全文获取类型
收费全文 | 460篇 |
免费 | 37篇 |
国内免费 | 1篇 |
专业分类
化学 | 359篇 |
晶体学 | 25篇 |
力学 | 4篇 |
数学 | 52篇 |
物理学 | 58篇 |
出版年
2023年 | 6篇 |
2022年 | 2篇 |
2021年 | 6篇 |
2020年 | 3篇 |
2019年 | 14篇 |
2018年 | 16篇 |
2017年 | 16篇 |
2016年 | 15篇 |
2015年 | 23篇 |
2014年 | 20篇 |
2013年 | 36篇 |
2012年 | 44篇 |
2011年 | 43篇 |
2010年 | 20篇 |
2009年 | 19篇 |
2008年 | 33篇 |
2007年 | 29篇 |
2006年 | 25篇 |
2005年 | 22篇 |
2004年 | 19篇 |
2003年 | 7篇 |
2002年 | 8篇 |
2001年 | 4篇 |
2000年 | 9篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1972年 | 1篇 |
1967年 | 1篇 |
1961年 | 1篇 |
1960年 | 1篇 |
排序方式: 共有498条查询结果,搜索用时 62 毫秒
21.
Dileep Kumar Kian-Eang Neo Malik Abdul Rub Ze Lene Tan Woan Lin Beh Hann Ling Wong 《Journal of Dispersion Science and Technology》2013,34(11):1657-1664
The present work is aimed at studying the interaction between copper-glycyltyrosine [(Cu(II)-Gly-Tyr)]+ and ninhydrin in water and in micelles formed by cetyltrimethylammonium bromide (CTAB) using spectrophometric measurements at 80°C and pH 5.0. The order of reaction remains the same in the two systems, that is, first- and fractional-order kinetics with respect to [Cu(II)-Gly-Tyr]+ and [ninhydrin], respectively, in the excess of ninhydrin over [Cu(II)-Gly-Tyr]+. It was observed that the product formed is same in both the media. The reaction is catalyzed by CTAB, and the maximum rate enhancement is about three fold. Quantitative kinetic analysis of kψ–[CTAB] data was explained in terms of pseudo-phase of the micelles (assuming the association/incorporation of both the reactants at the micellar surface). 相似文献
22.
Kabir-ud-Din Malik Abdul Rub Md. Sayem Alam 《Journal of Dispersion Science and Technology》2013,34(9):1182-1187
Herein we report the micellization and clouding behavior of promethazine hydrochloride (PMT) in absence and presence of NaCl/ureas. The critical micelle concentration (CMC) of PMT is measured by conductivity method and the values decrease with increasing the NaCl concentration. With increasing the temperature, the CMC first increases then decreases. At 25°C, the maximum CMC values were obtained (with or without NaCl). The thermodynamic parameters are evaluated which indicate more stability of the PMT solution in presence of NaCl. PMT shows phase separation also. The cloud point (CP) of PMT decreases with increase in pH due to deprotonation of the drug molecules. Ureas decreased the CP and the behavior is explained on the basis of removal of water from the head group region. 相似文献
23.
Noelia Negreira Isaac Rodríguez Rosario Rodil Elisa Rubí Rafael Cela 《International journal of environmental analytical chemistry》2013,93(11):1174-1188
A low solvent consumption method for the determination of eight ultraviolet (UV) filters, displaying low to medium polarities, in freeze-dried samples of marine bivalves and fish is proposed. Matrix solid-phase dispersion (MSPD) and gas chromatography with mass spectrometry (GC-MS) were used as sample preparation and determination techniques, respectively. This work describes the influence of several parameters (type and amount of dispersant and clean-up sorbents, as well as elution solvent) on the yield and the selectivity of the MSPD extraction. Under optimized conditions, samples (0.5?g) were ground with 2?g of Florisil in a mortar with a pestle and transferred into a polypropylene syringe, which contained 1?g of C18 as clean-up sorbent. Analytes were eluted with 5?mL of acetonitrile. This extract was concentrated to dryness, re-constituted with 1?mL of ethyl acetate and injected in the GC-MS system without any further clean-up. The global average recoveries, measured for three different biota samples, spiked at three different levels (between 50 and 1000?ng?g?1), ranged from 80% to 101% with associated standard deviations below 10%. The inter-day precision of the method varied from 4% to 15% and the achieved LOQs (defined for a signal to noise ratio of 10) ranged from 4 to 28?ng?g?1, referred to the freeze-dried matrix. Octocrylene (OCR) was found in some samples of fish and mussels at concentrations between 15 and 20?ng?g?1, referred to dry mass. 相似文献
24.
