全文获取类型
收费全文 | 9033篇 |
免费 | 391篇 |
国内免费 | 136篇 |
专业分类
化学 | 6693篇 |
晶体学 | 52篇 |
力学 | 497篇 |
数学 | 1039篇 |
物理学 | 1279篇 |
出版年
2024年 | 16篇 |
2023年 | 63篇 |
2022年 | 301篇 |
2021年 | 415篇 |
2020年 | 426篇 |
2019年 | 433篇 |
2018年 | 468篇 |
2017年 | 432篇 |
2016年 | 610篇 |
2015年 | 434篇 |
2014年 | 565篇 |
2013年 | 1031篇 |
2012年 | 771篇 |
2011年 | 682篇 |
2010年 | 461篇 |
2009年 | 435篇 |
2008年 | 425篇 |
2007年 | 353篇 |
2006年 | 241篇 |
2005年 | 200篇 |
2004年 | 140篇 |
2003年 | 129篇 |
2002年 | 110篇 |
2001年 | 41篇 |
2000年 | 20篇 |
1999年 | 31篇 |
1998年 | 22篇 |
1997年 | 26篇 |
1996年 | 23篇 |
1995年 | 15篇 |
1994年 | 17篇 |
1993年 | 16篇 |
1992年 | 22篇 |
1991年 | 12篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 15篇 |
1986年 | 8篇 |
1985年 | 17篇 |
1984年 | 18篇 |
1983年 | 4篇 |
1982年 | 15篇 |
1981年 | 9篇 |
1980年 | 16篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1971年 | 4篇 |
排序方式: 共有9560条查询结果,搜索用时 0 毫秒
51.
Dias HV Diyabalanage HV Eldabaja MG Elbjeirami O Rawashdeh-Omary MA Omary MA 《Journal of the American Chemical Society》2005,127(20):7489-7501
Synthetic details, solid-state structures, and photophysical properties of a group of trimeric copper(I) complexes containing pyrazolate ligands are described. The reaction of copper(I) oxide and the fluorinated pyrazoles [3-(CF(3))Pz]H, [3-(CF(3)),5-(Me)Pz]H, and [3-(CF(3)),5-(Ph)Pz]H leads to the corresponding trinuclear copper(I) pyrazolates, {[3-(CF(3))Pz]Cu}(3), {[3-(CF(3)),5-(Me)Pz]Cu}(3), and {[3-(CF(3)),5-(Ph)Pz]Cu}(3), respectively, in high yield. The {[3,5-(i-Pr)(2)Pz]Cu}(3) compound was obtained by a reaction between [Cu(CH(3)CN)(4)][BF(4)], [3,5-(i-Pr)(2)Pz]H, and NEt(3). These compounds as well as {[3,5-(Me)(2)Pz]Cu}(3) and {[3,5-(CF(3))(2)Pz]Cu}(3) adopt trimeric structures with nine-membered Cu(3)N(6) metallacycles. There are varying degrees and types of intertrimer Cu...Cu interactions. These contacts give rise to zigzag chains in the fluorinated complexes, {[3-(CF(3))Pz]Cu}(3), {[3-(CF(3)),5-(Me)Pz]Cu}(3), {[3-(CF(3)),5-(Ph)Pz]Cu}(3), and {[3,5-(CF(3))(2)Pz]Cu}(3), whereas the nonfluorinated complexes, {[3,5-(Me)(2)Pz]Cu}(3) and {[3,5-(i-Pr)(2)Pz]Cu}(3) form dimers of trimers. Out of all the compounds examined in this study, {[3-(CF(3)),5-(Ph)Pz]Cu}(3) has the longest (3.848 Angstroms) and {[3,5-(Me)(2)Pz]Cu}(3) has the shortest (2.946 Angstroms) next-neighbor intertrimer Cu...Cu distance. The Cu...Cu separations within the trimer units do not vary significantly (typically 3.20-3.26 Angstroms). All of these trinuclear copper(I) pyrazolates show bright luminescence upon exposure to UV radiation. The luminescence bands are hugely red-shifted from the corresponding lowest-energy excitations, rather broad, and unstructured even at low temperatures, suggesting metal-centered emissions owing to intertrimer Cu...Cu interactions that are strengthened in the phosphorescent state. The {[3-(CF(3)),5-(Ph)Pz]Cu}(3) compound exhibits an additional highly structured phosphorescence with a vibronic structure corresponding to the pyrazolyl (Pz) ring. The luminescence properties of solids and solutions of the trimeric compounds in this study show fascinating trends with dramatic sensitivities to temperature, solvent, concentration, and excitation wavelengths. 相似文献
52.
