全文获取类型
收费全文 | 15386篇 |
免费 | 707篇 |
国内免费 | 145篇 |
专业分类
化学 | 10043篇 |
晶体学 | 50篇 |
力学 | 323篇 |
综合类 | 1篇 |
数学 | 2927篇 |
物理学 | 2894篇 |
出版年
2023年 | 141篇 |
2022年 | 290篇 |
2021年 | 347篇 |
2020年 | 419篇 |
2019年 | 495篇 |
2018年 | 379篇 |
2017年 | 291篇 |
2016年 | 597篇 |
2015年 | 564篇 |
2014年 | 548篇 |
2013年 | 913篇 |
2012年 | 1078篇 |
2011年 | 1276篇 |
2010年 | 677篇 |
2009年 | 563篇 |
2008年 | 908篇 |
2007年 | 830篇 |
2006年 | 838篇 |
2005年 | 772篇 |
2004年 | 605篇 |
2003年 | 470篇 |
2002年 | 436篇 |
2001年 | 239篇 |
2000年 | 171篇 |
1999年 | 182篇 |
1998年 | 155篇 |
1997年 | 164篇 |
1996年 | 167篇 |
1995年 | 144篇 |
1994年 | 113篇 |
1993年 | 101篇 |
1992年 | 85篇 |
1991年 | 76篇 |
1990年 | 64篇 |
1989年 | 40篇 |
1988年 | 44篇 |
1987年 | 47篇 |
1986年 | 45篇 |
1985年 | 69篇 |
1984年 | 57篇 |
1983年 | 34篇 |
1982年 | 58篇 |
1981年 | 49篇 |
1980年 | 44篇 |
1979年 | 40篇 |
1978年 | 44篇 |
1977年 | 41篇 |
1976年 | 47篇 |
1974年 | 34篇 |
1973年 | 29篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
A Study of the Uptake of Toluidine Blue O by Porphyromonas gingivalis and the Mechanism of Lethal Photosensitization 总被引:2,自引:1,他引:2
Manpreet Bhatti Alexander MacRobert Sajeda Meghji Brian Henderson Michael Wilson 《Photochemistry and photobiology》1998,68(3):370-376
The purpose of the study was to determine the distribution of the photosensitizer toluidine blue O (TBO) within Porphyromonas gingivalis and the possible mechanism(s) involved in the lethal photosensitization of this organism. The distribution of TBO was determined by incubating P. gingivalis with tritiated TBO (3H-TBO) and fractionating the cells into outer membrane (OM), plasma membrane (PM), cytoplasmic proteins, other cytoplasmic constituents and DNA. The percentage of TBO in each of the fractions was found to be, 86.7, 5.4, 1.9, 5.7 and 0.3%, respectively. The involvement of cytotoxic species in the lethal photosensitization induced by light from a helium-neon (HeNe) laser and TBO was investigated by using deuterium oxide (D2O), which prolongs the lifetime of singlet oxygen, and the free radical and singlet oxygen scavenger L-tryptophan. There were 9.0 log10 and 2 log10 reductions in the presence of D2O and H2O (saline solutions), respectively, at a light dose of 0.44 J (energy density = 0.22 J/cm2), suggesting the involvement of singlet oxygen. Decreased kills were attained in the presence of increasing concentrations of L-tryptophan. The effect of lethal photosensitization on whole cell proteins was determined by measuring tryptophan fluorescence, which decreased by 30% using 4.3 J (energy density = 4.3 J/ cm2) of light. Effects on the OM and PM proteins were determined by sodium dodecyl sulfate polyacrylamide gel electrophoresis. There was evidence of change in the molecular masses of several PM proteins and OM proteins compared to controls. There was evidence of damage to the DNA obtained from irradiated cells. Scanning electron microscopic studies showed that there was coaggre-gation of P. gingivalis cells when sensitized and then exposed to laser light. These results suggest that lethal photosensitization of P. gingivalis may involve changes in OM and/or PM proteins and DNA damage mediated by singlet oxygen. 相似文献
92.
Alexander Aster Christopher Rumble Anna-Bea Bornhof Hsin-Hua Huang Naomi Sakai Tom olomek Stefan Matile Eric Vauthey 《Chemical science》2021,12(13):4908
1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imide functionalization. We report on the charge-transfer dynamics of a series of electron donor–acceptor dyads consisting of a NDI chromophore with one or two donors linked at the axial, imide position. Photo-population of the core-centred π–π* state is followed by ultrafast electron transfer from the electron donor to the NDI. Due to a solvent dependent singlet–triplet equilibrium inherent to the NDI core, both singlet and triplet charge-separated states are populated. We demonstrate that long-lived charge separation in the triplet state can be achieved by controlling the mutual orientation of the donor–acceptor sub-units. By extending this study to a supramolecular NDI-based cage, we also show that the triplet charge-separation yield can be increased by tuning the environment.Ultrafast electron transfer from singlet and triplet excited states in equilibrium results in the population of both singlet and triplet charge-separated states. 相似文献
93.
