全文获取类型
收费全文 | 423篇 |
免费 | 10篇 |
专业分类
化学 | 361篇 |
晶体学 | 2篇 |
力学 | 4篇 |
数学 | 30篇 |
物理学 | 36篇 |
出版年
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 13篇 |
2020年 | 7篇 |
2019年 | 9篇 |
2018年 | 8篇 |
2017年 | 10篇 |
2016年 | 14篇 |
2015年 | 10篇 |
2014年 | 12篇 |
2013年 | 19篇 |
2012年 | 23篇 |
2011年 | 27篇 |
2010年 | 15篇 |
2009年 | 12篇 |
2008年 | 27篇 |
2007年 | 21篇 |
2006年 | 30篇 |
2005年 | 18篇 |
2004年 | 26篇 |
2003年 | 18篇 |
2002年 | 12篇 |
2001年 | 11篇 |
2000年 | 4篇 |
1999年 | 7篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1962年 | 1篇 |
1961年 | 2篇 |
1958年 | 1篇 |
排序方式: 共有433条查询结果,搜索用时 19 毫秒
101.
A new Schiff base (SCH) was prepared using 8‐acetyl‐7‐hydroxy‐4‐methylcoumarin and sulfaclozine. Its silver complex was also synthesized. These compounds were subjected to elemental and spectral analyses. The silver complex was also subjected to thermogravimetric analysis, molar conductance measurements, scanning electron microscopy, energy‐dispersive X‐ray analysis and X‐ray diffraction measurements. The formula of the complex was determined as [(Ag2SCH(NO3)2]. The molar conductance indicates its non‐electrolyte character. The electronic structure and nonlinear optical parameters of SCH and its complex were investigated theoretically at the B3LYP/GENECP level. The geometry of the studied complex is non‐planar as indicated from the dihedral angles between central Ag metal ion and coordinated centres of SCH. Density functional theory calculations were also carried out to calculate the global properties of hardness, global softness and electronegativity. The calculated energy gap between HOMO and LUMO energies shows that charge transfer occurs within the studied complex. The total static dipole moment, the mean polarizability, the anisotropy of the polarizability and the mean first‐order hyperpolarizability were calculated and compared with those of urea as a reference material. The results of the mean first‐order hyperpolarizability showed that SCH and its silver complex are excellent candidates as nonlinear optical materials. The compounds were screened for their antimicrobial effect against various species of bacteria and fungi. Their anticancer activities were evaluated in vitro against the human cancer cell line MCF‐7 (human breast adenocarcinoma). 相似文献
102.
Haizarul Aida Sapahin Ahmad Makahleh Bahruddin Saad 《Arabian Journal of Chemistry》2019,12(8):1934-1944
An adequate and simple analytical method based on solid-phase microextraction (SPME) followed by gas chromatography–flame photometric detection (GC–FPD) for the determination of eleven organophosphorus pesticide residues (i.e., ethoprophos, sulfotep, diazinon, tolclofos-methyl, fenitrothion, chlorpyrifos, isofenphos, methidathion, ethion, triazophos, leptophos) in vegetables samples (cabbage, kale and mustard) was developed. Important parameters that influence the extraction efficiency (i.e., fibre type, extraction modes, extraction time, salt addition, desorption time and temperature) were systematically investigated. Four types of commercially available fibres (i.e., 50/30 μm divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS), 65 μm polydimethylsiloxane/divinylbenzene (PDMS/DVB), 100 μm polydimethylsiloxane (PDMS), and 85 μm polyacrylate (PA)) were evaluated. PA fibre exhibited the best performance and was used for the rest of the studies. The optimised extraction conditions were: extraction time, 30 min at room temperature; stirring speed, 1275 rpm; salt content, 10% NaCl; desorption time and temperature, 11 min at 260 °C; and no pH adjustment of the sample extract. The method was validated over the range 0.1–100 μg/L. Repeatabilities were satisfactory, ranging between 2.44% and 17.9% for all analytes. The limits of detection and quantitation ranged from 0.01 to 0.14 and 0.03 to 0.42 μg/L, respectively. The method was applied to twenty local vegetable (cabbage, kale and mustard) products. Chlorpyrifos (0.22–1.68 μg/kg) was the most detected pesticide in the tested samples. The obtained values are however lower than the Maximum Residue Limits (MRLs) as stipulated in the Food Act & Regulations of Malaysia. 相似文献
103.
