全文获取类型
收费全文 | 3120篇 |
免费 | 44篇 |
国内免费 | 33篇 |
专业分类
化学 | 1801篇 |
晶体学 | 61篇 |
力学 | 67篇 |
数学 | 668篇 |
物理学 | 600篇 |
出版年
2022年 | 53篇 |
2021年 | 66篇 |
2020年 | 30篇 |
2019年 | 35篇 |
2018年 | 39篇 |
2017年 | 56篇 |
2016年 | 81篇 |
2015年 | 79篇 |
2014年 | 86篇 |
2013年 | 212篇 |
2012年 | 140篇 |
2011年 | 181篇 |
2010年 | 117篇 |
2009年 | 127篇 |
2008年 | 175篇 |
2007年 | 163篇 |
2006年 | 151篇 |
2005年 | 127篇 |
2004年 | 147篇 |
2003年 | 99篇 |
2002年 | 105篇 |
2001年 | 51篇 |
2000年 | 44篇 |
1999年 | 42篇 |
1998年 | 41篇 |
1997年 | 53篇 |
1996年 | 56篇 |
1995年 | 32篇 |
1994年 | 34篇 |
1993年 | 43篇 |
1992年 | 27篇 |
1991年 | 30篇 |
1990年 | 33篇 |
1989年 | 31篇 |
1988年 | 20篇 |
1987年 | 26篇 |
1986年 | 18篇 |
1985年 | 30篇 |
1984年 | 41篇 |
1983年 | 24篇 |
1982年 | 24篇 |
1981年 | 31篇 |
1980年 | 23篇 |
1979年 | 23篇 |
1978年 | 20篇 |
1977年 | 30篇 |
1976年 | 14篇 |
1975年 | 13篇 |
1974年 | 10篇 |
1972年 | 11篇 |
排序方式: 共有3197条查询结果,搜索用时 0 毫秒
131.
Renate Borowski Dieter Rehder Klaus von Deuten 《Journal of organometallic chemistry》1981,220(1):45-54
Photo-reaction between the ligands Ph2ECH2EPh2 (E = P: dppm, E = As: dpam, E = Sb: dpsm), L, and the vanadium complexes η5-C5H5V(CO)4 and [Et4N][V(CO)6] yields monosubstituted mononuclear (dpsm) and dinuclear, ligand-bridged complexes (dpam, dpsm). With dppm, the final products are disubstituted chelate complexes, but monosubstituted mono- and dinuclear species are formed as intermediates.The shielding of the 51V nucleus decreases in the series dpsm > dppm > dpam and {M(CO)n} > {M(CO)n?1} L > {M(CO)n?1}2μ-L > {M(CO)n?2}dppm ({M(CO)n}[V(CO)6]?, η5-C5H5V(CO)4). The half-widths of the NMR signals are greater for dinuclear than for mononuclear complexes.The crystal and molecular structures of η5-C5H5V(CO)3As2Ph4 have been determined. The compound crystallizes in the space group P21/c with a = 1347.8, b = 1020.0, c = 2085.2 pm and β = 82.3°. Due to steric crowding, the 51V shielding is low composed to that of {η5-C5H5V(CO)3}2μ-dpam. 相似文献
132.
Chmielewski MK Marchán V Cieślak J Grajkowski A Livengood V Münch U Wilk A Beaucage SL 《The Journal of organic chemistry》2003,68(26):10003-10012
Thermolytic groups structurally related to well-studied heat-sensitive phosphate/thiophosphate protecting groups have been evaluated for 5'-hydroxyl protection of deoxyribonucleosides as carbonates and for potential use in solid-phase oligonucleotide synthesis. The spatial arrangement of selected functional groups forming an asymmetric nucleosidic 5'-O-carbonic acid ester has been designed to enable heat-induced cyclodecarbonation reactions, which would result in the release of carbon dioxide and the generation of a nucleosidic 5'-hydroxyl group. The nucleosidic 5'-O-carbonates 3-8, 10-15, and 19-21 were prepared and were isolated in yields ranging from 45 to 83%. Thermolytic deprotection of these carbonates is preferably performed in aqueous organic solvent at 90 degrees C under near neutral conditions. The rates of carbonate deprotection are dependent on the nucleophilicity of the functional group involved in the postulated cyclodecarbonation reaction and on solvent polarity. Deprotection kinetics increase according to the following order: 4 < 5 < 10 < 6 < 12 < 7 < 13 < 8 < 14 congruent with 19-21 and CCl4 < dioxane < MeCN < t-BuOH < MeCN:phosphate buffer (3:1 v/v, pH 7.0) < EtOH:phosphate buffer (1:1 v/v, pH 7.0). Complete thermolytic deprotection of carbonates 7, 8, 13, and 14 is achieved within 20 min to 2 h under optimal conditions in phosphate buffer-MeCN. The 2-(2-pyridyl)amino-1-phenylethyl and 2-[N-methyl-N-(2-pyridyl)]aminoethyl groups are particularly promising for 5'-hydroxyl protection of deoxyribonucleosides as thermolytic carbonates. 相似文献
133.