Kazi A. Azam Rahima Dilshad Shariff E. Kabir Rashid Miah Mohammad Shahiduzzaman Edward Rosenberg Kenneth I. Hardcastle Michael B. Hursthouse K. M. Abdul Malik 《Journal of Cluster Science》1996,7(1):49-70
The reaction of [Os3(CO)12] with tetramethylthiourea in the presence of a methanolic solution of Me3NO·2H2O at 60° yields the compounds [Os3(CO)11{η 1-SC(NMe2)2}] (1) in 56% yield and [Os3(CO)9(μ-OH)(μ-MeOCO){η 1-SC(NMe2)2}] (2) in 10% yield in which the tetramethylthiourea ligand is coordinatedvia the sulfur atom at an equatorial position. Compound2 is a 50 e? cluster with two metal-metal bonds and the hydroxy and methoxycarbonyl ligands bridging the open metal-metal edge. In contrast, the analogous reaction of [Os3(CO)12] with thiourea gives the compounts [(μ-H)Os3(CO)10{μ-NHC(S)NH2}] (3) in 8% yield and [(μ-H)Os3(CO)9{3-NHC(S)NH2}] (4) in 30% yield. In3, the thioureato ligand bridges two osmium atomsvia the sulfur atom, whereas in4 in addition to the sulfur bridge, one of the nitrogen atoms of thioureato moiety bonds to the remaining osmium atom. The decacarbonyl compounds 3 can also be obtained in 50% yield from the reaction of [Os3(CO)10(MeCN)2] with thiourea at ambient temperature. Compound3 converts to4 (65%) photochemically. Compound1 reacts with PPh3 and acetonitrile at ambient temperature to give the simple substitution products [Os3(CO)11(PPh3)] and [Os3(CO)11(MeCN)], respectively, while with pyridine, the oxidative addition product [(μ-H)Os3(CO)10(μ-NC5H4] is formed at 80°C. All the new compounds are characterized by IR,1-H-NMR and elemental analysis together with the X-ray crystal structures of1,2 and4. Compound1 crystallizes in the triclinic space group P $P\bar 1$ with unit cell parametersa = 8.626(3) Å,b = 11.639(3) Å,c = 12.568(3_ Å,α = 84.67(2)°,β = 75.36(2)°,γ = 79.49(3)°,V = 1199(1) Å3, andZ = 2. Least-squares refinement of 4585 reflections gave a final agreement factor ofR = 0.0766 (R w = 0.0823). Compound2 crystallizes in the monoclinic space group P21/n with unit cell parametersa = 9.149(5) Å,b = 17.483(5) Å,c = 15.094(4) Å,β = 91.75(2)°,V = 2413(2) Å3, andZ = 4. Least-squares refinement of 3632 reflections gave a final agreement factor ofR = 0.0603 (R w = 0.0802). Compound4 crystallizes in the monoclinic space group C2/c with unit cell parametersa = 13.915(7) Å,b = 14.718(6) Å,c = 17.109(6) Å,β = 100.44(3)°,V = 3446(5) Å3, andZ = 8. Least-squares refinement of 2910 reflections gave a final agreement factor ofR = 0.0763 (R w = 0.0863). 相似文献
53.
