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81.
When using capillary electrophoresis with a diode array detector, the wavelength at maximum absorbance is often chosen to quantify a given analyte. However, the background noise for every wavelength should be taken into account as it is by maximising the signal to noise ratio that the lowest limit of detection will be obtained. Here, we proposed an algorithm allowing to correct an electropherogram from its background absorption and to estimate the background noise. Applying it to all the electropherograms obtained in each wavelength channel allows obtaining the background noise as a function of the wavelength, which can be used to calculate the signal to noise ratio. This not only allows selecting the best wavelength to maximise the limit of detection of a given analyte, but also to generate a noise normalised base peak electropherogram (nn-BPE). It is shown that the noise normalised base peak electropherograms substantially improve the peaks visualisation. The algorithm is part of a graphic user interface that runs under MatLab environment; it does not require any programming knowledge and is freely available. 相似文献
82.
Michalak M Stodulski M Stecko S Mames A Panfil I Soluch M Furman B Chmielewski M 《The Journal of organic chemistry》2011,76(16):6931-6936
A formal synthesis of a powerful cholesterol inhibitor, ezetymibe 1, is described. The crucial step of the synthesis is based on Cu(I)-mediated Kinugasa cycloaddition/rearrangement cascade reaction between terminal acetylene derived from acetonide of L-glyceraldehyde and suitable C,N-diarylnitrone. The adduct with (3R,4S) configuration at the azetidinone ring, obtained with high stereoselectivity, was subsequently subjected to deprotection of the diol side chain followed by glycolic cleavage and base-induced isomerization at the C3 carbon atom to afford the (3S,4S) aldehyde, which has been already transformed into ezetimibe by the Schering-Plough group. 相似文献
83.
Mohamed MF Sánchez-Lombardo I Neverov AA Brown RS 《Organic & biomolecular chemistry》2012,10(3):631-639
The kinetics of cyclization of 2-hydroxypropyl p-nitrophenyl phosphate (1) promoted by two mononuclear Zn(II) catalytic complexes of bis(2-pyridylmethyl)benzylamine (4) and bis(2-methyl 6-pyridylmethyl)benzylamine (5) in methanol were studied under (s)(s)pH-controlled conditions (where (s)(s)pH refers to [H(+)] activity in methanol). Potentiometric titrations of the ligands in the absence and presence of Zn(2+) and a non-reactive model for 1 (2-hydroxylpropyl isopropyl phosphate (HPIPP, 6)) indicate that the phosphate is bound tightly to the 4:Zn(II) and 5:Zn(II) complexes as L:Zn(II):6(-), and that each of these undergoes an additional ionization to produce L:Zn(II):6(-):((-)OCH(3)) or a bound deprotonated form of the phosphate, L:Zn(II):6(2-). Kinetic studies as a function of [L:Zn(II)] indicate that the rate is linear in [L:Zn(II)] at concentrations well above those required for complete binding of the substrate. Plots of the second order rate constants (defined as the gradient of the rate constant vs. [complex] plot) vs. (s)(s)pH in methanol are bell-shaped with rate maxima of 23 dm mol(-1) s(-1) and 146 dm mol(-1) s(-1) for 4:Zn(II) and 5:Zn(II), respectively, at their (s)(s)pH maxima of 10.5 and 10. A mechanism is proposed that involves binding of one molecule of complex to the phosphate to yield a poorly reactive 1 : 1 complex, which associates with a second molecule of complex to produce a transient cooperative 2 : 1 complex within which the cyclization of 1 is rapid. The observations support an effect of the reduced polarity solvent that encourages the cooperative association of phosphate and two independent mononuclear complexes to give a reactive entity. 相似文献
84.
This paper is a continuation of [9], where short range perturbations of the flat Euclidian metric where considered. Here, we generalize the results of [9] to long-range perturbations (in particular, we can allow potentials growing like ?x?2?? at infinity). More precisely, we construct a modified quantum free evolution G 0(?s, hD z ) acting on Sjöstrand's spaces, and we characterize the analytic wave front set of the solution e ?itH u 0 of the Schrödinger equation, in terms of the semiclassical exponential decay of G 0(?th ?1, hD z )T u 0, where T stands for the Bargmann-transform. The result is valid for t < 0 near the forward non trapping points, and for t > 0 near the backward non trapping points. It is an extension of [12] to the analytic framework. 相似文献
85.
We establish functional central limit theorems for polygonal process constructed from consecutive estimators of a simple AR(1)
model. We consider both stationary and unit root cases. The results are applied to change segment analysis. 相似文献
86.
