全文获取类型
收费全文 | 1654篇 |
免费 | 69篇 |
国内免费 | 3篇 |
专业分类
化学 | 1062篇 |
晶体学 | 9篇 |
力学 | 57篇 |
数学 | 113篇 |
物理学 | 485篇 |
出版年
2023年 | 21篇 |
2022年 | 32篇 |
2021年 | 53篇 |
2020年 | 54篇 |
2019年 | 41篇 |
2018年 | 35篇 |
2017年 | 31篇 |
2016年 | 66篇 |
2015年 | 36篇 |
2014年 | 78篇 |
2013年 | 101篇 |
2012年 | 100篇 |
2011年 | 136篇 |
2010年 | 95篇 |
2009年 | 80篇 |
2008年 | 111篇 |
2007年 | 63篇 |
2006年 | 64篇 |
2005年 | 78篇 |
2004年 | 42篇 |
2003年 | 38篇 |
2002年 | 22篇 |
2001年 | 18篇 |
2000年 | 17篇 |
1999年 | 23篇 |
1998年 | 8篇 |
1997年 | 13篇 |
1996年 | 15篇 |
1995年 | 12篇 |
1994年 | 14篇 |
1993年 | 18篇 |
1992年 | 11篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 11篇 |
1985年 | 13篇 |
1984年 | 16篇 |
1983年 | 13篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1973年 | 4篇 |
排序方式: 共有1726条查询结果,搜索用时 0 毫秒
81.
The isolation and the X-ray crystal structure of physiological copper(II)-L-histidine complex are reported. The neutral five-coordinate complex shows distorted square pyramidal geometry with bidentate and tridentate L-histidine ligands. The basic character of the pendent imidazole group and H-bonding interactions of bidentate L-histidine ligand are important for copper transport. The unique structural features help explain the origin of its thermodynamic stability and kinetic reactivity in human blood along with the ternary copper(II)-amino acid complexes. The role of L-histidine in interaction with copper(II)-albumin, in cellular uptake of copper, and in treatment of Menkes disease can be studied using these results. 相似文献
82.
Multiresidue analysis of multiclass plant growth regulators in grapes by liquid chromatography/tandem mass spectrometry 总被引:1,自引:0,他引:1
Oulkar DP Banerjee K Ghaste MS Ramteke SD Naik DG Patil SB Jadhav MR Adsule PG 《Journal of AOAC International》2011,94(3):968-977
A selective and rapid multiresidue analysis method is presented for simultaneous estimation of 12 plant growth regulators (PGRs), namely, auxins (indol-3-acetic acid, indol-3-butyric acid, and naphthyl acetic acid), cytokinins (kinetin, zeatin, and 6-benzyladenine), gibberellic acid (GA3), abscisic acid, and synthetic compounds, namely, forchlorfenuron, paclobutrazole, isoprothiolane, and 2,4-dichlorophenoxy acetic acid (2,4-D) in bud sprouts and grape berries at the development stages of 2-3 and 6-8 mm diameters, which are the critical phases when exogenous application of PGRs may be necessary to achieve desired grape quality and yield. The sample preparation method involved extraction of plant material with acidified methanol (50%) by homogenization for 2 min at 15000 rpm. The pH of the extract was enhanced up to 6 by adding ammonium acetate, followed by homogenization and centrifugation. The supernatant extract was cleaned by SPE on an Oasis HLB cartridge (200 mg, 6 cc). The final extract was measured directly by LC/MS/MS with electrospray ionization in positive mode, except for 2,4-D, GA3, and abscisic acid extracts, which required analysis in negative mode. Quantification by multiple reaction monitoring (MRM) was supported with full-scan mass spectrometric confirmation using "information-dependent acquisition" triggered with MRM to "enhanced product ionization" mode of the hybrid quadrupole-ion trap mass analyzer. The LOQ of the test analytes varied between 1 and 10 ng/g with associated recoveries of 80-120% and precision RSD <25% (n = 8). Significant matrix-induced signal suppression was recorded when the responses for pre- and postextraction spikes of analytes were compared; this could be resolved by using matrix-matched calibration standards. The method could successfully be applied in analyzing incurred residue samples and would, therefore, be useful in precisely deciding the necessity and dose of exogenous applications of PGRs on the basis of measured endogenous levels. 相似文献
83.
Kedia N Sarkar A Shannigrahi M Bagchi S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,81(1):79-84
Spectral properties of a new fluorescent ketocyanine dye have been discussed. The energy of maximum absorption/fluorescence of the dye exhibits bathochromic shift with increasing polarity of the medium. Both dipolarity-polarisability and hydrogen bond donation interaction contribute to solvation of the dye. Study of fluorescence parameters points to existence of different emitting states of the dye for aprotic and protic solvents. While the emitting state is the (1)(π, π*) state for aprotic solvents, fluorescence supposedly take place from a different emitting state involving H-bond formation in the excited state in protic solvents. Fluorescence parameters of the dye have been compared with those for a structurally similar symmetric ketocyanine dye. The faster decay of the dye relative to its symmetric counterpart has been explained as due to an increase of nonradiative decay. 相似文献
84.
85.
