全文获取类型
收费全文 | 4734篇 |
免费 | 77篇 |
国内免费 | 220篇 |
专业分类
化学 | 1892篇 |
晶体学 | 39篇 |
力学 | 35篇 |
综合类 | 3篇 |
数学 | 9篇 |
物理学 | 3053篇 |
出版年
2024年 | 6篇 |
2023年 | 161篇 |
2022年 | 66篇 |
2021年 | 68篇 |
2020年 | 51篇 |
2019年 | 65篇 |
2018年 | 86篇 |
2017年 | 136篇 |
2016年 | 176篇 |
2015年 | 132篇 |
2014年 | 248篇 |
2013年 | 417篇 |
2012年 | 261篇 |
2011年 | 274篇 |
2010年 | 223篇 |
2009年 | 325篇 |
2008年 | 280篇 |
2007年 | 336篇 |
2006年 | 264篇 |
2005年 | 207篇 |
2004年 | 176篇 |
2003年 | 154篇 |
2002年 | 144篇 |
2001年 | 106篇 |
2000年 | 84篇 |
1999年 | 83篇 |
1998年 | 58篇 |
1997年 | 62篇 |
1996年 | 72篇 |
1995年 | 44篇 |
1994年 | 28篇 |
1993年 | 30篇 |
1992年 | 40篇 |
1991年 | 32篇 |
1990年 | 21篇 |
1989年 | 22篇 |
1988年 | 16篇 |
1987年 | 7篇 |
1986年 | 9篇 |
1985年 | 4篇 |
1984年 | 11篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 12篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1976年 | 5篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有5031条查询结果,搜索用时 0 毫秒
61.
Matrix isolation infrared studies of complexes formed between substituted phenols and trimethylamine
Infrared spectroscopy and matrix isolation technique have been used to study the 1 : 1 complexes formed between 2,4,5-trichlorophenol (TCP), pentachlorophenol (PCP) or 2-chloro-4,6-dinitrophenol (CNP) and trimethylamine (TMA) isolated in solid argon. The results were analyzed in relation to the type of complex formed. Depending on the proton-donor ability of the phenol three different types of hydrogen bonded complexes have been identified in argon matrices. The weakest phenol in the series, TCP (pKa = 6.72), forms a strong molecular hydrogen bonded complex with TMA as indicated by the broad ν(OHN) absorption with a maximum at 2490 cm−1 and a band at 811 cm−1 due to the νs(C3N) mode of the perturbed amine. The strongest phenol, CNP (pKa = 2.01), interacts with TMA in an argon matrix to form ionic complex with the proton transferred to the base molecule. This is evidenced by the presence of the ν(NH+---O−) absorption between 3000−1800 cm−1, by the νas(C3N+) and νs(C3N+) absorptions due to the protonated amine and by numerous product bands due to the relatively strongly perturbed modes of the phenol ring. The interaction between TMA and a phenol of intermediate strength, PCP (pKa = 4.74), in solid argon probably leads to the formation of two types of hydrogen bonded complexes: an ionic complex with the proton transferred to the amine molecule and a pseudosymmetric one with the proton more or less equally shared between the phenol and amine molecules. In this case the protonic absorption consists of two broad features situated in the 3000–1600 cm−1 and 950–400 cm−1 regions due to the ν(NH+O−) and ν(OHN) modes, respectively. 相似文献
62.
In completely stereospecific [4+2] cycloadditions, the perfluorinated selenocarbonyls 1 and 2 react both with trans‐trans‐2, 4‐hexadiene and cis‐trans‐2, 4‐hexadiene to yield 3, 6‐dihydro‐cis‐3, 6‐dimethyl‐2H‐selenapyrans 3 , 4a and 4b . The observed stereoselectivity leads to the conclusion, that the [4+2] cycloaddition of perfluorinated selenocarbonyls follows a concerted pathway. An identical mixture of isomers was isolated when using the precursor for 2 , trimethylstannyl (pentafluoroethyl)selane, which reacts with both 1, 3‐dienes over several weeks to form a mixture of syn‐2‐fluoro‐3, 6‐dihydro‐cis‐3, 6‐dimethyl‐2‐trifluoromethyl‐2H‐selenapyran ( 4a ) and anti‐2‐fluoro‐3, 6‐dihydro‐cis‐3, 6‐dimethyl‐2‐trifluoromethyl‐2H‐selenapyran ( 4b ) in the same ratio as found for 2 , thus proving the intermediate formation of Se=C(F)CF3 ( 2 ). Complex 2D NMR experiments were used to distinguish the isomers 4a and 4b and to assign the 1H, 13C and 19F NMR data of the selenaheterocycles. 相似文献
63.
