全文获取类型
收费全文 | 3794篇 |
免费 | 173篇 |
国内免费 | 25篇 |
专业分类
化学 | 2727篇 |
晶体学 | 52篇 |
力学 | 127篇 |
综合类 | 3篇 |
数学 | 399篇 |
物理学 | 684篇 |
出版年
2023年 | 32篇 |
2022年 | 38篇 |
2021年 | 91篇 |
2020年 | 94篇 |
2019年 | 92篇 |
2018年 | 65篇 |
2017年 | 66篇 |
2016年 | 130篇 |
2015年 | 102篇 |
2014年 | 115篇 |
2013年 | 259篇 |
2012年 | 234篇 |
2011年 | 248篇 |
2010年 | 162篇 |
2009年 | 151篇 |
2008年 | 217篇 |
2007年 | 187篇 |
2006年 | 156篇 |
2005年 | 160篇 |
2004年 | 129篇 |
2003年 | 129篇 |
2002年 | 133篇 |
2001年 | 71篇 |
2000年 | 63篇 |
1999年 | 56篇 |
1998年 | 52篇 |
1997年 | 47篇 |
1996年 | 43篇 |
1995年 | 32篇 |
1994年 | 41篇 |
1993年 | 43篇 |
1992年 | 35篇 |
1991年 | 36篇 |
1990年 | 20篇 |
1989年 | 22篇 |
1988年 | 24篇 |
1987年 | 17篇 |
1986年 | 19篇 |
1985年 | 20篇 |
1984年 | 12篇 |
1982年 | 26篇 |
1981年 | 16篇 |
1980年 | 19篇 |
1979年 | 14篇 |
1978年 | 20篇 |
1977年 | 19篇 |
1976年 | 20篇 |
1975年 | 18篇 |
1974年 | 17篇 |
1973年 | 11篇 |
排序方式: 共有3992条查询结果,搜索用时 93 毫秒
111.
We report here our findings on a new and highly efficient strategy for the synthesis of β-amino acids involving the addition of bis(O-silyl) ketene acetals on Mannich type iminium electrophiles. 相似文献
112.
The reaction of 2 equiv of LiSeCC-n-C(5)H(11) (1) with cis-PtCl(2)(Ph(3)P)(2) (2) gives a mixture of the cis and trans isomers of Pt(Ph(3)P)(2)(SeCC-n-C(5)H(11))(2) (3), which slowly isomerizes in CH(2)Cl(2) to the preferred trans form trans-3. The closely related cis-[Pt(dppf)(2)(SeCC-n-C(5)H(11))(2)] (4) (dppf = bis(diphenylphosphino)ferrocene) was prepared by a similar metathetical reaction using the platinum chloride complex of the chelating dppf to impose the cis geometry. The structures of the cis and trans complexes have been investigated in solution by heteronuclear NMR ((31)P, (77)Se, and (195)Pt) and, in the cases of trans-3 and 4, characterized in the solid state by single-crystal X-ray diffraction. Changing the coordination geometry from cis to trans induces significant changes in the structural and spectroscopic parameters, which do not comply with the previously anticipated donor-acceptor properties of selenolate ligands. 相似文献
113.
Thomas Novinson Keitaro Senga Joe Kobe Roland K. Robins Darrell E. O'Brien Anthony A. Albert 《Journal of heterocyclic chemistry》1974,11(5):691-695
The reaction of 3-aminopyrazole with imidate esters such as ethyl acetimidate, gave N-(pyrazol-3-yl)acetamidine (1) rather than the isomeric 2-acetamidoyl-3-aminopyrazole. Ring closure of 1 with orthoesters such as ethyl propionimidate, afforded unsymmetrically substituted 2.4-dialkylpyrazolo[1,5-a]-1,3,5-triazines such as 4-ethyl-2-methylpyrazolo[1,5-a]-1,3,5-triazine (3). The structure of 1 was confirmed by several alternate syntheses. The unique feature of this two-step synthetic approach to the synthesis of pyrazolo[1,5-a]-1,3,5-triazines is that it is a convenient method of preparing fused triazines based on available pyrazoles rather than the less accessible dialkyltriazines. 相似文献
114.
Branchadell V Crévisy C Grée R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5795-5803
The tandem isomerization-aldolization reaction between allyl alcohol and formaldehyde mediated by [Fe(CO)3] was studied with the density functional B3LYP method. Starting from the key [(enol)Fe(CO)3] complex, several reaction paths for the reaction with formaldehyde were explored. The results show that the most favorable reaction path involves first an enol/allyl alcohol ligand-exchange process followed by direct condensation of formaldehyde with the free enol. During this process, formation of the new C-C bond takes place simultaneously with a proton transfer between the enol and the aldehyde. Therefore, the role of [Fe(CO)3] is to catalyze the allyl alcohol to enol isomerization affording the free enol, which adds to the aldehyde in a carbonyl-ene type reaction. Similar results were obtained for the reaction between allyl alcohol and acetaldehyde. 相似文献
115.
