全文获取类型
收费全文 | 745篇 |
免费 | 17篇 |
国内免费 | 5篇 |
专业分类
化学 | 541篇 |
晶体学 | 10篇 |
力学 | 18篇 |
数学 | 34篇 |
物理学 | 164篇 |
出版年
2024年 | 1篇 |
2023年 | 12篇 |
2022年 | 64篇 |
2021年 | 36篇 |
2020年 | 14篇 |
2019年 | 29篇 |
2018年 | 22篇 |
2017年 | 14篇 |
2016年 | 22篇 |
2015年 | 14篇 |
2014年 | 21篇 |
2013年 | 72篇 |
2012年 | 32篇 |
2011年 | 56篇 |
2010年 | 25篇 |
2009年 | 21篇 |
2008年 | 29篇 |
2007年 | 26篇 |
2006年 | 26篇 |
2005年 | 37篇 |
2004年 | 29篇 |
2003年 | 35篇 |
2002年 | 18篇 |
2001年 | 18篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 10篇 |
1991年 | 3篇 |
1990年 | 9篇 |
1989年 | 1篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1970年 | 2篇 |
1938年 | 1篇 |
排序方式: 共有767条查询结果,搜索用时 15 毫秒
1.
I. V. Kuchin N. B. Ur’ev 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2007,81(3):349-353
The main rules governing the redistribution of microparticles in disperse systems were revealed by computer simulation. These rules predetermine the character and properties of the structure being formed, which opens up the possibility to control the properties of disperse materials, including sorbents and catalysts based on high-dispersity solid phases. 相似文献
2.
3.
A new tripodal ligand, tris[2-(((2-thiazolyl)methylidene)amino)ethyl]amine (Tatren), has been synthesized and characterized by NMR, IR, and UV-visible absorbance spectroscopy and elemental analysis. Tatren forms stable complexes with transition metal ions (Zn(2+), 1; Mn(2+), 2; Co(2+), 3) and the alkaline earth metal ions (Ca(2+), 4; Mg(2+), 5). Single-crystal X-ray structures of 1, 2, and 5 revealed six-coordinate chelate complexes with formula [M(Tatren)](ClO(4))(2) in which the metal centers are coordinated by three thiazolyl N atoms and three acyclic imine N atoms. Crystals of 1, 2, and 5 are monoclinic, P2(1)/c space group. Crystals of 4 are triclinic, P space group. The Ca(2+) complex is eight-coordinate with all N atoms of Tatren and one water molecule coordinated to the metal ion. Spectrophotometric titrations show that formation constants for the chelates of metal ions are >1 in methanol. Free Tatren inhibits the catalytic domain of matrix metalloproteinase-13 (MMP-13, collagenase-3) with K(i) = 3.5 +/- 0.6 microM. Molecular mechanics-based docking calculations suggest that one leg of Tatren coordinates to the catalytic Zn(2+) in MMPs-2, -9, and -13 with significant hydrogen bonding to backbone amide groups. High-level DFT calculations suggest that, in the absence of nonbonded interactions between Tatren and the enzyme, the most stable first coordination sphere of the catalytic Zn(2+) is achieved with three imidazolyl groups from His residues and two imine N atoms from one leg of Tatren. While complexes (1-3) do not inhibit MMP-13 to a significant extent, 4 does (K(i) = 30 +/- 10 microM). Hence, this study shows that tripodal chelating ligands of this class and their Ca(2+) complexes have potential as active-site inhibitors for MMPs. 相似文献
4.
Urška L. Štangar Urh Černigoj Polonca Trebše Ksenija Maver Silvia Gross 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):647-655
Summary. Transparent TiO2 films with a high photodegradation activity towards an azo dye in aqueous solution were prepared by sol–gel processing. Films
on soda–lime glass supports protected with a thin silica barrier layer exhibited better crystallization and monodisperse nanoparticles,
higher absorption of light below 370 nm, and higher photocatalytic activity than those films deposited on bare glass supports
proving the detrimental effect of interdiffused sodium ions on the development of the anatase nanostructure. The effect of
substrate was more pronounced in thinner films (300 nm) than in thicker ones (1200 nm), which were achieved by adding a template
(i.e. Pluronic F127) to the sol. 相似文献
5.
