全文获取类型
收费全文 | 2110篇 |
免费 | 167篇 |
国内免费 | 73篇 |
专业分类
化学 | 1565篇 |
晶体学 | 42篇 |
综合类 | 4篇 |
数学 | 6篇 |
物理学 | 733篇 |
出版年
2023年 | 21篇 |
2022年 | 29篇 |
2021年 | 37篇 |
2020年 | 55篇 |
2019年 | 41篇 |
2018年 | 33篇 |
2017年 | 36篇 |
2016年 | 63篇 |
2015年 | 59篇 |
2014年 | 68篇 |
2013年 | 205篇 |
2012年 | 122篇 |
2011年 | 122篇 |
2010年 | 94篇 |
2009年 | 117篇 |
2008年 | 167篇 |
2007年 | 181篇 |
2006年 | 137篇 |
2005年 | 120篇 |
2004年 | 115篇 |
2003年 | 92篇 |
2002年 | 61篇 |
2001年 | 65篇 |
2000年 | 49篇 |
1999年 | 40篇 |
1998年 | 42篇 |
1997年 | 25篇 |
1996年 | 18篇 |
1995年 | 29篇 |
1994年 | 16篇 |
1993年 | 8篇 |
1992年 | 33篇 |
1991年 | 12篇 |
1990年 | 4篇 |
1989年 | 13篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1970年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有2350条查询结果,搜索用时 15 毫秒
71.
Wang Q Barclay JE Blake AJ Davies ES Evans DJ Marr AC McInnes EJ McMaster J Wilson C Schröder M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(14):3384-3396
A novel [NiS4Fe2(CO)6]cluster (1: 'S(4)'=(CH(3)C(6)H(3)S(2))(2)(CH(2))(3)) has been synthesised, structurally characterised and has been shown to undergo a chemically reversible reduction process at -1.31 V versus Fc(+)/Fc to generate the EPR-active monoanion 1(-). Multifrequency Q-, X- and S-band EPR spectra of (61)Ni-enriched 1(-) show a well-resolved quartet hyperfine splitting in the low-field region due to the interaction with a single (61)Ni (I=3/2) nucleus. Simulations of the EPR spectra require the introduction of a single angle of non-coincidence between g(1) and A(1), and g(3) and A(3) to reproduce all of the features in the S- and X-band spectra. This behaviour provides a rare example of the detection and measurement of non-coincidence effects from frozen-solution EPR spectra without the need for single-crystal measurements, and in which the S-band experiment is sensitive to the non-coincidence. An analysis of the EPR spectra of 1(-) reveals a 24 % Ni contribution to the SOMO in 1(-), supporting a delocalisation of the spin-density across the NiFe(2) cluster. This observation is supported by IR spectroscopic results which show that the CO stretching frequencies, nu(CO), shift to lower frequency by about 70 cm(-1) when 1 is reduced to 1(-). Density functional calculations provide a framework for the interpretation of the spectroscopic properties of 1(-) and suggest that the SOMO is delocalised over the whole cluster, but with little S-centre participation. This electronic structure contrasts with that of the Ni-A, -B, -C and -L forms of [NiFe] hydrogenase in which there is considerable S participation in the SOMO. 相似文献
72.