104.
Aida Raauf Johannes Schläfer Isabel Gessner Andreas Lichtenberg Markus Zegke Thomas Fischer Sanjay Mathur 《印度化学会志》2022,99(3):100347
Bimetallic iron-lanthanide alkoxides were synthesized by reacting [Ln{N(SiMe3)2}3] (Ln ?= ?Pr, Nd, Er) with [Fe2(OtBu)6] in excess tert-butyl alcohol that triggered in-situ ligand exchange and Lewis acid-base interactions to form heterometallic compounds. Single crystal X-ray diffraction analyses of new compounds demonstrated that both Nd and Er containing compounds resulted in the formation of a hetero-bimetallic framework based on 1:1 Ln:Fe ratio, whereas higher Fe ratio (1:2) was observed when Pr was used as the rare earth metal, possibly due to its larger ionic radius (Pr(III): 0.99 ?Å). When the reaction was performed in the presence of chelating ligands (L: H-tfb-mea ?= ?N-(4,4,4-trifluorobut-1-en-3-on)-methoxyethyleneamine; H2-tfb-en ?= ?N–N′-bis-(4,4,4-trifluorobut-1-en-3-on)-ethylenediamine), heteroleptic Ln-Fe derivatives were formed that were used in a representative case ([NdFe(L)(OtBu)m(HOtBu)]) as efficient precursor to synthesize nanocrystalline NdFeO3 ceramic. 相似文献
105.
Zinc oxide (ZnO) thin films deposited by DC magnetron sputtering were annealed in nitrogen atmosphere at different temperatures ranging from 100 to 500 °C with a step of 100 °C; the annealing time was 6 h. In order to study the film’s crystallization kinetic, their structures were monitored by means of X-ray diffraction (XRD) analysis each hour. Variation in grain size, calculated from the XRD patterns, with annealing time and temperature, obeys the classical parabolic law of grain growth. Exponent n was found to be dependent on the annealing temperature; it ranged from 5.13 to 3.8 with increase in annealing temperature. From the obtained exponent n values we inferred that the grain growth mechanism is mainly governed by the atom jumping across the grain boundary. We have found that the grain growth is characterized by a low activation energy ranging from 22 to 24 kJ/mol. 相似文献
106.
We perform a molecular dynamics simulation for CO2 + ketone mixtures to study the molecular motility and elucidate how CO2 molecules are dissolved in a mixture. The self-diffusion coefficients increase with increasing CO2 mole fraction (xCO2) and decreased with increasing molecular weight. These results mean that the mobility of molecules depends on the molecular size. To study molecular aggregation around CO2 molecules, radial distribution functions (RDFs) and the distance from neighboring molecules to CO2 molecules were calculated. The RDFs indicate that the CO2 molecule exists near the carbonyl oxygen atom. Because of the distance of the neighboring molecule from the CO2 molecule, the CO2 molecule is less likely to exist around a branched alkyl ketone than a normal alkyl ketone. 相似文献
107.
