全文获取类型
收费全文 | 361篇 |
免费 | 22篇 |
国内免费 | 3篇 |
专业分类
化学 | 282篇 |
晶体学 | 8篇 |
力学 | 2篇 |
数学 | 16篇 |
物理学 | 78篇 |
出版年
2024年 | 2篇 |
2023年 | 3篇 |
2022年 | 10篇 |
2021年 | 7篇 |
2020年 | 8篇 |
2019年 | 12篇 |
2018年 | 10篇 |
2017年 | 11篇 |
2016年 | 16篇 |
2015年 | 18篇 |
2014年 | 24篇 |
2013年 | 40篇 |
2012年 | 35篇 |
2011年 | 29篇 |
2010年 | 18篇 |
2009年 | 19篇 |
2008年 | 17篇 |
2007年 | 12篇 |
2006年 | 8篇 |
2005年 | 10篇 |
2004年 | 9篇 |
2003年 | 6篇 |
2002年 | 15篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1992年 | 5篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1984年 | 2篇 |
1982年 | 1篇 |
排序方式: 共有386条查询结果,搜索用时 15 毫秒
61.
A near‐IR spectral study on pure water and aqueous salt solutions is used to investigate stoichiometric concentrations of different types of hydrogen‐bonded water species in liquid water and in water comprising the hydration shell of salts. Analysis of the thermodynamics of hydrogen‐bond formation signifies that hydrogen‐bond making and breaking processes are dominated by enthalpy with non‐negligible heat capacity effects, as revealed by the temperature dependence of standard molar enthalpies of hydrogen‐bond formation and from analysis of the linear enthalpy–entropy compensation effects. A generalized method is proposed for the simultaneous calculation of the spectrum of water in the hydration shell and hydration number of solutes. Resolved spectra of water in the hydration shell of different salts clearly differentiate hydrogen bonding of water in the hydration shell around cations and anions. A comparison of resolved liquid water spectra and resolved hydration‐shell spectra of ions highlights that the ordering of absorption frequencies of different kinds of hydrogen‐bonded water species is also preserved in the bound state with significant changes in band position, band width, and band intensity because of the polarization of water molecules in the vicinity of ions. 相似文献
62.
Lobana Tarlok S. Paul Seema Hundal Geeta Obrai Sangeeta 《Transition Metal Chemistry》1999,24(2):202-205
Reaction of 1-hydroxypyridine-2-thione (HpyOS) in CHCl3 with Ag2CO3 suspended in CHCl3 under magnetic stirring followed by addition of PPh3 yields a product of stoichiometry: Ag(pyOS)(PPh3). The compound adopts a dimeric structure [Ag(pyOS)(PPh3)]2 (1) where each Ag atom acquires a distorted tetrahedral geometry by co-ordinating to one oxygen, two sulphur and one phosphorus atoms. The Ag2S2 core forms a parallelogram [Ag—S 2.507(1), 2.822(1)Å] with Ag—S—Ag and S—Ag—S angles of 74.8(1) and 105.2(1)°, respectively. 相似文献
63.
Reactions of InCl3 with potassium salts of bifunctional tridentate (L1H2HOC6H4CH NCH2CHMeOH) and monofunctional bidentate (L2HHOC6H4CHN-i-Bu) Schiff bases in 1:1 and 1:2 molar ratio in benzene afford complexes In(L1)Cl and In(L2)2Cl, respectively. On reaction with potassium isopropoxymetallates KB(O-i-Pr)4, KAl(O-i-Pr)4, KTi(O-i-Pr)5, and KNb(O-i-Pr)6, they produce interes- ting heterobimetallic heterocyclic complexes. These are characterized by elemental (N, B, Al, Ti, and Nb) analyses, molecular weight measurements, and spectral [IR, NMR (1H, 13C, 11B, and 27Al)] studies. Probable structures are suggested for them. © 2003 Wiley Periodicals, Inc. 15:21–25, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10206 相似文献
64.
The oxidation of lower oxyacids of phosphorus by hexamethylenetetramine bromine (HABR) in glacial acetic acid resulted in the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibited 2:1 stoichiometry. The reaction is first order with respect to HABR. Michaelis–Menten‐type kinetics were observed with respect to the acids. The formation constant of the phenylphosphinic acid–HABR complex also has been determined spectrophotometrically. The thermodynamic parameters for the complex formation and the activation parameters for their decomposition were calculated. The reaction showed the presence of a substantial kinetic isotope effect. It is proposed that the HABR itself is the reactive oxidizing species. It has been shown that the pentacoordinated tautomer of the phosphorus oxyacid is the reactive reductant. A suitable mechanism has been proposed. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 165–170, 2000 相似文献
65.
The kinetics of oxidation of four vicinal diols, four nonvicinal diols, and one of their monoethers by pyridinium bromochromate (PBC) have been studied in dimethyl sulfoxide. The main product of oxidation is the corresponding hydroxyaldehyde. The reaction is first-order with respect to each the diol and PBC. The reaction is acid-catalyzed and the acid dependence has the form: kobs=a+b[H+]. The oxidation of [1,1,2,2-2H4]ethanediol exhibited a primary kinetic isotope effect (kH/k D=6.70 at 298 K). The reaction has been studied in 19 organic solvents including dimethyl sulfoxide and the solvent effect has been analyzed using multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 285–290, 1998. 相似文献
66.