Grigorii G. Sivets Elena N. Kalinichenko Igor A. Mikhailopulo 《Helvetica chimica acta》2007,90(9):1818-1836
Convergent syntheses of the 9‐(3‐X‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranosyl)adenines 5 (X=N3) and 7 (X=NH2), as well as of their respective α‐anomers 6 and 8 , are described, using methyl 2‐azido‐5‐O‐benzoyl‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranoside ( 4 ) as glycosylating agent. Methyl 5‐O‐benzoyl‐2,3‐dideoxy‐2,3‐difluoro‐β‐D ‐ribofuranoside ( 12 ) was prepared starting from two precursors, and coupled with silylated N6‐benzoyladenine to afford, after deprotection, 2′,3′‐dideoxy‐2′,3′‐difluoroadenosine ( 13 ). Condensation of 1‐O‐acetyl‐3,5‐di‐O‐benzoyl‐2‐deoxy‐2‐fluoro‐β‐D ‐ribofuranose ( 14 ) with silylated N2‐palmitoylguanine gave, after chromatographic separation and deacylation, the N7‐β‐anomer 17 as the main product, along with 2′‐deoxy‐2′‐fluoroguanosine ( 15 ) and its N9‐α‐anomer 16 in a ratio of ca. 42 : 24 : 10. An in‐depth conformational analysis of a number of 2,3‐dideoxy‐2‐fluoro‐3‐X‐D ‐ribofuranosides (X=F, N3, NH2, H) as well as of purine and pyrimidine 2‐deoxy‐2‐fluoro‐D ‐ribofuranosyl nucleosides was performed using the PSEUROT (version 6.3) software in combination with NMR studies. 相似文献
64.
Ihor R. Muts Falko M. Schappacher Vasyl’ I. Zaremba 《Journal of solid state chemistry》2007,180(8):2202-2208
New indides SrAu3In3 and EuAu3In3 were synthesized by induction melting of the elements in sealed tantalum tubes. Both indides were characterized by X-ray diffraction on powders and single crystals. They crystallize with a new orthorhombic structure type: Pmmn, Z=2, a=455.26(9), b=775.9(2), c=904.9(2) pm, wR2=0.0425, 485 F2 values for SrAu3In3 and a=454.2(2), b=768.1(6), c=907.3(6) pm, wR2=0.0495, 551 F2 values for EuAu3In3 with 26 variables for each refinement. The gold and indium atoms build up three-dimensional [Au3In3] polyanionic networks, which leave distorted hexagonal channels for the strontium and europium atoms. Within the networks one observes Au2 atoms without Au-Au contacts and gold zig-zag chains (279 pm Au1-Au1 in EuAu3In3). The Au-In and In-In distances in EuAu3In3 range from 270 to 290 and from 305 to 355 pm. The europium atoms within the distorted hexagonal channels have coordination number 14 (8 Au+6 In). EuAu3In3 shows Curie-Weiss behavior above 50 K with an experimental magnetic moment of 8.1(1) μB/Eu atom. 151Eu Mössbauer spectra show a single signal at δ=−11.31(1) mm/s, compatible with divalent europium. No magnetic ordering was detected down to 3 K. 相似文献
65.
