全文获取类型
收费全文 | 985篇 |
免费 | 47篇 |
国内免费 | 4篇 |
专业分类
化学 | 762篇 |
晶体学 | 4篇 |
力学 | 18篇 |
数学 | 118篇 |
物理学 | 134篇 |
出版年
2023年 | 6篇 |
2022年 | 8篇 |
2021年 | 51篇 |
2020年 | 34篇 |
2019年 | 38篇 |
2018年 | 27篇 |
2017年 | 17篇 |
2016年 | 48篇 |
2015年 | 67篇 |
2014年 | 49篇 |
2013年 | 76篇 |
2012年 | 77篇 |
2011年 | 71篇 |
2010年 | 58篇 |
2009年 | 63篇 |
2008年 | 65篇 |
2007年 | 63篇 |
2006年 | 54篇 |
2005年 | 37篇 |
2004年 | 30篇 |
2003年 | 18篇 |
2002年 | 17篇 |
2001年 | 7篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1974年 | 2篇 |
排序方式: 共有1036条查询结果,搜索用时 683 毫秒
991.
Adriana Dijanoi Sneana Miljani Ivo Piantanida Jorge Gonzlez‐García Enrique García‐Espaa 《Journal of Raman spectroscopy : JRS》2014,45(10):863-872
Surface‐enhanced Raman scattering spectroscopy (SERS) in the near‐infrared region had been applied to study interactions of polyaza pyridinophanes with single stranded RNA and double stranded DNA and RNA polynucleotides. Studied compounds, PYPOD and PHENPOD, differed in the central aromatic moiety, pyridine and phenanthroline, respectively, which linked two cyclic amines. An intense scattering was obtained from molecules adsorbed onto the silver nanoparticles, showing nonlinear concentration dependence in the 6.5 × 10−8−6.5 × 10−5 M range. New bands in spectra of PYPOD/polynucleotide and PHENPOD/polynucleotide mixtures were assigned to vibrational modes of polynucleotide moieties involved in interactions. SERS spectra of both polyaza pyridinophanes with single stranded RNA polynucleotides indicated hydrogen bonding between the small molecules and the nucleic bases of poly A, poly C and poly U, whereas an interaction of only PYPOD with poly G was suggested. SERS spectra implied that both compounds bound into the minor groove of the helical poly dAdT–poly dAdT polynucleotide, while none of polyaza pyridinophanes interacted with the grooves of the poly dGdC–poly dGdC polynucleotide. Nevertheless, intensity ratios suggested intercalation of the phenanthroline moiety of the PHENPOD molecules into the double helix of the guanine‐cytosine polynucleotide. Spectral features also indicated binding of the PYPOD molecules within the major groove of the double stranded RNA analog. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
992.
Adriana da Silva Fontes Bruno Luiz Santana Vicentin Daniel Farinha Valezi Marcello Ferreira da Costa Walter Sano Eduardo Di Mauro 《Applied magnetic resonance》2014,45(7):681-692
The free radicals generated during the polymerization process of Z100 (3 M ESPE) dental resin were examined by electron paramagnetic resonance (EPR) in X-, Q- and W-bands. Experimental generation and spectra simulations were associated with density functional theory (DFT) calculations to determine the molecular structure and explain the EPR spectrum formation. It was assumed that the EPR spectrum was formed by the sum of two different types of radicals: “propagating” and allylic. The spectra simulations and DFT calculations showed good agreement, indicating that the proposed model fully explained the nine lines of the EPR spectrum in X-band and showed that the spectrum formation is the sum of “9 + 5” lines, rather than the “5 + 4” lines predicted early. Simulations in Q- and W-bands showed very close correlation and were essential to support the proposed model. 相似文献
993.
Francisco W. P. Ribeiro Thisiania R. V. Soares Sameque do N. Oliveira Luisa C. Melo Janete E. Soares Helena Becker Djenaine De Souza Pedro de Lima-Neto Adriana N. Correia 《Journal of Analytical Chemistry》2014,69(1):62-71
The electrochemical behaviour and analytical detection procedure for nimesulide (NIM) and ofloxacin (OFX) and their assay in commercial formulations were evaluated using square-wave voltammetry (SWV) combined with a hanging mercury drop electrode (HMDE). All experimental and voltammetric conditions were previously optimized to obtain the best analytical signal in terms of intensities and profile of the reduction peaks. For NIM, the peak currents were related to the one-electron reduction of a nitro group to a stable radical anion, which is followed by a one-electron transfer and a protonation step with a consequent formation of a nitrosoanion. The voltammetric results indicated that the mechanism of OFX involved the transfer of two electrons and two protons in a totally irreversible reduction related to the conversion of a ketone group to an alcohol group. Analytical parameters such as linearity range, equations of the analytical curves, correlation coefficients, detection and quantification limits, recovery efficiency, and relative standard deviation for repeatability and reproducibility experiments were compared to similar results obtained by the use of UV-Vis spectrophotometry, and the results showed that the voltammetric procedure using HMDE is suitable to determine pharmaceutical compounds in complex samples. The applicability of the proposed procedure was tested on pharmaceutical formulations of NIM and OFX by observing the stability, specificity, recovery and precision of the procedure in tablets, oral solution and ophthalmic solution. 相似文献
994.