Ashraf Ghanem Mohammed Nabil Aboul-Enein Aida El-Azzouny Mohammed F. El-Behairy 《Journal of chromatography. A》2010,1217(7):1063-1074
The enantioselective resolution of a set of racemic acidic compounds such as non-steroidal anti-inflammatory drugs (NSAIDs) of the group arylpropionic acid derivatives is demonstrated. Thus, a set of lipases were screened and manipulated in either the esterification or hydrolysis mode for the enantioselective kinetic resolution of these racemates in non-standard organic solvents. The accurate determination of the enantiomeric excesses of both substrate and product during such reaction is demonstrated. This was based on the development of a direct and reliable enantioselective high performance liquid chromatography (HPLC) procedure for the simultaneous baseline separation of both substrate and product in one run without derivatization. This was achieved using the immobilized chiral stationary phase namely Chiralpak IB, a 3,5-dimethylphenylcarbamate derivative of cellulose (the immobilized version of Chiralcel OD) which proved to be versatile for the monitoring of the lipase-catalyzed kinetic resolution of racemates in non-standard organic solvents. 相似文献
108.
Akai N Harada T Shin-Ya K Ohno K Aida M 《The journal of physical chemistry. A》2006,110(18):6016-6022
The photoreaction of 2-amino-5-methylpyridine was investigated by matrix-isolation infrared spectroscopy and DFT calculation. Photoinduced reversible amino (N=C-NH(2))-imino (NH-C=NH) tautomerism was found between 2-amino-5-methylpyridine and 5-methyl-2(1H)-pyridinimine; the amino tautomer changes to the imino tautomer by UV irradiation (340>lambda>or= 300 nm) and the reverse change occurs by longer-wavelength light irradiation (420>lambda>or= 340 nm). The results of the CASSCF calculation revealed that the amino-imino tautomerism proceeds in vibrational relaxation process from electronic excited state to the ground state. The IR spectra of 2-amino-5-methylpyridine in the T(1) state and 5-methyl-2-pyridinamino radical were also obtained by UV irradiation (lambda>or= 300 nm). 相似文献
109.
Motoyanagi J Fukushima T Ishii N Aida T 《Journal of the American Chemical Society》2006,128(13):4220-4221
A coumarin-appended amphiphilic hexa-peri-hexabenzocoronene (1) self-assembled to form graphitic nanotubes. Upon irradiation of lambda > 300 nm, the nanotubes in the solid state and suspension both underwent dimerization of the coumarin pendants, affording covalently stitched nanotubes, which were hardly soluble in CHCl3, a good solvent of 1. In contrast, a thin film cast from a homogeneous solution of 1 was intact to photoirradiation. Owing to the reversible nature of the photochemical stitching, both negative and positive patterns of the graphitic nanotubes were developed on a silicon substrate by a lithographic post processing. 相似文献
110.
Li WS Kim KS Jiang DL Tanaka H Kawai T Kwon JH Kim D Aida T 《Journal of the American Chemical Society》2006,128(32):10527-10532
Dendritic molecules appended with multiple zinc porphyrin units (DPm, m [number of zinc porphyrin units] = 6, 12, and 24) trap bipyridine compounds carrying multiple fullerene units (Py2Fn, n [number of C60 units] = 1-3), affording coordination complexes DPm superset Py2Fn having a photoactive layer consisting of spatially segregated donor and acceptor arrays on their surface. Complexes DPm superset Py2Fn are stable enough (K [average binding affinity] = 1.1 x 10(6)-4.4 x 10(6) M(-1) in CHCl3 at 25 degrees C) to be isolated by gel permeation chromatography. UHV-STM microscopy enables clear visualization of a petal-like structure of DP12 superset Py2F3. Photoexcitation of the zinc porphyrin units in DPm superset Py2Fn results in a zinc porphyrin-to-fullerene electron transfer to generate a charge separation. The charge-separation rate constant (kCS) in CH2Cl2 at 20 degrees C increases from 0.26 x 10(10) to 2.3 x 10(10) s(-1) upon increment of m and n, whereas the charge-recombination rate constant (kCR) remains almost unchanged at 4.5 x 10(6)-6.7 x 10(6) s(-1). Consequently, DP24 supersetPy2F3 furnishes the largest ratio of kCS/kCR (3400) among the family. 相似文献