Mohammad M. Fares Adeeb S. El-Faqeeh 《Journal of Thermal Analysis and Calorimetry》2005,82(1):161-166
Summary Thermal degradation under N2atmosphere and thermoxidative degradation under air atmosphere of increasingly grafting efficiency values (i.e. GE%=0.0 to 35.5) for starch and starch grafted with N-tert-butylacrylamide thermosensitive copolymers (starch-g-BAM) by Ozawa and Kissinger methods using thermogravimetric analysis
(TG) and differential scanning calorimetry techniques (DSC) at 10, 30 and 50% mass losses respectively have been studied.
Influence of physical inter and intra molecular interactions on grafting and consequently on activation energy of degradation
(Ea,d) was investigated using Ozawa's method, whereas linear dependence of Ea,don GE% by scaling relations using Kissinger's method was determined. Furthermore, the thermoxidative degradation induces the possibility
of molecular rearrangement, cyclization and partial crosslinking that is deduced from the activation energy of degradation
(Ea,d) and residual mass of TG profile. Thermal stability of starch does not alter as a result of different grafting efficiency
percentages. 相似文献
54.
Theoretical determination of chromophores in the chromogenic effects of aromatic neurotoxicants 总被引:3,自引:0,他引:3
Zhan CG Dixon DA Sabri MI Kim MS Spencer PS 《Journal of the American Chemical Society》2002,124(11):2744-2752
We report the first computational study of the chromophores responsible for the chromogenic effects of aromatic neurotoxicants containing a 1,2-diacetyl moiety in their oxidation metabolites. A series of ab initio electronic structure calculations was performed on two representative aromatic compounds, 1,2-diacetylbenzene (1,2-DAB) and 1,2-diacetyl tetramethyl tetralin (1,2-DATT), the putative active metabolites of the neurotoxic aromatic hydrocarbon compounds 1,2-diethylbenzene (1,2-DEB) and acetyl ethyl tetramethyl tetralin (AETT), and on the products of their possible reactions with proteins that result in chromogenic effects. The electronic excitation energies determined by three different computational approaches were found to be consistent with each other. The calculated results are consistent with the conclusion/prediction that the chromogenic effects of 1,2-DAB (or 1,2-DEB) and 1,2-DATT (or AETT) could result from ninhydrin-like reactions, rather than the formation of pyrrole-like compounds. Our pK(a) calculations further indicate that the chromophore, i.e., the product of the ninhydrin-like reaction showing the blue color, is deprotonated in neutral aqueous solution. The corresponding protonated structure has a different color as it absorbs in the blue region of the visible spectrum, and its chromogenic contribution would be significant in solution at low pH. 相似文献
55.
New mixed-ligand copper(I) complexes, [Cu(Phca2en)(PPh3)X], [Phca2en = N,N′-bis(β-phenylci-nnamaldehyde)-1,2-diiminoethane and X=Cl (1), Br (2), I (3), NCS (4), N3 (5)] have been synthesized and characterized by various techniques. 1H and 13C-NMR and IR spectral data of these copper(I) complexes are compared with the free ligand to elucidate some structural features. The structures of [Cu(Phca2en)(PPh3)Br] (2) and [Cu(Phca2en)(PPh3)I] (3) have been determined from single-crystal data showing that the coordination geometry around copper atom is a distorted tetrahedron. Furthermore, these Cu(I) complexes exhibit supramolecular motifs of the type multiple phenyl embraces resulting from attractive interactions between phenyl rings of PPh3 moieties. The presence of the C–H…Cu weak intramolecular hydrogen bonds, due to the trapping of C–H bonds in the vicinity of the metal atoms, is also reported. 相似文献
56.
Aliphatic and aromatic 1,3‐dithiane are oxidized to the corresponding carbonyl compounds in good yields under mild conditions by N,N′‐diiodo‐N,N′‐1,2‐ethanediyl‐bis(p‐toluenesulphonamide) [NIBTS] and silver nitrate. 相似文献
57.