A simple continuous flow generation of volatile bromine is described for the determination of low concentrations of the elements by atmospheric-pressure argon microwave induced plasma (MIP) surfatron. Bromine is continuously generated by mixing the bromide with sulphuric acid and hypochlorite solutions. The bromine vapor is separated from the aqueous phase by a gas-liquid separator and is desiccated by passing it through concentrated sulphuric acid. The detection limit attained was 2 microg/l. and the precision was +/-0.7% (at the 80 microg/l. level). The proposed determination is very selective if oxidizing/reducing agents are absent. The procedure has been tested for bromide determination in two drug preparations. Good agreement between the experimental results and the certified values has been obtained. 相似文献
6.
Ur?ka L. ?tangar Urh ?ernigoj Polonca Treb?e Ksenija Maver Silvia Gross 《Monatshefte für Chemie / Chemical Monthly》2006,1(6):647-655
Transparent TiO2 films with a high photodegradation activity towards an azo dye in aqueous solution were prepared by sol–gel processing. Films
on soda–lime glass supports protected with a thin silica barrier layer exhibited better crystallization and monodisperse nanoparticles,
higher absorption of light below 370 nm, and higher photocatalytic activity than those films deposited on bare glass supports
proving the detrimental effect of interdiffused sodium ions on the development of the anatase nanostructure. The effect of
substrate was more pronounced in thinner films (300 nm) than in thicker ones (1200 nm), which were achieved by adding a template
(i.e. Pluronic F127) to the sol. 相似文献
7.
Rajapakshe A Gruhn NE Lichtenberger DL Basta R Arif AM Ernst RD 《Journal of the American Chemical Society》2004,126(43):14105-14116
Molecules of the form Cp(6,6-dmch)ZrX(2) (Cp = eta(5)-cyclopentadienyl, X = Cl, Br, I; 6,6-dmch = eta(5)-6,6-dimethylcyclohexadienyl) have been synthesized, and the molecular and electronic structures have been investigated. These molecules allow direct comparison of the bonding and properties of pentadienyl and cyclopentadienyl ligands in the same high-oxidation-state metal complexes. Unlike the well-known Cp(2)ZrX(2) analogues, these Cp(6,6-dmch)ZrX(2) molecules are intensely colored, indicating significantly different relative energies of the frontier orbitals. Also unusual, the average Zr-C distances to the 6,6-dmch pentadienyl ligand are about 0.1 A longer than the average Zr-C distances to the cyclopentadienyl ligand for these Zr(IV) complexes, opposite of what is observed for the Zr(II) complex Cp(2,6,6-tmch)Zr(PMe(3))(2) (tmch = eta(5)-2,6,6-trimethylcyclohexadienyl), reflecting a dramatic reversal in the favorability of the bonding depending on the metal oxidation state. The experimental and computational results indicate that the color of the Cp(6,6-dmch)ZrX(2) complexes is due to a 6,6-dmch ligand-to-metal charge-transfer band. Compared to the Cp(2)ZrX(2) analogues, the Cp(6,6-dmch)ZrX(2) molecules have a considerably less stable HOMO that is pentadienyl-based and an essentially unchanged metal-based LUMO. Also, the lowest unoccupied orbital of pentadienyl is stabilized relative to cyclopentadienyl and becomes a better potential delta electron acceptor, thus contributing to the differences in structure and reactivity of the low-valent and high-valent metal complexes. 相似文献
8.
