全文获取类型
收费全文 | 1757篇 |
免费 | 84篇 |
国内免费 | 5篇 |
专业分类
化学 | 1247篇 |
晶体学 | 1篇 |
力学 | 26篇 |
数学 | 389篇 |
物理学 | 183篇 |
出版年
2023年 | 11篇 |
2022年 | 15篇 |
2021年 | 32篇 |
2020年 | 31篇 |
2019年 | 46篇 |
2018年 | 24篇 |
2017年 | 17篇 |
2016年 | 54篇 |
2015年 | 54篇 |
2014年 | 52篇 |
2013年 | 62篇 |
2012年 | 113篇 |
2011年 | 138篇 |
2010年 | 65篇 |
2009年 | 51篇 |
2008年 | 77篇 |
2007年 | 80篇 |
2006年 | 105篇 |
2005年 | 94篇 |
2004年 | 60篇 |
2003年 | 62篇 |
2002年 | 54篇 |
2001年 | 46篇 |
2000年 | 44篇 |
1999年 | 45篇 |
1998年 | 42篇 |
1997年 | 33篇 |
1996年 | 37篇 |
1995年 | 30篇 |
1994年 | 31篇 |
1993年 | 26篇 |
1992年 | 42篇 |
1991年 | 34篇 |
1990年 | 22篇 |
1989年 | 14篇 |
1988年 | 13篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1983年 | 13篇 |
1982年 | 6篇 |
1979年 | 6篇 |
1976年 | 5篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1971年 | 3篇 |
1905年 | 2篇 |
1890年 | 2篇 |
1889年 | 2篇 |
排序方式: 共有1846条查询结果,搜索用时 31 毫秒
21.
Multiply differential cross sections for two- and three-electron escape are parametrised in terms of generalised tensorial asymmetry parameters. The analysis is based exclusivly on rotational invariance as an exact symmetry for the experimental set up. No approximate assumptions are made on the correlated dynamics of many- electron systems. Results are valid for any atomic and molecular target. The new parameters may be used to describe experimental and theoretical data in a compact way, but also to link e.g. coincidence and non-coincidence measurements with each other. 相似文献
22.
Dimethylformamide (DMF) acts as an efficient source of carbon monoxide and dimethylamine in the palladium-catalyzed aminocarbonylation (Heck carbonylation) of p-tolyl bromide to provide the dimethylamide. Addition of amines to the reaction mixture in excess delivers the corresponding aryl amides in good yields. The amines employed, benzylamine, morpholine, and aniline, all constitute good reaction partners. The reaction proceeds smoothly with bromobenzene and more electron-rich aryl bromides, but electron-deficient aryl bromides fail to undergo aminocarbonylation. The reactions are conducted at 180-190 degrees C for 15-20 min with microwave heating in a reaction mixture containing imidazole and potassium tert-butoxide: the latter is required to promote decomposition of the DMF solvent at a suitable rate. The beneficial effects of controlled microwave irradiation as an energy source for the rapid heating of the carbonylation reaction mixture are demonstrated. The carbonylation procedure reported herein, which relies on the in situ generation of carbon monoxide, serves as a convenient alternative to other carbonylation methods and is particularly applicable to small-scale reactions where short reaction times are desired and the direct use of carbon monoxide gas is impractical. 相似文献
23.
It is demonstrated that thiols can adsorb to gold without losing hydrogen. Dodecyl sulfide-capped gold clusters have been prepared and subjected to ligand exchange reactions in perdeuterated benzene by addition of dodecanethiol and subsequently dodecyl disulfide. It is shown by 1H NMR spectroscopy that dodecanethiol molecules are readily taken up as ligands producing characteristic broad signals corresponding to the alpha-methylene and S-H protons, with chemical shifts close to those found for thiol in solution; these signals are absent in spectra of thiolate-capped clusters. Addition of excess disulfide to such clusters capped with both dialkyl sulfides and thiols leads to the appearance of sharp signals for free dialkyl sulfide and intact thiol. Amounts of thiols up to 50% of the ligand shell are, however, taken up by the clusters under rapid and irreversible loss of hydrogen. 相似文献
24.
