首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   4321篇
  免费   469篇
  国内免费   596篇
化学   3833篇
晶体学   28篇
力学   80篇
综合类   28篇
数学   288篇
物理学   1129篇
  2024年   10篇
  2023年   43篇
  2022年   109篇
  2021年   118篇
  2020年   144篇
  2019年   136篇
  2018年   113篇
  2017年   113篇
  2016年   167篇
  2015年   162篇
  2014年   185篇
  2013年   402篇
  2012年   274篇
  2011年   291篇
  2010年   235篇
  2009年   283篇
  2008年   262篇
  2007年   254篇
  2006年   259篇
  2005年   241篇
  2004年   219篇
  2003年   204篇
  2002年   177篇
  2001年   112篇
  2000年   104篇
  1999年   106篇
  1998年   98篇
  1997年   72篇
  1996年   76篇
  1995年   64篇
  1994年   53篇
  1993年   47篇
  1992年   44篇
  1991年   35篇
  1990年   26篇
  1989年   31篇
  1988年   24篇
  1987年   15篇
  1986年   17篇
  1985年   6篇
  1984年   16篇
  1983年   6篇
  1982年   7篇
  1981年   3篇
  1979年   6篇
  1978年   4篇
  1977年   4篇
  1976年   3篇
  1975年   2篇
  1972年   2篇
排序方式: 共有5386条查询结果,搜索用时 15 毫秒
161.
The charge exchange spin-dipole (SD) excitations of \begin{document}$ ^{90} $\end{document}Zr are studied using the Skyrme Hartee-Fock plus proton-neutron random phase approximation with SAMi-J interactions. The experimental value of the model-independent sum rule obtained from the SD strength distributions of \begin{document}$ ^{90} $\end{document}Zr(p, n)\begin{document}$ ^{90} $\end{document}Nb and \begin{document}$ ^{90} $\end{document}Zr(n, p)\begin{document}$ ^{90} $\end{document}Y is used to deduce the neutron skin thickness. The neutron skin thickness \begin{document}$ \Delta r_{np} $\end{document} of \begin{document}$ ^{90} $\end{document}Zr is extracted as \begin{document}$ 0.083\pm0.032 $\end{document} fm, which is similar to the results of other studies. Based on the correlation analysis of the neutron skin thickness \begin{document}$ \Delta r_{np} $\end{document} and the nuclear symmetry energy J as well as its slope parameter L, a constraint from the extracted \begin{document}$ \Delta r_{np} $\end{document} leads to the limitation of J to \begin{document}$ 29.2 \pm 2.6 $\end{document} MeV and L to \begin{document}$ 53.3 \pm 28.2 $\end{document} MeV.  相似文献   
162.
臧二乐  梁树权 《应用化学》1995,12(3):107-108
磷钼酸四氢三铵的制备及其交换性能臧二乐,梁树权(北京农业大学应用化学系北京100094)(中国院学院化学研究所北京)关键词磷钼酸四氢三铵,制备,离子交换性能通式为M_nXY_(12)O_(40)·pH_2O(其中M为一价阳离子;X为P、As、Si、G...  相似文献   
163.
Abstract

Diffèrents modes de synthèse d'oxazolidones 1.2.4-7 et de dioxolonnes 8-11 germaniées sont décrites.

La stabilité thermique de germadioxolonnes a été étudiée. La décomposition procède d'un méchanisme du type (2 + 2 + 1), avec ouverture du cycle et formation de germylène.

La réactivité chimique des oxazolidones et dioxolonnes germaniées a été étudité. Des réactions d'échange avec des dérives organominéraux dichlorés conduit facilement et avec de bons rendements aux derives isologues, phosphorés(III). arseniés(III), soufrés. ou germaniés(IV). La réaction d'échange entre une dioxolonne germaniée et le dichlorogermylène nous a permis d'obtenir un nouveau germylène fonctionnel cyclique stable 20 qui a été caractérisé par spectrographie (RMN 1H. masse).

Different synthetic ways for germaoxazolidones 1.2.4-7 or dioxolonnes 8-11 have been described.

The thermal stability of germadioxolonnes has been studied. Decomposition occurs by a [2 + 2 + 1] ring opening with formation of germylene.

The chemical reactivity of germaoxazolidones or dioxolonnes has been studied. Exchange reactions with dihalogenated covalent compounds occur readily lcading to phosphorus(III). arsenic(III). sulphur or germanium(IV) analogs.

From dichlorogermylene, new stable fonctionnal cyclic germylene 20 is obtained and characterized.  相似文献   
164.
The present study shows new aspects of the synthesis of polyhalogenoarylphosphanes. The sterically hindered anions Ph(R)P-Y? (1a–c, Y = O, lone pair; R = Ph, But) have been used to show the complexity of the reaction between phosphorus nucleophiles and hexahalogenobenzenes or 9-bromofluorene (E3). The Ph(But)P-O? (1a) anion reacts with hexachlorobenzene (E1), hexafluorobenzene (E2), or E3 to give Ph(R)P(O)X (4a–c, X = F, Cl, Br) with the release of the corresponding carbanion as a nucleofuge, followed by side reactions. In contrast, the lithium phosphides Ph(R)PLi (1b,c) react with hexahalogenobenzenes to give the corresponding diphosphanes 5a,b as the main product and traces of P-arylated products, i.e., Ph(R)P-C6X5 (10a,b, X = Cl, F). Unexpectedly, Ph(But)PLi (1b) reacts with an excess of 9-bromofluorene to give only halogenophosphane Ph(But)P-X.  相似文献   
165.
2-Acyltetrahydro-β-carbolines 7 have been obtained by cyclization of adducts 5 from imines 3 of tryptamine 1 and aldehydes 2 with acyl chlorides 4 as a result of an intramolecular a-amidoalkylation reaction in the presence of bases as N,N-dimethylaniline or Et3N.  相似文献   
166.
ABSTRACT

