全文获取类型
收费全文 | 6743篇 |
免费 | 278篇 |
国内免费 | 37篇 |
专业分类
化学 | 4706篇 |
晶体学 | 26篇 |
力学 | 218篇 |
数学 | 1083篇 |
物理学 | 1025篇 |
出版年
2022年 | 40篇 |
2021年 | 69篇 |
2020年 | 85篇 |
2019年 | 105篇 |
2018年 | 93篇 |
2017年 | 84篇 |
2016年 | 161篇 |
2015年 | 155篇 |
2014年 | 178篇 |
2013年 | 286篇 |
2012年 | 358篇 |
2011年 | 399篇 |
2010年 | 245篇 |
2009年 | 244篇 |
2008年 | 366篇 |
2007年 | 350篇 |
2006年 | 382篇 |
2005年 | 339篇 |
2004年 | 300篇 |
2003年 | 270篇 |
2002年 | 308篇 |
2001年 | 121篇 |
2000年 | 119篇 |
1999年 | 70篇 |
1998年 | 64篇 |
1997年 | 78篇 |
1996年 | 83篇 |
1995年 | 64篇 |
1994年 | 73篇 |
1993年 | 65篇 |
1992年 | 62篇 |
1991年 | 61篇 |
1990年 | 56篇 |
1989年 | 55篇 |
1988年 | 47篇 |
1987年 | 51篇 |
1986年 | 48篇 |
1985年 | 99篇 |
1984年 | 97篇 |
1983年 | 63篇 |
1982年 | 98篇 |
1981年 | 66篇 |
1980年 | 87篇 |
1979年 | 66篇 |
1978年 | 84篇 |
1977年 | 70篇 |
1976年 | 65篇 |
1975年 | 50篇 |
1974年 | 53篇 |
1973年 | 45篇 |
排序方式: 共有7058条查询结果,搜索用时 382 毫秒
81.
Direct optical detection of singlet oxygen from a single cell 总被引:1,自引:0,他引:1
Zebger I Snyder JW Andersen LK Poulsen L Gao Z Lambert JD Kristiansen U Ogilby PR 《Photochemistry and photobiology》2004,79(4):319-322
Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level. 相似文献
82.
Electron attachment to polar molecules and their non-covalent complexes can lead to different kinds of anions which differ from their excess electron localization. Spectroscopic methods for studying anion structures are reviewed. In many cases, the neutral and anion structures are identical and can be deduced from the electron attachment properties. Examples are given for complexes containing polar solvents or building blocks of biomolecules (nucleobases, amino acid residues...). 相似文献
83.
Sb4Te3 and Sb8Te9 are members of the homology (Sb2Te3)m.(Sb2)n, with structures consisting of Sb2- and Sb2Te3-type slabs stacked along [001]; electrical conductivity and thermopower are reported for several members of this family. 相似文献
84.
The uncatalyzed 1,4-addition of phenylmagnesium bromide and furylmagnesium iodide to methyl 5-methoxy-1,5-cyclohexadienylcarboxylate (), directly followed by alkylation and hydrolysis leads to the corresponding cyclohexanones of type (R1 and R2 trans) in moderate to high yield. 相似文献
85.
Daniel Bellu Hanspeter Fischer Hans Greuter Pierre Martin 《Helvetica chimica acta》1978,61(5):1784-1813
Syntheses of Moniliformin, a Mycotoxine with a Cyclobutenedione Structure Six different routes to 3-hydroxy-3-cyclobutene-1, 2-dione ( 4 ), the free acid of the mycotoxine Moniliformin (=alkali salt of 4 ) are described. A common feature of all pathways is the synthesis of cyclobutanes having the oxidation level 6. Moniliformin precursors which are easily transformed to 4 by acid catalysed hydrolysis include [2+2]-cycloadducts of ketene with tetraalkoxy-olefins, 3,4,4-trialkoxycyclobutenes, derivatives of polyfluorinated cyclobutenes, the brominated [2+2]-cycloadduct of ethyl vinyl ether and dichloroketene, tetrabromocyclobutanone, [2+2]-photocycloadducts of dichlorovinylenecarbonate with dichloroethylenes, and the dimer of chloroketene. The most convenient synthesis via the [2+2]-cycloadduct of tetraethoxyethylene and ketene ( 14b ) is reported in detail and produces 4 in four simple steps in 57% overall yield. In addition, two new syntheses of squaric acid ( 56 ) are described. 相似文献
86.
The structures of alloys can be described in terms of polyhedrapacking. We studiedall structure types found in the binary systemsT 5 orT 6 withB 3 orB 4 (T 5: V, Nb, Ta;T 6: Cr, Mo, W;B 3: Al, Ga, In, Tl;B 4: Si, Ge, Sn, Pb) elements. Most of the structures examined until now could be built up with one or two polyhedra, only in a few cases more than two polyhedra are required. It is found that there are two types: a three-dimensional distribution of discrete polyhedra sharing corners, edges or faces and a layer-like distribution. This model proved valid for all structure types studied. Classification of the structures according to their polyhedrapacking criteria is introduced (Table 1). Table 2 includes the coordination numbers of all atoms in the studied structures. 相似文献
87.
