首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   3930篇
  免费   92篇
  国内免费   21篇
化学   2283篇
晶体学   22篇
力学   234篇
数学   748篇
物理学   756篇
  2023年   28篇
  2022年   70篇
  2021年   75篇
  2020年   69篇
  2019年   69篇
  2018年   48篇
  2017年   56篇
  2016年   122篇
  2015年   103篇
  2014年   108篇
  2013年   227篇
  2012年   240篇
  2011年   227篇
  2010年   153篇
  2009年   133篇
  2008年   222篇
  2007年   231篇
  2006年   192篇
  2005年   175篇
  2004年   195篇
  2003年   145篇
  2002年   145篇
  2001年   51篇
  2000年   37篇
  1999年   41篇
  1998年   45篇
  1997年   48篇
  1996年   56篇
  1995年   45篇
  1994年   49篇
  1993年   39篇
  1992年   40篇
  1991年   30篇
  1990年   28篇
  1989年   20篇
  1988年   34篇
  1987年   29篇
  1986年   22篇
  1985年   48篇
  1984年   35篇
  1983年   31篇
  1982年   33篇
  1981年   31篇
  1980年   29篇
  1979年   31篇
  1978年   20篇
  1977年   16篇
  1976年   17篇
  1975年   15篇
  1974年   17篇
排序方式: 共有4043条查询结果,搜索用时 15 毫秒
31.
In Italy an extensive survey has been carried out with the aim to evaluate annual average radon concentration in underground workplaces.The survey covered 933 underground rooms located in 311 bank workplaces spread throughout in all Italian regions; at this scope the sampling was stratified random in order to be representative on national scale. The annual radon concentration was estimated by using passive radon dosemeters (NRPB/SSI type holder and CR-39 as detector): the devices were exposed for a period of about 3 months and 4 cycles were performed to cover a solar year. The radon levels in underground workplaces ranged from 27 to 4851 Bq/m3 with an overall mean value of 153 Bq/m3. As expected, radon distribution is not uniform throughout Italy: in several regions high radon annual averages have been found, confirming previous surveys.The analysis of data shows a high variability among regions and intra-region but low spread among rooms belonging to the same workplace.About 5% of underground workplaces displayed radon concentration exceeding 400 Bq/m3, and the 4.4% exceeds 500 Bq/m3, the national action level for the exposure to natural radioactivity in workplaces.  相似文献   
32.
A general method is presented for the evaluation of the spin rovibronic energy levels of triatomic molecules with up to three interacting potential energy surfaces. The full theory is outlined in detail, both for singlet and for doublet electronic states and the method is then applied to the benchmark example of C2H. High quality multireference configuration interaction calculations have been carried out to generate the 3-dimensional near-equilibrium adiabatic potential energy surfaces of the three lowest 12A'(X2Σ+), 22A'(A2Π), 12A''(A2Π) electronic states of C2H, and the pair of interacting states of A 0 symmetry have then been diabatized. Results are presented for J up to 7/2 and compared with gas-phase high resolution experimental results for energies up to 5600 cm1.  相似文献   
33.
34.
. Existence of minimizers for a volume-constrained energy $ E(u) := \int_{\Omega} W(\nabla u)\, dx Existence of minimizers for a volume-constrained energy E(u) : = òW W(?udx E(u) := \int_{\Omega} W(\nabla u)\, dx where LN({u = zi}) = ai, i = 1, ?, P, {\cal L}^N(\{u = z_i\}) = \alpha_i, i = 1, \ldots, P, is proved for the case in which ziz_i are extremal points of a compact, convex set in \Bbb Rd\Bbb R^d and under suitable assumptions on a class of quasiconvex energy densities W. Optimality properties are studied in the scalar-valued problem where d=1d=1, P=2P=2, W(x)=|x|2W(\xi)=|\xi|^2, and the &-limit as the sum of the measures of the 2 phases tends to \L(W)\L(\Omega) is identified. Minimizers are fully characterized when N=1N=1, and candidates for solutions are studied for the circle and the square in the plane.  相似文献   
35.
The photoenolization/Diels–Alder strategy offers straightforward access to synthetically valuable benzannulated carbocyclic products. This historical light‐triggered process has never before succumbed to efforts to develop an enantioselective catalytic approach. Herein, we demonstrate how asymmetric organocatalysis provides simple yet effective catalytic tools to intercept photochemically generated hydroxy‐o‐quinodimethanes with high stereoselectivity. We used a chiral organic catalyst, derived from natural cinchona alkaloids, to activate maleimides toward highly stereoselective Diels–Alder reactions. An unconventional mechanism of stereocontrol is operative, wherein the organocatalyst is actively involved in both the photochemical pathway, by leveraging the formation of the reactive photoenol, and the stereoselectivity‐defining event.  相似文献   
36.
