全文获取类型
收费全文 | 28858篇 |
免费 | 87篇 |
国内免费 | 271篇 |
专业分类
化学 | 10547篇 |
晶体学 | 264篇 |
力学 | 1375篇 |
综合类 | 12篇 |
数学 | 8959篇 |
物理学 | 8059篇 |
出版年
2021年 | 44篇 |
2020年 | 35篇 |
2019年 | 28篇 |
2018年 | 1189篇 |
2017年 | 1446篇 |
2016年 | 709篇 |
2015年 | 552篇 |
2014年 | 470篇 |
2013年 | 655篇 |
2012年 | 3118篇 |
2011年 | 2306篇 |
2010年 | 1794篇 |
2009年 | 1533篇 |
2008年 | 549篇 |
2007年 | 602篇 |
2006年 | 595篇 |
2005年 | 4440篇 |
2004年 | 3914篇 |
2003年 | 2299篇 |
2002年 | 483篇 |
2001年 | 281篇 |
2000年 | 87篇 |
1999年 | 171篇 |
1998年 | 108篇 |
1997年 | 68篇 |
1996年 | 43篇 |
1995年 | 39篇 |
1994年 | 42篇 |
1992年 | 169篇 |
1991年 | 154篇 |
1990年 | 134篇 |
1989年 | 106篇 |
1988年 | 99篇 |
1987年 | 57篇 |
1986年 | 42篇 |
1985年 | 40篇 |
1984年 | 32篇 |
1983年 | 29篇 |
1979年 | 30篇 |
1976年 | 79篇 |
1975年 | 38篇 |
1974年 | 40篇 |
1973年 | 49篇 |
1972年 | 39篇 |
1971年 | 25篇 |
1970年 | 34篇 |
1969年 | 37篇 |
1968年 | 35篇 |
1967年 | 30篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Yellow-orange single crystals of CuSbF6, were prepared by reacting Cu wire (∼10 mmol) with SbF5 (∼3 mmol) in liquid anhydrous hydrogen fluoride (aHF) and by reduction of Cu(SbF6)2 with Cu metal in aHF. CuSbF6 crystallizes rhombohedral at 296 K with the LiSbF6 structure type, with a = 530.4(4) pm, c = 1453(1) pm and Z = 3, space group R (no. 148). The structure is dominated by isolated layers of regular [SbF6]− octahedra and Cu+ cations.An attempt to prepare CuF by reaction between CuSbF6 and CsF in aHF at ∼190 K failed. Instead of CuF, a mixture of Cu and CuF2 was obtained. 相似文献
992.
Tushar S. Basu Baul Keisham Surjit Singh Michal Hol?apek 《Journal of organometallic chemistry》2005,690(6):1581-1587
The complex, [(PhCH2)2{O2CC6H4{N(H)N(C6H3-4(O)-5-O)}-o}Sn]2 (1), is obtained as the exclusive reaction product from the reaction of sodium 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyl]benzoate and (PhCH2)3SnCl. The reaction possibly proceeds via Dakin type rearrangements where arylazosalicylaldehyde is oxidized to arylazocatechol, followed by facile Sn-C bond cleavage. Complete assignments were achieved by 1H, 13C, 2D 1H-119Sn HMQC (119Sn chemical shift), 1D gs 1H-15N HMQC (1J(15N, 1H) coupling constant) NMR and ESI-MS. The crystal structure of compound 1 as determined by X-ray diffraction analyses shows a cyclic centrosymmetric dinuclear moiety linked into extended chains by pairs of long Sn?O contacts of approximately 3.2 Å. Two polymorphs were identified and their structures differ primarily in the packing arrangement afforded by the benzyl groups. In one polymorph, when viewed along the Sn?Sn vector, the benzyl groups at each Sn-atom are oriented to form an S-shape, while they form a U-shape in the second polymorph. 相似文献
993.
