全文获取类型
收费全文 | 76036篇 |
免费 | 20123篇 |
国内免费 | 331篇 |
专业分类
化学 | 71220篇 |
晶体学 | 309篇 |
力学 | 3669篇 |
综合类 | 12篇 |
数学 | 12063篇 |
物理学 | 9217篇 |
出版年
2024年 | 189篇 |
2023年 | 4750篇 |
2022年 | 1607篇 |
2021年 | 2809篇 |
2020年 | 5154篇 |
2019年 | 2557篇 |
2018年 | 3723篇 |
2017年 | 2096篇 |
2016年 | 6802篇 |
2015年 | 6633篇 |
2014年 | 5947篇 |
2013年 | 6309篇 |
2012年 | 6561篇 |
2011年 | 3387篇 |
2010年 | 5515篇 |
2009年 | 5215篇 |
2008年 | 1672篇 |
2007年 | 1386篇 |
2006年 | 696篇 |
2005年 | 4495篇 |
2004年 | 3949篇 |
2003年 | 2335篇 |
2002年 | 513篇 |
2001年 | 334篇 |
1999年 | 203篇 |
1997年 | 159篇 |
1995年 | 222篇 |
1994年 | 157篇 |
1993年 | 270篇 |
1992年 | 294篇 |
1991年 | 247篇 |
1990年 | 200篇 |
1989年 | 189篇 |
1988年 | 236篇 |
1987年 | 171篇 |
1982年 | 162篇 |
1981年 | 186篇 |
1980年 | 216篇 |
1979年 | 235篇 |
1978年 | 243篇 |
1977年 | 352篇 |
1976年 | 473篇 |
1975年 | 515篇 |
1974年 | 541篇 |
1973年 | 371篇 |
1972年 | 494篇 |
1971年 | 441篇 |
1970年 | 659篇 |
1969年 | 496篇 |
1968年 | 537篇 |
排序方式: 共有10000条查询结果,搜索用时 421 毫秒
991.
Compared to the general ionic liquids (ILs), a significant deviation of the binary mixtures of 1-decyl-3-methylimidazolium tri(hexafluoroacetylaceto)-copper(II) ([C10mim][Cu(hfacac)3]) with methanol was found, indicating the way methanol interacts with ILs might be governed by the special structure of the chelating anion. IR results showed that the (C2-H) of 1-decyl-3-methylimidazolium hexafluoroacetylacetonate ([C10mim][hfacac]) blue-shifted more significantly than that of [C10mim][Cu(hfacac)3], meanwhile the (C=O) red-shifted in [C10mim][Cu(hfacac)3], which is contrast with that in [C10mim][hfacac]. Two-dimensional correlation analysis of the FTIR spectra indicated that the chelating cavity has little effect on the sequence of the ILs sites that interact with methanol. Combined with small angle X-ray scattering (SAXS) results, the picture of mixing processes in these two systems were proposed. Methanol interacts directly with the anion followed by the cation in [C10mim][hfacac], while methanol preferentially enters the chelating cavity and enhances the packing effect in the [C10mim][Cu(hfacac)3] system. 相似文献
992.
A simple modification of a previously published ellipticine synthesis is reported, which decreases the reaction time and increases the yield and purity of the product. Benzylic oxidations of 1,4-dimethylcarbazole and ellipticine derivatives were studied and 13-hydroxyellipticine was prepared. 相似文献
993.
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
994.
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
995.
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
996.
L. Ramakrishnan Prof. Dr. S. Soundararajan 《Monatshefte für Chemie / Chemical Monthly》1977,108(1):225-231
Complexes of 2,6-dimethylpyridine 1-oxide with lanthanide iodides of the formulaeLn(2,6-LTNO)5I3 whereLn=La, Tb and Yb,Ln(2,6-LTNO)4I3 whereLn=Pr and Nd and Er(2,6-LTNO)4.5I3 have been prepared and characterised by chemical analysis, infrared and conductance studies. Infrared and conductance data have been interpreted in terms of dimeric (or polymeric) structures involving bridging amine oxide groups.
Mit 2 Abbildungen 相似文献
Mit 2 Abbildungen 相似文献
997.
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
998.
Prof. Dr. O. Hromatka D. Binder K. Eichinger 《Monatshefte für Chemie / Chemical Monthly》1974,105(1):123-126
The synthesis of 5-(o-trifluoromethylphenyl)-1H-thieno-[3,4-e]1,4-diazepin-2(3H)-one (7) and its nitration and chlorination in pos. 8 are described. 相似文献
999.
Prof. Dr. Enrique J. Baran 《Monatshefte für Chemie / Chemical Monthly》1975,106(1):121-126
Mean amplitudes of vibration of a series of tetrahedralXY 4 molecules and ions (hydrides, halides, oxides and oxoanions) have been calculated using the “Method of the Characteristic Vibrations” ofA. Müller. The results indicate that this method leads to very good values for most of the investigated species, and especially in the cases of highM X/MY mass ratio. 相似文献
1000.
The electronic structure and spectrum of tropone were studied by paying special attention to an assignment of the 300 m band. The band was shown to have a single * character overlapped by an n
* transition from the following experimental and theoretical studies: (i) From the comparison of the observed transition energies and intensities with theoretical values obtained by the Pariser-Parr-Pople calculation in which the values of W
X
2p
(valence state ionization potential of the oxygen atom) and k (bond alternation parameter) taken as guiding parameters were changed widely and their adequateness was carefully examined, (ii) From the correlation among the electronic absorption spectra of tropone, troponeimine, and heptafulvene. (iii) From the finding that the 300 m band increases its intensity with the increasing polarity of the solvent. (iv) From the position and intensity of a band newly observed in the vacuum ultraviolet region.
Zusammenfassung An Tropon wurden Elektronenstruktur und Spektrum untersucht, speziell die 300 m-Bande. Diese entsteht aus einem einzigen - *-Übergang, überlagert von einer schwachen n-*-Bande, und nicht aus 2 - *-Banden. Als Stütze dienen: 1. eine PPP-Rechnung, bei der das Valenzzustandsionisationspotential von Sauerstoff und der Bindungsalternierungsparameter sorgfältig variiert wurden, 2. die Korrelation der Spektren von Tropon, Troponimin und Heptafulven, 3. der Lösungsmitteleinfluß auf die Bande, 4. eine neuaufgefundene UV-Bande.
Résumé La structure électronique et le spectre de la tropolone ont été étudiés en accordant une attention particulière à l'identification de la bande à 300 m. Cette bande a été caractérisée comme résultant d'une transition * recouverte par une transition n *, à l'aide des arguments théoriques et expérimentaux suivants: 1. à partir de la comparaison des énergies et des intensités de transition observées, avec les valeurs théoriques obtenues par un calcul Pariser-Parr-Pople où les valeurs de W X 2p (potentiel d'ionisation de l'état de valence de l'atome d'oxygène) et de k (paramètre d'alternance des liaisons), considérés comme paramètres régulateurs, ont été largement variées et soigneusement analysées. 2. à partir de la corrélation entre les spectres d'absorption électronique de la tropolone, de la tropolonéimine et de l'heptafulène. 3. à partir du fait que la bande à 300 m voit son intensité croitre avec la polarité du solvent. 4. à partir de la position et de l'intensité d'une bande nouvelle observée dans la région de l'ultra-violet lointain.相似文献