The response of a single TE102 and double TE104 rectangular cavity to the insertion of samples contained in tubes with variable wall thickness and a quartz Dewar into the cavity has been analyzed. A direct, indirect, and concurrent (positive or negative) “lens effect” inside the double TE104 rectangular cavity is discussed. The experimental dependence of the EPR signal intensity on the wall thickness of the sample tube, δ, for the line-like samples with identical length of the sample material column, L=30 mm, recorded in the microwave cavity showed a directly proportional increase of the relative “lens effect” with the increase of the wall thickness of the tube in the interval, δ∈<0.1 mm, >0.5 mm. The insertion of the variable-temperature double-wall quartz Dewar (home-built, resonant frequency shift, ca. −300 MHz) into the single TE102 rectangular cavity showed the same relative “lens effect”, with ca. 1.5-time increase of the EPR signal intensity, for a point-like sample and the line-like samples with material columns of diameter of 1 and 1.3 mm, and wall thickness of the sample tubes, δ∈<0.1 mm, >0.5 mm. The increased effect of the Dewar arises because the active volume of the quartz Dewar tube walls is always much more larger than the active volume of the sample tube wall. In the case of the double TE104 rectangular cavity, the insertion of the quartz Dewar: (i) into the same cavity, in which the sample is present, caused a direct “lens effect”, with ca. 1.8-fold increase of the EPR signal intensity; however, (ii) into the complementary cavity, in which the sample is absent, caused an indirect “lens effect”, with ca. 0.6-fold decrease of the EPR signal intensity. With the Dewar and sample in one cavity and a large empty sample tube in the complementary cavity, a concurrent (positive or negative) “lens effect” can be observed. Thus, the possible increase/decrease of the EPR signal intensity depends on the volume ratio of the quartz Dewar tube walls and large sample tube wall inserted into the double TE104 rectangular cavity. Each of the above phenomena may be a significant source error in quantitative EPR spectrometry unless the samples to be compared in the quantitative EPR analysis are contained in sample tubes having the same wall thickness and each EPR spectra should be recorded inside an identical quartz Dewar. 相似文献
73.
《Magnetic resonance in chemistry : MRC》2018,56(3):190-195
The local distortions and electron paramagnetic resonance parameters for Cu2+ in the mixed alkali borate glasses xNa2O‐(30–x)K2O‐70B2O3 (5 ≤ x ≤ 25 mol%) are theoretically studied with distinct modifier Na2O compositions x. Owing to the Jahn–Teller effect, the octahedral [CuO6]10− clusters show significant tetragonal elongation ratios p ~19% along the C4 axis. With the increase of composition x, the cubic field parameter Dq and the orbital reduction factor k exhibit linearly and quasi‐linearly decreasing tendencies, respectively, whereas the relative tetragonal elongation ratio p has quasi‐linearly increasing rule with some fluctuations, leading to the minima of g factors at x = 10 mol%. The composition dependences of the optical spectra and the electron paramagnetic resonance parameters are suitably reproduced by the linear or quasi‐linear relationships of the relevant quantities (i.e., Dq, k, and p) with x. The above composition dependences are analyzed from mixed alkali effect, which brings forward the modifications of the local crystal‐fields and the electronic cloud distribution around Cu2+ with the variation of the composition of Na2O. 相似文献
74.
Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study
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)
Tobias Heurich Dr. Zheng‐Wang Qu Dr. Senada Nožinović Dr. Gregor Schnakenburg Dr. Hideto Matsuoka Prof. Dr. Stefan Grimme Prof. Dr. Olav Schiemann Prof. Dr. Rainer Streubel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10102-10110
Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph2POTEMP), which was obtained by the reaction of Ph2PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph2P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph2P(S)H ( 6 ) or Ph2P(BH3)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph2P(O)STEMP) in CDCl3 at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP‐H2][Ph2P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates. 相似文献
75.
76.
77.
W. J. M. J. Josquin 《辐射效应与固体损伤》2013,168(1-4):221-224
The trapping of 5 keV deuterium in ~ 165 and ~ 4000 nm thick BeO films grown by thermal oxidation on Be substrates was investigated at different temperatures using the D(3He,H)4He nuclear reaction. The ratio of implanted D to BeO molecules obtained at saturation is 0.24 to 0.34. The D migrates from its end of range location and distributes itself uniformly in the BeO film. With increasing implant temperature the BeO layer flakes from the Be substrate. The distribution of D in BeO films at high concentrations is not consistent with diffusivity measurements at low concentrations of T in BeO. 相似文献
78.
