全文获取类型
收费全文 | 1036篇 |
免费 | 44篇 |
国内免费 | 1篇 |
专业分类
化学 | 768篇 |
晶体学 | 10篇 |
力学 | 31篇 |
数学 | 143篇 |
物理学 | 129篇 |
出版年
2023年 | 9篇 |
2022年 | 14篇 |
2021年 | 13篇 |
2020年 | 38篇 |
2019年 | 17篇 |
2018年 | 15篇 |
2017年 | 15篇 |
2016年 | 23篇 |
2015年 | 29篇 |
2014年 | 17篇 |
2013年 | 50篇 |
2012年 | 55篇 |
2011年 | 71篇 |
2010年 | 27篇 |
2009年 | 36篇 |
2008年 | 56篇 |
2007年 | 55篇 |
2006年 | 42篇 |
2005年 | 57篇 |
2004年 | 41篇 |
2003年 | 38篇 |
2002年 | 42篇 |
2001年 | 15篇 |
2000年 | 14篇 |
1999年 | 7篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 23篇 |
1995年 | 10篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 11篇 |
1991年 | 6篇 |
1990年 | 9篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1986年 | 9篇 |
1985年 | 11篇 |
1984年 | 15篇 |
1982年 | 12篇 |
1981年 | 15篇 |
1980年 | 11篇 |
1979年 | 12篇 |
1977年 | 11篇 |
1976年 | 6篇 |
1975年 | 6篇 |
1974年 | 6篇 |
1973年 | 11篇 |
1972年 | 5篇 |
1970年 | 5篇 |
排序方式: 共有1081条查询结果,搜索用时 31 毫秒
101.
Li J Stasch A Schenk C Jones C 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10448-10456
The preparation of a series of extremely bulky secondary amines, Ar*N(H)SiR(3) (Ar* = C(6)H(2){C(H)Ph(2)}(2)Me-2,6,4; R(3) = Me(3), MePh(2) or Ph(3)) is described. Their deprotonation with either LiBu(n), NaH or KH yields alkali metal amide complexes, several monomeric examples of which, [Li(L){N(SiMe(3))(Ar*)}] (L = OEt(2) or THF), [Na(THF)(3){N(SiMe(3))(Ar*)}] and [K(OEt(2)){N(SiPh(3))(Ar*)], have been crystallographically characterised. Reactions of the lithium amides with germanium, tin or lead dichloride have yielded the first structurally characterised two-coordinate, monomeric amido germanium(II) and tin(II) chloride complexes, [{(SiR(3))(Ar*)N}ECl] (E = Ge or Sn; R = Me or Ph), and a chloride bridged amido-lead(II) dimer, [{[(SiMe(3))(Ar*)N]Pb(μ-Cl)}(2)]. DFT calculations on [{(SiMe(3))(Ar*)N}GeCl] show its HOMO to exhibit Ge lone pair character and its LUMO to encompass its Ge based p-orbital. A series of bulky amido silicon(IV) chloride complexes have also been prepared and several examples, [{(SiR(3))(Ar*)N}SiCl(3)] (R(3) = Me(3), MePh(2)) and [{(SiMe(3))(Ar*)N}SiHCl(2)], were crystallographically characterised. The sterically hindered group 14 complexes reported in this study hold significant potential as precursors for kinetically stabilised low oxidation state and/or low coordination number group 14 complexes. 相似文献
102.