Sambhu Bhadra 《European Polymer Journal》2007,43(10):4332-4343
In situ synthesis of polyaniline (PAni) coated pyrogenic or fumed silica (PCFS) and precipitated silica (PCPS) were carried out by the oxidative polymerization of aniline in presence of fumed silica (FS) and precipitated silica (PS). Both uncoated and PAni coated silica fillers were characterized through scanning electron microscope (SEM), infrared spectroscopy and thermo-gravimetric analysis (TGA) to evaluate particle morphology and physico-chemical character of coated and uncoated silica particles. Semi-conducting composites made from two different types of PAni coated silica fillers with NBR exhibit different trend in the variation of electrical properties under different temperature and pressure. These differences in electrical properties of two types of composites are mainly due to physico-chemical characteristics of filler particles as well as their distribution in the polymer matrix. This type of composites may be used as semi-conducting and ESD (electrostatic discharge) material. 相似文献
66.
Susan Robertson David Ellis Georgina M. Rosair Alan J. Welch 《Journal of organometallic chemistry》2003,680(1-2):286-293
The reaction of the labelled carborane ligand [3-Et-7,8-Ph2-7,8-nido-C2B9H8]2− with a source of {Pt(PMe2Ph)2}2+ affords non-isomerised 1,2-Ph2-3,3-(PMe2Ph)2-6-Et-3,1,2-closo-PtC2B9H8 (1). The analogous reaction between [3-F-7,8-Ph2-7,8-nido-C2B9H8]2− and {Pt(PMe2Ph)2}2+ yields 1,8-Ph2-2,2-(PMe2Ph)2-4-F-2,1,8-closo-PtC2B9H8 (3). Compound 1 has a heavily slipped structure (Δ 0.72 Å), which to some degree obviates the need for C atom isomerisation. However, that it is a kinetic product of the reaction is evident from the fact that it reverts to isomerised 1,8-Ph2-2,2-(PMe2Ph)2-4-Et-2,1,8-closo-PtC2B9H8 (2) slowly at room temperature but more rapidly with gentle warming. The heteroatom and labelled-B atom positions in the isomerised compounds 2 and 3 may be explained most simply by the rotation of a CB2 face of an intermediate based on the structure of 1. Compounds 1–3 were characterised by a combination of spectroscopic and crystallographic techniques. 相似文献
67.
68.
FlorianC. Stintzing Florian Kugler Reinhold Carle Jürgen Conrad 《Helvetica chimica acta》2006,89(5):1008-1016
Due to their inherent liability towards highly acidic conditions previously considered to be a prerequisite for data acquisition, betaxanthin structure dereplication by NMR spectroscopy has been scarcely reported and was, hitherto, exclusively based on 1H‐NMR data interpretation. Applying only slightly acidic conditions, we herein report the first 13C‐NMR data of two betaxanthins, i.e., indicaxanthin ( 1 ), isolated from yellow‐orange cactus pear fruits (Opuntia ficus‐indica [L.] Mill . cv. ‘Gialla’), and of miraxanthin V ( 2 ) from yellow Swiss chard petioles (Beta vulgaris L. ssp. cicla [L.] Alef . cv. ‘Bright Lights’), as derived by gHSQC‐ and gHMQC‐NMR experiments and inverse detection. 相似文献
69.
11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC6H4CH=NR oro-HOC10H6CH=NR (R=C2H5,n-C3H7,n-C4H9 or C6H5) and bibasic tridentateSchiff bases,o-HOC6H4CH=NR(OH) oro-HOC10H6CH=NR(OH) (R=–CH2CH(CH3)- or —CH2CH2CH2–) have been studied and derivates of the type UO2(OAc)2(SBH), UO2(OAc)2(SBH)2, UO2(OAc)2(SBH
2) and UO2(OAc)2(SBH
2)2 (whereSBH andSBH
2 represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.
UO2 2+-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen
Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO2(OAc)2·2H2O mitSchiff-Basen (L) Komplexe des Typs UO2(OAc)2 L bzw. UO2(OAc)2 L 2 isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.相似文献
70.
D. Mihrin Dr. P. W. Jakobsen A. Voute Dr. L. Manceron Prof. R. Wugt Larsen 《Chemphyschem》2019,20(23):3238-3244
The high-resolution infrared absorption spectrum of the donor bending fundamental band ν of the homodimer (HCN)2 has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν transition has the typical appearance of a perpendicular type band associated with a Σ–Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν0 of 779.05182(50) cm−1 together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm−1 relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol−1. The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19 , 3257–3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol−1 for the dissociation energy D0 of this prototypical homodimer. 相似文献