全文获取类型
收费全文 | 1812篇 |
免费 | 43篇 |
国内免费 | 1篇 |
专业分类
化学 | 1352篇 |
晶体学 | 10篇 |
力学 | 50篇 |
数学 | 79篇 |
物理学 | 365篇 |
出版年
2023年 | 15篇 |
2022年 | 32篇 |
2021年 | 27篇 |
2020年 | 35篇 |
2019年 | 54篇 |
2018年 | 37篇 |
2017年 | 29篇 |
2016年 | 58篇 |
2015年 | 55篇 |
2014年 | 62篇 |
2013年 | 122篇 |
2012年 | 94篇 |
2011年 | 134篇 |
2010年 | 84篇 |
2009年 | 57篇 |
2008年 | 102篇 |
2007年 | 105篇 |
2006年 | 84篇 |
2005年 | 94篇 |
2004年 | 81篇 |
2003年 | 65篇 |
2002年 | 65篇 |
2001年 | 23篇 |
2000年 | 14篇 |
1999年 | 15篇 |
1998年 | 10篇 |
1997年 | 8篇 |
1996年 | 17篇 |
1995年 | 27篇 |
1994年 | 18篇 |
1993年 | 8篇 |
1992年 | 15篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1985年 | 21篇 |
1984年 | 11篇 |
1983年 | 5篇 |
1982年 | 14篇 |
1981年 | 11篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1978年 | 8篇 |
1976年 | 5篇 |
1974年 | 5篇 |
1960年 | 5篇 |
1959年 | 6篇 |
1958年 | 5篇 |
1957年 | 5篇 |
排序方式: 共有1856条查询结果,搜索用时 31 毫秒
31.
Thermal behaviour of blends based on N,N'-bis(4-itaconimidophenyl) ether (IE) and 4,4'-bis(4-allyl-2-methoxyphenoxy) benzophenone
(R1) or 4,4'-bis(2-allylphenoxy) benzophenone (R2) are described in this paper. The reactive diluent content was varied from 5-50% (mass/mass) in these blends. A decrease
in the melting point and exothermic peak temperature was observed with increasing mass percent of reactive diluent. Thermal
stability of blends was affected at high mass percentage of reactive diluents.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
32.
Photoaffinity labeled (3-diazoacetoxy)-9-cis-retinal (1) and (9-methylenediazoacetoxy)-9-cis-retinal (20) were synthesized and bound to absorption maxima at 465 and 460 nm respectively. Binding studies established that synthetic retinals 1 and 2 bind to the natural binding site and that the integrity of the diazoacetoxy photoaffinity label is preserved in the process. Incorporation of 3-(O14COCHN2)-labeled 9-cis retinal could be conveniently carried out in high yield using apomembrane solubilized in CHAPS as detergent to afford the pigment analog in a pure form. Photolysis of the diazoacetoxy group within the binding site led to 15–20%, crosslinking of rhodopsin as estimated by using radiocarbon containing labeled retinal 1 thus showing that this synthetic retinal is suitable for photoaffinity labeling of the active site in rhodopsin. Subsequent experiments to establish the site(s) of crosslinking by sequencing studies will then contribute to our knowledge of the structure of rhodopsin. 相似文献
33.
Preferred conformers around the central C-C and C-O bonds in n-propanol have been determined using the quantum-mechanical PCILO method and compared with those observed experimentally by microwave spectroscopy. The agreement between theory and experiment is excellent, thus minimizing time consuming searches for microwave transitions corresponding to the preferred conformers. 相似文献
34.
