全文获取类型
收费全文 | 16988篇 |
免费 | 419篇 |
国内免费 | 117篇 |
专业分类
化学 | 12087篇 |
晶体学 | 98篇 |
力学 | 330篇 |
数学 | 2921篇 |
物理学 | 2088篇 |
出版年
2021年 | 140篇 |
2020年 | 167篇 |
2019年 | 169篇 |
2018年 | 136篇 |
2017年 | 130篇 |
2016年 | 278篇 |
2015年 | 304篇 |
2014年 | 309篇 |
2013年 | 717篇 |
2012年 | 726篇 |
2011年 | 947篇 |
2010年 | 474篇 |
2009年 | 419篇 |
2008年 | 867篇 |
2007年 | 888篇 |
2006年 | 910篇 |
2005年 | 974篇 |
2004年 | 867篇 |
2003年 | 726篇 |
2002年 | 635篇 |
2001年 | 209篇 |
2000年 | 204篇 |
1999年 | 173篇 |
1998年 | 169篇 |
1997年 | 217篇 |
1996年 | 276篇 |
1995年 | 181篇 |
1994年 | 178篇 |
1993年 | 167篇 |
1992年 | 167篇 |
1991年 | 156篇 |
1990年 | 158篇 |
1989年 | 138篇 |
1988年 | 146篇 |
1987年 | 156篇 |
1986年 | 123篇 |
1985年 | 272篇 |
1984年 | 242篇 |
1983年 | 184篇 |
1982年 | 257篇 |
1981年 | 210篇 |
1980年 | 267篇 |
1979年 | 232篇 |
1978年 | 236篇 |
1977年 | 245篇 |
1976年 | 206篇 |
1975年 | 168篇 |
1974年 | 162篇 |
1973年 | 156篇 |
1971年 | 86篇 |
排序方式: 共有10000条查询结果,搜索用时 16 毫秒
271.
Kortes Richard A. Lin Fu-Tyan Ward Matthew S. Shepherd Rex E. 《Transition Metal Chemistry》2000,25(3):251-259
1:1 and 2:1 palladium(II) complexes of egta4– (egta4– = glycine, N,N-(1,2-ethanediylbis)(oxy-2,1-ethanediyl)bis[N-carboxymethyl]) were prepared by 1:1 and 2:1 addition of K2PdCl4 to K4egta, and examined by 1H-, 13C- and 15N-n.m.r. methods. The 1:1 complex, [Pd(egta)]2– in solution, utilizes a square-planar coordination comprised of two nitrogen and two glycinato carboxylate donors of egta4–, leaving two glycinato carboxylates pendant. The complex has a cis-(R,S) stereochemistry which places both pendant carboxylates below the PdN2O2 square plane and the tether backbone of egta4– in the up, up sense above the same plane. The cis-(R,S) assignment was assisted by computer simulations of the 13C-n.m.r. spectrum for four possible isomers. Only cis-(R,S) and trans-(R,R) calculated 13C-spectra were compatible with the observed 13C-n.m.r. pattern. The HH NOESY spectrum of [Pd(egta)]2– detects long range coupling of the backbone –OCH2CH2O– linkage with both coordinated and pendant glycinato CH2 moieties. The cis-(R,S) isomer's tortional movements allow such contacts whereas a trans-(R,R) isomer does not. The 2:1 complex, [Pd2(egta)(H2O)2] in solution has an extended-chain structure with each palladium(II) center coordinated in the mer-iminodiacetate-like coordination with two bound glycinato-functionalities. 相似文献
272.
Stevan W. Djuri Richard B. Herbert Frederick G. Holliman 《Journal of heterocyclic chemistry》1985,22(5):1425-1428
A novel procedure for the chemoselective reduction of 2-acyl-1H-indole-3-carboxaldehydes has been developed. Low temperature lithium triethylborohydride reduction affords the indol-2-yl carbinol whilst sodium cyanoborohydride reduction in acetic acid affords the 3-hydroxymethyl analogs. Both processes are high yield, and provide access to intermediates of potential utility for indole alkaloid synthesis. 相似文献
273.