H. Oliveira E. A. N. Fernandes E. S. B. Ferraz 《Journal of Radioanalytical and Nuclear Chemistry》1997,217(1):125-129
The elemental composition of pine trees as a function of age was achieved by the tree-ring method. By using instrumental neutron activation analysis, trace elements were determined in individual rings ofPinus elliottii var.elliottii of 32, 14 and 9 years, from an implanted forest ofPinus sp., Buri, São Paulo, far away from industrial pollution. Different components of the system such as needles, pith, bark, soil and litter were also analyzed for 18 elements (As, Br, Ce, Co, Cs, Eu, Fe, Hf, K, La, Mn, Na, Rb, Sc, Sm, Yb, Zn, and Zr). Al, B, Ba, Ca, Fe, K, Mg, and P concentrations were determined by atomic absorption and/or emission spectrometry (AAS; ICP-AES). Some elements have showed similar radial distribution of the concentration for the three ages. Abrupt concentration changes in the pith and ring-bark boundary corresponding to the first and last growth rings were observed. 相似文献
116.
117.
The ab initio two-state model for electron transfer induced by an external electric field has been applied to the chloride oxidation on Cu, Rh, Pd, Ag, Pt and Au (001) surface models. The two electronic states involved in the model represent physical situations where the electron transferred from the chloride anion to the metal surface lies either on the halide or on the metal substrate. The model assumes that electron transfer takes place when these two states become degenerate and this is achieved by applying an external electric field. Two different situations representing either ultrahigh vacuum or electrochemical conditions have been considered. For the former the present study shows that electric field necessary to achieve degeneracy of the two electronic states is directly related to the metal surface work function whereas for the latter, it is found to be rather insensitive to the metal surface. 相似文献
118.
Mrcia Sousa Bispo Maria das Graas Andrade Korn Elane Santos da Boa Morte Leonardo Sena Gomes Teixeira 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):2175-2180
An analytical method for separation and pre-concentration of lead in seawater for determination by inductively coupled plasma optical emission spectrometry has been investigated. Lead was retained in the solid phase (0.5 g) composed of co-precipitated naphthalene and alizarin red. The solid phase quantitatively sorbs Pb(II) at pH 8–9, and the metal was eluted using 5.0 ml of 2 mol l−1 nitric acid. The effect of NaCl, KCl, BaCl2, CaCl2, Na2SO4, MgCl2 and Na3PO4 on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amounts of electrolytes (0.5; 1.0; 3.0 and 5.0% m/v) with Pb (50 μg) was prepared and the recommended procedure applied. The Na3PO4 was found to interfere; the other electrolytes did not interfere up to 5% m/v. A pre-concentration factor of 40 was obtained in this analytical procedure. The limit of detection and limit of quantification for Pb(II) were 53 and 176 μg l−1, respectively. Lead was determined in seawater samples collected in Salvador city, Bahia, Brazil. The precision, expressed as R.S.D., was 1.8–4.6%, and the recovery of lead added to seawater samples was 95–97%. 相似文献
119.
Nataša Bukovec Peter Bukovec Jože Šiftar 《Monatshefte für Chemie / Chemical Monthly》1980,111(4):957-961
Compounds of the type CsLn(SO4)2, (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were prepared at 300°C. IR spectra were recorded in the range 4,000-250cm–1 and tentatively assigned. The number of observed bands exceeds the predicted number by site symmetry selection rules. Streching bands show bathochromic shifts whereas the deformations exibit hypsochromic shifts on going to heavier lanthanides. At the same time there is an increased splitting of these bands in the same direction. All these facts indicate an increased coupling in the layer structure which is in accordance with the lanthanide contraction.
N. Bukovec, P. Bukovec undJ. iftar, Vest. Slov. Kem. Drus.26, 103 (1979). 相似文献
120.
Jože Slivnik Mateja Žvanut Borka Sedej 《Monatshefte für Chemie / Chemical Monthly》1968,99(5):1713-1717
Zusammenfassung Die Reaktion zwischen MgCO3 und wässerigen Lösungen von Hydraziniumdifluorid und Flußsäure führt zum Hydraziniumfluoromagnesat. Diese Verbindung ist auch aus Magnesiumchlorid-und Hydraziniumdifluorid-Lösungen herstellbar. Es werden röntgenographische, IR-spektrographische und thermogravimetrische Untersuchungen dieser Verbindung angegeben.
Mit 3 Abbildungen 相似文献
Hydrazinium(+2) fluoromagnesate is formed in the reaction between MgCO3 and hydrazinium difluoride dissolved in hydrogen fluoride. The reaction of magnesium chloride and an aqueous solution of hydrazinium difluoride yields the same product. The results of X-ray diffraction studies, IR spectroscopical studies and thermogravimetrical investigation are given.
Mit 3 Abbildungen 相似文献