Sanyal R Cameron SA Brooker S 《Dalton transactions (Cambridge, England : 2003)》2011,40(45):12277-12287
An N(4) tetradentate [1 + 1] Schiff base metal free macrocycle HL was prepared, by 1?:?1 condensation of 2,2'-iminobisbenzaldehyde (1) and diethylenetriamine, and characterised. Seven mononuclear complexes, [Zn(II)L(py)](BF(4)) (2), [Cu(II)L](BF(4))]·H(2)O (3), [Ni(II)L](BF(4))·H(2)O (4), [Co(II)L](BF(4))]·H(2)O (5), Fe(III)L(BF(4))(2)·2H(2)O·MeCN (6), [Co(III)L(NCS)(2)]·0.3py (7) and [Fe(III)L(NCS)(2)] (8), of L(-) are reported. The Cu(II) and Ni(II) complexes were prepared by a template approach whereas the others were accessed by metallation of pre-formed HL. The X-ray crystal structure determinations show that [Cu(II)L](BF(4)) and [Ni(II)L](BF(4)) feature square planar N(4) coordinated Cu(II) and Ni(II) centres, respectively, whereas [Fe(III)L(NCS)(2)]·NO(2)Me features an octahedral N(6) coordinated Fe(III) centre (two NCS anions bound axially) and the Zn(II) complex, which crystallised as 2{[Zn(II)L(py)](BF(4))}·py, features square pyramidal Zn(II) ions (a pyridine molecule bound axially). In all cases the N(4) macrocycle is bound equatorially to the metal ion. Cyclic voltammograms of the soluble BF(4) complexes, 2-5, were carried out in MeCN vs. 0.01 mol L(-1) AgNO(3)/Ag and revealed multiple, mostly irreversible or quasi-reversible, redox processes. The Zn(II) complex 2 exhibited two irreversible oxidation processes and one irreversible reduction process, all of which are ligand-centered. The Ni(II) complex 4 showed a process with a weak return wave at E(m) = +0.57 V (ΔE = 0.05 V). Interestingly, after controlled potential coulometry experiments on 2, 3 and 4 (at +0.48, +0.61 and +0.71 V which transferred 1.2, 1.0 and 1.6 e(-) equiv. per complex, respectively), a new reversible or quasi-reversible process was obtained, with a lower potential than beforehand (E(m) (ΔE)/V = +0.16 (0.08), +0.31 (0.13) and +0.45 (0.11) respectively). 相似文献
103.
Feltham HL Klöwer F Cameron SA Larsen DS Lan Y Tropiano M Faulkner S Powell AK Brooker S 《Dalton transactions (Cambridge, England : 2003)》2011,40(43):11425-11432
A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution. 相似文献
104.
Southon PD Price DJ Nielsen PK McKenzie CJ Kepert CJ 《Journal of the American Chemical Society》2011,133(28):10885-10891
The metal-organic host material [{Co(III)(2)(bpbp)(O(2))}(2)bdc](PF(6))(4) (1·2O(2); bpbp(-) = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc(2-) = 1,4-benzenedicarboxylato) displays reversible chemisorptive desorption and resorption of dioxygen through conversion to the deoxygenated Co(II) form [{Co(II)(2)(bpbp)}(2)bdc](PF(6))(4) (1). Single crystal X-ray diffraction analysis indicates that the host lattice 1·2O(2), achieved through desorption of included water guests from the as-synthesized phase 1·2O(2)·3H(2)O, consists of an ionic lattice containing discrete tetranuclear complexes, between which lie void regions that allow the migration of dioxygen and other guests. Powder X-ray diffraction analyses indicate that the host material retains crystallinity through the dioxygen desorption/chemisorption processes. Dioxygen chemisorption measurements on 1 show near-stoichiometric uptake of dioxygen at 5 mbar and 25 °C, and this capacity is largely retained at temperatures above 100 °C. Gas adsorption isotherms of major atmospheric gases on both 1 and 1·2O(2) indicate the potential suitability of this material for air separation, with a O(2)/N(2) selectivity factor of 38 at 1 atm. Comparison of oxygen binding in solution and in the solid state indicates a dramatic increase in binding affinity to the complex when it is incorporated in a porous solid. 相似文献
105.
