全文获取类型
收费全文 | 42401篇 |
免费 | 2451篇 |
国内免费 | 2725篇 |
专业分类
化学 | 20635篇 |
晶体学 | 555篇 |
力学 | 2287篇 |
综合类 | 228篇 |
数学 | 10567篇 |
物理学 | 13305篇 |
出版年
2023年 | 186篇 |
2022年 | 411篇 |
2021年 | 457篇 |
2020年 | 474篇 |
2019年 | 545篇 |
2018年 | 1649篇 |
2017年 | 1958篇 |
2016年 | 1361篇 |
2015年 | 1266篇 |
2014年 | 1273篇 |
2013年 | 1698篇 |
2012年 | 4333篇 |
2011年 | 3525篇 |
2010年 | 2717篇 |
2009年 | 2517篇 |
2008年 | 1604篇 |
2007年 | 1569篇 |
2006年 | 1531篇 |
2005年 | 5143篇 |
2004年 | 4579篇 |
2003年 | 2853篇 |
2002年 | 1156篇 |
2001年 | 882篇 |
2000年 | 493篇 |
1999年 | 489篇 |
1998年 | 319篇 |
1997年 | 199篇 |
1996年 | 165篇 |
1995年 | 144篇 |
1994年 | 127篇 |
1993年 | 108篇 |
1992年 | 217篇 |
1991年 | 196篇 |
1990年 | 176篇 |
1989年 | 145篇 |
1988年 | 122篇 |
1987年 | 78篇 |
1986年 | 60篇 |
1985年 | 53篇 |
1984年 | 34篇 |
1979年 | 32篇 |
1976年 | 79篇 |
1975年 | 38篇 |
1974年 | 40篇 |
1973年 | 48篇 |
1972年 | 39篇 |
1970年 | 34篇 |
1969年 | 37篇 |
1968年 | 35篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 359 毫秒
871.
Salgado-Petinal C Lamas JP Garcia-Jares C Llompart M Cela R 《Analytical and bioanalytical chemistry》2005,382(6):1351-1359
In this paper a solid-phase microextraction–gas chromatography–mass spectrometry (SPME–GC–MS) method is proposed for a rapid analysis of some frequently prescribed selective serotonin re-uptake inhibitors (SSRI)—venlafaxine, fluvoxamine, mirtazapine, fluoxetine, citalopram, and sertraline—in urine samples. The SPME-based method enables simultaneous determination of the target SSRI after simple in-situ derivatization of some of the target compounds. Calibration curves in water and in urine were validated and statistically compared. This revealed the absence of matrix effect and, in consequence, the possibility of quantifying SSRI in urine samples by external water calibration. Intra-day and inter-day precision was satisfactory for all the target compounds (relative standard deviation, RSD, <14%) and the detection limits achieved were <0.4 ng mL–1 urine. The time required for the SPME step and for GC analysis (30 min each) enables high throughput. The method was applied to real urine samples from different patients being treated with some of these pharmaceuticals. Some SSRI metabolites were also detected and tentatively identified. 相似文献
872.
Rogatsky E Jayatillake H Goswami G Tomuta V Stein D 《Journal of the American Society for Mass Spectrometry》2005,16(11):1805-1811
The development of a sensitive assay for the quantitative analysis of carbohydrates from human plasma using LC/MS/MS is described in this paper. After sample preparation, carbohydrates were cationized by Cs(+) after their separation by normal phase liquid chromatography on an amino based column. Cesium is capable of forming a quasi-molecular ion [M + Cs](+) with neutral carbohydrate molecules in the positive ion mode of electrospray ionization mass spectrometry. The mass spectrometer was operated in multiple reaction monitoring mode, and transitions [M + 133] --> 133 were monitored (M, carbohydrate molecular weight). The new method is robust, highly sensitive, rapid, and does not require postcolumn addition or derivatization. It is useful in clinical research for measurement of carbohydrate molecules by isotope dilution assay. 相似文献
873.
Time-dependent density-functional theory(TDDFT)has been applied to calculate the electronic structure and second-order nonlinear optical(NLO) properties of some organic molecules.The two-dimensional(2-D)charge transfer charateristics of calculated molecules were studied and compared with corresponding experimental results.All the theoretical results agree well with the measurement.For 2-D molecule with two-fold symmetry,the dominant charge transfer is off-diagonal,while for three-fold symmetry 2-D molecule,the dominant charge transfer is not only between branches and central group but also among branches. 相似文献
874.
Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions
The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on
a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer
to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects.
The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to
predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results
of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore,
the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon,
and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect
leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio
reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during
or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor,
a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator
as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene. 相似文献
875.
876.
We demonstrate that a technique is available to investigate glycoprotein synthesis in organ cultures of human breast and prostate surgical specimens where the 3-dimensional epithelial cell arrangement remains intact. Malignant breast and prostate epithelium maintained their capacity to synthesize glycoproteins for at least 3 days as followed by the incorporation of [3H]glucosamine into macromolecules. Over 70% of incorporation was by malignant cells as judged by autoradiography. Labeled glycoproteins were released into glandular lumina and consequently into the culture fluid. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis revealed predominantly one group of macrmolecules released with an apparent molecular weight of 48,000 +/- 6,000 daltons. This glycoprotein was found in all of the breast specimens studied, which included 1 medullary, 1 infiltrating lobular, and 8 infiltrating duct carcinomas. The pattern was independent of the availability of estrogen receptors. A similar glycoprotein was also observed in the culture media from a Grade I and a Grade II well-differentiated infiltrating prostate carcinoma. Incorporation was below the level of detection in 4 of 6 cases of benign prostatic hyperplasia. A more complex pattern of labeled glycoproteins was found in the media of a Grade II and a Grade III poorly-differentiated prostate carcinoma. The established human mammary carcinoma cell line MCF-7 synthesized and released a similar 48,000 molecular weight glycoprotein but additional components with larger molecular weights were also released. An intriguing interpretation that 3-dimensional tissue integrity restricts some glycoprotein synthesis is discussed. Cells grown in 2-dimensional monolayers could escape from such a topographic restriction and express additional families of glycoproteins. 相似文献
877.
878.
Qing‐Ling Ni Fa‐Si Li Xiu‐Jian Wang Xian‐Su Bi Sen Liao 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(9):m416-m418
The title compound, {[Cu(C14H9NO3)(C5H5N)]·C3H7NO}n or {[Cu2L2(py)2]·2DMF}n [py is pyridine, L is 4‐(salicylideneamino)benzoate and DMF is dimethylformamide], is composed of dimeric dicopper [CuL(py)]2 building units, which are interlinked into a one‐dimensional chain through the formation of Cu—OCOO bonds. The dimeric unit is centrosymmetric, containing two CuII atoms linked by bridging phenolate O atoms into a Cu2O2 plane with a chelating Cu—O bond length of 1.927 (2) Å and a bridging Cu—O bond length of 2.440 (2) Å. Interchain C—H...O and π–π stacking interactions are responsible for an extensive three‐dimensional structure in which the resulting channels are filled by DMF solvent molecules. 相似文献
879.
An amperometric cholesterol biosensor based on immobilization of cholesterol oxidase in a Prussian blue (PB)/polypyrrole (PPy) composite film on the surface of a glassy carbon electrode was fabricated. Hydrogen peroxide produced by the enzymatic reaction was catalytically reduced on the PB film electrode at 0 V with a sensitivity of 39 μA (mol/L)?1. Cholesterol in the concentration range of 10?5 ? 10?4 mol/L was determined with a detection limit of 6 × 10?7 mol/L by amperometric method. Normal coexisting compounds in the bio‐samples such as ascorbic acid and uric acid do not interfere with the determination. The excellent properties of the sensor in sensitivity and selectivity are attributed to the PB/PPy layer modified on the sensor. 相似文献
880.
Ana M. Gómez Ana PedregosaSeraf?&#x;n Valverde J.Cristóbal López 《Tetrahedron letters》2003,44(32):6111-6116
Halo-exo-glycals of the gluco-, manno- and galacto- series, readily prepared by reaction of 1-exo-methylene pyranoses with iodonium dicollidinium triflate (IDCT), undergo Suzuki or B-alkyl Suzuki cross-coupling reactions with boronic acids or alkyl boranes to yield, in a stereoselective manner, functionalized exo-glycals. 相似文献