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11.
Philippe Gerbier Daniel Ruiz-Molina Neus Domingo David B. Amabilino José Vidal-Gancedo Javier Tejada David N. Hendrickson Jaume Veciana 《Monatshefte für Chemie / Chemical Monthly》2003,134(2):265-276
Summary. A new modified approach for the synthesis of Mn12 clusters, based on the use of complex [Mn12O12(O2C
t
Bu)16(H2O)4] (2) as starting material to promote the acidic ligand replacement, is presented here. This new synthetic approach allowed us
to obtain complex [Mn12O12(O2CC6H4N(O•)
t
Bu)16(H2O)4] (3), whose preparation remained elusive by direct replacement of the acetate groups of Mn12Ac (1). Complex 3 bearing open-shell radical units, was prepared to increase the total spin number of its ground state, and consequently, to
increase T
B
, with the expectation that the radical ligands may couple ferromagnetically with the Mn12 core. Unfortunately, magnetic measurements of complex 3 revealed that the sixteen radical carboxylate ligands interact antiferromagnetically with the Mn12 core to yield a S = 2 magnetic ground state.
Corresponding author. E-mail: vecianaj@icmab.es
Received March 27, 2002; accepted May 2, 2002 相似文献
12.
CE-MS has evolved into a strong alternative to LC-MS. Most of CE-MS applications deal with characterization and identification. However, quantitative aspects have gained importance in, e.g., pharmaceutical and biotechnological applications. Here we summarize and evaluate various methodological aspects in order to achieve sensitive and reproducible results. Similar to LC-MS, aspects of matrix influence on the electrospray process need to be carefully addressed when quantitative results are intended by CE-MS. Due to a more complicated coupling special emphasis needs to be put on the CE-MS interface. Generally linearity over more than three orders of magnitude can be achieved by CE-ESI-MS. Furthermore, a literature survey has been performed in order to give an overview over quantitative measurements performed by CE-MS. The precision can be doubled when changing from a structural related to an isotopically labeled internal standard. Thus a level of precision better than 5% RSD can be achieved. 相似文献
13.
M. F. Braa Maria L. Lpez Rodriguez J. Garrido C. M. Roldn 《Journal of heterocyclic chemistry》1981,18(7):1305-1308
Reaction of N-(4-pyridylmethyl)benzamide N-oxides with acetic anhydride yielded dimerization compounds. This dimerization occurs at the atom attached to the pyridine ring. These compounds so obtained were evaluated for analgesic and antiinflammatory activity. 相似文献
14.
Workman JA Garrido NP Sançon J Roberts E Wessel HP Sweeney JB 《Journal of the American Chemical Society》2005,127(4):1066-1067
The first examples of highly enantioselective [2,3]-sigmatropic rearrangements of acyclic allylic ammonium ylids are reported. Thus, a range of N-{2'-[(N'-allyl-N',N'-dialkyl)ammonium]}acetyl camphor sultams undergo rearrangement at 0 degrees C in DME solution with high diastereofacial control (up to 99:1 dr) to give allylglycines in generally high yield. The power of the method has been demonstrated in a rapid and efficient synthesis of (R)-allyl glycine. 相似文献
15.
Baeten V von Holst C Garrido A Vancutsem J Michotte Renier A Dardenne P 《Analytical and bioanalytical chemistry》2005,382(1):149-157
In this paper we present an alternative method for detection of meat and bone meal (MBM) in feedstuffs by near-infrared microscopic (NIRM) analysis of the particles in the sediment fraction (dense fraction (d >1.62) from dichloroethylene) of compound feeds. To apply this method the particles of the sediment fraction are spread on a sample holder and presented to the NIR microscope. By using the pointer of the microscope the infrared beam is focussed on each particle and the NIR spectrum (1112–2500 nm) is collected. This method can be used to detect the presence of MBM at concentrations as low as 0.05% mass fraction. When results from the NIRM method were compared with the classical microscopic method, a coefficient of determination (R2) of 0.87 was obtained. The results of this study demonstrated that this method could be proposed as a complementary tool for the detection of banned MBM in feedstuffs by reinforcement of the monitoring of feeds. 相似文献
16.
J. L. Martínez Vidal A. Garrido Frenich T. López López I. Martínez Salvador L. Hajjaj el Hassani M. Hassan Benajiba 《Chromatographia》2005,61(3-4):127-131
An analytical method for determining residues of twenty pesticides by liquid chromatography (LC) coupled to electrospray ionisation (ESI) tandem mass spectrometry (MS-MS) in eight commodities, cucumber, tomato, pepper, green bean, eggplant, zucchini, melon and watermelon, has been developed and validated. On one hand, calibration curves prepared in solvent were compared with calibration curves prepared in a blank matrix extract of each target matrix. On the other hand, calibration curves and recoveries for each commodity were compared. Cucumber was selected as potential reference matrix for the target vegetables. 相似文献
17.
