全文获取类型
收费全文 | 3099篇 |
免费 | 149篇 |
国内免费 | 44篇 |
专业分类
化学 | 2236篇 |
晶体学 | 19篇 |
力学 | 201篇 |
数学 | 360篇 |
物理学 | 476篇 |
出版年
2023年 | 31篇 |
2022年 | 115篇 |
2021年 | 131篇 |
2020年 | 153篇 |
2019年 | 166篇 |
2018年 | 177篇 |
2017年 | 124篇 |
2016年 | 202篇 |
2015年 | 135篇 |
2014年 | 199篇 |
2013年 | 322篇 |
2012年 | 243篇 |
2011年 | 216篇 |
2010年 | 161篇 |
2009年 | 131篇 |
2008年 | 141篇 |
2007年 | 102篇 |
2006年 | 80篇 |
2005年 | 55篇 |
2004年 | 39篇 |
2003年 | 49篇 |
2002年 | 38篇 |
2001年 | 17篇 |
2000年 | 20篇 |
1999年 | 8篇 |
1998年 | 19篇 |
1997年 | 14篇 |
1996年 | 11篇 |
1995年 | 9篇 |
1994年 | 14篇 |
1993年 | 11篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1989年 | 15篇 |
1988年 | 13篇 |
1987年 | 11篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 10篇 |
1982年 | 12篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1968年 | 2篇 |
1967年 | 3篇 |
排序方式: 共有3292条查询结果,搜索用时 15 毫秒
21.
Khodayar Gholivand Zahra Hosseini Mehrdad Pourayoubi Zahra Shariatinia 《无机化学与普通化学杂志》2005,631(15):3074-3079
Some new N‐carbonyl, phosphoramidates with formula C6H5C(O)N(H)P(O)R2 (R = NC3H6 ( 1 ), NC6H12 ( 2 ), NHCH2CH=CH2 ( 3 ), N(C3H7)2 ( 4 )) and CCl3C(O)N(H)P(O)R′2 (R′ = NC3H6 ( 5 ), NHCH2CH=CH2 ( 6 )) were synthesized and characterized by 1H, 13C, 31P NMR and IR spectroscopy and elemental analysis. The structures were determined for compounds 1 and 2 . Compound 1 exists as two crystallographically independent molecules in crystal lattice. Both compounds 1 and 2 produced dimeric aggregates via intermolecular ‐P=O…H‐N‐ hydrogen bonds, which in compound 2 is a centrosymmetric dimer. In compounds with four‐membered ring amine groups, 3J(P,C)>2J(P,C), in agreement with our previous studies about five‐membered ring amine groups. Also, 3J(P,C) values in compounds 1 and 5 are greater than in compounds with five‐, six‐ and seven‐membered ring amine groups. 相似文献
22.
The dependency of adsorption energy (E) and affinity coefficient (beta) of Dubinin equations (Dubinin-Radushkevich (DR) or Dubinin-Astakhov (DA)) on surface chemistry and porosity of activated carbons was investigated by analyzing adsorption of nitrogen, benzene, trichloroethylene (TCE), and water vapor by several surface-modified activated carbons and carbon fibers. For all studied nonpolar adsorbates, carbons with smaller average micropores showed higher adsorption energies independent of their surface chemistry. For water vapor, carbons with higher surface polarities showed higher adsorption energies due to specific adsorbate-adsorbent interactions. Adsorption energies increased with decreasing average micropore widths. betaN2,DR for different carbons were observed to vary in the 0.292-0.539 range. Carbons with higher degrees of mesoporosity had higher betaN2,DR values, while no dependency was observed between betaN2,DR and surface chemistry. A comparison of DR and DA cases indicates that: (1) the average value of betaN2,DA is considerably above the classical value of this parameter; and (2) the range of betaN2,DA values were smaller compared to betaN2,DR, despite a wide range of mesoporosity of carbons examined. Obtained beta(TCE,DR) values varied in the 0.952-1.243 range, with an average value of 1.085+/-0.083, independent of surface chemistry or porosity of activated carbons. A similar result was observed for beta(TCE,DA). betaH2O,DR values of different granular and fibrous activated carbons changed in the range of 0.081-0.271. They depended more on the carbon surface chemistry and less on the porosity. A similar result was obtained when DA equation was considered. 相似文献
23.
