全文获取类型
收费全文 | 3272篇 |
免费 | 141篇 |
国内免费 | 35篇 |
专业分类
化学 | 1882篇 |
晶体学 | 67篇 |
力学 | 139篇 |
综合类 | 1篇 |
数学 | 659篇 |
物理学 | 700篇 |
出版年
2023年 | 30篇 |
2022年 | 48篇 |
2021年 | 69篇 |
2020年 | 80篇 |
2019年 | 96篇 |
2018年 | 135篇 |
2017年 | 129篇 |
2016年 | 175篇 |
2015年 | 112篇 |
2014年 | 172篇 |
2013年 | 403篇 |
2012年 | 239篇 |
2011年 | 217篇 |
2010年 | 192篇 |
2009年 | 134篇 |
2008年 | 209篇 |
2007年 | 189篇 |
2006年 | 132篇 |
2005年 | 98篇 |
2004年 | 103篇 |
2003年 | 72篇 |
2002年 | 55篇 |
2001年 | 29篇 |
2000年 | 42篇 |
1999年 | 21篇 |
1998年 | 26篇 |
1997年 | 27篇 |
1996年 | 31篇 |
1995年 | 19篇 |
1994年 | 18篇 |
1993年 | 9篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 14篇 |
1982年 | 7篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1976年 | 5篇 |
1975年 | 6篇 |
1974年 | 4篇 |
1972年 | 4篇 |
1970年 | 3篇 |
排序方式: 共有3448条查询结果,搜索用时 15 毫秒
81.
Riadi Y Abrouki Y Mamouni R El Haddad M Routier S Guillaumet G Lazar S 《Chemistry Central journal》2012,6(1):60
ABSTRACT: Two efficient reactions were successfully carried out using Animal Bone Meal (ABM) and potassium fluoride or sodium nitrate doped ABMs as new heterogeneous catalysts under very mild conditions. After preparation and characterization of the catalysts, we first report their use in a simple and convenient synthesis of various chalcones by Claisen-Schmidt condensation and then in an aza-Michael addition involving several synthesized chalcones with aromatic amines. All the reactions were carried out at room temperature in methanol; the chalcone synthesis was also achieved in water environment under microwave irradiation. Doping ABM enhances the rate and yield at each reaction. Catalytic activities are discussed and the ability to re-use the ABM is demonstrated. RESULTS: For Claisen-Schmidt the use of ABM alone, yields never exceeded 17%. In each entry, KF/ABM and NaNO3/ABM (79-97%) gave higher yields than using ABM alone under thermic condition. Also the reaction proceeded under microwave irradiation in good yields (72-94% for KF/ABM and 81-97% for NaNO3/ABM) and high purity. For aza-Michael addition the use of ABM doped with KF or NaNO3 increased the catalytic activity remarkably. The very high yields could be noted (84-95% for KF/ABM and 81-94% for NaNO3/ABM). CONCLUSION: The present method is an efficient and selective procedure for the synthesis of chalcones anaaza-Michael adducts. The ABM and doped ABMs are a new, inexpensive and attractive solid supports which can contribute to the development of catalytic processes and reduced environmental problems. 相似文献
82.
83.
Gülhan Turan-Zitouni Ahmet Özdemir Zafer Asim Kaplancikli Pierre Chevallet Yagmur Tunali 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):2717-2724
The increasing clinical importance of drug-resistant fungal and bacterial pathogens has lent additional urgency to microbiological research and new antimicrobial compound development. For this purpose, new pyrazoline derivatives were synthesized and evaluated for antimicrobial activity. Some 1-[(N, N-disubstitutedthiocarbamoylthio)acetyl]-3,5-diaryl-2-pyrazolines derivatives were synthesized by reacting 1-(chloroacetyl)-3,5-diaryl-2-pyrazolines with appropriate potassium salts of secondary amine dithiocarbamic acids. The chemical structures of the compounds were elucidated by IR, 1 H-NMR, and FAB+-MS spectral data. Their antimicrobial activities against Staphylococcus aureus (B-767), Escherichia coli (B-3704), Pseudomonas aeruginosa (ATCC 27853), Proteus vulgaris (NRLL B-123), and Candida albicans (NRRL-27077) were investigated. The results showed that some of the compounds have notable activity against S. aureus and C. albicans. 相似文献
84.
Acrylamide based monomer, 5-methyl-2-thiozyl methacrylamide (MTMAAm) was synthesized by the reaction of 2-Amino-5-methyl thiazole with methacryloyl chloride in the presence of triethylamine(NR3) at 0–5°C. The monomer MTMAAm was characterized by FT-IR and 1H-and 13C-NMR spectral studies. A new chelating resin, poly(5-methyl-2-thiozyl methacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid-co-divinylbenzene) [MTMAAm/AMPS/DVB] was synthesized. This resin was characterized by FT-IR. In order to determine the adsorption behavior of chelating resin, the adsorption isotherm of Cr(III) and Cu(II) were studied. It was found that the adsorption isotherm of the ions fitted with Langmuir-type isotherms. From the Langmuir equation, the adsorption capacity of chelating resin for Cr(III) and Cu(II) was found to be 7.77 mg g? 1 and 4.27 mg g? 1, respectively. Binding equilibrium constant was calculated to be 0.155 L mg? 1 and 0.106 L mg? 1 for Cu(II) and Cr(III), respectively. 相似文献
85.