Choudhary V. Varma H. S. Varma I. K. 《Journal of Thermal Analysis and Calorimetry》1987,32(2):579-593
The effects of EPDM rubber on the crystallization behaviour of isotactic polypropylene (iPP) in the ternary iPP/HDPE/EPDM blends were studied by means of DSC and X-ray diffraction. Analysis of the crystallization exotherm peaks in terms of crystallization nucleation and growth rates and crystallinity revealed variations in the morphology of the iPP component in the blends as a function of the EPDM content. The DSC and X-ray diffraction results showed that the overall crystallinity decreased as the weight percentage of EPDM was increased in the iPP/HDPE blends.The morphology of these blends was studied by scanning electron microscopy, which revealed a random distribution of EPDM throughout the iPP matrix. The size and number of these rubber particles increased with increase of the EPDM weight percentage in the ternary iPP/HDPE/EPDM blends. The probable existence of composite inclusions of EPDM-HDPE in an iPP matrix is suggested.
Zusammenfassung Die Effekte von EPDM-Kautschuk auf das Kristallisationsverhalten von isotaktischem Polypropylen (iPP) in den ternären Gemischen iPP/HDPE/EPDM wurden mittels DSC und Röntgendiffraktometrie untersucht. Die Analyse der exothermen Kristallisationspeaks mit Hinblick auf die Kristallisationskeimbildung und die Geschwindigkeit des Kristallwachstums und die Kristallinität deuten auf morphologische Varianten der iPP-Komponente in den Gemischen in Abhängigkeit vom EPDM-Gehalt hin. Die durch DSC und Röntgendiffraktometrie erhaltenen Ergebnisse zeigen, daß die Kristallinität mit steigendem Gehalt an EPDM in den iPP/HDPE-Gemischen abnimmt. Die Morphologie dieser Gemische wurde durch Scanningelektronenmikroskopie untersucht. Es wurde eine random-Verteilung des EPDM in der iPP-Matrix festgestellt. Größe und Zahl dieser Kautschukpartikel nehmen mit zunehmendem EPDM-Gewichtsanteil in den ternären iPP/HDPE/EPDM-Gemischen zu. Auf die wahrscheinliche Existenz von EPDM/HDPE-Einschlüssen in einer iPP-Matrix wird hingewiesen.
(-) - -. , , , . , --. , . ---. - - .相似文献
35.
The reactions of fluorophosphazenes, endo ansa FcCH(2)P(S)(CH(2)O)(2)[P(F)N](2)(F(2)PN) (1) (Fc = ferrocenyl) and spiro [RCH(2)P(S)(CH(2)O)(2)PN](F(2)PN)(2) (R = Fc (2), C(6)H(5) (3)], with dilithiated diols have been explored. The study resulted in the formation of the first examples of ansa-spiro substituted fluorinated cyclophosphazenes as well as a bisansa substituted fluorophosphazene. The bisansa compound [1,3-[FcCH(2)P(S)(CH(2)O)(2)]][1,5-[CH(2)(CH(2)O)(2)]]N(3)P(3)F(2) (4) was found to be nongeminaly substituted with both the ansa rings in cis configuration, which is in stark contrast to the observations on cyclic chlorophosphazenes where geminal bisansa formation has been observed. The ansa-spiro compounds (5-7) underwent the ansa to spiro transformation leading to dispiro compounds in the presence of catalytic amounts of CsF at room temperature. Two of the ansa-spiro compounds, endo-[3,5-[FcCH(2)P(S)(CH(2)O)(2)]][1,1-[CH(2)(CH(2)O)(2)]]N(3)P(3)F(2) (5) and endo-[3,5-[FcCH(2)P(S)(CH(2)O)(2)]][1,1-[FcCH(2)P(S)(CH(2)O)(2)]]N(3)P(3)F(2) (6), were structurally characterized, and the crystal structures indicate boat-chair conformation as well as crown conformation for the eight-membered ansa rings. Weak C-H.F-P interactions observed in the crystal structures of the ansa-spiro substituted fluorophosphazene derivatives have been analyzed and compared with C-H.F-P interactions of other fluorinated phosphazenes and thionyl phosphazenes. 相似文献
36.
Conformational properties of 3-deazapurine nucleosides (namely, 3-deazaadenosine and 3-deazaguanosine) have been investigated by the PCILO method. Both C(2′)-endo and C(3′)-endo sugar puckers have been considered and the results indicate that the conformational preferences of these nucleoside analogs are quite different from those of their parent nucleosides adenosine and guanosine, respectively. This result has been correlated in terms of the biological inactivity of these nucleoside analogs. 相似文献
37.
