全文获取类型
收费全文 | 23689篇 |
免费 | 838篇 |
国内免费 | 143篇 |
专业分类
化学 | 15305篇 |
晶体学 | 275篇 |
力学 | 604篇 |
数学 | 4226篇 |
物理学 | 4260篇 |
出版年
2023年 | 177篇 |
2022年 | 298篇 |
2021年 | 392篇 |
2020年 | 520篇 |
2019年 | 554篇 |
2018年 | 442篇 |
2017年 | 443篇 |
2016年 | 1003篇 |
2015年 | 774篇 |
2014年 | 939篇 |
2013年 | 1568篇 |
2012年 | 1528篇 |
2011年 | 1757篇 |
2010年 | 1008篇 |
2009年 | 852篇 |
2008年 | 1457篇 |
2007年 | 1347篇 |
2006年 | 1284篇 |
2005年 | 1105篇 |
2004年 | 959篇 |
2003年 | 679篇 |
2002年 | 663篇 |
2001年 | 288篇 |
2000年 | 254篇 |
1999年 | 213篇 |
1998年 | 193篇 |
1997年 | 177篇 |
1996年 | 231篇 |
1995年 | 161篇 |
1994年 | 154篇 |
1993年 | 149篇 |
1992年 | 126篇 |
1991年 | 152篇 |
1990年 | 113篇 |
1989年 | 125篇 |
1988年 | 139篇 |
1987年 | 126篇 |
1986年 | 116篇 |
1985年 | 201篇 |
1984年 | 204篇 |
1983年 | 129篇 |
1982年 | 175篇 |
1981年 | 192篇 |
1980年 | 161篇 |
1979年 | 136篇 |
1978年 | 151篇 |
1977年 | 124篇 |
1976年 | 115篇 |
1975年 | 107篇 |
1973年 | 97篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
Santos E Schühle DT Jones H Schmickler W 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6406-6421
The nonlinear optical properties of self-assembled monolayers obtained from bonding two different alpha-functionalized terthiophenes (alpha-T3) to (111) silver electrode surfaces have been investigated using second harmonic generation (SHG). The two (alpha-T3) compounds used were functionalized with alkane chains of different lengths (C8 and C4), and each was terminated with a thiol anchoring group. A nitrile group was attached to the terminal thiophene ring of the (alpha-T3) compound with the C4 chain. The orientation of the polarization of the incident beam was changed systematically and gradually between "p" and "s" orientation and the SH signal (isotropic and anisotropic contributions) analyzed in both directions ("P" and "S"). The symmetry of the system was reduced by the presence of the adlayers from C3v to C3. The dependence on the applied potential and the incident wavelength has also been studied. The relative magnitudes and phases of the various second-order tensor elements have been estimated and compared with the values for a bare surface. A resonance process in the (alpha-T3) pi moiety has been investigated, and from this, the effective "band-gap" energies of the organic semiconductor SAMs (i.e., the energy difference between the pi-pi bands) have been estimated. 相似文献
102.
P. Staszczuk J. C. Bazan M. Błachnio D. Sternik N. J. Garcia 《Journal of Thermal Analysis and Calorimetry》2006,86(1):57-68
This paper presents possible applications of thermal analysis, sorptometry
and porosimetry to study physico-chemical properties of Na- and La-montmorillonite
samples, especially for determination of total surface heterogeneity. The
quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative
(Q-DTG) curves with respect to temperature and time obtained during programmed
liquid thermodesorption under quasi-isothermal conditions have been used to
study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites.
Calculations of the desorption energy distribution functions by analytical
procedure using mass loss Q-TG and differential mass loss Q-DTG curves of
thermodesorption under quasi-isothermal conditions of polar and non-polar
liquid vapours preadsorbed on a material surface are presented. Parameters
relating to porosity of samples were determined by sorptometry, mercury porosimetry
and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry
and porosimetry methods, the fractal dimensions of montmorillonites have been
calculated. Moreover, a new approach is proposed to calculate fractal dimensions
of materials obtained from Q-TG curve; this is compared with values obtained
by the above methods. The total heterogeneous properties (energy distribution
function and pore-size distribution functions) of samples studied were estimated.
The radius and pore volume of the tested samples calculated on the basis of
thermogravimetry, sorptometry and porosimetry techniques were compared and
good correlations obtained. 相似文献
103.