Summary Five-coordinate bis(benzeneseleninato)tris(ethylenediamine) cobalt (II)complexes are obtained by reaction of Co(H2O)2 (XC6 H4 SeO2)2 complexes (X = H, p-Cl, m-CI, p-Br, ni-Br, p-Me,p-NO2) with ethylenediamine. The diaquo complexes (one mole)react with ethylenediamine (three moles)to form O-seleninato derivatives. Spectral and magnetic properties show that the complexes are low-spin (s = 1/2) and,on the basis of the electronic spectra a distorted trigonal geometry,D 3h , is suggested. Assignments for the electronic spectra are proposed. Conductivity data indicate that these derivatives are nonelectrolytes. Both ethylenediamine and [RSeO2 ] behave as monodentate ligands.  相似文献   
37.
The recent introduction of polymerase chain reaction (PCR)-massively parallel sequencing (MPS) technologies in forensics has changed the approach to allelic short tandem repeat (STR) typing because sequencing cloned PCR fragments enables alleles with identical molecular weights to be distinguished based on their nucleotide sequences. Therefore, because PCR fidelity mainly depends on template integrity, new technical issues could arise in the interpretation of the results obtained from the degraded samples. In this work, a set of DNA samples degraded in vitro was used to investigate whether PCR-MPS could generate “isometric drop-ins” (IDIs; i.e., molecular products having the same length as the original allele but with a different nucleotide sequence within the repeated units). The Precision ID GlobalFiler NGS STR panel kit was used to analyze 0.5 and 1 ng of mock samples in duplicate tests (for a total of 16 PCR-MPS analyses). As expected, several well-known PCR artifacts (such as allelic dropout, stutters above the threshold) were scored; 95 IDIs with an average occurrence of 5.9 IDIs per test (min: 1, max: 11) were scored as well. In total, IDIs represented one of the most frequent artifacts. The coverage of these IDIs reached up to 981 reads (median: 239 reads), and the ratios with the coverage of the original allele ranged from 0.069 to 7.285 (median: 0.221). In addition, approximately 5.2% of the IDIs showed coverage higher than that of the original allele. Molecular analysis of these artifacts showed that they were generated in 96.8% of cases through a single nucleotide change event, with the C > T transition being the most frequent (85.7%). Thus, in a forensic evaluation of evidence, IDIs may represent an actual issue, particularly when DNA mixtures need to be interpreted because they could mislead the operator regarding the number of contributors. Overall, the molecular features of the IDIs described in this work, as well as the performance of duplicate tests, may be useful tools for managing this new class of artifacts otherwise not detected by capillary electrophoresis technology.  相似文献   
38.
Cholesterylbutyrate (Chol-but) was chosen as a prodrug of butyric acid. Butyrate is not often used in vivo because its half-life is very short and therefore too large amounts of the drug would be necessary for its efficacy. In the last few years butyric acid's anti-inflammatory properties and its inhibitory activity towards histone deacetylases have been widely studied, mainly in vitro. Solid Lipid Nanoparticles (SLNs), whose lipid matrix is Chol-but, were prepared to evaluate the delivery system of Chol-but as a prodrug and to test its efficacy in vitro and in vivo. Chol-but SLNs were prepared using the microemulsion method; their average diameter is on the order of 100-150 nm and their shape is spherical. The antineoplastic effects of Chol-but SLNs were assessed in vitro on different cancer cell lines and in vivo on a rat intracerebral glioma model. The anti-inflammatory activity was evaluated on adhesion of polymorphonuclear cells to vascular endothelial cells. In the review we will present data on Chol-but SLNs in vitro and in vivo experiments, discussing the possible utilisation of nanoparticles for the delivery of prodrugs for neoplastic and chronic inflammatory diseases.  相似文献   
39.
Bilin-1,19(21H,24H)-diones interact with O2·- in DMSO giving rise to adducts showing charge-transfer character. This reaction can be reversed by addition of O2·- consuming compounds. The O2·-biliverdin dimethyl ester adduct collapses partially to 10-oxobilirubin dimethyl ester when treated with thiourea and 2-mercaptoethanol.  相似文献   
40.
Standard pH(S) values for 0.05 mol kg?1 potassium hydrogenphthalate (KHpH) reference buffer solutions in 10, 30 and 50% (w/w) 1,4-dioxane/water solvent mixtures within the temperature range 288.15–318.15 K are determined from e.m.f. measurements of the cell without transference Pt|H2|KHPh + KCl|AgCl|Ag|Pt. The consistency of the results is analysed by a recently described method of multilinear regression of the quantity p(aHγCl) as a function of both solution composition and temperature. The standard pH(S) determined can be reproduced to within ±0.01 by the equation pH(S) - 4.004 + 3.309w + 0.408z + 1.037w3 - 14.95zw2 + 27.1zw3, where w is the weight fraction of dioxane in the solvent mixture,z = (Tθ)/θ, and θ - 298.15 K. Values of the first ionization constant of phthalic acid (H2Ph; benzene-1,2-dicarboxylic acid) in the above solvent mixtures are also determined from e.m.f. measurements of the cell without transference Pt|H2|H2Ph + KHPh + KCl|AgCl|Ag|Pt.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号