全文获取类型
收费全文 | 6303篇 |
免费 | 266篇 |
国内免费 | 56篇 |
专业分类
化学 | 4681篇 |
晶体学 | 47篇 |
力学 | 235篇 |
综合类 | 2篇 |
数学 | 856篇 |
物理学 | 804篇 |
出版年
2024年 | 12篇 |
2023年 | 61篇 |
2022年 | 324篇 |
2021年 | 320篇 |
2020年 | 218篇 |
2019年 | 248篇 |
2018年 | 237篇 |
2017年 | 176篇 |
2016年 | 310篇 |
2015年 | 219篇 |
2014年 | 229篇 |
2013年 | 577篇 |
2012年 | 384篇 |
2011年 | 420篇 |
2010年 | 257篇 |
2009年 | 225篇 |
2008年 | 282篇 |
2007年 | 279篇 |
2006年 | 233篇 |
2005年 | 194篇 |
2004年 | 181篇 |
2003年 | 157篇 |
2002年 | 153篇 |
2001年 | 62篇 |
2000年 | 72篇 |
1999年 | 48篇 |
1998年 | 39篇 |
1997年 | 50篇 |
1996年 | 45篇 |
1995年 | 40篇 |
1994年 | 44篇 |
1993年 | 35篇 |
1992年 | 33篇 |
1991年 | 33篇 |
1990年 | 46篇 |
1989年 | 31篇 |
1988年 | 27篇 |
1987年 | 31篇 |
1986年 | 32篇 |
1985年 | 36篇 |
1984年 | 21篇 |
1983年 | 24篇 |
1982年 | 28篇 |
1981年 | 22篇 |
1980年 | 14篇 |
1979年 | 21篇 |
1978年 | 19篇 |
1977年 | 14篇 |
1976年 | 12篇 |
1975年 | 10篇 |
排序方式: 共有6625条查询结果,搜索用时 15 毫秒
111.
Ahmed A. El-Asmy Yehia M. Shaibi Abdallah S. Babaqi Mohamed Mounir Salah A. Ashour 《Transition Metal Chemistry》1988,13(5):332-335
Summary The interaction of 1-benzoin-4-phenylthiosemicarbazone (H2 BPS) with some transition metal ions has been investigated. The ligand can function as a tridentate chelating agent, giving M(HBPS)2 and M(BPS). Potentiometric studies proved that the mechanism of chelation is based on hydrogen ion liberation. Spectral studies in solution show that the ligand could be used for the microdetermination of CuIIions. On the basis of magnetic and spectral data, an octahedral structure is proposed for the CoII and NiII complexes and a square-planar structure for the CuII complex. The corrosion inhibition of aluminium in Cl3CCO2H using H2BPS is studied. The electrical conductivity of H2BPS and of its complexes have been measured. The ligand shows an activation energy in the range of semiconducting materials. The antimicrobial activity of all compounds has also been demonstrated. 相似文献
112.
Tetrabromo-p-benzoquinone reacted with excess aromatic amines to give 2,5-dirylamino-3,6-dibromo-p-benzoquinones. The latter molecules on heating with sodium sulfide in alcohol in the presence of air gave triphenodithiazinediones.
Heating with copper powder in nitrobenzene transformed these compounds into the respective indolocarbazolediones. Comparative
antimicrobial and antifungal activities of the studied compounds were determined and discussed. 相似文献
113.
Mohamed Zaki Barakat Mohamed Fathy Abdel-Wahab 《Monatshefte für Chemie / Chemical Monthly》1961,92(5):1061-1065
Zusammenfassung Die Reaktionen von Natrium-1,2-naphthochino-4-sulfonat mit -Aminosäuren, primären aliphatischen Aminen, Dicarbonsäuren, aliphatischen -Hydroxysäuren und primären Alkoholen werden beschrieben. In allen diesen Fällen reagiert Natrium-1,2-naphtochinon-4-sulfonat als Oxydationsmittel und wird zu dem entsprechenden Diphenol reduziert. 相似文献
114.
The Claisen rearrangement of the N‐protected, silylated allyl glycinates 11 and 12 led to the formation of allyl/silyl‐functionalized amino acids 13 and 14 in yields up to 80%. The diastereoisomer ratio varied from 2 : 1 to 29 : 1 for 11mb , and from 2 : 1 to 46 : 1 (syn/anti) for 12mb , depending on reaction conditions, as shown by X‐ray crystallographic analysis of 14mb . The relationship between the size of the alkyl groups on the chlorosilane reagent (Me2R″SiCl, R″=Cl, Me, t‐Bu, Ph) used as an enolate trap and the observed stereoselectivity was investigated in the case of the Ireland–Claisen variant. Me3SiCl gave the best results. However, the size of the alkyl groups on the silylated ester (Me2R″Si, R=Me, t‐Bu, Ph, i‐Pr) did not exert a significant effect on the diastereoselectivity or yield of the rearrangement. 相似文献
115.