Accurate Zygote‐Specific Discrimination of Single‐Nucleotide Polymorphisms Using Microfluidic Electrochemical DNA Melting Curves 下载免费PDF全文
Allen H. J. Yang Kuangwen Hsieh Adriana S. Patterson B. Scott Ferguson Michael Eisenstein Prof. Kevin W. Plaxco Prof. H. Tom Soh 《Angewandte Chemie (International ed. in English)》2014,53(12):3163-3167
We report the first electrochemical system for the detection of single‐nucleotide polymorphisms (SNPs) that can accurately discriminate homozygous and heterozygous genotypes using microfluidics technology. To achieve this, our system performs real‐time melting‐curve analysis of surface‐immobilized hybridization probes. As an example, we used our sensor to analyze two SNPs in the apolipoprotein E (ApoE) gene, where homozygous and heterozygous mutations greatly affect the risk of late‐onset Alzheimer’s disease. Using probes specific for each SNP, we simultaneously acquired melting curves for probe–target duplexes at two different loci and thereby accurately distinguish all six possible ApoE allele combinations. Since the design of our device and probes can be readily adapted for targeting other loci, we believe that our method offers a modular platform for the diagnosis of SNP‐based diseases and personalized medicine. 相似文献
995.
Determination of fluoroquinolones in bovine milk samples using a pipette‐tip SPE step based on multiwalled carbon nanotubes prior to CE separation 下载免费PDF全文
Valeria Springer Johan Jacksén Patrik Ek Adriana G. Lista Åsa Emmer 《Journal of separation science》2014,37(1-2):158-164
A simple CE–UV method was developed for the simultaneous determination of ciprofloxacin, norfloxacin, and ofloxacin in milk samples. The optimum separation was obtained using a 20 mM ammonium dihydrogenphosphate solution with 2 mM cetyltrimethylammonium bromide at pH 3.0 as the BGE. Satisfactory resolution for structurally very similar analytes, like norfloxacin and ciprofloxacin, was achieved without including any organic solvent. Milk samples were prepared using a simple/extraction procedure based on acidic protein precipitation followed by an SPE step using only 5 mg of multiwalled carbon nanotubes as the sorbent material. The LODs for the three compounds were between 7.5 and 11.6 μg/L and the RSDs for the peak areas were between 2.6 and 4.9%. The complete method was applied to spiked real milk samples with satisfactory recoveries for all analytes (84–106%). 相似文献
996.
Adriana?BotezEmail author Tanase?Dobre Eugenia?Panturu Antoaneta?Filcenco-Olteanu 《Central European Journal of Chemistry》2014,12(7):769-773
This paper characterizes uranium (VI) sorption from synthetic solutions using a fixed bed Purolite resin SGA 600 U/3472 system. The effect of the sulphate anion presence in the liquid phase on sorbtion dynamics and equilibrium is analysed. In the industrial processing of solutions obtained from leaching of uranium ore (alkaline/acid), in a continuous system, there are several compounds which strongly compete with uranium for ion exchange sites and consequently these substances depress the uranium adsorption. The influence of vanadate, molybdate, chloride, and nitrate is known, therefore, in this paper, the adsorption equilibrium isotherms for uranium (VI) are obtained for different sulphate ion concentrations in solution. The adsorption capacity variation of the Purolite resin SGA 600U/3472 with the number of adsorption/desorption cycles is also studied. The experimental results reveal the negative impact of high sulphate ion content in solution on the adsorption capacity of the resin Purolite SG 600 U / 3472 with uranium (VI) and therefore it is considered one of the compounds which strongly affect the uranium adsorption.
相似文献
997.
The conformations of monomeric 1,2-dichloropropane isolated in low temperature xenon matrix were characterized experimentally using FTIR spectroscopy. The interpretation of the experimental spectra was aided by ab initio MP2/6-311++G(3df,3pd) calculations. Relative energies of three structures, differing by the orientation of the Cl−C−C−Cl dihedral angle, fall within 0–6 kJ mol−1 range. The spectral signatures of all three conformers were identified experimentally. Infrared irradiation of the matrix isolated compound resulted in selective conversion of the most stable Trans conformer into the higher energy Gauche+ rotamer, while the Gauche− conformer remained unaffected. This result was interpreted in terms of calculated energy barriers and dipole moments. 相似文献
998.
Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (beta-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S = 1) is the ground state, CASSCF calculations indicate that a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond. 相似文献
999.
Arenas LT Pinheiro AC Ferreira JD Livotto PR Pereira VP Gallas MR Gushikem Y Costa TM Benvenutti EV 《Journal of colloid and interface science》2008,326(1):96-102
Anisotropic self-organized hybrid silica based xerogels were obtained. The ordered structure was imposed by the double charged 1,4-diazoniabicycle[2.2.2]octane chloride group bonded in a bridged way. This was confirmed by the presence of well defined X-ray diffraction peaks corresponding to an interplanar distance with the same length estimated for the organic bridged groups. The material was characterized by elemental analysis using CHN technique and the chloride ion was analyzed by a potentiometric titration. (13)C and (29)Si CP MAS solid state NMR spectroscopy and thermogravimetric analysis were also performed. The material that can be obtained in the form of powders and transparent monoliths or films, is thermally stable up to 260 degrees C and the samples with high organic content presented birefringence properties. 相似文献
1000.
A simple FI-fluorimetric analytical methodology for the continuous and sequential determination of rhodamine B (RhB) in cosmetic products has been developed and evaluated in terms of sensibility and selectivity. The influence of several surfactant solutions on RhB fluorescence signal has been studied; particular attention was paid in the aggregation behavior of RhB-SDS system. Linear response has been obtained in the range of 1.6 x 10(-9) and 1 x 10(-6) mol L(-1), with a detection limit of 5 x 10(-10) mol L(-1). The novel technique provides a simple dissolution of sample, on-line filtration with sampling rate higher than 100 samples h(-1) and has been satisfactorily applied to the RhB determination in commercial lipsticks. 相似文献