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151.
Hammond C Lopez-Sanchez JA Ab Rahim MH Dimitratos N Jenkins RL Carley AF He Q Kiely CJ Knight DW Hutchings GJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(15):3927-3937
The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO(2). This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, (13)C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed. 相似文献
152.
Panda SK Al-Hajji AA Müller H Koseoglu OR 《Analytical and bioanalytical chemistry》2011,400(5):1231-1239
In the present study, we established a statistical distribution pattern of indigenous sulfur, nitrogen, and oxygen species in Arabian Heavy crude oil and its distilled fractions: naphtha, gas oil, and vacuum gas oil (VGO) using chemical derivatization with methyl iodide and subsequent characterization by positive electrospray Fourier transform mass spectrometry. It was observed that sulfur species for naphtha and gas oil were accumulated at lower double bond equivalent values and at lower carbon numbers compared to VGO, whereas crude oil encompassed a complete range of the sulfur species detected in all distilled fractions. Moreover, the use of alumina column chromatography and ligand exchange chromatography (LEC) on a palladium-bonded silica stationary phase revealed additional structural features of sulfur heterocycles in terms of condensed and non-condensed thiophenes. During LEC separation, in addition to sulfur heterocycles, interesting results were obtained for oxygen-containing compounds. Ortho-substituted alkyl phenols were separated from meta- and para-substituted alkyl phenols on a palladium-bonded silica stationary phase. 相似文献
153.
Latif U Mujahid A Afzal A Sikorski R Lieberzeit PA Dickert FL 《Analytical and bioanalytical chemistry》2011,400(8):2507-2515
Polymers as coating materials were combined with quartz crystal microbalances (QCMs) to design sensor devices for the detection
of both ionic and neutral analytes in liquid phase. The design and geometry of dual and tetraelectrode QCMs have been optimized
to reduce electric field interferences. An unusual Sauerbrey effect was observed while exposing potassium salt solution to
10- and 20-MHz QCMs, i.e. increase in the frequency shifts by a factor of seven, which is attributed to electro-acoustic phenomena.
Non-functionalized sol-gel materials were synthesized by templating with hydrophobic salt such as tetraethyl ammonium picrate.
Imprinting with these ions of low charge density leads to sensitive layers, and UV–Vis spectroscopy was used to check re-inclusion
of this analyte. In the next strategy, functionalized polyurethane for potassium ions and sol-gel materials with aminopropyl
group as ligand were generated to tune selectivity and sensitivity towards Ni2+ and Cu2+. Methacrylic acid polymers were optimized for the detection of atrazine by hydrogen bonding; double molecular imprinted polyurethane
approach was followed for pyrene recognition. Finally, these imprinted polymers were combined with tetraelectrode QCM to develop
sensor platform. 相似文献
154.
The investigation presented in this paper concerns on the computational simulation of emissions characteristics in compression ignition engine with hydrogen substitution. Combustion process has been modeled based on Equilibrium Constants Method (ECM) with MATLAB program to calculate the mole fractions of 18 combustion products when hydrogen is burnt along with diesel fuel at variable equivalence ratios. It can be observed that hydrogen substitution causes significant increase in NH3, H2, atom H emissions during rich combustion and OH, NO2, HNO3 emissions during lean combustion. As the equivalence ratio increases during rich combustion, mole fractions of HCN, CH4, CO and atom C decreases with increment of hydrogen substitution. N2, atom N and CO2 emissions decrease whereas no significant changes in O2, NO, O3 and atom O emissions throughout all equivalence ratios as hydrogen is added to the combustion. 相似文献
155.
Boubakeur Benahmed Hocine Mokhtar-Kharroubi Bruno de Malafosse Adnan Yassine 《Journal of Global Optimization》2011,49(3):365-379
In the first part of this paper, we give a survey on convergence rates analysis of quasi-Newton methods in infinite Hilbert
spaces for nonlinear equations. Then, in the second part we apply quasi-Newton methods in their Hilbert formulation to solve
matrix equations. So, we prove, under natural assumptions, that quasi-Newton methods converge locally and superlinearly; the
global convergence is also studied. For numerical calculations, we propose new formulations of these methods based on the
matrix representation of the dyadic operator and the vectorization of matrices. Finally, we apply our results to algebraic
Riccati equations. 相似文献
156.
Lactic acid produced by fermentation process mostly contains a number of aliphatic carboxylic acids as impurities. In this work, carboxylic acid impurities in lactic acid samples from a number of sources were determined at ppm levels. A simple HPLC method was developed that utilized a new generation polar embedded reverse phase, 20mM phosphate buffer at pH 2.20 (±0.05) and UV detection at 210 nm. The method enabled quantitative analysis of the above acids in lactic acid matrix. The experimental conditions for column temperature, mobile phase pH and flow rate were optimized. A detailed validation of the method was performed for linearity, precision, accuracy, selectivity, limit of detection (LOD), limit of quantitation (LOQ), ruggedness and repeatability and reproducibility (R&R). 相似文献
157.
