全文获取类型
收费全文 | 81648篇 |
免费 | 450篇 |
国内免费 | 394篇 |
专业分类
化学 | 26556篇 |
晶体学 | 827篇 |
力学 | 6785篇 |
数学 | 32666篇 |
物理学 | 15658篇 |
出版年
2022年 | 59篇 |
2021年 | 125篇 |
2020年 | 98篇 |
2019年 | 123篇 |
2018年 | 10519篇 |
2017年 | 10316篇 |
2016年 | 6176篇 |
2015年 | 951篇 |
2014年 | 404篇 |
2013年 | 565篇 |
2012年 | 3975篇 |
2011年 | 10734篇 |
2010年 | 5775篇 |
2009年 | 6187篇 |
2008年 | 6784篇 |
2007年 | 8933篇 |
2006年 | 419篇 |
2005年 | 1490篇 |
2004年 | 1679篇 |
2003年 | 2086篇 |
2002年 | 1108篇 |
2001年 | 310篇 |
2000年 | 336篇 |
1999年 | 189篇 |
1998年 | 229篇 |
1997年 | 177篇 |
1996年 | 223篇 |
1995年 | 138篇 |
1994年 | 102篇 |
1993年 | 126篇 |
1992年 | 69篇 |
1991年 | 95篇 |
1990年 | 66篇 |
1989年 | 72篇 |
1988年 | 68篇 |
1987年 | 72篇 |
1986年 | 78篇 |
1985年 | 69篇 |
1984年 | 72篇 |
1983年 | 56篇 |
1982年 | 63篇 |
1981年 | 66篇 |
1980年 | 68篇 |
1979年 | 69篇 |
1978年 | 60篇 |
1977年 | 45篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 296 毫秒
991.
Keith E. Johnson Richard M. Pagni John Bartmess 《Monatshefte für Chemie / Chemical Monthly》2007,138(11):1077-1101
Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent
conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and
basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common
method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that
the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than
is the dissociation constant of the said acid in water. 相似文献
992.
The synthesis and anion binding properties of new ruthenium(II) and cobalt(II) phenanthroline complexes, containing two amide
subunits are described. Evidence for anion binding in dimethyl sulfoxide (DMSO) solution was obtained from u.v.–vis titration
experiments. Results indicated that these receptors showed strong affinity for F− and AcO−, and showed weak affinity for OH− and H2PO
4
−
, and showed no affinity for Cl−, Br−, I−. These receptors interacted with various anions examined through hydrogen-bond formation. 相似文献
993.
Jingjing Xu Yidong Lu Baohong Liu Chunhe Xu Jilie Kong 《Journal of Solid State Electrochemistry》2007,11(12):1689-1695
An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium
chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced
counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron
transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission
spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins,
respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences
between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that
ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P+ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The
photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting
the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper
provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes
in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially
valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices. 相似文献
994.
M. Blaauw I. H. Degenaar J. J. M. de Goeij 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(3):765-770
In order to correct for neutron self-shielding in large-sample prompt gamma NAA, a method has been developed to determine
the macroscopic scattering and absorption cross sections, i.e., Σ
a and Σ
s, using four Cu flux monitors placed around the sample. With Monte Carlo computations, the neutron densities throughout the
sample and the resulting and the corresponding self-shielding factor as calculated from the Σ
a and Σ
s as obtained through the Cu monitors were compared to the true values. The derived Σ
a and Σ
s were found to be sufficiently accurate as long as Σ
t = Σ
a + Σ
s was less than 0.6 cm−1 and Σ
s/Σ
t was greater than 0.1. 相似文献
995.
J. Kaloustian Paulette Lechene De La Porte T. El-Moselhy H. Lafont H. Portugal 《Journal of Thermal Analysis and Calorimetry》2005,82(2):331-338
Summary Cholesterol constitutes the major component of most gallstones. It was identified and determined in gallstones by thermal
analysis technique (DSC and TG-DTA), mainly by the use of the melting temperature (Tonset=145°C and Tmax=149°C) and by DTG peak decomposition (Tmax=364°C). Cholesterol anhydrous (ChA), which showed endothermic polymorphic peak, Tmax=40°C, without mass loss, was differentiated from cholesterol monohydrate (ChH), which showed a broad endothermic peak, Tmax=59°C, attributed to loss of water of crystallization (theoretical 4.45%). Morphological studies of gallstones were performed
by optical microscopy and scanning electron microscopy (SEM). The stones consisted of a pigmented core with a variably-sized
irregular central cavity, surrounded by a radially arranged deposits of plate-like ChH. The outer part of the stones showed
ChA crystal arborescences. X-ray microanalysis gave a typical spectrum rich in C and O, and in some instances the presence
of P, which was attributed to the presence of phospholipids. CaCO3 was easily characterized by TG with the use of DTG decomposition peak at 674°C. 相似文献
996.
