全文获取类型
收费全文 | 10807篇 |
免费 | 1569篇 |
国内免费 | 2394篇 |
专业分类
化学 | 10444篇 |
晶体学 | 192篇 |
力学 | 127篇 |
综合类 | 104篇 |
数学 | 26篇 |
物理学 | 3877篇 |
出版年
2024年 | 23篇 |
2023年 | 112篇 |
2022年 | 247篇 |
2021年 | 325篇 |
2020年 | 399篇 |
2019年 | 374篇 |
2018年 | 357篇 |
2017年 | 420篇 |
2016年 | 524篇 |
2015年 | 509篇 |
2014年 | 616篇 |
2013年 | 1117篇 |
2012年 | 824篇 |
2011年 | 684篇 |
2010年 | 545篇 |
2009年 | 691篇 |
2008年 | 657篇 |
2007年 | 685篇 |
2006年 | 673篇 |
2005年 | 612篇 |
2004年 | 597篇 |
2003年 | 522篇 |
2002年 | 497篇 |
2001年 | 344篇 |
2000年 | 342篇 |
1999年 | 306篇 |
1998年 | 235篇 |
1997年 | 209篇 |
1996年 | 179篇 |
1995年 | 183篇 |
1994年 | 145篇 |
1993年 | 126篇 |
1992年 | 131篇 |
1991年 | 86篇 |
1990年 | 66篇 |
1989年 | 62篇 |
1988年 | 69篇 |
1987年 | 40篇 |
1986年 | 35篇 |
1985年 | 26篇 |
1984年 | 23篇 |
1983年 | 18篇 |
1982年 | 21篇 |
1981年 | 12篇 |
1980年 | 18篇 |
1979年 | 17篇 |
1978年 | 17篇 |
1977年 | 13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.
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
172.
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
173.
Measurements of acoustic absorption and velocity as a function of frequency and concentration in KH2PO4–K2HPO4 buffers at 4°C and pH 5-7 are reported. The dependence of the observed acoustic relaxation parameters on concentration is consistent with that to be expected from perturbation of a monomer-dimer equilibrium with an equilibrium constant [for 2H2PO
4
–
(H2PO4)2
2–] of 0.21 M–1, a bimolecular rate constant of 5×108 M–1-sec–1 and a standard volume change of –5 cm3 mole. The equilibrium constant for H2PO
4
–
+ HPO4
2–H3(PO4)2
3– is estimated to be 0.7 M–1. 相似文献
174.
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
175.
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
176.
The overall stability constantsK
1 andK
2 of NdNO
3
2+
and Nd(NO3)
2
+
complexes were determined (K
1=1.77;K
2=1.28) using an extraction method with tri-n-butyl phosphate as the extractant. The ratio 1/2 of the stepwise stability constants is discussed. It was established that the Nd(NO3)
2
+
complex was an outer-sphere ion pair.
Die Assoziation von Nitrat-Ion mit Nd3+
Zusammenfassung Mittels einer Extraktionsmethode wurden die StabilitätskonstantenK 1 undK 2 von NdNO 3 2+ - und Nd(NO3)+-Komplexen bestimmt (K 1=1.77;K 2=1.28; Tri-n-butylphosphat als Extraktionsmittel). Das Verhältnis 1/2 der stufenweisen Stabilitätskonstanten wird diskutiert. Es stellte sich heraus, daß der Nd(NO3)+-Komplex als ein Outer-Shere-Ionenpaar vorliegt.相似文献
177.
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
178.
Samuel K Yin W Stearns RA Tang YS Chaudhary AG Jewell JP Lanza T Lin LS Hagmann WK Evans DC Kumar S 《Journal of mass spectrometry : JMS》2003,38(2):211-221
Metabolic activation of drug candidates to electrophilic reactive metabolites that can covalently modify cellular macromolecules may result in acute and/or idiosyncratic immune system-mediated toxicities in humans. This presents a significant potential liability for the future development of these compounds as safe therapeutic agents. We present here an example of an approach where sites of metabolic activation within a new drug candidate series were rapidly identified using online liquid chromatography/multi-stage mass spectrometry on an ion trap mass spectrometer. This was accomplished by trapping the reactive intermediates formed upon incubation of compounds with rat and human liver microsomes as their corresponding glutathione conjugates and mass spectral characterization of these thiol adducts. Based on the structures of the GSH adducts identified, potential sites and mechanisms of bioactivation within the chemical structure were proposed. These metabolism studies were interfaced with iterative structural modifications of the chemical series in order to block these bioactivation sites within the molecule. This strategy led to a significant reduction in the propensity of the compounds to undergo metabolic activation as evidenced by reductions in the irreversible binding of radioactivity to liver microsomal material upon incubation of tritium-labeled compounds with this in vitro system. With the efficiency and throughput achievable with such an approach, it appears feasible to identify and address the metabolic activation potential of new drug leads during routine metabolite identification studies in an early drug discovery setting. 相似文献
179.
J. Al Andari A. M. Diamy J. C. Legrand R. I. Ben-Aim 《Plasma Chemistry and Plasma Processing》1993,13(1):103-116
Electron temperature and ion density are measured in an air microwave-induced plasma (2450 MHz) by means of a floating double probe. A 'cinetic scheme for ion formation and decay is set up, and a relationship between atomic oxygen and ion densities is obtained. From this relationship an order-of-magnitude of atomic oxygen concentration in the discharge is derived and compared with results obtained by optical actinometry in another work. 相似文献
180.
Börries Kübel 《Monatshefte für Chemie / Chemical Monthly》1982,113(6-7):793-803
3-Acetonyl-1,2,4-oxadiazoles and 2-acetonyl-1,3,4-oxadiazoles are accessible starting with the ketal of acetoacetamide oxime and the ketal of acetoacetic acid hydrazide, respectively. 5-Acetonyl-1,2,4-thiadiazoles are obtained from 5-chloro-1,2,4-thiadiazoles andtert.-butyl acetoacetate. These Acetonyl-azoles are starting materials for three series of azolylvinyl phosphates and phosphonates.
Herrn Prof. Dr.Klaus Weissermel zu seinem 60. Geburtstag. 相似文献