全文获取类型
收费全文 | 442篇 |
免费 | 20篇 |
国内免费 | 4篇 |
专业分类
化学 | 332篇 |
晶体学 | 4篇 |
力学 | 2篇 |
数学 | 42篇 |
物理学 | 86篇 |
出版年
2023年 | 1篇 |
2022年 | 8篇 |
2021年 | 9篇 |
2020年 | 8篇 |
2019年 | 6篇 |
2018年 | 6篇 |
2017年 | 5篇 |
2016年 | 20篇 |
2015年 | 15篇 |
2014年 | 19篇 |
2013年 | 23篇 |
2012年 | 28篇 |
2011年 | 37篇 |
2010年 | 21篇 |
2009年 | 15篇 |
2008年 | 31篇 |
2007年 | 25篇 |
2006年 | 24篇 |
2005年 | 18篇 |
2004年 | 29篇 |
2003年 | 15篇 |
2002年 | 8篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 13篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1975年 | 3篇 |
1967年 | 1篇 |
1903年 | 1篇 |
排序方式: 共有466条查询结果,搜索用时 15 毫秒
1.
Astrid Baumann 《Mathematische Semesterberichte》1998,45(2):167-188
Zusammenfassung. Mit Hilfe der projektiven Geometrie werden neuartige Summationsformeln hergeleitet, die die Tschebyscheff-Polynome und modifizierte Polynome enthalten; z. B. gilt für alle :
Daraus ergeben sich wiederum interessante Summationsformeln für die Hyperbelfunktionen; es gilt z. B. für positive reelle
Zahlen t:
Eingegangen am 28.02.96, revidierte Fassung am 25.08.97 / Angenommen am 09.10.97 相似文献
2.
Simulation of coupled chemical reactions and fluid flow in porous sedimentary basins over long time periods is a numerical
challenge. Most models representing such a physical problem are solved as PDEs where efficient timestepping with controlled
error is difficult. We use the differential algebraic equation system approach where robust adaptive timestepping algorithms
are available in the solvers, e.g., RADAU5 and DASSL. Mathematical and numerical models for coupled chemical reactions and
fluid flow are derived. The models have several interesting properties, e.g., strong nonlinearities and stiffness, which are
discussed. We test the performance of our code.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
3.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
4.
Cellulose synthesis in maize: isolation and expression analysis of the cellulose synthase (CesA) gene family 总被引:7,自引:0,他引:7
Laura Appenzeller Monika Doblin Roberto Barreiro Haiyin Wang Xiaomu Niu Krishna Kollipara Lori Carrigan Dwight Tomes Mike Chapman Kanwarpal S. Dhugga 《Cellulose (London, England)》2004,11(3-4):287-299
Stalk lodging in maize results in significant yield losses. We have determined that cellulose per unit length of the stalk is the primary determinant of internodal strength. An increase in cellulose concentration in the wall might allow simultaneous improvements in stalk strength and harvest index. Cellulose formation in plants can be perturbed by mutations in the genes involved in cellulose synthesis, post-synthetic cellulose alteration or deposition, N-glycosylation, and some other genes with as yet unknown functions. We have isolated 12 members of the cellulose synthase (CesA) gene family from maize. The genes involved in primary wall formation appear to have duplicated relatively independently in dicots and monocots. The deduced amino acid sequences of three of the maize genes, ZmCesA10–12, cluster with the Arabidopsis CesA sequences that have been shown to be involved in secondary wall formation. Based on their expression patterns across multiple tissues, these three genes appear to be coordinately expressed. The remaining genes show overlapping expression to varying degrees with ZmCesA1, 7, and 8 forming one group, ZmCesA3 and 5 a second group, and ZmCesA2 and 6 exhibiting independent expression of any other gene. This suggests that the varying levels of coexpression may just be incidental except in the case of ZmCesA10–12, which may interact with each other to form a functional enzyme complex. Isolation of the expressed CesA genes from maize and their association with primary or secondary wall formation has made it possible to test their respective roles in cellulose synthesis through mutational genetics or transgenic approaches. This information would be useful in improving stalk strength. 相似文献
5.
Campa C Oust A Skjåk-Braek G Paulsen BS Paoletti S Christensen BE Ballance S 《Journal of chromatography. A》2004,1026(1-2):271-281
The average degree of polymerisation (DP) and distribution of oligosaccharides in partially acid hydrolysed mannuronans were quantitatively evaluated by 1H NMR, electrospray ionisation mass spectrometry (ESI-MS), micellar electrokinetic capillary chromatography with UV detection (MEKC-UV), and high-pressure anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Our investigation shows that 1H NMR, MEKC-UV and, in particular, HPAEC-PAD can be used as quantitative tools to aid the investigation of polysaccharide structure, function and synthesis. For the latter two techniques, especially, this represents a significant new development as it enables calculation of the quantity of individual oligomers of nominal DP by direct analysis of a defined oligomer mixture. Appropriate statistical averages of number and weight distributions were also calculated and found to fit very well to predicted Kuhn distributions that assume random depolymerisation. 相似文献
6.