Anish Khan Abdullah M. Asiri Aftab Aslam Parwaz Khan Malik Abdul Rub Naved Azum Mohammed M. Rahman Sher Bahadar Khan Khalid A. Alamry Sulaiman Ab Ghani 《Journal of Sol-Gel Science and Technology》2013,65(2):160-169
Nano tetrapod based on conducting polythiophene (PTh) and tin-phosphate (SnP) were synthesized by in situ chemical oxidative polymerization. The morphology of the resulting polythiophene tinphosphate composite was characterized by elemental analysis, fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The physico-chemical characterization carried out on the composite showed that SnP was modified by conducting PTh with an enhancement of various properties. On the basis of highest distribution coefficient values for Hg(II), the composite was also used for the preparation of Hg(II) selective membrane electrode. The electrode showed working concentration range of 1 × 10?1 to 1 × 10?7 with Nernstian slope of 29.29 mV per decade change in concentration and the electrode may be used for wide working pH range of 4–8 having quick response time about 23 s. The life of electrode is 4 months without any notable drift in potential. 相似文献
25.
Dr. Rubén D. Costa Dr. Juan Aragó Prof. Dr. Enrique Ortí Dr. Ted M. Pappenfus Prof. Dr. Kent R. Mann Dr. Katarzyna Matczyszyn Prof. Dr. Marek Samoc Dr. José L. Zafra Prof. Dr. Juan T. López Navarrete Prof. Dr. Juan Casado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1476-1488
The linear and non‐linear optical properties of a family of dumbbell‐shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2′‐bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non‐linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4 , with 3 and 6 thiophene rings, respectively), owing to the presence of the 3π? π* state of the conjugated bridge below the 3MLCT‐emitting states of the end‐capping RuII complexes. In contrast, the compound with the shortest bridge ( 2 , one thiophene ring) shows excellent photophysical features. Non‐linear optical experiments showed that the investigated compounds were strong non‐linear absorbers in wide energy ranges. Indeed, their non‐linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two‐photon absorption (TPA) but also noteworthy three‐photon‐absorption behavior, with a cross‐section value of 4×10?78 cm6 s2 at 1450 nm. This characteristic was complemented by the strong excited‐state absorption (ESA) that was observed for compounds 3 and 4 . As a matter of fact, the overlap between the non‐linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical‐power‐limiting applications. 相似文献
26.
27.
Malik Abdul Rub Dileep Kumar Naved Azum Farah Khan Abdullah M. Asiri 《Journal of solution chemistry》2014,43(5):930-949
In the present paper, the micellization of an amphiphilic drug, promazine hydrochloride, and gemini surfactants (16-s-16) with s = 4–6 and the monomeric hexadecyltrimethylammonium bromide (CTAB) counterparts has been examined conductometrically in the pure and mixed states in aqueous solutions at different compositions and temperatures (298.15–308.15 K). Dicationic gemini surfactants provide much better environment for the micellization behavior than the corresponding monocationic counterpart CTAB. The critical micelle concentration (cmc) values are lower than the cmc for ideal mixing, cmc id, suggesting attractive interactions between the two components in mixed micelles. The micellar mole fractions of surfactants, evaluated by different models, show greater contributions of surfactants in mixed micelles and increase with increasing concentrations of these surfactants. The negative values of β suggest synergism in the mixtures, which is highly beneficial as it reduces the total amount of surfactants required in a particular application, leading to reductions of cost and environmental impact. Activity coefficients (f 1 and f 2) are always less than unity showing nonideality in the systems. The data have been also used for evaluation of thermodynamic parameters. 相似文献
28.