M. Mohammad A. Y. Khan M. S. Subhani N. Bibi Safeer Ahmad Saba Saleemi 《Research on Chemical Intermediates》2001,27(3):259-267
Rate constants for the reaction of superoxide O-
2 with various substrates were obtained through stationary electrode polarography theory and technique. In solvent acetonitrile, the substrate and the rate constants of the reaction O-
2 + AH-
k2Product, are, AH = isopropanol (k2 < 0.01 M-1 s-1); ethanol (k2 = 1.42 × 102 M-1 s-1); methanol (k2 = 1.1 × 107 M-1 s-1), H2O (k2 = 1.0 × 105 M-1 s-1). In MeCN, O-2 was found to be rather unreactive towards glucose and acetone but it reacts with fructose and sucrose catalytically. However, in DMF2, O-
2reacts with glucose and fructose with k2 order of 105 M-1 s-1. The mechanism of the reaction of O-
2 with the substrates (AH) is proposed as O-
3 + AH k2O, AHk2
k-1 k [O2H + AH]-, k-2O2H + A- with k1 = 109 M-1 s-1 and k-1 = 108 -109 s-1. With these values of k-1 and k1, k k2(obs). The reversible E1/2 for O2 + e O-
2 in various solvents: MeCN, acetone, isopropanol, methanol, H2O were obtained either directly from the reversible voltammogram or from experimental voltammograms and the rate constants obtained (as above) using stationary electrode polargraphy theory; E1/2 being -0.82 (MeCN),-0.85 (acetone),-0.72 (isopropanol);-0.66 (MeOH),-0.56 (H2O) vs SCE. 相似文献
58.
Talebi M Ghassempour A Talebpour Z Rassouli A Dolatyari L 《Journal of separation science》2004,27(13):1130-1136
A simple and rapid microwave-assisted extraction (MAE) procedure was developed and optimized for the extraction of paclitaxel (Taxol) from the needles of yew trees Taxus baccata L. grown in Iranian habitats. The samples, immersed in a methanol-water mixture, were irradiated with microwaves in a closed-vessel system. The method was evaluated using a factorial design approach based on parameters such as extraction time, temperature, methanol concentration in water (v/v), and the ratio of grams of sample to 10 mL of solvent. Statistical treatment of the results revealed that the selected parameters were all significant except the extraction time. Optimum conditions would be 1.5 g samples in 10 mL solvent (90% methanol), an extraction temperature of 95 degrees C, and an extraction time of 7 min. The extracts has been analyzed by reverse-phase high-performance liquid chromatography with UV detection (LC/UV) at 227 nm for quantification. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for confirmation. The main advantage of the proposed MAE method versus conventional solvent extraction (CSE) are the considerable reductions in time (7 min versus 16 h) and in solvent consumption (20 mL versus 150 mL). The MAE procedure yielded extracts that could be analyzed directly without any preliminary clean-up or solvent exchange steps. Both extraction methods show RSDs lower than 10% and lead to comparable recoveries of paclitaxel (87-92%). 相似文献
59.
Ahmad?ShaabaniEmail author Mohammad Bagher?Teimouri Hamid Reza?Bijanzadeh 《Monatshefte für Chemie / Chemical Monthly》2004,135(5):589-593
Summary. The environment-friendly one-pot three-component condensation reactions of 4-hydroxycoumarin or 4-hydroxy-6-methylpyrone, p-substituted benzaldehyde, and alkyl or aryl isocyanides to afford furocoumarines or furopyranones in water in good yields after about one hour at 75°C are reported. 相似文献
60.
In this paper we, present some MATLAB and GAP programs and use them to find the automorphism group of the Euclidean graph
of the C80 fullerence with connectivity and geometry of I
h
symmetry point group. It is proved that this group has order 120 and is isomorphic to I
h
≊Z2×A5, where Z2 is, a cyclic group of order 2 and A5 is the alternating group on five symbols. 相似文献