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21.
A non‐targeted, ultra‐high‐resolution mass spectrometric, direct analysis of oak‐wood extracts from two species (Quercus robur L. and Quercus petraea Liebl.) from three French forests, and of a wine aged in barrels derived therefrom has been performed to identify families of metabolites that could discriminate both the species and the geographical origin of woods. From 12 T ultra‐high‐resolution Fourier transform ion cyclotron resonance mass spectra of wood extracts, hundreds of mass signals were identified as possible significant biomarkers of the two species, with phenolic and carbohydrate moieties leading the differentiation between Q. robur and Q. petraea, respectively, as corroborated by both FTMS and NMR data. For the first time, it is shown that oak woods can also be discriminated on the basis of hundreds of forest‐related compounds, and particular emphasis is put on sessile oaks from the Tronçais forest, for which sugars are significantly discriminant. Despite the higher complexity and diversity of wine metabolites, forest‐related compounds can also be detected in wines aged in related barrels. It is only by using these non‐targeted analyses that such innovative results, which reveal specific chemodiversities of natural materials, can be obtained.  相似文献   
22.

1,4-Dichlorobenzene is a frequently used lavatory deodorant although it has strong endocrine disrupting and potential carcinogenic effects. A large amount (approximately 15,000 tonnes annually worldwide) of this compound is released into the environment. This paper deals with the determination of 1,4-dichlorobenzene in a variety of environmental matrices. Various extraction and concentration methods such as charcoal absorbtion tubes and headspace sampling were applied. Sensitive and selective ion monitoring GC-MS measurements were used for determination. Significant concentrations of the compound have been identified in lavatory air, waste water, waste water sludge and human breast milk.

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23.
In this paper, we present three new mathematical techniques for evaluating the predictive skills of structure-activity experts. The question addressed in this paper is how to evaluate the predictive ability of structure-activity experts in identifying the most active compounds of a set of drug candidates. The three proposed mathematical techniques are based on the Phi-square Distance, the Rank Comparison, and the Shuffle method, respectively. They have been used to evaluate the performance of a new computer system and three human experts in predicting the antibacterial potencies of a series of chemical compounds in five different biological tests. The expert system, an artificial intelligence structure-activity program called MULTICASE, performed significantly better than one of the human experts and somewhat better than the other two.On leave from the Department of General and Analytical Chemistry, Technical University of Budapest, Szt. Gellert ter 4, 1111 Budapest, Hungary.  相似文献   
24.
The coupled-cluster method is applied to high sectors of the Fock space (up to five electrons outside a closed shell). Ionization potentials and excitation energies are calculated for atomic N, O, F, P, and S and their ions. The effect of virtual triple excitations is included, exactly or at several levels of appoximation. These terms are important for accurate results in the high sectors. © 1995 John Wiley & Sons, Inc.  相似文献   
25.
The Hungarian-born American chemistry Nobel laureate George A. Olah used superacids to give longer life to carbocations. He resolved a long-standing debate on reaction mechanism in organic chemistry and, more importantly, opened new vistas in hydrocarbon chemistry to produce hosts of new compounds. The concerted utilization of organic synthesis, physical techniques, and computational methods led to spectacular achievements in hydrocarbon chemistry. Olah has always been on the lookout for the practical applications of his discoveries in fundamental chemistry. He continued his research after his Nobel award and has worked out the idea, which he labeled “the methanol economy.” Olah’s example shows that a great researcher can also be a devoted and caring human being.  相似文献   
26.
In four-point bending, the rollers that are used for load application impose additional constraints on the specimen that affect the anticlastic specimen curvature and cause the specimen displacement and stress profiles to deviate from the pure beam bending case. In this study, x-ray microdiffraction is used to map both the principal and anticlastic curvatures of elastically bent, rectangular (100)-type Si strips possessing width:thickness ratios of 40:1. We quantify the amount of roller constraint and show that the region over which the anticlastic specimen curvature is affected away from the roller is approximately five times the roller diameter. Consequently, for bending tests used to determine Poisson's ratio, if a region on the sample that is free from roller effects is not chosen, measurement errors as high as 46% can occur. Furthermore, we show that, due to the anisotropy of single crystal Si, this roller-constraining effect depends on crystallographic orientation and is more pronounced when the principal bending axis lies along the <100> direction as compared with the <100> direction.  相似文献   
27.
This article describes the development and full characterization of a microfluidic chip for electrofusion of human peripheral blood B-cells and mouse myeloma (NS-1) cells to generate hybridomas. The chip consists of an array of 783 traps, with dimensions that were optimized to obtain a final cell pairing efficiency of 33±6%. B cells were stained with a cytoplasmic stain CFDA to assess the different stages of cell fusion, i.e. dye transfer to NS-1 cells (initiating fusion) and membrane reorganization (advanced fusion). Six DC pulses of 100 μs (2.5 kV/cm) combined with an AC field (30 s, 2 MHz, 500 V/cm) and pronase treatment resulted in the highest electrofusion efficiency of paired cells (51±11%). Hybridoma formation, with a yield of 0.33 and 1.2%, was observed after culturing the fused cells for 14 days in conditioned medium. This work provides valuable leads to improve the current electrofusion protocols for the production of human antibodies for diagnostic and therapeutic applications.  相似文献   
28.
The discovery of quasicrystals by Dan Shechtman in the early 1980s was a conspicuous event in materials science not only because it led to the production of a plethora of new materials but also because it signified the demise of a dogma in the science of condensed phase materials concerning symmetry restrictions. Having the discovery recognized was not easy and it required stamina on Shechtman??s part. The story of the quasicrystal discovery offers a set of lessons that might be useful to remember in similar situations.  相似文献   
29.
2‐Methyl‐4‐(trifluoromethyl)‐1H‐indole‐5‐carbonitrile is a key intermediate in the synthesis of selective androgen receptor modulators discovered in these laboratories. A practical and convergent synthesis of the title compound starting from 4‐nitro‐3‐(trifluoromethyl)phenol and tert‐butyl acetoacetate was developed, including a telescoped procedure for synthesis (without isolation) and Nenitzescu reaction of 2‐trifluoromethyl‐1,4‐benzoquinone. Conversion of the known Nenitzescu indole product to a novel triflate intermediate followed by palladium‐catalyzed cyanation afforded a penultimate carbonitrile. Removal of the C‐3 tert‐butyl ester group on the indole through a decarboxylative pathway completed the synthesis of the title compound in six steps (27% overall yield) from 4‐nitro‐3‐(trifluoromethyl)phenol (five steps, 37% overall yield from tert‐butyl acetoacetate). J. Heterocyclic Chem., (2011).  相似文献   
30.
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