The transport of Hg (II) ions from an aqueous solution into an aqueous receiving solution through bulk and supported liquid membranes containing a calix[4]arene derivative 1 as a carrier was examined. The kinetic parameters of bulk liquid membrane studies were analyzed assuming two consecutive, irreversible first‐order reactions. The influence of temperature, stirring rate, carrier concentration and solvent on the kinetic parameters (k1, k2, Rm max, tmax, Jd max, Ja max) has also been investigated. The membrane entrance rate, k1, and the membrane exit rate, k2, increased with increasing temperature and stirring rate. The activation energy values are calculated as 4.87 and 48.63 kj mol?1 for extraction and reextraction, respectively. The values of calculated activation energy indicate that the process is diffusionally controlled by species. Also, the transport behavior of Hg2+ from aqueous solution through a flat‐sheet supported liquid membrane has been investigated by the use of calix[4]arene derivative 1 as carrier and Celgard 2500 as the solid support. A Danesi mass transfer model was used to calculate the permeability coefficients for each parameter studied. The highest values of permeability were obtained with 2‐nitrophenyloctyl‐ether (NPOE) solvent and the influence was found to be in the order of NPOE>chloroform>xylene. 相似文献
86.
The article describes the syntheses and extraction properties of two p‐tert‐butylcalix[6]arene nitrile derivatives (3 and 4). The trinitrile derivative 3 has been synthesized from 5,11,17,23,29,35‐hexa‐tert‐butyl‐37,38,39,40,41,42‐hexahydroxycalix[6]arene 1. The compound 1 was directly converted to its hexanitrile derivative 4. In these syntheses, it was thought to explore the role of nitrile sites in the extraction of various metal cations and HCr2O7 ?/Cr2O7 2? anions. The liquid‐liquid extraction properties of 3 and 4 towards selected alkali/transition metal cations and HCr2O7 ?/Cr2O7 2? anions are reported. It has been observed that receptor 3 does not extract alkali/transition metal cations effectively, but shows affinity towards HCr2O7 ?/Cr2O7 2? anions at low pH. The compound 4 is an effective form for transferring Ni2+ selectively, while it shows poor transferring ability for HCr2O7 ?/Cr2O7 2? anions from an aqueous into a dichloromethane layer. It was observed that the cavity size of the calix[n]arenes and the cooperativity of the functionalities play important roles in two phase extraction systems. 相似文献
87.
Electrically conductive composite systems based on polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA) filled with metal powders of Al and Cu have been studied. The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer matrix. Dependence of the dielectric and conductivity properties of the PVC and PMMA/fillers was studied over a broad range of frequency and volume fraction of metal fillers. The experimental results could be explained by means of the conductivity of fillers and the interface polarization between polymers and fillers. Percolation was also seen in this study when the volume fraction of conducting fillers was close to critical value, in which the composites undergo an insulator‐conductor transition. The relation among the dielectric property and the fillers with different conductivity was proposed. 相似文献
88.
Conductive polythiophene (PTh)/poly(ethylene terephthalate) (PET) composite fibers were prepared by polymerization of thiophene in the presence of PET fibers in acetonitrile medium using FeCl3. The effects of polymerization conditions such as oxidant/monomer mol ratio and polymerization temperature and time on PTh content and surface electrical resistivity of PTh/PET composite fiber were investigated in detail. It was observed that the usage of preswelled PET fibers in dichloromethane increased the PTh content and decreased surface resistivity of composite fiber. Composite fiber having the highest PTh content (5.7%) and the lowest surface resistivity (80 kΩ) was obtained at 20°C with 1.25 M FeCl3 and 0.42 M thiophene concentrations. The washing effects of laundering detergent and dry cleaning liquid on surface resistivity of composite fibers were investigated. The electromagnetic shielding effectiveness (EMSE) and relative shielding efficiency by absorption and reflection of composite fibers were measured in the radio and microwave frequency range. The results show that the EMSE values decreased with increasing frequency from radio waves to microwaves with an attenuation of 21 dB to 4 dB. 相似文献
89.
Sonochemical synthesis and electrochemical characterization of α-nickel hydroxide: precursor effects
F. Sinem Ertaş Recep Kaş Uğur Ünal Özgür Birer 《Journal of Solid State Electrochemistry》2013,17(5):1455-1462
Sonochemical degradation of urea was employed to synthesize alpha-nickel hydroxide from different nickel salts. Utilization of ultrasound yielded products with properties significantly different than the products obtained by thermal degradation of urea. The effect of intercalating chloride, nitrate, acetate, and sulfate anions on morphology and electrochemical performance was studied. The sulfate-intercalated sample had the smallest interlayer spacing when obtained by the sonochemical method, contradicting all the previous thermal synthesis results. The specific capacitance trend also differed from the literature values, and the value for the sulfate-intercalated sample was larger than that of acetate- and nitrate-intercalated samples. Ultrasonic synthesis increased the specific capacitance of the sulfate-intercalated sample significantly. This sample was also the most reversible and had the highest charge efficiency. 相似文献
90.
Deniz Altunöz-Erdoğan Nevin Erk Esma Kılıç 《Central European Journal of Chemistry》2013,11(5):706-716
Reboxetine (RBX) electrochemical redox behavior at hanging mercury drop (HMDE) and glassy carbon electrodes (GCE) was studied in various pH Britton-Robinson universal buffers using cyclic voltammetry and square-wave voltammetry. RBX was reduced at the HMDE and oxidized at the GCE with reversible adsorption controlled and irreversible diffusion controlled processes respectively. The anodic peak is due to the amine and the cathodic peak may correspond to oxygen protonation. An oxidation reaction mechanism is proposed. The linear relation between peak currents and RBX concentration allowed simple, sensitive, precise and inexpensive voltammetric procedures to be developed. The limit of detection was 0.04 µM RBX. The procedures were successfully applied to human urine and RBX tablet assay. Therapeutic RBX concentrations in human serum were not detected due to strong drug-protein binding. Using bovine serum albumin, the methods were used to investigate the effect of serum protein binding on RBX determination. 相似文献