The isomerization of 1,2-epcxycyclopentane ( 1 ) to enantiomerically enriched (R)-cyclopent-2-enol ( 2 ) in protic solvents is catalyzed by cob(I)alamin. The enantiomeric excess (e.e.) of (R)- 2 is usually ca. 60%; it is only slightly dependent on the temperature, but increases with decreasing dielectric constant ε of the solvent. Standard kinetic methods show the reaction to be first order in vitamin B12 and zero order in 1 . The rate constant increases exponentially with increasing ε of the solvent. An Arrhenius plot at ε = 40 gives activation parameters ΔH≠ = 78 ± 4 kJ·mol?1 and ΔS≠ = ?49 ± 1 J·mol?1·K?1. The isomerization 1 → 2 proceeds in two steps (Schemes 2 and 7): (i) The epoxide ring is first opened by the proton-assisted fast and irreversible nucleophilic attack of the chiral CoI catalyst to form diastereoisomeric (1R,2R)- and (1S,2S)-(2-hydroxycyclo-pentyl)cob(III)alamins 6 in a ratio of ca. 4:1 which are the dominant species in the steady state; (ii) The intermediates 6 then decompose in the rate-limiting step to form 2 and recycled catalyst. Experiments with specifically 2H-labeled 1 showed the hydro-cobalt elimination 6 → 2 to be non-stereoselective. It proceeds via reversible Co? C bond homolysis to a free 2-hydroxycyclopentyl radical from which stereoelectronically controlled H-abstraction by Co11 takes place. 相似文献
88.
The cofacial bisporphyrins H4DPS (DPS = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene), H4DPO (DPO = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzofuran), H4DPX (DPX = 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene), H4DPA (DPA = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]anthracene), and H4DPB (DPB = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene) have been monometalated by Zn(OAc)2.2H2O and by GaCl3 to explore the singlet-singlet energy transfer from the photoexcited metal porphyrin center to the linked free base porphyrin. The spectroscopic (UV-vis and fluorescence) and photophysical properties (fluorescence lifetimes, tauF, and quantum yields, phiF) have been investigated at 298 and 77 K in degassed 2-MeTHF for the donor-acceptor systems, (Zn)H2DPS, (Zn)H2DPO, (Zn)H2DPA, (Zn)H2DPX, and (Zn)H2DPB, as well as for the bis-zinc complexes, (Zn)2DPS, (Zn)2DPO, (Zn)2DPX, and (Zn)2DPB, respectively, and the monoporphyrin derivatives, H2P, (Zn)P, and (Ga-OMe)P (P2- = 5-phenyl-2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrin-dianion). The singlet-singlet energy transfer rate constants (KET) were obtained using KET = (1/tauF -1/tauFo), where tauFo is the fluorescence lifetime of the corresponding bis-zinc(II) systems (or (Zn)P and (Ga-OMe)P) where no energy transfer occurs. The tauF value for three bis-zinc(II) compounds varies from 1.69 to 2.01 ns and is 1.84 (at 298 K) and 3.20 ns (at 77 K) for (Ga-OMe)P. In the donor-acceptor bismacrocycles, depending on the spacer and the temperature, the fluorescence lifetimes decrease down to 50-240 ps. The KET values range from approximately 4 to approximately 21 (ns(-1)) and have been analyzed considering both the F?rster and the Dexter mechanisms. Using the C(meso)-C(meso) distance parameters in the calculations, the F?rster and Dexter mechanisms operate for DPS and DPO, and for DPA, DPX, and DPB spacer systems, respectively. The limit distance where one mechanism dominates over the other is estimated to be around 5-6 A. 相似文献
89.
Total synthesis of amaryllidaceae alkaloid buflavine 总被引:1,自引:0,他引:1
A concise synthesis of the amaryllidaceae alkaloid buflavine (1) and its regioisomer (2) involving sequential Meyers' biaryl coupling, enecarbamate formation, and hydrogenation followed by ultimate intramolecular reductive amination is presented. 相似文献
90.
THE EFFECTS OF PORPHYRIN STRUCTURE AND AGGREGATION STATE ON PHOTOSENSITIZED PROCESSES IN AQUEOUS AND MICELLAR MEDIA 总被引:2,自引:0,他引:2
C. R. Lambert E. Reddi J. D. Spikes M. A. J. Rodgers G. Jori 《Photochemistry and photobiology》1986,44(5):595-601
The efficiency of several porphyrins at 10 μM and 83 μM as sensitizers of the photooxidation of 0.1 mM tryptophan and histidine via a singlet oxygen-mechanism was studied in pH 7.4-buffered aqueous solutions and in aqueous dispersions of Triton X-100 micelles. The porphyrins were either solubilized in the bulk aqueous medium or associated with the micellar phase, whereas the amino acids were always located in the aqueous phase. With those porphyrins, such as uroporphyrin I, meso-tetra (4-sulfonatophenyl)porphine, meso-tetra(4-carboxyphenyl)porphine and meso-tetra)N,N,N-trimethylanilinium)porphine, which are > 98% monomeric in both media, the efficiency of histidine photooxidation was independent of the site of O2(1Δg) generation, as shown by the closely similar values for the photooxidation rate constant and oxygen-consumption quantum yield in the presence and absence of Triton micelles; the same indications were provided by photokinetic experiments with tryptophan. Actually, laser flash photolysis studies showed that the micelle-incorporation of the above mentioned porphyrins brought about only minor changes in their photophysical properties, including the relative yield of O2(1Δg) generation. On the other hand, hematoporphyrin IX, its Zn2+-complex, and coproporphyrin III are largely aggregated in homogeneous aqueous solution; their incorporation into Triton micelles caused an increase of the triplet quantum yield and an enhancement of the oxygen-consumption quantum yield and photooxidation rate constant for both histidine and tryptophan. The lower photosensitizing efficiency of aggregated porphyrin species in comparison with the corresponding monomeric porphyrin was confirmed by measuring the initial rate and quantum yield of oxygen consumption upon irradiation of 1 mM histidine and tryptophan in the presence of different hematoporphyrin concentrations within the 0.3-100μM range. 相似文献