Marchand P Griffe L Caminade AM Majoral JP Destarac M Leising F 《Organic letters》2004,6(8):1309-1312
The functionalization of phosphorus-containing dendrimers was easily achieved through thioacylation reactions involving new dendrimers capped with dithioester end groups and various functionalized amines. These reactions were successfully applied to the first generation (12 end groups) and the third generation of the dendrimer (48 end groups) and allowed their functionalization by various primary or secondary amines, alcohols, glycols, and azides. [reaction: see text] 相似文献
25.
CoSm(SeO3)2Cl, CuGd(SeO3)2Cl, MnSm(SeO3)2Cl, CuGd2(SeO3)4 and CuSm2(SeO3)4: Transition Metal containing Selenites of Samarium and Gadolinum The reaction of CoCl2, Sm2O3, and SeO2 in evacuated silica ampoules lead to blue single crystals of CoSm(SeO3)2Cl (triclinic, , Z = 4, a = 712.3(1), b = 889.5(2), c = 1216.2(2) pm, α = 72.25(1)°, β = 71.27(1)°, γ = 72.08(1)°, Rall = 0.0586). If MnCl2 is used in the reaction light pink single crystals of MnSm(SeO3)2Cl (triclinic, , Z = 2, a = 700.8(2), b = 724.1(2), c = 803.4(2) pm, α = 86.90(3)°, β = 71.57(3)°, γ = 64.33(3)°, Rall = 0.0875) are obtained. Green single crystals of CuGd2(SeO3)2Cl (triclinic, , Z = 4, a = 704.3(4), b = 909.6(4), c = 1201.0(7) pm, α = 70.84(4)°, β = 73.01(4)°, γ = 70.69(4)°, Rall = 0.0450) form analogously in the reaction of CuCl2 and Gd2O3 with SeO2. CoSm(SeO3)2Cl contains [CoO4Cl2] octahedra, which are connected via one edge and one vertex to infinite chains. The Mn2+ ions in MnSm(SeO3)2Cl are also octahedrally coordinated by four oxygen and two chlorine ligands. The linkage of the polyhedra to chains occurs exclusively via edges. Both, the cobalt and the manganese compound show the Sm3+ ions in eight and ninefold coordination of oxygen atoms and chloride ions. In CuGd(SeO3)2Cl the Cu2+ ions are coordinated by three oxygen atoms and one Cl— ion in a distorted square planar manner. One further Cl— and one further oxygen ligand complete the [CuO3Cl] units yielding significantly elongated octahedra. The latter are again connected to chains via two common edges. For the Gd3+ ions coordination numbers of ?8 + 1”? and nine were found. Single crystals of the deep blue selenites CuM2(SeO3)4 (M = Sm/Gd, monoclinic, P21/c, a = 1050.4(3)/1051.0(2), b = 696.6(2)/693.5(1), c = 822.5(2)/818.5(2) pm, β = 110.48(2)°/110.53(2)°, Rall = 0.0341/0.0531) can be obtained from reactions of the oxides Sm2O3 and Gd2O3, respectively, with CuO and SeO2. The crystal structure contains square planar [CuO4] groups and irregular [MO9] polyhedra. 相似文献
26.
Reaction of 2,3,7,8,12,13,17,18-octaethylporphyrin with LiR reagents containing functional groups readily yields meso substituted derivatives suitable for further transformations with residues such as -p-C6H5Br, -p-C6H5-CCH, -p-C6H5-NH2 or -(CH2)3-CHCH2. Similar reactions of tetrabenzoporphyrin with alkyllithium reagents afforded the first entry into meso mono- and dialkylsubstituted tetrabenzoporphyrins while reaction of bicyclo[2.2.2]oct-type masked isoindole precursors with LiR followed by in situ retro-Diels-Alder reaction also afforded the 5-phenyl and 5,10-diphenyltetrabenzoporphyrins in high purity. 相似文献
27.