Yasser M. Loksha Per T. Jrgensen Erik B. Pedersen Mahmoud A. El‐Badawi Ahmed A. El‐Barbary Claus Nielsen 《Journal of heterocyclic chemistry》2002,39(2):375-382
5‐Alkyl‐4‐benzyl‐1,3‐dihydroimidazol‐2‐ones ( 3a‐d ) and 5‐alkyl‐4‐benzyl‐1,3‐dihydroimidazole‐2‐thiones (7a‐d) were prepared via Dakin West reaction on DL‐phenylalanine with the appropriate aliphatic acid anhydrides followed by hydrolysis and reaction with potassium cyanate or potassium thiocyanate. Compounds 3a‐d were alkylated with ethoxymethyl chloride to give the alkylated imidazoles 5a‐d which were considered analogues of Emivirine with deletion of carbonyl group at the 4‐position. Alkylation of 7a‐d afforded the corresponding S‐alkylated derivatives 8a‐p which in a similar way were considered analogues of S‐DABO. However all the imidazole derivatives were devoid of activity against HIV. 相似文献
24.
Behzad Haghighi Mohammad Reza Hussaindokht Mohammad Reza Bozorgmehr Naser Seyed Matin 《中国化学快报》2007,18(9):1154-1158
In this paper five equations of state are tested for checking their ability to predict the Joule-Thomson inversion curve.These five equations of state are:Mohsennia-Modarres-Mansoori(MMM),Ji-Lemp(JL),modified Soave-Redlich-Kwang(SRK)equation of state by Graboski(MSRK1),modified SRK equation of state by Peneloux and Rauzy(MSRK2),and modified Peng-Robinson (PR)equation of state by Rauzy(PRmr).The investigated equations of state give good prediction of the low-temperature branch of the inversion curve,except for MMM equation of state.The high-temperature branch and the peak of the inversion curve have been observed,in general,to be sensitive to the applied equation of state.The values of the maximum inversion temperature and maximum inversion pressure are calculated for each component used in this work. 相似文献
25.
Solid Phase Extraction and Flame Atomic Absorption Spectrometric Determination of Trace Amounts of Zinc and Cobalt Ions in Water Samples 总被引:1,自引:0,他引:1
A simple and rapid method for the preconcentration of Co2+ and Zn2+ as their 2-guanidino-benzimidazole chelates is proposed using an octadecyl silica cartridge. The retained analytes were recovered with a mixture of 5mL of 0.01M HNO3 and 5mL of methanol. The metal ions in the effluent were determined by flame atomic absorption spectrometry. The effect of different parameters, such as sample matrix, amount of ligand, type of eluent for elution of ions from cartridge, flow rates of sample solution and eluent, breakthrough volume, and limit of detection, were evaluated. The effects of various cationic and anionic interferences on the percent recovery of Co2+ and Zn2+ were also studied. Quantitative extraction efficiencies were obtained by elution of the cartridge with a minimal amount of solvent. Hence, with a typical preconcentration factor of 50, the limits of detections of the proposed method are 0.26 and 1.62ngmL–1 for Zn2+ and Co2+, respectively. The method was applied to the determination of zinc and cobalt ions in different water samples. 相似文献
26.
Hamza A. S. Abujabal Mahmoud M. El-Borai 《Journal of Applied Mathematics and Computing》1996,3(2):279-290
In the present paper, we study the Cauchy problem in a Banach spaceE for an abstract nonlinear differential equation of form $$\frac{{d^2 u}}{{dt^2 }} = - A\frac{{du}}{{dt}} + B(t)u + f(t,W)$$ whereW = (A 1(t)u,A 2(t)u,?,A ?(t)u), (A i (t),i = 1, 2, ?,?), (B(t),t ∈I = [0,b]) are families of closed operators defined on dense sets inE intoE, f is a given abstract nonlinear function onI ×E ? intoE and ?A is a closed linear operator defined on dense set inE intoE, which generates a semi-group. Further, the existence and uniqueness of the solution of the considered Cauchy problem is studied for a wide class of the families (A i(t),i = 1, 2, ?,?), (B(t),t ∈I). An application and some properties are also given for the theory of partial diferential equations. 相似文献
27.