Photoinduced charge separation is a fundamental step in photochemical energy conversion. In the design of molecularly based systems for light-to-chemical energy conversion, this step is studied through the construction of two- and three-component systems (dyads and triads) having suitable electron donor and acceptor moieties placed at specific positions on a charge-transfer chromophore. The most extensively studied chromophores in this regard are ruthenium(II) tris(diimine) systems with a common 3MLCT excited state, as well as related ruthenium(II) bis(terpyridyl) systems. This Forum contribution focuses on dyads and triads of an alternative chromophore, namely, platinum(II) di- and triimine systems having acetylide ligands. These d8 chromophores all possess a 3MLCT excited state in which the lowest unoccupied molecular orbital is a pi orbital on the heterocyclic aromatic ligand. The excited-state energies of these Pt(II) chromophores are generally higher than those found for the ruthenium(II) tris(diimine) systems, and the directionality of the charge transfer is more certain. The first platinum diimine bis(arylacetylide) triad, constructed by attaching phenothiazene donors to the arylacetylide ligands and a nitrophenyl acceptor to 5-ethynylphenanthroline of the chromophore, exhibited a charge-separated state of 75-ns duration. The first Pt(tpy)(arylacetylide)+-based triad contains a trimethoxybenzamide donor and a pyridinium acceptor and has been structurally characterized. The triad has an edge-to-edge separation between donor and acceptor fragments of 27.95 Angstroms. However, while quenching of the emission is complete for this system, transient absorption (TA) studies reveal that charge transfer does not move onto the pyridinium acceptor. A new set of triads described in detail here and having the formula [Pt(NO2phtpy)(p-C triple-bond C-C6H4CH2(PTZ-R)](PF6), where NO2phtpy = 4'-{4-[2-(4-nitrophenyl)vinyl]phenyl}-2,2';6',2'-terpyridine and PTZ = phenothiazine with R = H, OMe, possess an unsaturated linkage between the chromophore and a nitrophenyl acceptor. While the parent chromophore [Pt(ttpy)(C triple-bond CC6H5)]PF6 is brightly luminescent in a fluid solution at 298 K, the triads exhibit complete quenching of the emission, as do the related donor-chromophore (D-C) dyads. Electrochemically, the triads and D-C dyads exhibit a quasi-reversible oxidation wave corresponding to the PTZ ligand, while the R = H triad and related C-A dyad display a facile quasi-reversible reduction assignable to the acceptor. TA spectroscopy shows that one of the triads possesses a long-lived charge-separated state of approximately 230 ns. 相似文献
274.
Weil Joseph Brewer Mark Hendrickson Richard Sarikaya Ayda Ladisch Michael R. 《Applied biochemistry and biotechnology》1998,(1):99-111
Yellow poplar wood sawdust consists of 41% cellulose and 19% hemicellulose. The goal of pressure cooking this material in
water is to hydrate the more chemically resistive regions of cellulose in order to enhance enzymatic conversion to glucose.
Pretreatment can generate organic acids through acid-catalyzed degradation of monosaccharides formed because of acids released
from the biomass material or the inherent acidity of the water at temperatures above 160°C. The resulting acids will further
promote the acid-catalyzed degradation of monomers that cause both a reduction in the yield and the formation of fermentation
inhibitors such as hydroxymethyl furfural and furfural. A continuous pH-monitoring system was developed to help characterize
the trends in pH during pretreatment and to assist in the development of a base (2.0 M KOH) addition profile to help keep
the pH within a specified range in order to reduce any catalytic degradation and the formation of any monosac-charide degradation
products during pretreatment. The results of this work are discussed. 相似文献
275.
Dissociative recombination of the weakly bound NO-dimer cation: cross sections and three-body dynamics 总被引:1,自引:0,他引:1
Petrignani A Andersson PU Pettersson JB Thomas RD Hellberg F Ehlerding A Larsson M van der Zande WJ 《The Journal of chemical physics》2005,123(19):194306
Dissociative recombination (DR) of the dimer ion (NO)(2) (+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.2 eV. The fragmentation products reveal that the breakup into the three-body channel NO+O+N dominates with a probability of 0.69+/-0.02. The second most important channel yields NO+NO fragments with a probability of 0.23+/-0.03. Furthermore, the dominant three-body breakup yields electronic and vibrational ground-state products, NO(upsilon=0)+N((4)S)+O((3)P), in about 45% of the cases. The internal product-state distribution of the NO fragment shows a similarity with the product-state distribution as predicted by the Franck-Condon overlap between a NO moiety of the dimer ion and a free NO. The dissociation dynamics seem to be independent of the NO internal energy. Finally, the dissociation dynamics reveal a correlation between the kinetic energy of the NO fragment and the degree of conservation of linear momentum between the O and N product atoms. The observations support a mechanism in which the recoil takes place along one of the NO bonds in the dimer. 相似文献
276.
