全文获取类型
收费全文 | 2660篇 |
免费 | 126篇 |
国内免费 | 9篇 |
专业分类
化学 | 2258篇 |
晶体学 | 23篇 |
力学 | 23篇 |
数学 | 258篇 |
物理学 | 233篇 |
出版年
2023年 | 20篇 |
2022年 | 31篇 |
2021年 | 35篇 |
2020年 | 55篇 |
2019年 | 53篇 |
2018年 | 28篇 |
2017年 | 32篇 |
2016年 | 75篇 |
2015年 | 78篇 |
2014年 | 90篇 |
2013年 | 121篇 |
2012年 | 197篇 |
2011年 | 248篇 |
2010年 | 112篇 |
2009年 | 101篇 |
2008年 | 211篇 |
2007年 | 204篇 |
2006年 | 194篇 |
2005年 | 195篇 |
2004年 | 168篇 |
2003年 | 130篇 |
2002年 | 116篇 |
2001年 | 33篇 |
2000年 | 23篇 |
1999年 | 24篇 |
1998年 | 20篇 |
1997年 | 15篇 |
1996年 | 27篇 |
1995年 | 13篇 |
1994年 | 8篇 |
1993年 | 19篇 |
1992年 | 18篇 |
1991年 | 9篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1977年 | 2篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1973年 | 4篇 |
1972年 | 2篇 |
1969年 | 4篇 |
1968年 | 2篇 |
排序方式: 共有2795条查询结果,搜索用时 125 毫秒
981.
N-[(Dialkylamino)(thiocarbonyl)]benzimidoyl chlorides react with functionalized amines such as 2-aminophenol, 2-methylaminopyridine, and 2-aminobenzoic acid in clean and high-yield procedures with the formation of the novel tridentate N-[(N', N'-dialkylamino)(thiocarbonyl)]- N'-substituted benzamidine ligands H2L1, HL2, and H2L3. By starting from (NBu4)[MOCl4] (M = Re, Tc) or [ReOCl3(PPh3)2] and H2L1, a series of oxorhenium(V) and oxotechnetium(V) complexes of the composition [MOCl(L1)] were synthesized and characterized by spectroscopic methods and X-ray crystallography. The monomeric, five-coordinate compounds are air-stable and bind (L1)(2-) tridentate in the equatorial coordination sphere. Dimeric products of the compositions [(ReOCl(L2))2O] and [ReOCl(L3)]2 were isolated during reactions with HL2 and H2L3. While dimerization in [(ReOCl(L2))2O] is established via an oxo bridge, the metal atoms in [ReOCl(L3)]2 are connected by the carboxylic group of the ligand, and the product represents the first example of a high-oxidation state rhenium complex displaying such a bonding feature. 相似文献
982.
Goodwin JA Coor JL Kavanagh DF Sabbagh M Howard JW Adamec JR Parmley DJ Tarsis EM Kurtikyan TS Hovhannisyan AA Desrochers PJ Standard JM 《Inorganic chemistry》2008,47(17):7852-7862
Complexes of the (nitro)( meso-tetrakis(2- N-methylpyridyl)porphyinato)cobalt(III) cation, [LCoTMpyP(2)(NO 2)] (4+), in which L = water or ethanol have been immobilized through ionic attraction within Nafion films (Naf). These immobilized six-coordinate species, [LCoTMPyP(2)(NO 2)/Naf], have been found to catalyze the oxidation of triphenylphosphine in ethanol solution by dioxygen, therefore retaining the capacity to activate dioxygen catalytically without an additional reducing agent as was previously observed in nonaqueous solution for the non-ionic (nitro)cobalt porphyrin analogs. Heating these immobilized six-coordinate species under vacuum conditions results in the formation of the five-coordinate nitro derivatives, [CoTMPyP(2)(NO 2)/Naf] at 85 degrees C and [CoTMPyP(2)/Naf] at 110 degrees C. The catalytic oxidation of gas-phase cyclohexene with O 2 is supported only by the resulting immobilized five-coordinate nitro complex as was previously seen with the corresponding solution-phase catalyst in dichloromethane solution. The simultaneous catalytic oxidation of triphenylphosphine and cyclohexene with O 2 in the presence of the Nafion-bound six-coordinate ethanol nitro complex is also observed; however, this process is not seen for the CoTPP derivative in dichloromethane solution. The oxidation reactions do not occur with unmodified Nafion film or with Nafion-supported [BrCo(III)TmpyP]/Naf or [Co(II)TmpyP]/Naf, indicating the necessity for the nitro/nitrosyl ligand in the oxidation mechanism. The existence of a second reactive intermediate is indicated because the two simultaneous oxidation reactions depend on two distinct oxygen atom-transfer steps having different reactivity. The absence of homogeneous cyclohexene oxidation by the six-coordinate (H 2O)CoTPP(NO 2) derivatives in the presence of Ph 3P and O 2 in dichloromethane solution indicates that the second reactive intermediate is lost by an unidentified route only in solution, implying that the immobilization of it in Nafion allows it to react with cyclohexene. Although direct observation of this species has not been achieved, a comparitive DFT study of likely intermediates in several catalytic oxidation mechanisms at the BP 6-31G* level supports the possibility that this intermediate is a peroxynitro species on the basis of relative thermodynamic accessibility. The alternate intermediates evaluated include the reduced cobalt(II) porphyrin, the dioxygen adduct cobalt(III)-O 2 (-), the oxidized cobalt(II) pi-cation radical, and the nitrito complex, cobalt(III)-ONO. 相似文献
983.