Three new bis-terdentate Schiff base [2 + 2] macrocycles (H(2)L(Et), H(2)L(Pr), and H(2)L(Bu)) have been prepared in high yields by 1:1 condensation of 2,2'-iminobisbenzaldehyde with 1,2-diaminoethane, 1,3-diaminopropane, and 1,4-diaminobutane, respectively. Metalation of these macrocycles yields the corresponding dicopper(II) acetate (1, 2, and 3) and tetrafluoroborate (4, 5, and 6) complexes. The structures of H(2)L(Et), H(2)L(Pr), H(2)L(Bu), [Cu(II)(2)L(i)(OAc)(2)]·solvents (where i is Et, Pr or Bu) and [Cu(II)(2)L(Pr)(DMF)(4)] (BF(4))(2)·0.5H(2)O are reported. Intramolecular hydrogen bonding is a feature of the metal-free macrocycles. The copper(II) centers in [Cu(II)(2)L(i)(OAc)(2)]·solvents are four coordinate, and the macrocycles have U-shaped (Et, Bu) or stepped (Pr) conformations. Complex 5 crystallizes with two dimethylformamide (DMF) molecules bound per five coordinate copper(II) center. Electrochemical studies revealed ligand based oxidations for all of the macrocycles and complexes. Complexes 1 and 2 undergo two quasi-reversible oxidations in DCM which are associated with the deposition of a visible film on the electrode after multiple scans in this oxidative region, suggestive of electropolymerization. Complexes 4-6, studied in MeCN, have Cu(II) → Cu(I) redox potentials at more positive potentials than for 1-3. 相似文献
106.
Clifton LA Sanders MR Castelletto V Rogers SE Heenan RK Neylon C Frazier RA Green RJ 《Physical chemistry chemical physics : PCCP》2011,13(19):8881-8888
The self-assembly in solution of puroindoline-a (Pin-a), an amphiphilic lipid binding protein from common wheat, was investigated by small angle neutron scattering, dynamic light scattering and size exclusion chromatography. Pin-a was found to form monodisperse prolate ellipsoidal micelles with a major axial radius of 112 ± 4.5 ? and minor axial radius of 40.4 ± 0.18 ?. These protein micelles were formed by the spontaneous self-assembly of 38 Pin-a molecules in solution and were stable over a wide pH range (3.5-11) and at elevated temperatures (20-65 °C). Pin-a micelles could be disrupted upon addition of the non-ionic surfactant dodecyl-β-maltoside, suggesting that the protein self-assembly is driven by hydrophobic forces, consisting of intermolecular interactions between Trp residues located within a well-defined Trp-rich domain of Pin-a. 相似文献
107.
Nitin KarwaTatiana Gambaryan-Roisman Peter Stephan Cameron Tropea 《Experimental Thermal and Fluid Science》2011,35(7):1435-1443
An experimental study of heat transfer during quenching of a cylindrical stainless steel test specimen has been performed. A subcooled water jet is directed onto the upward facing flat face of the cylinder. The test specimen is heated to an initial temperature slightly above 900 °C and then quenched. The resulting boiling curves and heat transfer distributions are presented for impingement velocities of 2.85 and 6.4 m/s (Re = 7900 and 18,900). High-speed imaging shows that three distinct regions on the quenched surface can be identified: an expanding circular wetted region surrounding the impinging point, annular transition zone just outside the wetting front, and a unwetted region outside this zone. The free-surface of the liquid in the wetted region is smooth in the nucleate and transition boiling regimes. The annular transition zone or the wetting front region outside the wetted region is characterized by a highly disturbed liquid-gas interface, which can be attributed to intense vapor generation. At the outer edge of the transition zone, the liquid is deflected away from the surface. The velocity of the wetting front significantly increases with the jet impact velocity, which indicates that the wetting front position is governed by the ability of the flowing liquid to transport the bubbles radially outwards from the wetted region. 相似文献
108.
Peter J. Cameron 《Discrete Mathematics》2011,311(13):1074
Open problems from the problem session at the 22nd British Combinatorial Conference at St Andrews, on 10 July 2009. 相似文献
109.
Dendronized polymers based on a poly(L-lysine) backbone have been synthesized up to the fourth generation. The hydroxyl-terminated polymers are completely water-soluble, which makes them good candidates for drug delivery applications. The dendronized polypeptide backbones are helical at lower generations, but undergo a dramatic conformational change from alpha-helical to disordered upon increasing the dendron size to the third generation. This conformational change, attributed to steric repulsions between dendrons, is supported by spectroscopic measurements while chain extension upon dendronization is confirmed by scanning force microscopy. 相似文献
110.
The structure of the N‐heterocyclic gallium hydride complex, [GaH2I{CN(Mes)C2H2N(Mes)}], Mes = mesityl, shows both hydride ligands to be bonded to the distorted tetrahedral gallium centre. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献