Guy Guelachvili K. Narahari Rao Richard H. Tipping Brenda P. Winnewisser Manfred Winnewisser 《Mikrochimica acta》1988,95(1-6):339-343
This paper reports the observation of the far infrared absorption spectrum of a single crystal of N2, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed. 相似文献
277.
The Photochemistry of Open-Chained 2,6- or 2,7-Dien-Carbonyl Compounds On 1n, π*-excitation (λ > 347 nm) citral (5) and the methyl ketone 10 isomerize to compounds A (7, 19) and B (6, 20) , whereas the phenyl ketone 11 changes into the isomer 24 of type E. Evidence is given that the conversions to A and B may arise from the 3n, π*-state of the 2,6-diene-carbonyl compounds. On 1n, π*-excitation (λ = 254 nm) 5 and 10 yield the isomers A (7, 19) and D (18, 22) , but no products of type B. Furthermore, conversion of 10 to the isomer 21 of type C is observed. Selective 1n, π*-excitation (λ = 254 nm) as well as selective 1n, π*-excitation (λ > 347 nm) of the 2,7-diene-carbonyl compounds 12 and 13 give rise to isomerization to the compounds F (25, 28) , exclusively. The intramolecular [2 + 2]-photocycloadditions are shown to be triplet processes. UV.-irradiation (λ > 280 nm) of compounds F (25, 28) furnishes the isomeric products G (26, 29) which photoisomerize to oxetanes of type H (27, 30). 相似文献
278.
The hexamolybdenum cluster complex [Mo6(3-Cl)8(O2CMe)6]2–, 1 was isolated as the Bu4N+ salt in 71% yield from the reaction of (Bu4N)2[Mo6(3-Cl)8Cl6] with AgO2CMe in CH2Cl2 solvent. The compound was characterized by single crystal X-ray diffraction analysis. The cluster contains an octahedral arrangement of six molybdenum atoms with eight chloride ligands bridging the eight trianglar faces and six carboxylate ligands terminally coordinated through one oxygen atom to each of the six molybdenum atoms. Crystal data: space group =P21/n,a=10.713(3)Å,b=14.43(1)Å,c=21.919(4)Å, =94.37(2)°,Z=2, 1965 reflections,R=0.036. 相似文献
279.
May JP Ting R Lermer L Thomas JM Roupioz Y Perrin DM 《Journal of the American Chemical Society》2004,126(13):4145-4156
A DNAzyme, synthetically modified with both primary amines and imidazoles, is found to act as a M2+ -independent AP lyase-endonuclease. In the course of the cleavage reaction, this DNAzyme forms a covalent Schiff base intermediate with an abasic site on a complementary oligodeoxyribonucleotide. This intermediate, which is inferred from NaCNBH3 trapping as well as cyanide inhibition, does not evidently accumulate because the second step, dehydrophosphorylative elimination, is fast compared to Schiff base formation. The 5'-product that remains linked to the catalyst hydrolyzes slowly to regenerate free catalyst. The use of duly modified DNAzymes to perform Schiff base catalysis demonstrates the value of modified nucleotides for enhancing the catalytic repertoire of nucleic acids. This work suggests that DNAzymes will be capable of catalyzing aldol condensation reactions. 相似文献
280.
Haiss W Raisch P Schiffrin DJ Bitsch L Nichols RJ 《Faraday discussions》2002,(121):167-80; discussion 229-51
In situ FTIR spectroscopy has been used in the attenuated total reflectance (ATR) mode to investigate the surface chemistry of etching Si(100) surfaces in aqueous KOH. The effect of solution concentration and electrode potential on the Si-H vibrations has been explored and the experimental results compared with density functional theory calculations. In addition. the kinetics of surface passivation of n-Si(100) has been investigated using FTIR spectroscopy. 相似文献