Patra S Sarkar B Ghumaan S Patil MP Mobin SM Sunoj RB Kaim W Lahiri GK 《Dalton transactions (Cambridge, England : 2003)》2005,(7):1188-1194
The isomeric title complexes were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and L. Crystal structure analyses of the perchlorate hemihydrates, electrochemical and spectroscopic (NMR, UV/VIS, EPR) studies, supported by DFT calculations, reveal distinct differences between the isomeric redox series [1]n+(tetrazine-Nt trans to Cl) and [2]n+(pyrazolyl-Np trans to Cl; n= 0, 1, 2). The latter system with the pi acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidation, lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidised (RuIII) state. According to partially resolved EPR spectra of one-electron reduced neutral compounds and they have the unpaired electron predominantly in the tetrazine ring of L. 相似文献
86.
Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes 下载免费PDF全文
David Schweinfurth Yvonne Rechkemmer Stephan Hohloch Naina Deibel Irina Peremykin Jan Fiedler Raphael Marx Dr. Petr Neugebauer Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3475-3486
The complexes [{(tmpa)CoII}2(μ‐L1)2?]2+ ( 12+ ) and [{(tmpa)CoII}2(μ‐L2)2?]2+ ( 22+ ), with tmpa=tris(2‐pyridylmethyl)amine, H2L1=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H2L2=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 22+ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin CoII centers. Superconducting quantum interference device (SQUID) magnetometric studies on 12+ and 22+ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 12+ and ferromagnetic for 22+ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 12+ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 13+ and the two‐electron oxidized isovalent 14+ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 22+ , for 14+ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin CoIII centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps. 相似文献
87.
Highly Luminescent Colloidal Eu3+‐Doped KZnF3 Nanoparticles for the Selective and Sensitive Detection of CuII Ions 下载免费PDF全文
Shyam Sarkar Manjunath Chatti Dr. Venkataramanan Mahalingam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3311-3316
This article describes a green synthetic approach to prepare water dispersible perovskite‐type Eu3+‐doped KZnF3 nanoparticles, carried out using environmentally friendly microwave irradiation at low temperature (85 °C) with water as a solvent. Incorporation of Eu3+ ions into the KZnF3 matrix is confirmed by strong red emission upon ultraviolet (UV) excitation of the nanoparticles. The nanoparticles are coated with poly(acrylic acid) (PAA), which enhances the dispersibility of the nanoparticles in hydrophilic solvents. The strong red emission from Eu3+ ions is selectively quenched upon addition of CuII ions, thus making the nanoparticles a potential CuII sensing material. This sensing ability is highly reversible by the addition of ethylenediaminetetraacetic acid (EDTA), with recovery of almost 90 % of the luminescence. If the nanoparticles are strongly attached to a positively charged surface, dipping the surface in a CuII solution leads to the quenching of Eu3+ luminescence, which can be recovered after dipping in an EDTA solution. This process can be repeated for more than five cycles with only a slight decrease in the sensing ability. In addition to sensing, the strong luminescence from Eu3+‐doped KZnF3 nanoparticles could be used as a tool for bioimaging. 相似文献
88.
Das MR Sarma RK Saikia R Kale VS Shelke MV Sengupta P 《Colloids and surfaces. B, Biointerfaces》2011,83(1):16-22
A solution-based approach to the synthesis of silver (Ag) nanoparticles by chemical reduction of AgNO(3) in a graphene oxide (GrO) suspension is demonstrated. X-ray diffraction and transmission electron microscopy indicate that the Ag nanoparticles, of size range 5-25nm, were decorated on the GrO sheets. The size and shape of the Ag nanoparticles are dependent on the concentration of the AgNO(3) solution. Antimicrobial activity of such hybrids materials is investigated against the Gram negative bacteria Escherichia coli and Pseudomonous aeruginosa. The bacterial growth kinetics was monitored in nutrient broth supplemented with the Ag nanoparticle-GrO suspension at different conditions. It was observed that P. aeruginosa is comparatively more sensitive to the Ag nanoparticle-GrO suspension. 相似文献
89.
Sarkar B Kaim W Klein A Schwederski B Fiedler J Duboc-Toia C Lahiri GK 《Inorganic chemistry》2003,42(20):6172-6174
The Ru(2)(III,II) mixed-valent state is strongly stabilized in [(bpy)(2)Ru(mu-bttz)Ru(bpy)(2)](5+) (3(5+), bttz = 3,6-bis(2-thienyl)-1,2,4,5-tetrazine, as evident from lowered oxidation potentials and isolability, a strongly increased comproportionation constant K(c) = 10(16.6), and a high-energy intervalence charge transfer band at 10100 cm(-1). Curiously, no such effects were observed for the diosmium(III,II) analogue, whereas the related systems [(bpy)(2)M(mu-bmptz)M(bpy)(2)](5+), bmptz = 3,6-bis(4-methyl-2-pyridyl)-1,2,4,5-tetrazine, exhibit conventional behavior, i.e., a slightly higher K(c) value of the Os(2)(III,II) analogue. EPR signals were observed at 4 K for 3(5+) but not for the other mixed-valent species, and high-frequency (285 GHz) EPR was employed to study the diruthenium(II) radical complexes 2(3+) and 3(3+). 相似文献
90.