Garner DK Fitch SB McAlexander LH Bezold LM Arif AM Berreau LM 《Journal of the American Chemical Society》2002,124(34):9970-9971
The synthesis and properties of mononuclear zinc methoxide ([(ebnpa)Zn-OCH3]ClO4) (1) and hydroxide ([(ebnpa)Zn-OH]ClO4) (2) complexes of a new mixed nitrogen/sulfur ligand (ebnpa = N-2-(ethylthio)ethyl-N,N-bis(6-neopentylamino-2-pyridylmethyl)amine) are reported. The structures of 1 and 2 were determined by X-ray diffraction. Each possesses a single zinc-coordinated anion (methoxide or hydroxide) and exhibits an overall trigonal bipyramidal geometry. Structural and spectroscopic studies indicate the presence of two hydrogen-bonding interactions involving the oxygen atom of the zinc-bound anion in each complex. Treatment of [(ebnpa)Zn-OH]ClO4 with CH3OH results in the formation of an equilibrium mixture of 1 and 2. 1H NMR spectroscopic methods were used to examine the equilibrium as a function of temperature, yielding KMe (304 K) = 0.30(8), DeltaHMe = -0.9(1) kcal/mol, and DeltaSMe = -5(1) eu. The negative enthalpy indicates that spontaneous zinc alkoxide formation from a hydroxide precursor occurs in this system at low temperature. Using the experimentally determined DeltaHMe value, we found the homolytic Zn-O bond dissociation energy (BDE) in the Zn-OCH3 unit to be approximately -14 kcal/mol relative to the Zn-O BDE in the Zn-OH unit. 相似文献
9.
H.?Hussain H.?U.?Rehman Z.?AhmadEmail author 《Journal of Sol-Gel Science and Technology》2005,36(3):239-248
Nano-composites from aramid-silica system have been prepared via sol-gel process. Poly (phenyleneterephthalamide) copolymer
chains were prepared by reacting a mixture of p- and m-phenylenediamines with terephthaloyl chloride in dimethylacetamide used as solvent. The sol-gel process in the polymer
matrix was carried out through hydrolysis and condensation of a mixture of tetraethoxysilane and (3-glycidoxypropyl) trimethoxysilane.
The latter was used to develop linkage, on one hand with silica network structure using alkoxy groups and on the other hand
with aramid chains at its secondary amine groups through glycidal groups of silane. Mutual interaction between the two disparate
phases aramid and silica network was thus created. Thin films of the composites containing different proportions of silica
ranging from 5.0 to 25.0-wt% were cast by the solvent elution technique. The α-relaxation temperature associated with the
glass transition was measured by the dynamic mechanical thermal analysis. The results showed an increase in the glass transition
temperature from 328°C for the pure aramid to 352°C for the hybrid materials containing 25-wt% silica, an indicative of the
increased interfacial interaction between the two phases. Films having relatively low silica content were flexible and transparent,
but those with high silica content were opaque and brittle. These films were tested for their tensile strength, modulus and
toughness. The mechanical strength of the composites as compared to the pure aramid increased initially but with further addition
of silica the strength decreased. The initial increase can be explained due to increased interfacial interaction between the
two phases, however agglomeration of silica particles was responsible for decreasing strength at higher silica contents. 相似文献
10.
Chatterjee B Noveron JC Resendiz MJ Liu J Yamamoto T Parker D Cinke M Nguyen CV Arif AM Stang PJ 《Journal of the American Chemical Society》2004,126(34):10645-10656
The syntheses, structures, and N2 adsorption properties of six new supramolecular metallacycles are reported. Flexible ditopic linkers, 1-4, with systematically varied lengths and conformational degrees of freedom were synthesized utilizing ester linkages. They were used in combination with (dppp)M(OTf)2, where M = Pt(II) and Pd(II), and cis-(Me3P)2Pt(OTf)2 to form flexible supramolecular metallacycles 5-10 in 88-98% isolated yields. Their structures were characterized via multinuclear NMR and X-ray crystallography. The metallacycles stack to form porous structures in the crystalline state. The pore dimensions depend on both the phosphorus ligands attached to the metals and the flexible linkers. Adsorption studies on the porous materials show that 5a, 6, 8, and 9 held 11.7, 16.5, 5.7, and 6.8 cm3/g STP of N2 at 77 K, respectively. A guest-exchange study with nitromethane and toluene reveals that the nanopore in 5 is flexible, a property which was transferred from the linker to the supramolecular structure in the solid state. 相似文献