全文获取类型
收费全文 | 1331篇 |
免费 | 61篇 |
国内免费 | 9篇 |
专业分类
化学 | 711篇 |
晶体学 | 6篇 |
力学 | 39篇 |
数学 | 358篇 |
物理学 | 287篇 |
出版年
2023年 | 12篇 |
2022年 | 24篇 |
2021年 | 34篇 |
2020年 | 32篇 |
2019年 | 28篇 |
2018年 | 17篇 |
2017年 | 21篇 |
2016年 | 60篇 |
2015年 | 41篇 |
2014年 | 58篇 |
2013年 | 96篇 |
2012年 | 97篇 |
2011年 | 83篇 |
2010年 | 43篇 |
2009年 | 41篇 |
2008年 | 64篇 |
2007年 | 68篇 |
2006年 | 61篇 |
2005年 | 39篇 |
2004年 | 51篇 |
2003年 | 46篇 |
2002年 | 31篇 |
2001年 | 22篇 |
2000年 | 26篇 |
1999年 | 17篇 |
1998年 | 16篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 14篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 14篇 |
1991年 | 10篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 15篇 |
1984年 | 15篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 14篇 |
1979年 | 8篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1969年 | 6篇 |
1886年 | 5篇 |
1884年 | 5篇 |
1880年 | 4篇 |
1878年 | 4篇 |
排序方式: 共有1401条查询结果,搜索用时 0 毫秒
91.
Jocelyn D Laughton Philippe Bittar Yves Charnay Luc Pellerin Enikö Kovari Pierre J Magistretti Constantin Bouras 《BMC neuroscience》2007,8(1):35
Background
For a long time now, glucose has been thought to be the main, if not the sole substrate for brain energy metabolism. Recent data nevertheless suggest that other molecules, such as monocarboxylates (lactate and pyruvate mainly) could be suitable substrates. Although monocarboxylates poorly cross the blood brain barrier (BBB), such substrates could replace glucose if produced locally. 相似文献92.
In this review anti-metatype antibodies are described invoking new principles in immunoassay development. Anti-metatype antibodies are immunological reagents specific for the conformation of the liganded antibody active site which do not interact with bound ligand or unliganded antibody. Relationships between anti-metatype antibody reactivity and the ligand-induced conformational state of monoclonal antibodies are reviewed with emphasis on the fluorescein hapten as a small molecule model system. One characteristic result of the interaction of anti-metatype antibodies with liganded antibodies is a significant delay in the dissociation rate (k2) of the ligand bound within the primary immune complex. The latter is an important consideration for assay development. Polyclonal and monoclonal anti-metatype antibody reagents are characterized in terms of their differential effects on the ligand dissociation rate. Anti-metatype antibody reactivity is further discussed in terms of protein-protein specificity patterns and relative interactions with idiotype-family members, structural derivatives, and site-specific mutants. Incorporation of principles inherent in the anti-metatype concept and their application to assay development are summarized.Abbreviations D2O
deuterium oxide
- Fab
50 kd antibody fragment containing VHCH1 + VLCL domains
- FITC(I)
fluorescein isothiocyanate (isomer I)
- Fv
26 kd fragment of the antibody molecule containing the variable domains of the H and L chains
- Ig
immunoglobulin
- IgG
immunoglobulin G with a mol. wt. of 150 kd.
- IgM
immunoglobulin M with a mol. wt. of 106d
- Id
idiotype
- Ka
antibody affinity (k1/k2) in M–1
- k1
second order rate of ligand association in M–1s–1
- k2
first order rate of ligand dissociation in s–1
- KD
dissociation constant or the reciprocal of the affinity constant (1/Ka)
- Mab
monoclonal antibody
- Met
metatype
- NMR
nuclear magnetic resonance
- SCA
single chain Fv derivative containing a synthetic linker between the two variable domains
- VH
variable domain of the antibody H chain
- VL
variable domain of the antibody L chain 相似文献
93.
High-resolution Fourier-transform infrared spectra between 1235 and 1680 cm−1 and subterahertz spectra between 250 and 630 GHz of monoisotopic 13CH335Cl have been recorded and analyzed simultaneously, with all Coriolis, α-resonance, and l-type interactions in the polyad of the v2 = 1, v5 = 1, and v3 = 2 levels taken into account. Several α-resonances (Δk = ±2, Δl = ?1) generating perturbation-allowed transitions have been assigned in the rovibrational spectra. These resonances enabled us to determine accurately and independently the ground state rotational and centrifugal distortion parameters A0 = 5.205 746 9 (55) cm−1 and . Even , which is, however, correlated to higher-order α-resonance terms, was determined. With 51 upper state parameters varied, about 5800 rovibrational wavenumbers and more than 550 rotational frequencies pertaining to the excited vibrational states were fitted within their experimental accuracy. 相似文献
94.
Gabriela Ionita Petre Ionita Victor EM. Sahini Constantin Luca 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(3-4):269-271
The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin. 相似文献
95.
Trambitas AG Melcher D Hartenstein L Roesky PW Daniliuc C Jones PG Tamm M 《Inorganic chemistry》2012,51(12):6753-6761
Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity. 相似文献
96.