Mathias Höfler Jürgen Scheuren Detlef Spilker 《Journal of organometallic chemistry》1975,102(2):205-211
The complexes CpFe(CO)2SiBr3, CpFe(CO)2SiI3, CpFe(CO)2SiBr2(OMe), and CpFe(CO)2SiI(NH-cyclo-C6H11)2 are prepared by the reaction of CpFe(CO)2SiR3 (R = OMe, NH-cyclo-C6H11) with HBr, HI and CH3I. Treating CpFe(CO)2SiCl3 with a large excess of NaN3, KOCN or KSCN yields the first tri-pseudohalogensilyl—transition-metal-complexes. The compounds are characterized by IR and mass spectra. A new method of preparation of the already known complex CpFe(CO)2SiH3 is described starting from CpFe(CO)2SiCl3 and LiAlH4. 相似文献
28.
Duygu Avci Selim H. Kseflu Robert D. Thompson Lon J. Mathias 《Journal of polymer science. Part A, Polymer chemistry》1994,32(15):2937-2945
New ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using acid chlorides (traditional solution reactions), sodium salts of acids (with phase transfer catalysis), and trifluoroacetic anhydride (trifluoroacetate). The interfacial process gave high yields of clean products under very mild conditions. Derivatives obtained include the formate, acetate, hexanoate, stearate, benzoate, trifluoroacetate, and adamantanoate. Bulk polymerizations with 2,2′-azobis (isobutyronitrile) gave high molecular weight polymers with intrinsic viscosities of over 2 dL/g and molecular weights of several million [based on size-exclusion chromatography (SEC) comparison to polystyrene standards]. These high molecular weights were the result of autoacceleration in the bulk as shown by monitoring molecular weight with respect to conversion. Solution polymerization in benzene gave more typical polymer, e.g., the acetate derivative showed an SEC molecular weight of 52,000. Glass transition temperatures for the n-alkyl esters decreased from the formate (77°C) to the hexanoate (15°C); the stearate showed a side-chain melting point of 40°C but no Tg. Glass transitions were observed for the trifluoroacetate, benzoate, and adamantanoate polymers at 69, 130, and 214°C, respectively. Solution 13C-NMR showed evidence of tacticity information for the formate and acetate derivatives with appaent preference for syndiotactic polymer formation similar to that of methyl methacrylate. FTIR and solid-state 13C-NMR analysis gave spectra with functional group peaks and chemical shift values expected based on composition. The stearate monomer and polymer gave solid-state 13C chemical shifts of 34 and 33 ppm, respectively, for the central CH2 units consistent with monoclinic and orthorhombic crystal packing. © 1994 John Wiley & Sons, Inc. 相似文献
29.
Protein-protein interactions play crucial roles in various biological pathways and functions. Therefore, the characterization of protein levels and also the network of interactions within an organism would contribute considerably to the understanding of life. The availability of the human genome sequence has created a range of new possibilities for biomedical research. A crucial challenge is to utilize the genetic information for better understanding of protein distribution and function in normal as well as in pathological biological processes. In this review, we have focused on different platforms used for systematic genome-based proteome analyses. These technologies are in many ways complementary and should be seen as various ways to elucidate different functions of the proteome. 相似文献
30.
Reaction of aminosilanetriol RSi(OH)(3) (1) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) with diethyl zinc at room temperature in 1:1 stoichiometric ratio affords [(THF)Zn(O(2)(OH)SiR)](4) (2) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) in good yield. The single-crystal X-ray diffraction studies reveal that 2 is monoclinic, P2(1), with a = 17.117(3) A, b = 16.692(5) A, c = 17.399(4) A, alpha = gamma = 90 degrees, beta = 91.45(7) degrees, and Z = 2. The molecular structure of 2 contains two puckered eight-membered Zn(2)Si(2)O(4) rings, which are connected by the Zn-O bonds and form two planar four-membered Zn(2)O(2) rings. Compound 2 contains an unreacted hydroxyl group on each silicon atom, and hence, we carried out the reactions of 2 with dimethylzinc and methyllithium to form [Zn(4)(THF)(4)(MeZn)(4)(O(3)SiR)(4)] (3) (R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))) and [(L)ZnLi(O(3)SiR)](4) (4) (L = 1,4-(Me(2)N)(2)C(6)H(4), R = (2,6-i-Pr(2)C(6)H(3))N(SiMe(3))), respectively. This suggested that 2 could be an intermediate product formed during the synthesis of 3 and 4. 相似文献