Yuying Qu Yingchun Li Xiaoli Tan Weixiang Zhai Dr. Guifang Han Dr. Jingli Hou Prof. Guoquan Liu Prof. Yuguang Song Prof. Yangping Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7888-7895
Tetrathiatriarylmethyl (TAM, trityl) radicals have found wide applications as spin probes/labels for EPR spectroscopy and imaging, and as polarizing agents for dynamic nuclear polarization. The high hydrophilicity of TAM radicals is essential for their biomedical applications. However, the synthesis of hydrophilic TAM radicals (e.g., OX063) is extremely challenging and has only been reported in the patent literature, to date. Herein, an efficient synthesis of a highly water-soluble TAM radical bis(8-carboxyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)-mono-(8-carboxyl-2,2,6,6-tetrakis(2-hydroxyethyl)benzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)methyl (TFO), which contains four additional hydroxylethyl groups, relative to the Finland trityl radical CT-03, is reported. Similar to OX063, TFO exhibits excellent properties, including high water solubility in phosphate buffer, low log P, low pKa, long relaxation times, and negligible binding with bovine serum albumin. On the other hand, TFO has a sharper EPR line and higher O2 sensitivity than those of OX063. Therefore, in combination with its facile synthesis, TFO should find wide applications in magnetic resonance related fields and this synthetic approach would shed new light on the synthesis of other hydrophilic TAM radicals. 相似文献
79.
Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling
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. Gaëlle Charron Dr. Elena Malkin Dr. Guillaume Rogez Dr. Luke J. Batchelor Dr. Sandra Mazerat Dr. Régis Guillot Dr. Nathalie Guihéry Dr. Anne‐Laure Barra Dr. Talal Mallah Dr. Hélène Bolvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):16850-16862
By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C2v, has been investigated. Four complexes have the general formula [Ni(bpy)X2]n+ (bpy=2,2′‐bipyridine; X2=bpy ( 1 ), (NCS?)2 ( 2 ), C2O42? ( 3 ), NO3? ( 4 )). In the fifth complex, [Ni(HIM2‐py)2(NO3)]+ ( 5 ; HIM2‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM2‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and gi) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the eg‐like orbitals and is due to the difference in the σ‐donor strength of NO3? and bpy or HIM2‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model. 相似文献
80.
Dr. Nicoló Zuin Fantoni Dr. Zara Molphy Sinéad O'Carroll Dr. Georgia Menounou Dr. George Mitrikas Dr. Marios G. Krokidis Dr. Chryssostomos Chatgilialoglu Dr. John Colleran Dr. Anna Banasiak Prof. Martin Clynes Dr. Sandra Roche Suainibhe Kelly Prof. Vickie McKee Prof. Andrew Kellett 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):971-983
We report a series of copper(II) artificial metallo-nucleases (AMNs) and demonstrate their DNA damaging properties and in-vitro cytotoxicity against human-derived pancreatic cancer cells. The compounds combine a tris-chelating polypyridyl ligand, di-(2-pycolyl)amine (DPA), and a DNA intercalating phenanthrene unit. Their general formula is Cu-DPA-N,N' (where N,N'=1,10-phenanthroline (Phen), dipyridoquinoxaline (DPQ) or dipyridophenazine (DPPZ)). Characterisation was achieved by X-ray crystallography and continuous-wave EPR (cw-EPR), hyperfine sublevel correlation (HYSCORE) and Davies electron-nuclear double resonance (ENDOR) spectroscopies. The presence of the DPA ligand enhances solution stability and facilitates enhanced DNA recognition with apparent binding constants (Kapp) rising from 105 to 107 m −1 with increasing extent of planar phenanthrene. Cu-DPA-DPPZ, the complex with greatest DNA binding and intercalation effects, recognises the minor groove of guanine–cytosine (G-C) rich sequences. Oxidative DNA damage also occurs in the minor groove and can be inhibited by superoxide and hydroxyl radical trapping agents. The complexes, particularly Cu-DPA-DPPZ, display promising anticancer activity against human pancreatic tumour cells with in-vitro results surpassing the clinical platinum(II) drug oxaliplatin. 相似文献