全文获取类型
收费全文 | 29926篇 |
免费 | 5596篇 |
国内免费 | 3224篇 |
专业分类
化学 | 21453篇 |
晶体学 | 349篇 |
力学 | 1770篇 |
综合类 | 137篇 |
数学 | 2983篇 |
物理学 | 12054篇 |
出版年
2024年 | 90篇 |
2023年 | 666篇 |
2022年 | 816篇 |
2021年 | 1155篇 |
2020年 | 1377篇 |
2019年 | 1345篇 |
2018年 | 1130篇 |
2017年 | 997篇 |
2016年 | 1555篇 |
2015年 | 1436篇 |
2014年 | 1873篇 |
2013年 | 2306篇 |
2012年 | 2811篇 |
2011年 | 2869篇 |
2010年 | 1869篇 |
2009年 | 1781篇 |
2008年 | 1993篇 |
2007年 | 1738篇 |
2006年 | 1625篇 |
2005年 | 1279篇 |
2004年 | 975篇 |
2003年 | 764篇 |
2002年 | 755篇 |
2001年 | 586篇 |
2000年 | 467篇 |
1999年 | 592篇 |
1998年 | 510篇 |
1997年 | 497篇 |
1996年 | 491篇 |
1995年 | 426篇 |
1994年 | 342篇 |
1993年 | 282篇 |
1992年 | 279篇 |
1991年 | 224篇 |
1990年 | 203篇 |
1989年 | 151篇 |
1988年 | 92篇 |
1987年 | 79篇 |
1986年 | 103篇 |
1985年 | 73篇 |
1984年 | 37篇 |
1983年 | 43篇 |
1982年 | 26篇 |
1981年 | 22篇 |
1980年 | 7篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1957年 | 4篇 |
1923年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
961.
The technique of diffusive gradients in thin films (DGT) is a newly developed analytical technique capable of measuring in situ concentrations of trace metals in the environment. The technique employs a thin film diffusive hydrogel (with well-defined diffusion properties) in contact with a binding phase capable of binding metal ions of interest. In this work, we demonstrate, for the first time, the use of a commercially available solid ion exchange membrane (Whatman P81) as the binding phase in DGT analysis. The cellulose phosphate-based Whatman P81 membrane is a strong cation exchange membrane. Its performance characteristics as a new binding phase in DGT measurement of Cu2+ and Cd2+ were systematically investigated. Several advantages over the conventional ion exchange resin-embedded hydrogel binding phases used in DGT were observed including simple preparation, ease of handling, and reusability. The binding capacities of the material to various metal ions were examined both collectively and individually. The binding phase preferentially binds to transition metal ions rather than matrix ions such as potassium, sodium, calcium and magnesium, which are competitive species in natural waters. Within the optimum pH range (pH 4.0-9.0), the maximum non-competitive binding capacities of the membrane for Cu2+ and Cd2+ were 3.22 and 3.07 μmol cm−2, respectively. The suitability of the new membrane-based binding phase for DGT applications was validated experimentally. The experimental results demonstrated excellent agreement with theoretically predicted trends. The measurement was not degraded after four consecutive reuses of the cellulose phosphate binding phase. 相似文献
962.
Tiantian Liu Xiaojie Chen Juan Zhao Weichun Wei Zhu Mao William Wu Shibo Jiao Yang Liu Zhiyong Yang Zhenguo Chi 《Chemical science》2021,12(14):5171
Pure organic emitters with full utilization of triplet excitons are in high demand for organic light-emitting diodes (OLEDs). Herein, through modulation of electron donors and introduction of phenyl rings as π spacers, we present three pure organic fluorophores (BCz, BTCz and BPTCz) with the hybridized local and charge-transfer (HLCT) excited state feature for OLED fabrication. Importantly, the introduction of π spacers in BPTCz not only enhances locally excited character with a fast radiative decay but also promotes intermolecular interactions to suppress non-radiative decays, contributing to a high solid-state fluorescence efficiency over 90%. Significantly, BPTCz not only endows its doped OLEDs with an external quantum efficiency (EQE) up to 19.5%, but also its non-doped OLED with a high EQE of 17.8%, and these outstanding efficiencies are the state-of-the-art performances of HLCT-based OLEDs.Three purely organic fluorophores with a hybridized local and charge-transfer excited state feature are presented and enabled organic light-emitting diodes with record high external quantum efficiencies close to 20%. 相似文献
963.
964.