M.?Prasad S.?P.?MoulikEmail author A. Al.?Wardian S.?Moore A.?van?Bommel R.?PalepuEmail author 《Colloid and polymer science》2005,283(8):887-897
The clouding points (CP) of the nonionic surfactants p-tert-octyl phenyl polyoxyethylene ether (Triton X 100), Brij-56 and Brij-97, and the water soluble polymer polyvinylmethylether (PVME) have been measured in the presence of the ionic surfactants alkyl (C10, C12, C14 and C16) triphenyl phosphonium bromides (ATPBs). The threshold additive concentrations required for efficient CP enhancement of the systems that were studied have been determined. Considering CP as the threshold state of phase separation, the energetics of the process at different additive concentrations has been evaluated. The spontaneity of free energy of the clouding process (G
c
0
) at the transition concentrations followed the order PVME > TX 100 Bj 56 > Bj 97. The clouding process has been found to be energetically endothermic with fairly large enthalpy and entropy changes that nicely compensate each other. The compensation temperature has been evaluated and compared with different types of the clouding agents.This revised version was published online in January 2005 with corrections to the names of the authors. 相似文献
994.
Light-stable micelles with azo dyes were prepared by micelle formation of a nonamphiphilic diblock copolymer containing azobenzene and UV absorbent at ca. 1 mol% as the unit ratios. The nonamphiphilic block copolymer consists of two different kinds of random copolymer blocks: poly[4-(phenylazophenoxymethyl)styrene-co-vinylphenol] (P(AS-co-VPh)) and poly[4-(2-hydroxybenzophenoxymethyl)styrene-co-styrene] (P(HBS-co-St)). This random block copolymer, P(AS-co-VPh)-b-P(HBS-co-St) formed the micelles in the presence of 1,4-butanediamine (BDA) through hydrogen bond cross-linking between the VPh units via BDA. The micelles had the azobenzene moieties at the cores and the UV absorbents at the coronas. The micelles showed a small color difference in color fading experiments, in comparison with the unimers and with micelles having no UV absorbent at the coronas. It is significant that the diblock copolymer forms the micelles and has the UV absorbents at the coronas to suppress the color fading. Furthermore, the chain length of ,-diamines had no effect on the hydrodynamic radius of the micelles, but affected the aggregation number and the cmc. 相似文献
995.
The magneto-structural correlation between a Mn(ll) ion, coordinated in an octahedral environment, and two nitronyl nitroxide
radical ligands in trans- and cis-metal-radical complexes is investigated by the broken symmetry (BS) approach within density functional theory (DFT).
The dependences of coupling constants J on three structural parameters: (i) bond angle θ (Mn-O-N (nitroxide)); (ii) rotating angle ψ, defined by the nitronyl nitroxide radical plane rotating around the axial Mn-O (nitroxide); (iii) bond distance R (Mn-O (nitroxide)) are directly calculated. Our calculations showed that both trans- and cis-Mn(ll)-radical complexes behave a stronger antiferromagnetic interaction, consistent with experiments. In view of
molecular orbital theory, the direct exchanges, including σ-type and π-type exchanges, are responsible for the magnetic exchange
pathways. There is a preferable linear correlation between the calculated coupling constants J and the overlap integral squares S b between the local magnetic orbitals at the various rotating angle ψ at the fixed bond angle θ and bond distance R, in both trans- and cis-Mn(ll)-radical complexes. 相似文献
996.
Courtney?L.?Sherman Jennifer?S.?BrodbeltEmail author Alan?P.?Marchand Bhaskar?Poola 《Journal of the American Society for Mass Spectrometry》2005,16(7):1162-1171
The self-assembly of ligand-metal-ligand sandwich complexes involving a novel quinoxaline-containing crown ether, 1, was studied by electrospray ionization mass spectrometry (ESI-MS). Donor-acceptor π-stacking interactions between the electron-poor
quinoxaline group of 1 and electron-rich benzene groups from benzo- or dibenzo-18-crown-6 were found to significantly enhance the formation of mixed-ligand
sandwich complexes with a free energy gain of up to 17 kJ/mol relative to sandwich formation involving macrocycles without
such aromatic functionalities. The relative intensities of the sandwich complexes were greatest with the alkali metals Na+, K+, and Rb+ as well as with the ammonium ion in equimolar concentrations with the macrocycles. The preferential formation of the mixed-ligand
sandwich complexes demonstrated that donor-acceptor π-stacking interactions contribute to the assembly of molecular structures
and can be monitored by ESI-MS. 相似文献
997.