Fedushkin IL Morozov AG Rassadin OV Fukin GK 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(19):5749-5757
Compounds [Sr(dpp-bian)(thf)4] (2), [Ba(dpp-bian)(dme)2.5] (3) and [Mg(dtb-bian)(thf)2] (4) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dtb-bian = 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene) were prepared by reduction of dpp-bian and dtb-bian with an excess of metallic Mg, Sr, or Ba in THF or DME. Reactions of [Mg(dpp-bian)(thf)3], 3, and 4 with diphenylacetonitrile gave keteniminates [Mg(dpp-bianH)(NCCPh2)(thf)2] (5), [Mg(dtb-bianH)(NCCPh2)(thf)2] (6), and [Ba(dpp-bianH)(NCCPh2)(dme)2] (7), respectively. The reaction of 2 with CH3C[triple chemical bond]N in THF gave [{Sr(dpp-bianH)[N(H)C(CH3)C(H)CN](thf)}2] (8). The compounds 2, 3, 5-8 were characterized by elemental analysis, and IR and NMR spectroscopy. Molecular structures of 2, 3, 7, and 8 were determined by single-crystal X-ray diffraction. In contrast to reactions of alkali-metal reagents, magnesium amides, or yttriumalkyls with alpha-H acidic nitriles, which are accompanied by an amine or an alkane elimination, the reactions of [Mg(dpp-bian)(thf)3] (1), 2, 3, and 4 with such nitriles proceeded with formation of Mg, Sr, and Ba keteniminates and simultaneous protonation of one nitrogen atom of the bian ligand. The NMR spectroscopic data obtained for complex 5 indicated that in solution the amino hydrogen atom underwent the fast (on the NMR timescale) shuttle transfer between both nitrogen atoms of the dpp-bianH ligand. 相似文献
94.
Rodolphe Clérac Dieter Fenske Ibrahim Issac Alexander Rothenberger 《Journal of Cluster Science》2004,15(2):189-198
Two Fe–Ta containing sulfido complexes were prepared by the reaction of the metal halide salts with bis-trimethylsilylsulfide in the presence of PMe3. The complexes demonstrate that coordination chemistry with iron sulfides can give access to a range of heterometallic complexes. In [Cl(Me3P)Ta(
2-S)2(
3-S)Fe(PMe3)2]2 the two [Cl(Me3P)Ta] units are arranged around one central Fe2(
2-S)2 unit. In [(Me3P)4(MeCN)2FeII]2+[(Me3P)2TaIVFeII
3(
3-S)4Br4]2– a [TaFe3S4]2+ cuboidal arrangement was observed. The complex salt forms a polymeric structure in the solid-state with weak H-bonds between the ions. The [(Me3P)2TaIVFeII
3(
3-S)4Br4]2– ion was characterised by magnetic measurements showing strong antiferromagnetic interactions between the metal centres. 相似文献
95.
Zubarev DY Boldyrev AI Li X Cui LF Wang LS 《The journal of physical chemistry. A》2005,109(50):11385-11394
Photoelectron spectroscopy and ab initio calculations are used to investigate the electronic structure and chemical bonding of Si5(-) and Si5(2-) in NaSi5(-). Photoelectron spectra of Si5(-) and NaSi5(-) are obtained at several photon energies and are compared with theoretical calculations at four different levels of theory, TD-B3LYP, R(U)OVGF, UCCSD(T), and EOM-CCSD(T), all with 6-311+G(2df) basis sets. Excellent agreement is observed between experiment and theory, confirming the obtained ground-state structures for Si5(-) and Si5(2-), which are both found to be trigonal bipyramid with D3h symmetry at several levels of theory. Chemical bonding in Si5, Si5(-), and Si5(2-) is analyzed using NPA, molecular orbitals, ELF, and NICS indices. The bonding in Si5(2-) is compared with that in the isoelectronic and isostructural B5H5(2-) species, but they are found to differ due to the involvement of electron densities, which are supposed to be lone pairs in the skeletal bonding in Si5(2-). 相似文献
96.
Volodkin DV Petrov AI Prevot M Sukhorukov GB 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3398-3406
A new approach to fabricate polyelectrolyte microcapsules is based on exploiting porous inorganic microparticles of calcium carbonate. Porous CaCO3 microparticles (4.5-5.0 microns) were synthesized and characterized by scanning electron microscopy and the Brunauer-Emmett-Teller method of nitrogen adsorption/desorption to get a surface area of 8.8 m2/g and an average pore size of 35 nm. These particles were used as templates for polyelectrolyte layer-by-layer assembly of two oppositely charged polyelectrolytes, poly(styrene sulfonate) and poly(allylamine hydrochloride). Calcium carbonate core dissolution resulted in formation ofpolyelectrolyte microcapsules with an internal matrix consisting of a polyelectrolyte complex. Microcapsules with an internal matrix were analyzed by confocal Raman spectroscopy, scanning electron microscopy, force microscopy, and confocal laser-scanning fluorescence microscopy. The structure was found to be dependent on a number of polyelectrolyte adsorption treatments. Capsules have a very high loading capacity for macromolecules, which can be incorporated into the capsules by capturing them from the surrounding medium into the capsules. In this paper, we investigated the loading by dextran and bovine serum albumin as macromolecules. The amount of entrapped macromolecules was determined by two independent methods and found to be up to 15 pg per microcapsule. 相似文献
97.