The reaction of monomeric and dimeric rhodium(I) amido complexes with unactivated olefins to generate imines is reported. Transamination of {(PEt(3))(2)RhN(SiMePh(2))(2)} (1a) or its -N(SiMe(3))(2) analogue 1b with p-toluidine gave the dimeric [(PEt(3))(2)Rh(mu-NHAr)](2) (Ar = p-tolyl) (2a) in 80% isolated yield. Reaction of 2a with PEt(3) generated the monomeric (PEt(3))(3)Rh(NHAr) (Ar = p-tolyl) (3a). PEt(3)-ligated arylamides 2a and 3a reacted with styrene to transfer the amido group to the olefin and to form the ketimine Ph(Me)C=N(p-tol) (4a) in 48-95% yields. The dinuclear amido hydride (PEt(3))(4)Rh(2)(mu-NHAr)(mu-H) (Ar = p-tolyl) (5a) was formed from reaction of 2a in 95% yield, and a mixture of this dimeric species and the (PEt(3))(n)RhH complexes with n = 3 and 4 was formed from reaction of 3a in a combined 75% yield. Propene reacted with 2a to give Me(2)C=N(p-tol) (4b) and 5a in 90 and 57% yields. Propene also reacted with 3a to give 4b and 5a in 65 and 94% yields. Analogues of 2a and 3a with varied electronic properties also reacted with styrene to form the corresponding imines, and moderately faster rates were observed for reactions of electron-rich arylamides. Kinetic studies of the reaction of 3a with styrene were most consistent with formation of the imine by migratory insertion of olefin into the rhodium-amide bond to generate an aminoalkyl intermediate that undergoes beta-hydrogen elimination to generate a rhodium hydride and an enamine that tautomerizes to the imine. 相似文献
965.
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
966.
N-phosphorylamino acids are chemically active species that have many biomimic activities. alpha-COOH in amino acids and peptides behaviors rather differently than beta-COOH in many biochemical processes and takes a more important role in the origin of life. Activity differences between alpha-COOH and beta-COOH in the peptide formation of phosphoryl amino acids are studied by 1D, 2D NMR techniques and by ab initio and density functional theory (DFT) calculations in this paper. Phosphoryl dipeptide is formed directly from phosphoryl aspartic acids without any coupling reagents. Only the alpha-dipeptide ester is observed by 1D (1)H, (13)C, and (31)P NMR and 2D NMR. In the ab initio and DFT calculations, the pentacoordinate phosphorane intermediates containing five-membered rings are predicted to be more favored than those with six-membered rings. Both the experimental results and the theoretical calculations suggest that only the alpha-COOH group is activated by N-phosphorylation in N-phosphorylaspartic acid under mild conditions. 相似文献
967.
Xian‐Fa Zhang Shan Gao Li‐Hua Huo Hui Zhao 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(12):m617-m619
In the title coordination polymer, [Pb(C5H2N2O4)(H2O)]n, the PbII atom is seven‐coordinated by one N atom and five O atoms from four individual imidazole‐4,5‐dicarboxylate (HIDC2−) groups and one water molecule. It is interesting to note that the HIDC2− group serves as a bridging ligand to link the PbII atoms into a three‐dimensional microporous open‐framework. 相似文献
968.
Solid phase microextraction (SPME) then capillary gas chromatography with mass spectrometric detection have been used for determination of nine phenyl compounds in snow water in Beijing City. Headspace extraction with a fiber coated with 100 µm PDMS was used to extract the compounds. Extraction and desorption times were optimized at 8 and 2 min, respectively. Relative standard deviation (RSD) of the analytical method was found to be less than 5%. The linear range was wide and limits of detection were less than 5 ng mL−1 for the nine target analytes. Several phenyl compounds at ng mL−1 levels were detected in snow samples in Beijing, indicating the corresponding air pollution. 相似文献
969.
Jian Zhang Zhao‐Ji Li Yi‐Hang Wen Yao Kang Jian‐Kai Cheng Yuan‐Gen Yao 《无机化学与普通化学杂志》2004,630(15):2731-2735
Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C4H4O4)·1/4H2O ( 1 ) and Cu(2, 2′‐bpy)(C4H4O4)0.5(NO3)(H2O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) Å3, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) Å3, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the CuII atom adopts a distorted octahedral in which the CuII atoms are bridged by two H2O molecules into an infinite zigzag chain, [Cu2(H2O)2(C4H4O4)]n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure. 相似文献
970.
Xu Zhao Sarah E. Cleary Ceren Zor Nicole Grobert Holly A. Reeve Kylie A. Vincent 《Chemical science》2021,12(23):8105
Heterogeneous biocatalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction. This approach relies on enzymes powered by H2-driven NADH recycling. Commercially available carbon-supported metal (metal/C) catalysts are investigated here for direct H2-driven NAD+ reduction. Selected metal/C catalysts are then used for H2 oxidation with electrons transferred via the conductive carbon support material to an adsorbed enzyme for NAD+ reduction. These chemo-bio catalysts show improved activity and selectivity for generating bioactive NADH under ambient reaction conditions compared to metal/C catalysts. The metal/C catalysts and carbon support materials (all activated carbon or carbon black) are characterised to probe which properties potentially influence catalyst activity. The optimised chemo-bio catalysts are then used to supply NADH to an alcohol dehydrogenase for enantioselective (>99% ee) ketone reductions, leading to high cofactor turnover numbers and Pd and NAD+ reductase activities of 441 h−1 and 2347 h−1, respectively. This method demonstrates a new way of combining chemo- and biocatalysis on carbon supports, highlighted here for selective hydrogenation reactions.Heterogeneous chemo-bio catalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction. 相似文献