Ricard López-Coll Rubén Álvarez-Yebra Dr. Ferran Feixas Dr. Agustí Lledó 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(39):10099-10106
The conformational equilibria and guest exchange process of a resorcin[4]arene derived self-folding cavitand receptor have been characterized in detail by molecular dynamics simulations (MD) and 1H EXSY NMR experiments. A multi-timescale strategy for exploring the fluxional behaviour of this system has been constructed, exploiting conventional MD and accelerated MD (aMD) techniques. The use of aMD allows the reconstruction of the folding/unfolding process of the receptor by sampling high-energy barrier processes unattainable by conventional MD simulations. We obtained MD trajectories sampling events occurring at different timescales from ns to s: 1) rearrangement of the directional hydrogen bond seam stabilizing the receptor, 2) folding/unfolding of the structure transiting partially open intermediates, and 3) guest departure from different folding stages. Most remarkably, reweighing of the biased aMD simulations provided kinetic barriers that are in very good agreement with those determined experimentally by 1H NMR. These results constitute the first comprehensive characterization of the complex dynamic features of cavitand receptors. Our approach emerges as a valuable rational design tool for synthetic host-guest systems 相似文献
29.
Naved Azum Malik Abdul Rub Abdullah M. Asiri Mohd. Akram 《Russian Journal of Physical Chemistry B, Focus on Physics》2015,9(6):940-945
Aggregation behavior of cationic gemini (hexanediyl-1,5-bis(dimethylcettylammonium bromide) (16-5-16)) surfactant with conventional single chain surfactants cetyltrimethylammonium bromide (CTAB) and tetradecyltrimethylammonium bromide (TTAB) were studied with the help of fluorescence measurements. Fluorescence probe is a proficient technique for examining the surfactant-surfactant interaction and aggregation. The micelle aggregation number (N agg) was measured using steady-state fluorescence quenching method. The micelle aggregation numbers of binary combinations fall between those of constituent surfactants. The micropolarity (I 1/I 3), binding constant (K sv) and dielectric constant (D exp) of mixed systems were determined from the ratio of peaks intensity in the pyrene fluorescence spectrum. The I 1/I 3 values were found to be more than >1, showing more polar environment around pyrene in the mixed micelle as compared to the pure micelles. 相似文献
30.
Cytochrome P450 Catalyzed Oxidative Hydroxylation of Achiral Organic Compounds with Simultaneous Creation of Two Chirality Centers in a Single CH Activation Step 下载免费PDF全文
Dr. Gheorghe‐Doru Roiban Dr. Rubén Agudo Prof. Dr. Manfred T. Reetz 《Angewandte Chemie (International ed. in English)》2014,53(33):8659-8663
Regio‐ and stereoselective oxidative hydroxylation of achiral or chiral organic compounds mediated by synthetic reagents, catalysts, or enzymes generally leads to the formation of one new chiral center that appears in the respective enantiomeric or diastereomeric alcohols. By contrast, when subjecting appropriate achiral compounds to this type of C? H activation, the simultaneous creation of two chiral centers with a defined relative and absolute configuration may result, provided that control of the regio‐, diastereo‐, and enantioselectivity is ensured. The present study demonstrates that such control is possible by using wild type or mutant forms of the monooxygenase cytochrome P450 BM3 as catalysts in the oxidative hydroxylation of methylcyclohexane and seven other monosubstituted cyclohexane derivatives. 相似文献