Efstathia G SakellariouAntonio Garrido Montalban Scott L BeallDavid Henderson Hubert G MeunierDavid Phillips Klaus SuhlingAnthony G.M Barrett Brian M Hoffman 《Tetrahedron》2003,59(46):9083-9090
Co-macrocyclizations of 2,3-dipropylmaleonitrile and 2,3-di-(4-(methoxycarbonyl)phenyl)maleonitrile, respectively, with N,N′-dibenzyl-N,N′-di-(11-tetrahydropyranyloxy-3,6,9-trioxo-undecyl))maleonitrile and N,N,N′,N′-tetramethylmaleonitrile were used to prepare derivatives of the 4,5-diamino-porphyrazine systems including the zinc(II) complexes. Subsequent oxidation of the macrocycles with potassium permanganate gave the corresponding seco-porphyrazines. These were shown to be efficient sensitizers for the production of singlet oxygen (ΦΔ=0.15-0.57) by the determination of their photophysical properties. 相似文献
18.
Monitoring multi-class pesticide residues in fresh fruits and vegetables by liquid chromatography with tandem mass spectrometry 总被引:6,自引:0,他引:6
Frenich AG Vidal JL López TL Aguado SC Salvador IM 《Journal of chromatography. A》2004,1048(2):199-206
A new analytical method was developed using liquid chromatography with tandem mass spectrometry for the routine analysis of 31 multi-class pesticide residues and applied to approximately 50 fresh fruit and vegetable samples (green bean, cucumber, pepper, tomato, eggplant, watermelon, melon and zucchini). Extraction of the pesticides with ethyl acetate was carried out. The optimal ionisation conditions were selected for each pesticide in the same run. The procedure was validated and the values of some merit figures, such as recovery, precision, linear range, detection limit and quantification limit for each pesticide were calculated together with its calculated expanded uncertainty (U). The average recoveries in cucumber obtained for each pesticide ranged between 74 and 105% at two different fortification levels (n = 10 each) that ranged between 9 and 250 ng g(-1) (depending on the pesticide). The uncertainty associated to the analytical method was lower than 23% for all compounds tested. The calculated limits of detection and quantitation were typically <1 ng g(-1) that were much lower than the maximum residue levels established by European legislation. 相似文献
19.
Vidal JL Vega AB Arrebola FJ González-Rodríguez MJ Sánchez MC Frenich AG 《Rapid communications in mass spectrometry : RCM》2003,17(18):2099-2106
A fast method for the determination of eight organotin compounds (OTs), monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), tetrabutyltin (TeBT), monophenyltin (MPhT), diphenyltin (DPhT), triphenyltin (TPhT) and tetraphenyltin (TePhT), in water, sediments and mussels, was developed using low-pressure gas chromatography/tandem mass spectrometry (LPGC/MS/MS). The method is based on sodium diethyldithiocarbamate (DDTC) complexation of the ionic organotins, followed by extraction of the target matrices and derivatization by a Grignard reagent, as described in a previously published method for water samples. Solid-phase extraction was selected as extraction method from water samples after comparison with liquid-liquid extraction, but extraction of the OTs from sediment and mussel samples was performed using toluene. Matrix-matched calibration standards were used to minimize matrix effects. The analytical process was validated by the analysis of spiked blank samples. Performance characteristics such as linearity, detection limit (LOD), quantitation limit (LOQ), precision, and recovery were determined. Recoveries of OTs in spiked matrices ranged from 86-108% in water and from 78-110% in sediments and mussels, with precision values lower than 18%. Detection limits ranged from 0.1-9.6 ng L(-1) in water, and 0.03-6.10 microg kg(-1) in the other matrices. The present implementation of LPGC rather than conventional capillary GC permitted use of large-volume injection and reduced analysis time by a factor of two. The proposed methodology was applied to the determination of OTs in real samples of water, marine sediments and mussels from the west coast of the Mediterranean Sea (Spain). 相似文献
20.
Davies SG Díez D El Hammouni MM Garner AC Garrido NM Long MJ Morrison RM Smith AD Sweet MJ Withey JM 《Chemical communications (Cambridge, England)》2003,(19):2410-2411
Comparison of the kinetic and parallel kinetic resolutions of methyl (RS)-5-tert-butyl-cyclopentene-1-carboxylate allows for the efficient synthesis of both (1R,2S,5S)- and (1S,2R,5R)-enantiomers of methyl 2-amino-5-tert-butyl-cyclopentane-1-carboxylate. 相似文献