Martina Dotzler Astrid Schmidt Jochen Ellermann Falk A. Knoch Matthias Moll Walter Bauer 《Polyhedron》1996,15(24):4425-4433
BiBr3 or SbI3 react at 20°C with LiN(PPh2)2 (1) to give elementary Bi or Sb and the P---P coupled phosphazene ligand Ph2P---N=PPh2---PPh2=N---PPh2 (2). The reaction of AsI3 with 1 at room temperature formed yellow needles of the eight-membered heterocycle
(3), whereas AsI3 interacted at 80°C with 1 in the molar ratio of 1:3 to give elementary arsenic and 2. Treatment of AsI3 and 1 at 20°C in a 1:2 stoichiometry yielded the seven-membered, cyclic arsenium(I) salt I·4THF (5·4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis. 相似文献
7.
Astrid Döppenschmidt 《Czechoslovak Journal of Physics》1995,45(7-8):657-661
0-production in the system12C+12C was studied with the two-arm photon spectrometer TAPS at projectile energies of 800 and 1000 MeV/u. The experiments focus on the determination of the cross sections and the correspondingp
t
-distributions. The results will extend the existing systematics of
0-production in heavy-ion collisions to a system with small mass.Presented at the International School-Workshop Relativistic Heavy-Ion Physics, Prague (Czech Republic), 19–23 September 1994. 相似文献
8.
Rhodococcus equi A4, Rhodococcus erythropolis NCIMB 11540 and Rhodococcus sp. R312 were investigated towards their ability to produce β-amino amides and acids from β-amino nitriles. The microorganisms show comparable trends: five-membered alicyclic 2-amino nitriles were transformed significantly faster than the six-membered compounds and the products of trans-2-amino nitriles (amides and acids) were formed considerably faster than the cis-counterparts (amides). The trans-five membered nitriles gave the amides (1b, 5b) in excellent enantiomeric excess (94-99%), the biotransformation of trans-six membered substrates resulted in the formation of the acid (3c, 7c) in excellent ee (87-99%). The ee's of the cis-compounds were throughout lower. Fifteen new substances were synthesized and characterized in the course of this work. 相似文献
9.
Juliana Vaz Bevilaqua Lidia M. Lima Aline Gomes Cunha Eliezer J. Barreiro Tito L. M. Alves Lucia Moreira Campos Paiva Denise M.Guimarães Freire 《Applied biochemistry and biotechnology》2005,121(1-3):117-128
The last step of the production of four phthalimide-derived acids, designed to act as antiasthma drugs, was performed by enzymatic hydrolysis of the respective methyl or ethyl esters. The esters 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic methyl ester (PHT-MET), 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic ethyl ester, 4-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester, and 2-(1,3-dioxo-1, 3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester were hydrolyzed by immobilized lipase. The enzymatic reaction could be used only to produce the desired 4-substituted compounds. The best result that was found to hydrolysis of PHT-MET, and, therefore, that ester was selected for optimization experiments in a three-phase system. Reactions were performed with solid biocatalyst (Lipozyme® RM IM), organic solvent phase (ethyl acetate), and aqueous phase (saturated Na2CO3 solution). To optimize the reaction conditions, an experimental design optimization procedure was used. The variables studied were the amount of enzyme, the temperature, and the volume of the aqueous solution. Time course experiments were then performed for different initial enzyme concentrations (0.5, 0.9, and 1.4 UH/mL of solvent). The optimized reaction conditions found were 20 mg of Lipozyme (0.9 UH/mLsolvent) and 5.0 mL of Na2CO3(sat) at 40°C for 6 h. 相似文献
10.
The metabolic transformations of the psychotropic cannabinoid (3R, 4R)-Δ1-tetrahydrocannabinol (5) (=Δ1-THC) by cultures of Fusarium Nivale, Gibberella fujikuroi (both Ascomycetes) and Thamnidium elegans (Phycomycetes) were investigated. A number of metaboilites, 1–4 and 6–9 were isolated from the incubations, partly purified and their structures elucidated by combined gas chromatography/mass spectrometry. Four of these metabolites, 1″-hydroxy-Δ1-THC (4) 2″-hydroxy-β1-THC (1) 6Δ-hydroxy-ζ1-THC (8) and 2″,6Δ-dihydroxy-Δ1-THC (9) so far have not been reported as microbial transformation products of 5 . 相似文献