Mohamed A. F. Elmosallamy Mohamed M. Ghoneim Hamada M. A. Killa Amr L. Saber 《Mikrochimica acta》2005,151(1-2):109-113
A potentiometric poly(vinyl chloride) membrane sensor for determination of saccharin is described. It is based on the use of Aliquat 336S-saccharinateion-pair as an electroactive material in plasticized PVC membranes with o-nitrophenyloctylether or dioctylphthalate. The sensor is conditioned for at least two days in 0.1 mol L−1 sodium saccharinate before use. It exhibits fast, stable and Nernstian response for saccharinate ions over the concentration range of 1.0 × 10−1–5.0 × 10−5 mol L−1 and pH range of 4.5–11. The sensor is used for determination of saccharin in some dosage forms. Results with an average recovery of 101% and a mean standard deviation of 0.2% are obtained which is compared favourably with data obtained using the British pharmacopoeia method. The sensor shows reasonable selectivity towards saccharin in presence of many anions and natural sweeteners. 相似文献
116.
A unique approach to non-covalent electron and energy transfer is described that is based on the formation of salt bridges between oppositely charged porphyrin units. A new class of electrostatically linked dimeric and pentameric porphyrins was synthesized by interaction of novel anionic boron containing porphyrins such as 5-(benzamidodecahydro-closo-dodecaborate)-10,15,20-triphenylporphyrin (N1) and meso-tetrakis-benzamidodecahydro-closo-dodecaborate)porphyrin (N2) and a variety of cationic meso-tetraarylporphyrin units. A bipyridine linked dimer (N1 · bpy · N1) was also prepared by employing N,N′-dimethyl-4,4′-bipyridinium (bpy) as a spacer between two mono-anionic species. A quinone-porphyrin dyad was also prepared for electron or energy transfer demonstration. All the synthesized assemblies were characterized by NMR, IR, UV-Vis, and mass spectroscopy. Significant spectral changes occurred in the absorption spectra of these non-covalent porphyrin assemblies compared to those of the reference monomers, indicating the presence of electronic interaction between the adjacent porphyrin units. Resonance light scattering was also used to study the formation of these assemblies in solution. 相似文献
117.
Balkis Al‐Saleh Morsy Ahmed El‐Apasery Rasha Safwat Abdel‐Aziz Mohamed Hilmy Elnagdi 《Journal of heterocyclic chemistry》2005,42(4):563-566
The 3‐anilinoenones 3a,b were prepared from the corresponding 3‐dimemyl‐aminopropenones. The reactivity of 3a,b towards a variety of carbon and nitrogen nucleophiles as well as naphthoquinones is reported. 相似文献
118.
Issam SM Mohamed G Dominique LM Thierry M Farid L Nejib M 《Applied biochemistry and biotechnology》2004,112(2):63-78
The filamentous fungus Sclerotinia sclerotiorum, grown on a xylose medium, was found to excrete one beta-glucosidase (beta-glu x). The enzyme was purified to apparent homogeneity by ammonium sulfate precipitation, gel filtration, anion-exchange chromatography, and high-performance liquid chromatography (HPLC) gel filtration chromatography. Its molecular mass was estimated to be 130 kDa by HPLC gel filtration and 60 kDa by sodium dodecyl sulfate polyacrylamide gel electrophoresis, suggesting that beta-glu x may be a homodimer. For p-nitrophenyl beta-d-glucopyranoside hydrolysis, apparent Km and Vmax values were found to be 0.09 mM and 193 U/mg, respectively, while optimum temperature and pH were 55-60 degrees C and pH 5.0, respectively. beta-Glu x was strongly inhibited by Fe2+ and activated about 35% by Ca2+. beta-Glu x possesses strong transglucosylation activity in comparison with commercially available beta-glucosidases. The production rate of total glucooligosaccharides (GOSs) from 30% cellobiose at 50 degrees C and pH 5.0 for 6 h with 0.6 U/mL of enzyme preparation was 80 g/L. It reached 105 g/L under the same conditions when using cellobiose at 350 g/L (1.023 M). Finally, GOS structure was determined by mass spectrometry and 3C nuclear magnetic resonance spectroscopy. 相似文献
119.
Mohamed Y. El-Sheikh Abdel-Fattah M. Habib Fathy M. Ashmawy Ali H. Gemeay Ahmed B. Zaki 《Transition Metal Chemistry》1989,14(2):95-99
Summary The slow decomposition of H2O2 in the presence of Dowex-50 W resin in the form of an ethylenediaminecopper(II) complex ion in water is accompanied by an induction period. The reaction is first order with respect to [H2O2] and the rate constant (perg of dry resin) was deduced. Autocatalytic behaviour was found for the H2O2 decomposition with 2% crosslinked divinylbenzene. The induction period disappeared and the reaction rate increased when the decomposition was carried out with a resin in the form of a peroxo-copper complex, which proves that the formation of an intermediate (active species) retards the reaction rate. The precursor of the active species, formed during the induction period, was not the amine-copper(II) complex ion but a product of the latter with H2O2. It proved impossible to carry out the decomposition in acid or buffer solutions, in which the resin is regenerated. 相似文献
120.
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