Contamination of groundwater by heavy metal is one of the most emerging and serious environmental problems. There are so many methods which are available to overcome these problems. Among various available methods, hybrid organic–inorganic ion exchange resin has become more popular due to certain advantages over other available conventional methods; hence, in the present proposed work, we synthesised a hybrid organic–inorganic composite material polyacrylamide zirconium (IV) iodosulphosalicylate by using the sol-gel technique. Synthesised resin was characterised by various methods like Infrared spectroscopy and Thermogravimetric analysis-Differential thermal analysis. Various samples of this ion exchange resin are prepared by changing the condition of synthesis, i.e. concentration of acrylamide to rationalise the ion exchange capacity of the synthesise hybrid organic–inorganic ion exchange resins. A mixture of 0.1 M potassium iodate, 0.1 M sulphosalicylic acid and 0.1 M acrylamide was added dropwise to 0.4 M zirconium oxychloride accompanied by constant stirring for 8 h using magnetic stirrer at 70°C to yield polyacrylamide zirconium (IV) iodosulphosalicylate with maximum ion exchange capacity. Ion exchange capacity of synthesised resin was determined by column method and the maximum ion exchange capacity was found for Pb(II). Determination of kd values shows that the resin was highly selective for Pb (II).The selectivity for Pb was also evaluated by using certain binary mixture separation such as Ni (II)-Pb(II), Cu(II)-Pb(II), Cd(II)-Pb(II), Sr(II)-Pb(II), Ba(II)-Pb(II),Zn(II)-Pb(II) and Mg(II)-Pb(II).  相似文献   
167.
A new polymorph of FeOF (up to now only known in its rutile type structure) was prepared by using a new synthesis approach formally based on anionic exchange using the well-known layered FeOCl as precursor. The synthesis was achieved using [CH3C(CH2O–)2(COO–)B] to vehicle fluorine through the formation of soluble (CH3)4N+ [CH3C(CH2O–)2(COO–)BF] and using N,N-dimethylformamide (DMF) as the reacting medium. The XRD pattern of layered FeOF can be indexed with an orthorhombic cell which doubles along the b axis (which is the direction perpendicular to the layers) with respect to that of pristine FeOCl (a = 3.792(1) Å, b = 12.699(1) Å, c = 3.321(1) Å). Both thermal analysis and diffraction indicate similar stability for the layered and rutile polymorphs. Such findings are rationalized through Density Functional Theory calculations. It is found that the energy difference between the more stable rutile and layered polymorphs is practically nul. The origin of the similar stability lies in the fact that although the number of Fe–F and Fe–O bonds is different in the two structures, the strength of both the total number of Fe–O as well as Fe–F bonds are found to be almost identical. Even if the crystal and electronic structures are considerably different, the total bonding and thus, the stability of the two polymorphs, is comparable. The stability of different FeOF rutile type structures is also analyzed.  相似文献   
168.
Conformational exchanges of synthetic macrocyclic acceptors are rather fast, which is rarely studied in the absence of guests. Here, we report multiple stimuli-responsive conformational exchanges between two preexisting conformations of 2,2′,4,4′-tetramethoxyl biphen[3]arene (MeBP3) macrocycle. Structures of these two conformations are both observed in solid state, and characterized by 1H NMR, 13C NMR and 2D NMR in solution. In particular, conformational exchanges can respond to solvents, temperatures, guest binding and acid/base addition. The current system may have a role to play in the construction of molecular switches and other stimuli-responsive systems.  相似文献   
169.
Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show the design and preparation of an irreversible amide‐linked covalent organic framework (COF) JNU‐1 via a building block exchange strategy for efficient recovery of gold. JNU‐1 was synthesized through the exchange of 4,4′‐biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU‐1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X‐ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU‐1 for gold recovery results from the formation of hydrogen bonds C(N)?H???Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications.  相似文献   
170.
Various anion exchange membranes containing the 4,4′-bipyridine moiety as anion exchange groups were prepared from membranous copolymers of chloromethylstyrene and divinylbenzene and membranes of chloromethylated polysulfone and 4,4′-bipyridine. After evaluating the electrochemical properties of the obtained anion exchange membranes, the effect of membrane species on the generation of a photovoltage was examined by irradiation using a xenon lamp. The membranes swelled with ethylene glycol were clamped between two ITO electrodes and sealed by adhesive. The generated photovoltage and photocurrent from about a 120 μm thick membrane were about 80 mV and 400 nA, respectively, in a 200K Ω load resistance, though dependent of membrane species. The voltage decreased with increasing crosslinking by the divinylbenzene in the copolymer membranes. The effect of counter ion species on the voltage was examined and a chloride ion form of membrane showed the highest photovoltage. The membranes with different thicknesses, which were prepared from polysulfone derivatives, were evaluated and the voltage decreased with decreasing thickness. Even a porous membrane from polysulfone derivatives showed a photovoltage though a porous membrane in which a methyl viologen ethylene glycol solution had been impregnated did not have a stable voltage. Also, the anion exchange membrane containing the benzyl trimethylammonium moiety, which is the conventional anion exchange groups, did not show a high and stable photovoltage upon photoirradiation. © 1996 John Wiley & Sons, Inc.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号