Rodrigues LM Sivasubramanian A Pinto EM Oliveira-Campos AM Seijas JA Vázquez-Tato MP 《Magnetic resonance in chemistry : MRC》2009,47(1):84-86
A series of 21 substituted pyrazolo[3,4-d]pyrimidines-4-amines were studied by (1)H and (13)C NMR. The application of two-dimensional techniques, HMQC and HMBC, allowed the complete assignment of the spectra for all the compounds. 相似文献
67.
Bioassay‐guided Isolation and Antioxidant Activity of Sulfur‐containing Compounds from Clinacanthus nutans
下载免费PDF全文
![点击此处可从《中国化学会会志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hazrulrizawati Abd Hamid Izzah Hayati Yahya Mashitah M. Yusoff Seema Zareen 《中国化学会会志》2016,63(12):1033-1037
Clinacanthus nutans has been used in traditional herbal medicine for cancer prevention, but the specific bioactive compounds responsible for the observed activities have not been explored. Different polar solvents such as methanol, chloroform, ethyl acetate, and hexane were used for the extraction. The extracts, fractions, and isolated compounds were subjected to DPPH and ferric reducing antioxidant potential (FRAP) assays. Methanol extracts show significant free‐radical scavenging activity of 69.09% in DPPH and 56.49% FRAP. Purification of MeOH extracts afforded the fraction FB28 and two new sulfur‐containing compounds, named clinamide D and E ( 1 , 2 ). Compound ( 1 ) proved to be more active with an IC50 value for DPPH radical scavenging of 118.27 ± 0.01 µg/mL and reduction of Fe3+–TPTZ complex of 386.24 ± 0.02, higher than that of the standard ascorbic acid. Sulfur‐containing compounds isolated from C. nutans is a potential natural antioxidant. 相似文献
68.
Aravind Kumar Rengan Gopal Kundu Rinti Banerjee Rohit Srivastava 《Particle & Particle Systems Characterization》2014,31(3):398-405
Numerous gold nanostructures have the potential for photothermal therapy in cancers. Here, gold nanocages and gold nanoshells are synthesized, the sizes of which are fine‐tuned for a response at 750 nm wavelength. Their photothermal therapeutic efficiency is compared at gold concentration of 100 lg mL?1 using a near‐infrared laser (750 nm). The biocompatibility for varying concentrations of gold (1 to 100 lg mL?1) is performed in a normal cell line and laser‐mediated cell cytotoxicity for varying time intervals (7.5 and 10 min) is carried out in breast cancer cells. This study shows that when analyzed under similar conditions, the gold nanocages show better biocompatibility and are more efficient in near‐infrared absorption and photothermal conversion in comparison with conventional gold nanoshells. When subjected to photothermal laser ablation of breast cancer cell line for 7.5 min and 10 min, the nanocages are able to induce 62.92 ± 3.25% and 96.41 ± 3.04% reduction in cell viability, respectively, in comparison to nanoshells, in which a 43.35 ± 1.91% and 79.89 ± 4.74% reduction in cell viability is observed. The current study shows that the gold nanocages can outperform gold nanoshells and effectively kill cancer cells without any significant cytotoxic effect on normal cells. 相似文献
69.
Arun Aravind K. Hasna M. K. Jayaraj Mukesh Kumar Ramesh Chandra 《Applied Physics A: Materials Science & Processing》2014,115(3):843-849
Phase pure Zn1?x Co x O thin films grown by pulsed laser deposition have transmittance greater than 75 % in the visible region. Raman studies confirm the crystalline nature of Zn1?x Co x O thin films. Zn0.95Co0.05O thin films show room temperature ferromagnetism with saturation magnetization of 0.4μ B /Co atom. The possible origin of paramagnetism at higher Co doping concentrations can be attributed to the increased nearest-neighbor antiferromagnetic interactions between Co2+ ions in ZnO matrix. XPS confirms the substitution of Co2+ ions into the ZnO host lattice. 相似文献
70.
P. M. Aneesh M. R. Shijeesh Arun Aravind M. K. Jayaraj 《Applied Physics A: Materials Science & Processing》2014,116(3):1085-1089
In this paper we report the synthesis of highly luminescent ZnS and Mn-doped ZnS nanoparticles with uniform particle size distribution by liquid phase pulsed laser ablation. The formation of nanosized ZnS crystallites was confirmed by high-resolution transmission electron microscopy (HRTEM) images. The optical properties of these nanoparticles were studied by room temperature photoluminescence (PL) spectra. The PL emission from the ZnS nanoparticles shows a sharp peak in the UV region (334 nm) corresponding to the band edge and a broad peak in the visible region which can be attributed to the sulphur vacancies, cation vacancies and surface states in the nanocrystals. The yellow emission from the Mn-doped ZnS nanoparticles can be attributed to the radiative transition between 4T1 and 6A1 levels within the 3d5 orbital of Mn2+. 相似文献