Stephanie Giraldo Irma Robles Luis A. Godínez Nancy Acelas Elizabeth Flrez 《Molecules (Basel, Switzerland)》2021,26(15)
Chemical and thermochemical transformations were performed on orange peel to obtain materials that were characterized and further tested to explore their potential as adsorbents for the removal of methylene blue (MB) from aqueous solutions. The results show the high potential of some of these materials for MB adsorption not only due to the surface area of the resulting substrate but also to the chemistry of the corresponding surface functional groups. Fitting of the kinetic as well as the equilibrium experimental data to different models suggests that a variety of interactions are involved in MB adsorption. The overall capacities for these substrates (larger than 192.31 mg g−1) were found to compare well with those reported for activated carbon and other adsorbents of agro-industrial origin. According to these results and complementary with theoretical study using Density Functional Theory (DFT) approximations, it was found that the most important adsorption mechanisms of MB correspond to: (i) electrostatic interactions, (ii) H-bonding, and (iii) π (MB)–π (biochar) interactions. In view of these findings, it can be concluded that adsorbent materials obtained from orange peel, constitute a good alternative for the removal of MB dye from aqueous solutions. 相似文献
87.
88.
Agnieszka Galanty Justyna Popi Magdalena Paczkowska-Walendowska Elbieta Studziska-Sroka Pawe Pako Judyta Cielecka-Piontek Elbieta Pkala Irma Podolak 《Molecules (Basel, Switzerland)》2021,26(17)
The study aimed to examine whether usnic acid—a lichen compound with UV-absorbing properties—can be considered as a prospective photoprotective agent in cosmetic products. Moreover, a comparison of two usnic acid enantiomers was performed to preselect the more effective compound. To meet this aim, an in vitro model was created, comprising the determination of skin-penetrating properties via skin-PAMPA assay, safety assessment to normal human skin cells (keratinocytes, melanocytes, fibroblasts), and examination of photostability and photoprotective properties. Both enantiomers revealed comparable good skin-penetrating properties. Left-handed usnic acid was slightly more toxic to keratinocytes (IC50 80.82 and 40.12 µg/mL, after 48 and 72 h, respectively) than its right-handed counterpart. The latter enantiomer, in a cosmetic formulation, was characterized by good photoprotective properties and photostability, comparable to the UV filter octocrylene. Perhaps most interestingly, (+)-usnic acid combined with octocrylene in one formulation revealed enhanced photoprotection and photostability. Thus, the strategy can be considered for the potential use of (+)-usnic acid as a UV filter in cosmetic products. Moreover, the proposed model may be useful for the evaluation of candidates for UV filters. 相似文献
89.
Marco A. Seia Sirley V. Pereira Martin A. Fernández-Baldo Irma E. De Vito Julio Raba Germán A. Messina 《Analytical and bioanalytical chemistry》2014,406(19):4677-4684
In this article, we present an innovative approach for congenital hypothyroidism (CHT) screening. This pathology is the most common preventable cause of mental retardation, affecting newborns around the world. Its consequences could be avoided with an early diagnosis through the thyrotropin (TSH) level measurement. To accomplish the determination of TSH, synthesized zinc oxide (ZnO) nanobeads (NBs) covered by chitosan (CH), ZnO-CH NBs, were covalently attached to the central channel of the designed microfluidic device. These beads were employed as platform for anti-TSH monoclonal antibody immobilization to specifically recognize and capture TSH in neonatal samples without any special pretreatment. Afterwards, the amount of this trapped hormone was quantified by horseradish peroxidase (HRP)-conjugated anti-TSH antibody. HRP reacted with its enzymatic substrate in a redox process, which resulted in the appearance of a current whose magnitude was directly proportional to the level of TSH in the neonatal sample. The structure and morphology of synthesized ZnO-CH NBs were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The calculated detection limits for electrochemical detection and the enzyme-linked immunosorbent assay procedure were 0.00087 μUI mL?1 and 0.015 μUI mL?1, respectively, and the within- and between-assay coefficients of variation were below 6.31 % for the proposed method. According to the cut-off value for TSH neonatal screening, a reasonably good limit of detection was achieved. These above-mentioned features make the system advantageous for routine clinical analysis adaptation. 相似文献
90.
Vania Mascioni 《Discrete Mathematics》2005,300(1-3):129-138
For a set of 3 or 4 points we compute the exact probability that, after assigning the distances between these points uniformly at random from the set 1,…,n , the space obtained is metric. The corresponding results for random real distances follow easily. We also prove estimates for the general case of a finite set of points with uniformly random real distances. 相似文献