Heterobimetallic complexes comprised of W(CO)4 adducts of (N2S2)M(NO) have been isolated and characterized by nu(CO) and nu(NO)IR spectroscopies and X-ray diffraction. The molecular structures of (N2S2)M(NO) compounds (bme-dach)Co(NO), [(bme-dach)Co(NO)]W(CO)4, and [(bme-dach)Fe(NO)]W(CO)4 [bme-dach = N, N'-bis(2-mercaptoethyl)-1,4-diazacycloheptane)] find the square-pyramidal (bme-dach)M(NO) unit to serve as a bidentate ligand via the cis-dithiolato sulfurs, with a hinge angle of the butterfly bimetallic structures of ca. 130 degrees . The W(CO)4 moiety is used as a probe of the electron-donor ability of the nitrosyl complexes through CO stretching frequencies that display a minor increase as compared to analogous [(N2S2)Ni]W(CO)4 complexes. These findings are consistent with the electron-withdrawing influence of the {Co(NO)}(8) and {Fe(NO)}(7) units on the bridging thiolate sulfurs relative to Ni(2+). Also sensitive to derivatization by W(CO)4 is the NO stretch, which blue shifts by ca. 30 and 50 cm(-1) for the Co and Fe complexes, respectively. Cyclic voltammetry studies find similar reduction potentials (-1.08 V vs NHE in N, N-dimethylformamide solvent) of the (bme-dach)Co(NO) and (bme-dach)Fe(NO) free metalloligands, which are positively shifted by ca. 0.61 and 0.48 V, respectively, upon complexation to W(CO)4. 相似文献
984.
A mixed-mode chromatographic (MMC) sorbent was prepared by functionalizing the silica sorbent with a pentafluorophenyl (PFP) ligand. The resulting stationary phase provided a reversed-phase (RP) retention mode along with a relatively mild strong cation-exchange (SCX) retention interaction. While the mechanism of interaction is not entirely clear, it is believed that the silanols in the vicinity of the perfluorinated ligand act as strongly acidic sites. The 2.1 mm x 150 mm column packed with such sorbent was applied to the separation of peptides. Linear RP gradients in combination with salt steps were used for pseudo two-dimensional (2D) separation and fractionation of tryptic peptides. An alternative approach of using linear cation-exchange gradients combined with RP step gradients was also investigated. Besides the attractive forces, the ionic repulsion contributed to the retention mechanism. The analytes with strong negatively charged sites (phosphorylated peptides, sialylated glycopeptides) eluted in significantly different patterns than generic tryptic peptides. This retention mechanism was employed for the isolation of phosphopeptides or sialylated glycopeptides from non-functionalized peptide mixtures. The mixed-mode column was utilized in conjunction with a phosphopeptide enrichment solid phase extraction (SPE) device packed with metal oxide affinity chromatography (MOAC) sorbent. The combination of MOAC and mixed-mode chromatography (MMC) provided for an enhanced extraction selectivity of phosphopeptides and sialylated glycopeptides peptides from complex samples, such as yeast and human serum tryptic digests. 相似文献
985.
The fundamental difficulties currently impeding the elucidation of retention mechanisms in RPLC are reviewed. The various definitions and conventions concerning void volume and excess adsorption in liquid-solid systems are compared and contrasted. The utility and integrity of various chromatographic methods for the measurement of excess adsorption isotherms of HPLC eluents are discussed. Finally, literature methods for obtaining absolute adsorption data from excess quantities are reviewed and evaluated. 相似文献
986.