The voltammetric determination of trace amounts of gold has been studied using a chemically modified electrode. The role played by the host molecule attached to a glassy carbon electrode (GCE), i.e. 8,9,17,18-dibenzo-1,7-dioxa-10,13,16-triazacyclooctadecane (DDTC), was examined by electrochemical and spectrochemical techniques. Cathodic stripping voltammetry (CSV) was applied to study the various parameters affecting the affinity of gold ions by a DDTC modified electrode as well as the interference by other ions. Finally, the method has been successfully applied to determine gold traces in a geological sample. In addition, the formation of an AuCl
4
–
-DDTC complex was followed and its formation constant was determined by spectrophotometry. 相似文献
104.
Exchange interactions in copper(II) complexes with tridentate Schiff bases: EPR and magnetic studies
Bogusława Jeżowska-Trzebiatowska Julia Jezierska Jerzy Baranowski 《Chemical physics letters》1977,52(3):590-594
The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure. 相似文献
105.
Daniel C. Grohs 《Tetrahedron letters》2005,46(25):4373-4376
We have recently described the synthesis of diazabicyclo[4.X.0]alkanes and their use as ligands for the prostate specific membrane antigene (PSMA). The key step of our synthetic route toward these diazabicycloalkanes is an oxidative cleavage of a bicyclic diol moiety followed by the attack of a nitrogen nucleophile to the resulting intermediate bisaldehyde. We herein describe the mechanism of this ring closure and its stereochemical consequences. In addition, we report a convenient method for trapping intermediate bisaldehydes by Wittig reagents. This trapping allows the synthesis of 3,5-disubstituted proline derivatives, which are shown to be versatile precursors for functionalized diazabicycloalkane dipeptide mimetics. 相似文献
106.
A new approach to micropatterning is demonstrated. The approach is based on driving an electrochemical process at the solid-liquid interface through the formation of a flux of ions from a micropipet that is held in close proximity to the surface. The flux of ions is generated by the so-called potential assisted ion transfer at the interface between two immiscible electrolyte solutions (ITIES). As a model system, the local deposition of silver was examined. Specifically, a constant potential, which was applied to a micropipet filled with an aqueous solution of silver ions, caused the transfer of Ag(+) into the outer nitrobenzene (NB) solution that consisted of an electrolyte, tetrabutylammonium tetrakis[4-chlorophenyl]borate (TBATPBCl). To facilitate the transfer of silver ions a macrocyclic ligand, that is, dibenzo-24-crown-8 (DB24C8), was added to the organic phase. The Faradaic current of this micro-ITIES was used as a means of controlling the tip-surface distance in scanning electrochemical microscopy (SECM) and depositing silver microstructures on a gold substrate. 相似文献
107.
Anilinium is strongly adsorbed at monolayers of the phospholipid L-alpha-dimyristoylphosphatidic acid (DMPA) and hexadecanesulfonic acid (HDSA) at the air-water interface, and undergoes chemical polymerisation under conditions where bulk polymerisation does not occur. 相似文献
108.
The syntheses of both diastereoisomers of 5′-ethyl-substituted thymidine dimers, the (5′R)- and (5′S)-configurated 33a and 33b respectively, in which the natural phosphodiester linkage is replaced by an amide group (C(3′)-CH2CONH-CH(5′)(Et)), arc described. Their fully protected derivatives 35a and 35b , respectively, are suitable for incorporation into antisense oligonucleotides. Unexpectedly, an attempted PdII-catalysed aza-Claisen rearrangement of trichloroacetimidate 7 provided the diastereoisomerically pure cyclopropane derivative 17 , whose structure was confirmed by X-ray analysis. 相似文献
109.
Bogusław Zegarliński 《Communications in Mathematical Physics》1984,96(2):195-221
The uniqueness and the global Markov property for the regular Gibbs measure corresponding to the interaction $$U_\Lambda (\varphi ): = \lambda \int\limits_\Lambda {d_2 x\int {d\varrho (\alpha ):e^{\alpha \varphi } :_0 (x)} } $$ [forλ>0,d?(α) a probability measure with support in \(( - 2\sqrt {\pi ,} 2\sqrt \pi )\) ] is proved. 相似文献
110.
Georghios P. Sphicas Daniel G. Shimshak 《The Journal of the Operational Research Society》1978,29(1):65-70
This paper considers the range of values of the coefficient of variation of waiting time in some general single-server queueing systems. It is shown that in M/G/1 systems with given ρ, the square of this coefficient increases linearly with m1m3/m22, where mi is the ith moment of the service distribution. This implies always a lower bound, and for some widely used distributions an upper bound as well. A few ranges are illustrated and compared to those implied in two GI/M/1 systems. The usefulness of knowing such ranges for modelling purposes is explained. 相似文献