Low-energy CAD product-ion spectra of various molecular species of phosphatidylserine (PS) in the forms of [M−H]− and [M−2H+Alk]− in the negative-ion mode, as well as in the forms of [M+H]+, [M+Alk]+, [M−H+2Alk]+, and [M−2H+3Alk]+ (where Alk=Li, Na) in the positive-ion mode contain rich fragment ions that are applicable for structural determination.
Following CAD, the [M−H]− ion of PS undergoes dissociation to eliminate the serine moiety (loss of C3H5NO2) to give a [M−H−87]− ion, which equals to the [M−H]− ion of a phoshatidic acid (PA) and give rise to a MS3-spectrum that is identical to the MS2-spectrum of PA. The major fragmentation process for the [M−2H+Alk]− ion of PS arises from primary loss of 87 to give rise to a [M−2H+Alk−87]− ion, followed by loss of fatty acid substituents as acids (RxCO2H, x=1,2) or as alkali salts (e. g., RxCO2Li, x=1,2). These fragmentations result in a greater abundance of [M−2H+Alk−87−R2CO2H]− than [M−2H+Alk−87−R1CO2H]− and a greater abundance of [M−2H+Alk−87−R2CO2Li]− than [M−2H+Alk−87−R1CO2Li]−; while further dissociation of the [M−2H+Alk−87−R2(or 1)CO2Li]− ions gives a preferential formation of the carboxylate anion at sn-1 (R1CO2−) over that at sn-2 (R2CO2−). Other major fragmentation process arises from differential loss of the fatty acid substituents as ketenes (loss of Rx′CH=CO, x=1,2). This results in a more prominent [M−2H+Alk−R2′CH=CO]− ion than [M−2H+Alk−R1′CH=CO]− ion. Ions informative for structural characterization of PS are of low abundance in the MS2-spectra of both the [M+H]+ and the [M+Alk]+ ions, but are abundant in the MS3-spectra. The MS2-spectrum of the [M+Alk]+ ion contains a unique ion corresponding to internal loss of a phosphate group probably via the fragmentation processes involving
rearrangement steps. The [M−H+2Alk]+ ion of PS yields a major [M−H+2Alk−87]+ ion, which is equivalent to an alkali adduct ion of a monoalkali salt of PA and gives rise to a greater abundance of [M−H+2Alk−87−R1CO2H]+ than [M−H+2Alk−87−R2CO2H]+. Similarly, the [M−2H+3Alk]+ ion of PS also yields a prominent [M−2H+3Alk−87]+ ion, which undergoes consecutive dissociation processes that involve differential losses of the two fatty acyl substituents.
Because all of the above tandem mass spectra contain several sets of ion pairs involving differential losses of the fatty
acid substituents as ketenes or as free fatty acids, the identities of the fatty acyl substituents and their positions on
the glycerol backbone can be easily assigned by the drastic differences in the abundances of the ions in each pair. 相似文献
998.
Klaus Burger Gabor Radics Lothar Hennig Christoph B?ttcher Jan Spengler Fernando Albericio 《Monatshefte für Chemie / Chemical Monthly》2005,5(3):763-776
Starting from L-malic, L-citramalic, and rac. thiomalic acids routes to L-homoisoserine, 2-methyl-L-homoisoserine and rac. homoisocysteine have been developed. The new orthogonally protected and carboxy-activated building blocks are GABA as well as -hydroxy and -mercapto acid derivatives, suitable for the construction of peptide and depsipeptide surrogates. 相似文献
999.
1000.
Renata Toczy?owska 《Analytica chimica acta》2005,540(1):167-172
Back-side contact Au and Ag microelectrodes were used as transducers to construct planar all-solid-state electrodes suitable for flow-through analysis. The microsensors were based on plasticized PVC potassium-selective membranes containing ion-electron conducting polymer—polypyrrole doped with di(2-ethylhexyl) sulfosuccinate. The proposed technique allowed simple construction of microsensors in one step, by membrane solution casting directly on the surface of the planar metallic transducers. The performance of the microsensors based on Au and Ag transducers were determined and compared with planar sensors based on internal electrolyte immobilized in polyHEMA. The addition of the polypyrrole to the membrane composition did not influence on the selectivity, reproducibility and long-term stability of the microsensors but improved their standard potential stability in time in comparison with coated-wire type sensors. Moreover, all-solid-state microsensors based on Au transducers exhibited better signal stability than Ag based sensors. 相似文献