Mohd. Imran Ansari Ravi Shankar Mohd. Kamil Hussain Ruchir Kant Prakash R. Maulik K. Ravi Kumar K. Hajela 《Journal of heterocyclic chemistry》2011,48(6):1336-1341
Mono‐ and bis‐diaryl‐2H‐1,4‐benzothiazines were obtained in quantitative yields through silica‐supported perchloric acid catalyzed reaction cascade of double condensation and 1,4 addition of diaroylacetylenes with 2‐aminothiophenol at room temperature. The structures were confirmed by spectroscopic analyses and X‐ray crystallographic studies. J. Heterocyclic Chem., (2011) 相似文献
158.
Bicyclams inhibit HIV replication by binding to the CXCR4 chemokine receptor, which is the main coreceptor for gp120 used by X4, T‐tropic strains of HIV for membrane fusion and cell entry. Bicyclam AMD3100 mainly interacts with the aspartic acid residues namely Asp171 and Asp262, which are located at the extracellular ends in the CXCR4 coreceptor. Incorporation of some metal ions by the macrocyclic rings of bicyclam enhances its binding affinity to the CXCR4 receptor and enhances their anti‐HIV activity because the acetate can make a strong coordination bond to the metal and one weaker hydrogen bond to nitrogen in the cyclam ring. The interaction energy (Eint) between 150 metal–bicyclam complexes and aspartic acid has been evaluated. The metal–bicyclam complexes are obtained by the incorporation of six metal ions namely Fe3+, Co3+, Ni2+, Cu2+, Zn2+, and Pd2+ in 25 well‐known bicyclams including AMD3100. In most of the cases, Fe and Co–bicyclam complexes interact best with aspartic acid. The anti‐HIV activity of metal–bicyclam complexes can be predicted on the basis of interaction energy before the synthesis of the metal–bicyclam complex. On the basis of interaction energy, the anti‐HIV activity of bicyclam complexes can be predicted in advance to their synthesis. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
159.
Saleh MI Kusrini E Mohd Sarjidan MA Abd Majid WH 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(1):52-58
A mononuclear of [Eu(NO3)(Pic)(H2O)2(EO3)](Pic)·(0.73)H2O complex, where EO3=trietraethylene glycol and Pic=picrate anion, shows a red emission when used as an active layer in a single layer of ITO/EO3-Eu-Pic/Al configuration. The crystal structure of the complex consists of [Eu(NO3)(Pic)(H2O)2(EO3)]+ cation and [Pic]- anion. The Eu(III) ion is coordinated to the 10 oxygen atoms from one EO3 ligand, one Pic anion, one nitrate anion, and two water molecules. The complex is crystallized in triclinic with space group P-1. The hybrids in thin films I and II were prepared in the respective order solution concentrations of 15 and 20 mg/mL the emissive center. Comparing the photoluminescence (PL) and electroluminescence (EL) spectra, we can find that all emissions come from the characteristic transitions of the Eu(III) ion. The EL spectra of both thin films showed the occurrence of the most intense red-light emission around at 612 nm. Comparison of organic light-emitting device (OLED) current intensity characteristics as a function of voltage (I-V) show that the thin film I is better than those found for the thin film II. The thickness of the emitting layer is an important factor to control the current-voltage curve. The sharp and intense emission of the complex at low voltage indicates that the complex is a suitable and promising candidate for red-emitting materials. 相似文献
160.
Malek SN Lee GS Hong SL Yaacob H Wahab NA Faizal Weber JF Shah SA 《Molecules (Basel, Switzerland)》2011,16(6):4539-4548
Investigations on the cytotoxic effects of the crude methanol and fractionated extracts (hexane, ethyl acetate) C. mangga against six human cancer cell lines, namely the hormone-dependent breast cell line (MCF-7), nasopharyngeal epidermoid cell line (KB), lung cell line (A549), cervical cell line (Ca Ski), colon cell lines (HCT 116 and HT-29), and one non-cancer human fibroblast cell line (MRC-5) were conducted using an in-vitro neutral red cytotoxicity assay. The crude methanol and fractionated extracts (hexane and ethyl acetate) displayed good cytotoxic effects against MCF-7, KB, A549, Ca Ski and HT-29 cell lines, but exerted no damage on the MRC-5 line. Chemical investigation from the hexane and ethyl acetate fractions resulted in the isolation of seven pure compounds, namely (E)-labda-8(17),12-dien-15,16-dial (1), (E)-15,16-bisnor-labda-8(17),11-dien-13-on (2), zerumin A (3), β-sitosterol, curcumin, demethoxycurcumin and bis-demethoxycurcumin. Compounds 1 and 3 exhibited high cytotoxic effects against all six selected cancer cell lines, while compounds 2 showed no anti-proliferative activity on the tested cell lines. Compound 1 also demonstrated strong cytotoxicity against the normal cell line MRC-5. This paper reports for the first time the cytotoxic activities of C. mangga extracts on KB, A549, Ca Ski, HT-29 and MRC-5, and the occurrence of compound 2 and 3 in C. mangga. 相似文献