Rybolt TR Wells CE Thomas HE Goodwin CM Blakely JL Turner JD 《Journal of colloid and interface science》2008,325(1):282-286
Gas-solid chromatography was used to determine B(2s) (gas-solid virial coefficient) values for 12 alkanes (10 branched and 2 cyclic) interacting with a carbon powder (Carbopack B, Supelco). B(2s) values were determined by multiple size variant injections within the temperature range of 393 to 623 K with each alkane measured at 5 or 6 different temperatures. The temperature variations of the gas-solid virial coefficients were used to find the experimental adsorption energy or binding energy values (E( *)) for each alkane. A molecular mechanics based, rough-surface model was used to calculate the molecule-surface binding energy (E(cal)( *)) using augmented MM2 parameters. The surface model consisted of three parallel graphene layers with each layer containing 127 interconnected benzene rings and two separated nanostructures each containing 17 benzene rings arranged in a linear strip. As the parallel nanostructures are moved closer together, the surface roughness increases and molecule-surface interactions are enhanced. A comparison of the experimental and calculated binding energies showed excellent agreement with an average difference of 3.8%. Linear regressions of E( *) versus E(cal)( *) for the current data set and a combined current and prior alkane data set both gave excellent correlations. For the combined data set with 18 linear, branched and cyclic alkanes; a linear regression of E( *)=0.9848E(cal)( *) and r(2)=0.976 was obtained. The results indicate that alkane-surface binding energies may be calculated from MM2 parameters for some gas-solid systems. 相似文献
987.
Wang X Guram A Bunel E Cao GQ Allen JR Faul MM 《The Journal of organic chemistry》2008,73(4):1643-1645
A one-pot procedure for the synthesis of 2-alkyl-2-arylcyanoacetates based on a Pd(OAc)2/DPPF (DPPF = 1,1'-diphenylphosphino ferreocene)-catalyzed enolate arylation followed by in situ alkylation has been developed. This procedure tolerates a diverse range of aryl and heteroaryl bromides, and provides a rapid entry to a variety of 2-alkyl-2-arylcyanoacetates in good to excellent yield. 相似文献
988.
Arylnaphthalene lignan lactones are valuable natural products with promising anticancer and antiviral properties. In an effort to simplify their synthesis, we investigated a one-pot multicomponent coupling reaction between phenylacetylene, carbon dioxide, and 3-bromo-1-phenyl-1-propyne. After the corresponding 1,6-diyne was generated in situ, cyclization afforded the desired product. The level of regioselectivity was enhanced through the tuning of electronic properties. The use of cinnamyl bromide which led to the formation of a 1,6-enyne intermediate was also studied. 相似文献
989.
Katz CE Ribelin T Withrow D Basseri Y Manukyan AK Bermudez A Nuera CG Day VW Powell DR Poutsma JL Aubé J 《The Journal of organic chemistry》2008,73(9):3318-3327
The influence of attractive, nonbonded interactions on the reactions of 1,2- and 1,3-hydroxyalkyl azides with ketones has been investigated through experimental and computational means. A series of 1,3-hydroxyalkyl azides bearing electronically tuned aromatic groups at the 2 position were prepared and reacted along with several derivatives designed to conformationally restrict the rotational orientation of the aromatic substituent. These studies showed that a cation-pi interaction between an aryl moiety and an N2(+) leaving group plays a role in determining the stereoselectivity of these reactions. A series of ab initio calculations supported this hypothesis. A computational and experimental analysis suggested a primarily steric model for the analogous reactions of substituted 2-azido-1-ethanol analogues. 相似文献
990.
Desymmetrization of an Octahedral Coordination Complex Inside a Self‐Assembled Exoskeleton
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Mark D. Johnstone Eike K. Schwarze Jennifer Ahrens Prof. Dr. Dirk Schwarzer Dr. Julian J. Holstein Dr. Birger Dittrich Dr. Frederick M. Pfeffer Prof. Dr. Guido H. Clever 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(31):10791-10795
The synthesis of a centrally functionalized, ribbon‐shaped [6]polynorbornane ligand L that self‐assembles with PdII cations into a {Pd2 L 4} coordination cage is reported. The shape‐persistent {Pd2 L 4} cage contains two axial cationic centers and an array of four equatorial H‐bond donors pointing directly towards the center of the cavity. This precisely defined supramolecular environment is complementary to the geometry of classic octahedral complexes [M(XY)6] with six diatomic ligands. Very strong binding of [Pt(CN)6]2? to the cage was observed, with the structure of the host–guest complex {[Pt(CN)6]@Pd2L4} supported by NMR spectroscopy, MS, and X‐ray data. The self‐assembled shell imprints its geometry on the encapsulated guest, and desymmetrization of the octahedral platinum species by the influence of the D4h‐symmetric second coordination sphere was evidenced by IR spectroscopy. [Fe(CN)6]3? and square‐planar [Pt(CN)4]2? were strongly bound. Smaller octahedral anions such as [SiF6]2?, neutral carbonyl complexes ([M(CO)6]; M=Cr, Mo, W) and the linear [Ag(CN)2]? anion were only weakly bound, showing that both size and charge match are key factors for high‐affinity binding. 相似文献