Wahl F Weiler A Landenberger P Sackers E Voss T Haas A Lieb M Hunkler D Wörth J Knothe L Prinzbach H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(24):6255-6267
“One‐pot” substitution of the twenty hydrogen atoms in pentagonal dodecahedrane (C20H20) by OH, F, Cl, and Br atoms is explored. Electrophilic insertion of oxygen atoms with DMDO and TFMDO as oxidizing reagents ended, far off the desired C20(OH)20, in complex polyol mixtures (up to C20H10(OH)10 decols, a trace of C20H(OH)19?). Perfluorination was successful in a NaF matrix but (nearly pure) C20F20 could be secured only in very low yield. “Brute‐force” photochlorination (heat, light, pressure, time) provided a mixture of hydrogen‐free, barely soluble C20Cl16 dienes in high yield and C20Cl20 as a trace component. Upon electron‐impact ionization of the C20Cl16 material sequential loss of the chlorine atoms was the major fragmentation pathway furnishing, however, only minor amounts of chlorine‐free C20+ ions. “Brute‐force” photobrominations delivered an extremely complex mixture of polybromides with C20HBr13 trienes as the highest masses. The MS spectra exhibited exclusive loss of the Br substituents ending in rather intense singly, doubly, and triply charged C20H4–0+(2+)(3+) ions. The insoluble ~C20HBr13 fraction (C20Br14 trienes as highest masses) obtained along a modified bromination protocol, ultimately allowed the neat mass selection of C20? ions. The C20Cl16 dienes and C20H0–3Br14–12 tri‐/tetraenes, in spite of their very high olefinic pyramidalization, proved resistant to oxygen and dimerization (polymerization) but added CH2N2 smoothly. Dehalogenation of the respective cycloaddition products through electron‐impact ionization resulted in C22–24H4–8+(2+) ions possibly constituting bis‐/tris‐/tetrakis‐methano‐C20 fullerenes or partly hydrogenated C22, C23, and C24 cages. 相似文献
97.
The increasing application of positron emission tomography (PET) in nuclear medicine has stimulated the extensive development of a multitude of novel and versatile techniques to introduce fluorine-18, especially for the radiolabelling of biologically or pharmacologically active molecules. Taking into consideration that the introduction of fluorine-18 (t1/2=109.8 min) mostly proceeds under harsh conditions, radiolabelling of such molecules represents a challenge and is of enormous interest. Ideally, it should proceed in a regioselective manner under mild physiological conditions, in an acceptable time span, with high yields and high specific activities. Special attention has been drawn to 2-fluoroethyl and 3-fluoropropyl groups, which are often the active sites of radiofluorinated compounds. Precursors containing an ammonium leaving group – such as a strained azetidinium or aziridinium moiety – can help to overcome these obstacles leading to a convenient and mild introduction of [18F]fluoride with high radiochemical yields. 相似文献
98.
The purpose of this work was to investigate the effect of several factors (anion type in the copper salt, pH and concentration of the salt solution) on the structure and thermo-oxidative degradation of the polyacrylamidoxime-copper chelates, by using elemental analysis, IR spectroscopy and dynamic thermogravimetry. The chelates containing copper ions as sulphate exhibit a better initial thermal stability than the polyacrylamidoxime fibre presumably due to the crosslinking generated by the intermolecular complexation of the ions; the removal of the sulphate anions takes place concomitantly with the second step of polymeric chain decomposition. The initial thermal decomposition of the chelates formed by copper ions as nitrate begins at lower temperatures as compared to the polyacrylamidoxime fibre, probably by the nitrate anion release, which partly overlaps the initial decomposition of the copper ion-crosslinked polymeric chains. Copper ions as either sulphate or nitrate catalyse the reactions involved in the main step of polyacrylamidoxime fibre decomposition; the higher the copper amount, the stronger the catalytic effect. 相似文献
99.
Denisa Dumitrescu Sergiu Shova Constantin Draghici Marcel Mirel Popa Florea Dumitrascu 《Molecules (Basel, Switzerland)》2021,26(12)
3-Arylsydnones bearing fluorine and bromine atoms on the benzene ring were synthesized from N-nitroso-2-fluorophenylglycines and characterized by NMR spectroscopy. These were employed further in synthesis of the corresponding 1-(2-fluorophenyl)pyrazoles by 1,3-dipolar cycloaddition reaction with dimethyl acetylenedicarboxylate (DMAD) as activated dipolarophile. The sydnones as reaction intermediates were characterized by single crystal X-ray diffraction analysis showing interesting features such as halogen bonding as an important interaction in modeling the crystal structure. 相似文献
100.
Hong-yu Li Yan Wang Arindam Chatterjee Sreenivasa R. Mundla Matthew Voss J. Scott Sawyer 《Tetrahedron》2007,63(47):11763-11770
A simple and efficient synthesis of dihydropyrrolopyrazole boronic acid intermediate (5) has been developed. Utilization of a three-component Suzuki-Miyaura/etherification with microwave heating led to advanced compound 11 in high yield and with easy purification. Reaction of compound 11 with methanesulfonyl chloride at room temperature furnished the 1,3 O-N rearranged product (12), which is postulated to proceed via an intramolecular mechanism. The outlined synthesis provides a highly efficient and high-yielding route that is amenable to rapid analog synthesis. 相似文献