the reported dissociation of proton-bound dimers to MH(+) species that, in turn, fragment according to the known paths of lowest energy. In addition, other important product ions form within the plasma, some in very high relative abundance, which are attributed to ion-molecule condensation reactions between neutral M and either MH(+) or M(2)H(+) resulting in the elimination of CO, R'OH, alkene from the alkoxy moiety of the ester and HCOOH. A general scheme is proposed to account for the experimental observations, which suggest that the encounter complex formed between MH(+) and M or between M(2)H(+) and M may either collisionally relax to the protonated dimer or trimer, respectively, or react via covalent bond forming and cleaving steps to eliminate stable neutral molecules. The proposed scheme is supported by both the observed concentration dependence and the temperature dependence of the products relative abundances within the plasma. Such reactions can be the dominant process, as in the case of formate esters. A second significant ionization route involves addition of NO(+) to form M(n)NO(+) (n = 1, 2, 3). An additional product corresponding to [M(2)NO(+) - CO(2)] is also observed with iso- and n-butyl formate esters. 相似文献
179.
Tomazela DM Gozzo FC Mayer I Engelmann FM Araki K Toma HE Eberlin MN 《Journal of mass spectrometry : JMS》2004,39(10):1161-1167
Ten homologous or isomeric singly, doubly, triply and quadruply charged cationic macrocyclic complexes I-Va, bn+ (n = 1-4) formed by the coordination of [Ru(bipy)2Cl]+ to the pyridyl N-atoms of a series of meso-(phenyl)m-(meta or para-pyridyl)n-porphyrins (m + n = 4) were transferred to the gas phase and structurally characterized by electrospray ionization (ESI) mass (MS) and tandem mass (MS/MS) spectrometry. Previously known to be stable in solution and in the solid state, I-Va, bn+ are found to constitute also a new class of stable, long-lived multiply charged gas-phase ions with spatially separated charge sites. Increasing intramolecular electrostatic repulsion from Ia, b+ to IVa, b3+ facilitates in-source and tandem collision-induced dissociation (CID). However, for the quadruply charged ions Va, b4+, electrostatic repulsion is alleviated mainly by ion pairing with the CF3SO3- counterion forming the salt clusters [Va,b/CF3SO3]3+ and [Va,b/(CF3SO3)2]2+ with reduced charge states. Ion-pairing that yields [IVa,b/CF3SO3]2+ is also observed as a minor ESI process for the triply charged ions IVa, b3+. The gaseous ions I-Va, bn+ (n = 2, 3 or 4) dissociate by sequential 'charge partitioning' with the formation of two cationic fragments by the release of [Ru(bipy)2Cl]+. The meta (a) and para (b) isomers and the positional isomers II2+ and III2+ display nearly identical ESI-MS and ESI-MS/MS spectra. ESI-MS/MS of I-Va, bn+ shows that the Ru-py(P) is, intrinsically, the weakest bond since this bond breaks preferentially upon CID. 相似文献
180.
利用离子阱质谱的原理和特点,研究了小分子醇、醚、胺、醛、酮等有机化合 物(分子量小于200)在离子阱里的分子离子反应,总结了反应特点和规律,并把 它归类为自身化学电离(SCI)反应。以丁酮、丙烯醇为例,采用FTMS对反应产物 离子进行准确质量测定,验证了它们各自的分子离子反应结果。另外,把该类化合 物(30个)SCI反应的质谱图与NIST98库中的标准EI质谱图进行了比较,建立了 SCI质谱图库,提高了在离子阱质谱上对这类小分子化合物定性分析的准确率。 相似文献