A method has been developed for species-selective analysis of organotin compounds in solid, biological samples. The procedure is based on accelerated solvent extraction (ASE) of analytes and includes extraction of the tin species with a methanol–water (90% methanol) solution of acetic acid/sodium acetate containing tropolone (0.03% w/v), their ethylation with NaBEt4, and separation and detection by GC–FPD. The analytical procedure was optimized with an unspiked sample of harbor porpoise (Phocoena phocoena) liver. Effects of ASE operational variables (extraction temperature and pressure, solvent composition, number of static extraction steps) are discussed. Method detection limits (MDL) were in the range 6–10 ng(Sn) g–1 dry weight and 7–17 ng(Sn) g–1 dry weight for butyl- and phenyltin compounds, respectively. Recoveries were comparable with or better than those obtained by use of other procedures reported in the literature. The analytical procedure was validated by analysis of NIES No. 11 (fish tissue) certified reference material. 相似文献
134.
The objective of this paper is to provide information about application of solid-phase extraction (SPE) for isolation of nine high-intensity sweeteners (acesulfame-K, alitame, aspartame, cyclamate, dulcin, neotame, saccharin, sucralose and neohesperidin dihydrochalcone) from aqueous solutions. The influence of several types of LC-MS compatible buffers (different pH values and compositions) on their recovery has been studied and discussed. A number of commercially available SPE cartridges, such as Chromabond C18ec, Strata-X RP, Bakerbond Octadecyl, Bakerbond SDB-1, Bakerbond SPE Phenyl, Oasis HLB, LiChrolut RP-18, Supelclean LC-18, Discovery DSC-18 and Zorbax C18 were tested in order to evaluate their applicability for the isolation of analytes. Very high recoveries (better than 92%) of all studied compounds were obtained using formic acid-N,N-diisopropylethylamine buffer adjusted to pH 4.5 and C18-bonded silica sorbents. Behaviour of polymeric sorbents strongly depends on their structure. Strata-X RP behaves much like a C18-bonded silica sorbent. Recoveries obtained using Oasis HLB were comparable with those observed for silica-based sorbents. The only compound less efficiently (83%) retained by this sorbent was cyclamate. Bakerbond SDB-1 shows unusual selectivity towards aspartame and alitame. Recoveries of these two sweeteners were very low (26 and 42%, respectively). It was also found that aspartame and alitame can be selectively separated from the mixture of sweeteners using formic acid-triethylamine buffer at pH 3.5. 相似文献
135.
Andrzej Rajca Prof. Velavan Kathirvelu Dr. Sandip K. Roy Dr. Maren Pink Dr. Suchada Rajca Dr. Santanu Sarkar Sandra S. Eaton Prof. Gareth R. Eaton Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5778-5782
Site‐directed spin labeling and EPR spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α‐amino acid and its N‐(9‐fluorenylmethoxycarbonyl) derivative, have been synthesized, which exhibit slow enough spin‐echo dephasing to permit accurate distance measurements by pulsed EPR spectroscopy at temperatures up to 125 K in 1:1 water/glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR spectroscopy to the study of structure and conformation of peptides and proteins. 相似文献
136.
Katarzyna Gajda Bartosz Zarychta Zdzisaw Daszkiewicz Andrzej A. Domaski Krzysztof Ejsmont 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(6):575-579
The crystal and molecular structures of two para‐substituted azobenzenes with π‐electron‐donating –NEt2 and π‐electron‐withdrawing –COOEt groups are reported, along with the effects of the substituents on the aromaticity of the benzene ring. The deformation of the aromatic ring around the –NEt2 group in N,N,N′,N′‐tetraethyl‐4,4′‐(diazenediyl)dianiline, C20H28N4, (I), may be caused by steric hindrance and the π‐electron‐donating effects of the amine group. In this structure, one of the amine N atoms demonstrates clear sp2‐hybridization and the other is slightly shifted from the plane of the surrounding atoms. The molecule of the second azobenzene, diethyl 4,4′‐(diazenediyl)dibenzoate, C18H18N2O4, (II), lies on a crystallographic inversion centre. Its geometry is normal and comparable with homologous compounds. Density functional theory (DFT) calculations were performed to analyse the changes in the geometry of the studied compounds in the crystalline state and for the isolated molecules. The most significant changes are observed in the values of the N=N—C—C torsion angles, which for the isolated molecules are close to 0.0°. The HOMA (harmonic oscillator model of aromaticity) index, calculated for the benzene ring, demonstrates a slight decrease of the aromaticity in (I) and no substantial changes in (II). 相似文献
137.