Ivan Němec Zorka Machá?ková Ivana Císa?ová Zdeněk Mi?ka 《Journal of solid state chemistry》2004,177(12):4655-4664
Aminoguanidinium(1+) dihydrogen phosphate was prepared by crystallization from aqueous solution. On the basis of the results of DSC measurements, X-ray structural analysis was carried out at temperatures of 160, 215 and 293 K for three aminoguanidinium(1+) dihydrogen phosphate phases ( |Z=2|non-ferroic |melting point 408 K; II |201-222 K|(2) |Z=2|non-ferroic|-; III |<201 K|(2)|Z=4|non-ferroic|-). The triclinic unit cell dimensions (a=6.8220(2), b=7.1000(2), c=7.4500(2) Å, α=86.925(2)°, β=80.731(2)°, γ=79.630(2)°, V=350.21(2) Å3—phase I) are similar for all three structural phases with the exception of phase III, where doubling of the c-axis length leads to an increase in the volume to 692.34(3) Å3. The crystal structure of all three modifications consists of parallel layers of dihydrogen phosphate anions that are interconnected by aminoguanidinium(1+) cations through hydrogen bonds of the N-H…O type. The planar aminoguanidinium(1+) cations are oriented almost parallel to each other and are perpendicular to the anion layers. The primary differences amongst phases I, II and III lie in the location of the H atom in the short O-H…O bonds connecting the dihydrogen phosphate anions in layers. The FTIR and FT Raman spectra of natural and deuterated compounds were recorded and interpreted. The FTIR spectra were studied down to a temperature of 90 K. 相似文献
997.
Quantitative investigation of the reaction of the ferri-heme model compound Fe(III)(TPPS)(H(2)O)(2) (1) to give Fe(II)(TPPS)(NO) (2) (TPPS = tetra(4-sulfonato-phenyl)porphinato) in buffered aqueous solution demonstrates a slow pH-independent reductive nitrosylation pathway in the pH range 4-6. The rate of this reaction is subject to modest general base catalysis. In the course of this study, a surprising catalytic pathway whereby nitrite ion (NO(2)(-)) strongly catalyzes the reduction of 1 to 2 under reductive nitrosylation conditions was demonstrated. 相似文献
998.
Klika KD Imrich J Danihel I Böhm S Kristian P Hamul'aková S Pihlaja K Koch A Kleinpeter E 《Magnetic resonance in chemistry : MRC》2005,43(5):380-388
The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S-allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the r(NOE). Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case-by-case basis. 相似文献
999.
In this paper, zinc tetraaminophthalocyanine (Zn-APc) was immobilized on cellulosic fiber by covalent bond to obtain a novel cellulosic fiber supported metallophthalocyanine, named Zn-TDTAPc-F. At pH 11, upon visible light irradiation for 6 h in the presence of O2, Zn-TDTAPc-F was found to be highly effective for the degradation of phenol in aqueous solution, and the degradation rate of phenol was more than 95%. HPLC was used to confirm formic acid, fumaric acid and maleic acid as its main degradation products. 相似文献
1000.
Evaluated in the present investigation are possible synthetic approaches to vinigrol based on the involvement of lactone rings as tools for the conformational rigidification of functionalized cis-octalins. Emphasis was placed on the structural arrangements resident in 3 and 5. The first of these systems proved to be highly strained and inaccessible. Especially notable was the finding that hydroxy ketenes 14 and 21 could be isolated and shown not to be amenable to cyclization when heated. The stereo-controlled assembly of 5 was successfully accomplished through exploitation of a related synthetic pathway. However, neither this attractive intermediate nor its close relative 33 could be processed in a manner that delivered the vinigrol framework. Nonetheless, several features of the routes deployed offer the prospect of wider application in other contexts. 相似文献