全文获取类型
收费全文 | 843篇 |
免费 | 23篇 |
国内免费 | 4篇 |
专业分类
化学 | 715篇 |
晶体学 | 7篇 |
力学 | 1篇 |
数学 | 60篇 |
物理学 | 87篇 |
出版年
2024年 | 1篇 |
2023年 | 13篇 |
2022年 | 86篇 |
2021年 | 95篇 |
2020年 | 35篇 |
2019年 | 27篇 |
2018年 | 28篇 |
2017年 | 29篇 |
2016年 | 36篇 |
2015年 | 30篇 |
2014年 | 36篇 |
2013年 | 61篇 |
2012年 | 43篇 |
2011年 | 63篇 |
2010年 | 25篇 |
2009年 | 39篇 |
2008年 | 46篇 |
2007年 | 37篇 |
2006年 | 30篇 |
2005年 | 27篇 |
2004年 | 20篇 |
2003年 | 7篇 |
2002年 | 8篇 |
2001年 | 4篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1991年 | 6篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
1963年 | 1篇 |
排序方式: 共有870条查询结果,搜索用时 15 毫秒
1.
Ching Sum Hui Lillian Sze Man Lam Chun Yin Wai Kin Chan Aleksandra B. Djurii 《Journal of polymer science. Part A, Polymer chemistry》2003,41(11):1708-1715
Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge‐transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12–14 Å and 10?3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708–1715, 2003 相似文献
2.
Sek S Tolak A Misicka A Palys B Bilewicz R 《The journal of physical chemistry. B》2005,109(39):18433-18438
Polyalanine derivatives containing cysteamine linker R-(Ala)14NH-(CH2)2-SH, where R is ferrocenecarbonyl or hydrogen, were synthesized and then used to form self-assembled monolayers on gold. The tilt angles and the packing density of the molecules within monolayer assemblies were determined by FTIR spectroscopy and scanning tunneling microscopy, respectively. Electrochemical properties of monolayer-modified electrodes were studied using cyclic voltammetry and impedance spectroscopy. Measurements of electron-transfer rates using electrochemical techniques and scanning tunneling spectroscopy revealed asymmetry dependent on the applied voltage. It is suggested that the observed electron-transfer behavior is connected with the electric field generated by the molecular dipole of the polyalanine helix. 相似文献
3.
A successful application of microwave irradiation, in which phthalocyanines were synthesized under solventless conditions from 1,2-phthalonitrile or phthalic anhydride and urea in the presence of metal templates is described. It was found that in comparison with conventional heating, the microwave process is a very useful alternative for cyclotetramerization processes because of reduction of the reaction time, better yield, and easy-to-perform procedure. 相似文献
4.
Korolczuk M Moroziewicz A Grabarczyk M 《Analytical and bioanalytical chemistry》2005,382(7):1678-1682
Procedures for trace cobalt determinations by adsorptive stripping voltammetry at in situ and ex situ plated bismuth film electrodes are presented. These exploit the enhancement of the cobalt peak obtained by using the Co(II)–dimethylglyoxime–cetyltrimethylammonium bromide–piperazine-N,N-bis(2-ethanesulfonic acid) system. The calibration graph for an accumulation time of 120 s was linear from 2 × 10–10 to 2 × 10–8 mol L–1. The relative standard deviation from five determinations of cobalt at a concentration of 5 × 10–9 mol L–1 was 5.2%. The detection limit for an accumulation time of 300 s was 1.8 × 10–11 mol L–1. The proposed procedure was applied to cobalt determination in certified reference materials and in tap and river water samples. 相似文献
5.
Aleksandra Gasperowicz Wodzimierz askawski 《Journal of polymer science. Part A, Polymer chemistry》1976,14(12):2875-2886
The grafting of styrene onto low molecular weight polybutadienes and butadiene–styrene co-polymers was studied. A mathematical method was used for the design of experiments and for the determination of the optimum grafting conditions with respect to the conversion of styrene and the efficiency of grafting. The reaction parameters were temperature (65–105°C), time (2–10 hr), concentration of the initiator, polymer to monomer ratio (10/90–90/10) and dilution by solvent (toluene). The optimum grafting conditions were chosen under which 50–60 wt-% of styrene was grafted onto backbone polymer at a high conversion of the monomer. It was found that the reactions producing graft copolymer prevailed over the styrene homopolymerization when the temperatures employed were lower (65–85°C), and the reaction time (8–10 hr), backbone polymer/monomer ratio, and the dilution by solvent were higher. The efficiency, density, and degree of grafting were found to increase with the increase in the molecular weight of the backbone polymer. The efficiencies and densities of grafting onto low molecular weight polybutedienes were higher than those of grafting onto low molecular weight butadiene–styrene copolymers. Grafting efficiencies and grafting densities were in the ranges 37.8–61.6 wt % and 0.06–0.26, respectively, in the studied range of number-average molecular weights (M?n = 2400–6000). 相似文献
6.