Structures of New SeII and TeII Complexes Containing 2,2-Dicyanethylene-1,1-dithiolate, 2,2-Dicyanethylene-1,1-thioselenolate, and 2,2-Dicyanethylene-1,1-diselenolate (NBu4)2{Se[S2C?C(CN)2]2} ( I ), (AsPh4)2 · {Te[SSeC?C(CN)2]2} ( II ), and (NBu4)2{Te[Se2C?C(CN)2]2} ( III ) containing the bidentate chelate ligands 2,2-dicyanethylene-1,1-dithiolate i-mnt , 2,2-dicyanethylene-1,1-thioselenolate i-mnts , and 2,2-dicyanethylene-1,1-diselenolate i-mns have been prepared and characterized by X-ray structure analysis. The central units consist of [M(X? X)2E2]2? (M = Se, Te; X? X = ligand; E = lone-pair) with fourfold coordinated SeII and TeII, respectively. The complex anions [Se(i-mnt)2E2]2? as well as [Te(i-mnts)2E2]2? show a trapezoide distortion with d(Se? S) = 2.276(5); 2.287(5); 2.803(5); 2.789(5) Å and d(Te? Se) = 2.611(2); 2.617(3); d(Te? S) = 2.889(5); 2.935(4) Å. In III there are centrosymmetric complex anions [Te(i-mns)2E2]2? with nearly identical Te? Se-bond-lengths: 2.674(3) and 2.692(2) Å. These Te? Se bonds are elongated compared to usual Te? Se bonds. 相似文献
98.
Matthias Westerhausen Alexander N. Kneifel Peter Mayer Heinrich Nth 《无机化学与普通化学杂志》2004,630(12):2013-2021
Synthesis and Molekular Structures of N‐substituted Diethylgallium‐2‐pyridylmethylamides (2‐Pyridylmethyl)(tert‐butyldimethylsilyl)amine ( 1a ) and (2‐pyridylmethyl)‐di(tert‐butyl)silylamine ( 1b ) form with triethylgallane the corresponding red adducts 2a and 2b via an additional nitrogen‐gallium bond. These oily compounds decompose during distillation. Heating under reflux in toluene leads to the elimination of ethane and the formation of the red oils of [(2‐pyridylmethyl)(tert‐butyldimethylsilyl)amido]diethylgallane ( 3a ) and [(2‐pyridylmethyl)‐di(tert‐butyl)silylamido]diethylgallane ( 3b ). In order to investigate the thermal stability solvent‐free 3a is heated up to 400 °C. The elimination of ethane is observed again and the C‐C coupling product N, N′‐Bis(diethylgallyl)‐1, 2‐dipyridyl‐1, 2‐bis(tert‐butyldimethylsilyl)amido]ethan ( 4 ) is found in the residue. Substitution of the silyl substituents by another 2‐pyridylmethyl group and the reaction of this bis(2‐pyridylmethyl)amine with GaEt3 yield triethylgallane‐diethylgallium‐bis(2‐pyridylmethyl)amide ( 5 ). The metalation product adds immediately another equivalent of triethylgallane regardless of the stoichiometry. The reaction of GaEt3 with 2‐pyridylmethanol gives quantitatively colorless 2‐pyridylmethanolato diethylgallane ( 6 ). 相似文献
99.
Christoph Luef Aloke Paul Jiri Vizdal Ales Kroupa Alexander Kodentsov Herbert Ipser 《Monatshefte für Chemie / Chemical Monthly》2006,137(4):381-395
Summary. The partial and integral enthalpies of mixing of liquid Bi–Sn–Zn alloys were determined at 500°C by a drop calorimetric technique
using a Calvet-type microcalorimeter. The ternary interaction parameters in the Bi–Sn–Zn system were fitted using the Redlich-Kister-Muggianu model for substitutional solutions, and isoenthalpy curves of the integral molar enthalpy of mixing at 500°C were constructed.
Furthermore, a DSC technique was used to determine the liquidus temperatures in three sections (3, 5, and 7 at.% Zn) as well
as the invariant reaction temperature of the ternary eutectic L ⇄ (Bi) + (Sn) + (Zn). The ternary eutectic reaction was found
at 135°C. 相似文献
100.
Kudrik EV Theodoridis A van Eldik R Makarov SV 《Dalton transactions (Cambridge, England : 2003)》2005,(6):1117-1122
Catalytic oxidation of N,N'-dimethylthiourea and thiourea by dioxygen in water using a new cobalt(II) complex of octasulfophenyltetrapyrazinoporphyrazine was performed under mild conditions. The reaction is shown to include the formation of an intermediate anionic five-coordinate complex followed by an unusual two-electron oxidation to produce the corresponding urea and elemental sulfur (S8). Kinetic and thermodynamic parameters for the different reaction steps of the process were determined. Drastic differences in catalytic activity of cobalt and iron octasulfophenyltetrapyrazinoporphyrazines were observed. 相似文献