Rajabian Mahmoud Gravelle Denis V. Vacquié Serge 《Plasma Chemistry and Plasma Processing》2004,24(2):261-284
An investigation of the plasma jet generated by a dc argon–nitrogen plasma torch, operated in association with a controlled-pressure chamber, is presented. The purpose of this article is to describe a study of the properties of a subsonic plasma jet under such operating conditions, when its transition to supersonic flow regime is nearly complete. The goal is that of performing plasma diagnostics not only in the initial region of the jet but also in the downstream region where the plasma emission is weak. For this purpose two different diagnostic methods are used. The first approach is based on non-intrusive optical emission spectroscopy, which yields both excitation and rotational temperatures as well as electron number density fields. The zone investigated by this method extends from the torch exit to about 10 nozzle diameters downstream. The second approach consisted of the use of the intrusive enthalpy probe technique for the measurement of the plasma gas temperature, mainly in the tail region of the plasma jet. In the present work, the effects of axial and radial distances across the jet, on the temperature and electron density profiles are discussed for subsonic flow conditions. Interesting features revealed are the data shown for the various diagnostic methods, which either disagree or overlap with each other. Finally, our results show the need for involving non-equilibrium models for the argon–nitrogen plasma due to the presence of significant differences between the temperatures of light and heavy particles. 相似文献
28.
Fatehy M. Abdel‐Haleem Azza Salah Mahmoud S. Rizk Hussein Moustafa Mikhael Bechelany Ahmed Barhoum 《Electroanalysis》2019,31(4):778-789
Thiourea derivative‐based carbon paste electrode (TUD1‐CPE) was constructed as a potentiometric sensor for the determination of salicylate anion in pharmaceutical formulations, Aspocid® and Aspirin®. The optimized CPE contained 45.5 % graphite, 0.5 % reduced graphene oxide (rGO), 46.0 % nitrophenyl octyl ether (NPOE) plasticizer, 5.0 % TUD1 ionophore, and 3.0 % tridodecylmethyl ammonium chloride as additive. The incorporation of NPOE of high dielectric constant, and rGO in electrode caused better performance of the sensor; Nernstian response of 59.0 mV decade?1 in the concentration range of 10?1–10?5 mole L?1, a detection limit of 1×10?5 mole L?1 in a very short response time of 6 seconds. The prepared sensor showed high selectivity against similar anions (i. e. , benzoate, I?, SCN?). Selectivity was confirmed by calculating the formation constant (Kβ) using sandwich membrane method, where Kβ for TUD1‐salicylate is 100.43. Theoretical calculations at DFT‐B3LY/6‐31G** level of theory were performed to find interaction mechanism, Energies of HOMO and LUMO orbitals, non‐linear optical (NLO) properties (the electronic dipole moment (μ), first‐order hyperpolarizability (β), the hyper‐Rayleigh scattering (βHRS) and the depolarization ratio (DR)), and other global properties; these calculations showed lower values of β and DR, higher value of βHRS, and the shortest lengths of the four N?H bonds between TUD1 and salicylate which confirm their strong complexation and salicylate‐selectivity. Also, all the studied anion‐TUD1 exhibited relatively high NLO properties, and these results were considered as a preliminary study for investigating new types of NLO bearing materials. The sensors were applied successfully for the determination of salicylate anion in Aspocid® and Aspirin®. 相似文献
29.
Dimethyl 1′,1′-ureylenedi(1-ferrocenecarboxylate) (1) formed during the synthesis of 1-amino, 1′-ferrocenecarboxylic acid shows virtual molecular centrosymmetry. Electronic coupling between the two Fc groups through the ureylene bridge results in both Fc groups being individually oxidizable (ΔE1/2?0.14 V). The possible existence of intermolecular electronic communication has discussed. The oxidation was followed by spectroelectrochemistry. The separation between the two halfwave potentials ΔE1/2=137±5 mV and the comproportionation constant Kc=207. 相似文献
30.
al-Ktaifani MM Bauer W Bergsträsser U Breit B Francis MD Heinemann FW Hitchcock PB Mack A Nixon JF Pritzkow H Regitz M Zeller M Zenneck U 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2622-2633
Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light-induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis-[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single-crystal X-ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13. 相似文献