Dagmara Jacewicz Agnieszka Łapińska Aleksandra Dąbrowska Lech Chmurzyński 《Transition Metal Chemistry》2006,31(1):111-117
The kinetics of the reaction between gaseous CO2 and the cis-[Cr(phen)2(OH2)2]3+ ion leading to the formation of the carbonato complex ion, have been studied over the pH and temperature ranges: 3 < pH <
6 and 5 < T < 25 °C, respectively, at a constant ionic strength of 1 m (NaClO4). Investigations were carried out using the stopped-flow spectrophotometry technique in the UV–Vis range: 340–700 nm. The
major reactant species in the pH range studied was cis-[Cr(phen)2(OH)(OH2)]2+ ion, which underwent reaction with CO2 to form cis-[Cr(phen)2(OH2)(HCO3)]2+ ion. Subsequently, slower ring closure of the latter species to form the bidentate carbonato chelate was observed. The possible
mechanism has been discussed and the activation parameters ΔH† and ΔS† were also determined for the reaction studied. 相似文献
7.
Snezana S.?MiticEmail author Gordana Z.?Miletic Aleksandra N.?Pavlovic Snezana B.?Tosic 《Monatshefte für Chemie / Chemical Monthly》2004,135(8):927-936
Summary. A new selective, sensitive, and simple kinetic method is developed for the determination of trace amounts of chromium (VI). The method is based on the catalytic effect of Cr(VI) on the reaction of sodium pyrogallol-5-sulphonate (PS) with hydrogen peroxide. The reaction is followed spectrophotometrically by tracing the oxidation product at 437nm within 1min after addition of H2O2. The optimum reaction conditions are PS (1.32·10–3mol·dm–3), H2O2 (0.32mol·dm–3), HClO4 (2.6·10–3mol·dm–3) at 25°C. Following this procedure, chromium (VI) can be determined with a linear calibration graph up to 0.25ng·cm–3 and a detection limit of 0.024ng·cm–3, based on the 3 criterion. The interference effect of several species was also investigated and it was found that the most common cations and anions do not interfere with the determination. The developed procedure was successfully applied to the determination of Cr(VI) and total Cr in river waters and total Cr in herbal samples. 相似文献
8.
Aleksandra Drzewiecka Krystyna Stepniak Anna Barcicka Anna E. Koziol 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(8):m346-m348
The asymmetric unit in the title compound, {[Cd2(C4H4O6)(SO4)(H2O)5]·3H2O}n, is composed of two cadmium cations, one (R,R)‐tartrate and one sulfate anion, five aqua ligands and three solvent water molecules. One of the cadmium ions is coordinated in an octahedral environment, whereas the second is surrounded by seven O atoms in a pentagonal–bipyramidal geometry. Both types of coordination polyhedra form two sets of perpendicular non‐intersecting polymeric chains. CdO6 octahedra share two corners, while CdO7 units are joined by a bridging carboxylate group. An extensive hydrogen‐bond pattern involving all of the OH groups contributes to the stabilization of the structure. 相似文献
9.
Nesković OM Veljković MV Velicković SR Petkovska LT Perić-Grujić AA 《Rapid communications in mass spectrometry : RCM》2003,17(3):212-214
Ionization energies of hypervalent Li(2)F, Li(2)Cl and Na(2)Cl molecules detected by surface ionization electron impact neutralization mass spectrometry are reported. The ionization energies were 3.78 +/- 0.2 eV for Li(2)F, 4.93 +/- 0.2 eV for Li(2)Cl, and 4.21 +/- 0.2 eV for Na(2)Cl. The ionization energies (IE) agree with theoretical ionization energies calculated by ab initio methods, supporting the theoretical prediction that Li(2)F has a hyperlithiated configuration in which the odd electron delocalizes over the two lithiums and with photoionization measurement. The first ionization energy of Na(2)Cl was experimentally confirmed earlier and for Li(2)Cl as well.8 We have developed and used this new approach for the problem--in the present work ions were first formed by surface ionization, followed by electron attachment (neutralization). 相似文献
10.
Frontera A Saczewski F Gdaniec M Dziemidowicz-Borys E Kurland A Deyà PM Quiñonero D Garau C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6560-6567
Several structures of pi complexes of isocyanuric acid and of several thio derivatives with anions have been computed by using high level ab initio calculations. The nature of the complexes has been studied by means of the method of molecular interaction potential with polarization (MIPp) and Bader's theory of atoms-in-molecules. These molecules form favorable complexes with anions and can be used as binding units for building receptors for the molecular recognition of anions. In several cases, the anion-pi interaction has been demonstrated experimentally by means of X-ray crystallography. 相似文献