Krystyna Kurdziel Andrzej Okruszek Tadeusz G?owiak Stefano Materazzi 《Journal of organometallic chemistry》2006,691(5):869-878
Two coordination compounds of palladium(II) with N-allylimidazole (l) of the general formula [PdL4]Cl2 · 3H2O (1) and trans-[PdL2Cl2] (2) have been synthesized. The crystal and molecular structure of complexes 1 and 2 was established by single-crystal X-ray diffraction analysis. The X-ray structural data were supplemented by solid-state 13C NMR measurements (CP MAS and PASS 2D). The 1D and 2D NMR studies in solution reveal that complex 1 is unstable at room temperature and undergoes reversible decomposition to 2. The method for how to preserve a complex with four allyl-imidazole ligands in solution is shown. 相似文献
138.
Milczarczyk-Piwowarczyk P Zywociński A Noworyta K Hołyst R 《Langmuir : the ACS journal of surfaces and colloids》2008,24(21):12354-12363
We study the Langmuir monolayers of four different ferroelectric liquid crystals on water surface. Two of them are attached to water surface by their polar groups, and the chiral groups, at the opposite ends of the elongated molecules, remain well above the interface. The other two ferroelectrics have both groups (polar and chiral) at close proximity, and therefore the chiral group is also attached to the surface or even submerged in water. We demonstrate that only when the chiral group of the ferroelectric liquid crystal in Langmuir monolayer is not attached to the interface and stays in the air does the system exhibit the collective rotations induced by evaporation of water (described for the first time by: Tabe, Y.; Yokoyama, H. Nat. Mater. 2003, 2, 806). The isotherms of surface pressure and surface potential versus molecular area of four compounds were measured with simultaneous observations using Brewster angle microscopy. Experimental data of the compression isotherms are described with a van der Waals model with very good accuracy, and the fitted parameters were used for calculations of compressibility coefficients for different phases found in the compounds under investigations. The ability of the two compounds for rotation and the disability of the two others is discussed in a context of thermodynamic properties of the monolayers. 相似文献
139.
Andrzej Mianowski Izabela Baraniec-Mazurek Rafał Bigda 《Journal of Thermal Analysis and Calorimetry》2012,107(3):1155-1165
For dehydration of CaC2O4·H2O and thermal dissociation of CaCO3 carried out in Mettler Toledo TGA/SDTA-851e/STARe thermobalance similar experimental conditions was applied: 9–10 heating rates, q = 0.2, 0.5, 1, 2, 3, 6, 12, 24, 30, and 36 K min−1, for sample mass 10 mg, in nitrogen atmosphere (100 ml min−1) and in Al2O3 crucibles (70 μl). There were analyzed changes of typical TGA quantities, i.e., T, TG and DTG in the form of the relative
rate of reaction/process intended to be analyzed on-line by formula (10). For comparative purposes, the relationship between experimental and equilibrium conversion degrees was used (for
P = P\ominus P = P^{{\ominus}} ). It was found that the solid phase decomposition proceeds in quasi-equilibrium state and enthalpy of reaction is easily
“obscured” by activation energy. For small stoichiometric coefficients on gas phase side (here: ν = 1) discussed decomposition
processes have typical features of phenomena analyzable by known thermokinetic methods. 相似文献
140.
Andrzej Chmura Sven Rustler Monica Paravidino Fred van Rantwijk Andreas Stolz Roger A. Sheldon 《Tetrahedron: Asymmetry》2013,24(19):1225-1232
Enantiomerically pure (S)-mandelic acid was synthesised from benzaldehyde by sequential hydrocyanation and hydrolysis in a bienzymatic cascade at starting concentrations up to 0.25 M. A cross-linked enzyme aggregate (CLEA) composed of the (S)-selective oxynitrilase from Manihot esculenta and the non-selective nitrilase from Pseudomonas fluorescens EBC 191 was employed as the biocatalyst. The nitrilase produces approx. equal amounts of (S)-mandelic acid and (S)-mandelic amide from (S)-mandelonitrile under standard conditions, but we surprisingly found that high (up to 0.5 M) concentrations of HCN induced a marked drift towards amide production. By including the amidase from Rhodococcus erythopolis in the CLEA we obtained (S)-mandelic acid as the sole product in 90% yield and >99% enantiomeric purity. 相似文献