Anil Saran 《International journal of quantum chemistry》1981,20(2):439-447
Minor modifications or substitutions in the sugar or in the base part of pyrimidine and purine nucleosides have a profound effect on their biological activity. These modified nucleosides usually become antiviral, antibacterial, or cancerostatic agents and they are collectively called nucleoside antibiotics. The conformational properties of some of these nucleoside antibiotics have been studied by the PCILO method. The results obtained from such study indicate that the conformational preferences of these nucleoside antibiotics are very similar to those of their parent nucleosides and especially so in the situations that occur in aqueous solutions. The important biological significance of these results is that these nucleoside antibiotics can easily get incorporated into growing chains of DNA and RNA by mimicking their parent nucleosides and can interfere with the protein synthesis of RNA or DNA synthesis. 相似文献
38.
Jayasinghe UL Kumarihamya BM Nadeemb M Choudhary MI Atta-Ur-Rahmanb Weerasooriya A 《Natural product letters》2001,15(3):151-155
Chemical investigation of the non-quaternary alkaloidal fraction of the aerial parts of Sarcococca zeylanica of the family Buxaceae furnished a steroidal alkaloid iso-N-formyl-5-en-chonemorphine, which has not been previously reported as a natural product. The structure of this alkaloid was established on the basis of spectroscopic evidence. 相似文献
39.
The evolving nature of a Stillinger-Weber modeled silicon glass is studied using two accelerated molecular dynamics scheme, specifically, hyperdynamics and self-guided algorithms due to Voter and due to Wu and Wang, respectively. We obtain an acceleration of the dynamics, a "boost," on the order of 20 without incurring any significant computational overhead. The validity of the results using accelerated methods is provided by comparison to a conventional molecular dynamics (MD) algorithm simulated under constant temperature conditions for more than 100 ns. We found that performing a sensitivity analysis of the effect of the parameters lambda and t1 before applying the self-guided MD scheme was important. Values of lambda greater than 0.1 and t1 equal to 1 ps were found to give improved structural evolution as compared to a conventional MD scheme. The hyperdynamics approximation scheme was found to be effective in obtaining boosts in the range of 4-12 for a small system without changing the dynamics of the evolution. However, for a large system size such an approach introduces significant perturbations to the pertinent equations of motion. 相似文献
40.
Mecke A Majoros IJ Patri AK Baker JR Holl MM Orr BG 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10348-10354
Polycationic polymers are used extensively in biology to disrupt cell membranes and thus enhance the transport of materials into the cell. The highly polydisperse nature of many of these materials makes obtaining a mechanistic understanding of the disruption processes difficult. To design an effective mechanistic study, a monodisperse class of polycationic polymers, poly(amidoamine) (PAMAM) dendrimers, has been studied in the context of supported dimyristoylphosphatidylcholine (DMPC) lipid bilayers using atomic force microscopy (AFM). Aqueous solutions of amine-terminated generation 7 (G7) PAMAM dendrimers caused the formation of 15-40-nm-diameter holes in lipid bilayers. This effect was significantly reduced for smaller G5 dendrimers. For G3, no hole formation was observed. In addition to dendrimer size, surface chemistry had a strong influence on dendrimer-lipid bilayer interactions. In particular, acetamide-terminated G5 did not cause hole formation in bilayers. In all instances, the edges of bilayer defects proved to be points of highest dendrimer activity. A proposed mechanism for the removal of lipids by dendrimers involves the formation of dendrimer-filled lipid vesicles. By considering the thermodynamics, interaction free energy, and geometry of these self-assembled vesicles, a model that explains the influence of polymer particle size and surface chemistry on the interactions with lipid membranes was developed. These results are of general significance for understanding the physical and chemical properties of polycationic polymer interactions with membranes that lead to the transport of materials across cell membranes. 相似文献