全文获取类型
收费全文 | 160篇 |
免费 | 10篇 |
国内免费 | 2篇 |
专业分类
化学 | 124篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 29篇 |
物理学 | 14篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 13篇 |
2020年 | 2篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 6篇 |
2015年 | 4篇 |
2014年 | 9篇 |
2013年 | 6篇 |
2012年 | 25篇 |
2011年 | 11篇 |
2010年 | 9篇 |
2009年 | 11篇 |
2008年 | 7篇 |
2007年 | 4篇 |
2006年 | 9篇 |
2005年 | 6篇 |
2004年 | 5篇 |
2003年 | 2篇 |
2002年 | 6篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1996年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 3篇 |
1982年 | 1篇 |
1929年 | 1篇 |
排序方式: 共有172条查询结果,搜索用时 78 毫秒
41.
Saracino MA Gandolfi O Dall'olio R Albers L Kenndler E Raggi MA 《Journal of chromatography. A》2006,1122(1-2):21-27
A sensitive and selective method was developed for the determination of the antipsychotic drug Olanzapine levels in rat brain tissue, based on HPLC with electrochemical detection. The analyses were carried out on a C8 reversed phase column (150 mm x 4.6 mm, 5 microm), using a mobile phase composed of methanol and a phosphate buffer (44.0 mM, pH 3.5), containing triethylamine (21:79, v/v), flowing at 1.2 mL min(-1). A high sensitivity coulometric detection analytical cell containing two flow-through low volume working electrodes was used: electrode 1 was set at +0.350 V and electrode 2 at -0.200 V. Olanzapine, administered to rats in different doses or in different times, was extracted from tissue homogenate of either the whole brain or specific areas (cortex, hyppocampus, nucleus striatum) with a rapid solid phase extraction procedure (SPE) on Oasis HLB cartridges. The method provided a high extraction yield of Olanzapine and internal standard (2-methylolanzapine) from brain tissue homogenate with absolute recovery values higher than 90.0%. The detector response was linear over a concentration range of 0.2-100.0 ng mL(-1) of Olanzapine. The limit of quantification (LOQ) was 0.2 ng mL(-1). Precision results, expressed by the intra-day and the inter-day relative standard deviation values, were satisfactory, better than 4.6%. Accuracy was satisfactory as well. This method proved to be suitable for the analysis of Olanzapine in rat brain tissues and for the study of distribution and pharmacokinetics of Olanzapine in rat brain after a single treatment with the antipsychotic drug. 相似文献
42.
An L(h,k)-labeling of a graph G is an integer labeling of vertices of G, such that adjacent vertices have labels which differ by at least h, and vertices at distance two have labels which differ by at least k. The span of an L(h,k)-labeling is the difference between the largest and the smallest label. We investigate L(h,k)-labelings of trees of maximum degree Δ, seeking those with small span. Given Δ, h and k, span λ is optimal for the class of trees of maximum degree Δ, if λ is the smallest integer such that every tree of maximum degree Δ has an L(h,k)-labeling with span at most λ. For all parameters Δ,h,k, such that h<k, we construct L(h,k)-labelings with optimal span. We also establish optimal span of L(h,k)-labelings for stars of arbitrary degree and all values of h and k. 相似文献
43.
Luca Gentilucci Lucia Cerisoli Rossella De Marco Alessandra Tolomelli 《Tetrahedron letters》2010,51(19):2576-9174
We investigated the Lewis acid-promoted Friedel-Crafts alkylation of indole and substituted indoles with dehydroalanine-containing dipeptides R-Xaa-Dha-OR1. The reaction proceeded with modest to sufficient diastereoselectivity, and yields strongly varied depending on the Lewis acid selected. The substituent R1 of the ester group revealed some impact on the preferential formation of (S)-Trp or (R)-Trp. We exploited the reaction to prepare different peptides containing substituted tryptophans. To test the efficacy of this method for preparing biologically relevant compounds, we synthesized two unprecedented analogues of endomorphin-1, the endogenous agonist of the μ-opioid receptor, having either (S)- or (R)-2-methyltryptophan in position 3. 相似文献
44.
Eloisa Liotta Rossella Gottardo Anna Bertaso Aldo Polettini 《Journal of mass spectrometry : JMS》2010,45(3):261-271
High‐resolution mass spectrometry (HRMS) enables the identification of a chemical formula of small molecules through the accurate measurement of mass and isotopic pattern. However, the identification of an unknown compound starting from the chemical formula requires additional tools: (1) a database associating chemical formulas to compound names and (2) a way to discriminate between isomers. The aim of this present study is to evaluate the ability of a novel ‘metabolomic’ approach to reduce the list of candidates with identical chemical formula. Urine/blood/hair samples collected from real positive cases were submitted to a screening procedure using ESI‐MS‐TOF (positive‐ion mode) combined with either capillary electrophoresis or reversed phase liquid chromatography (LC). Detected peaks were searched against a Pharmaco/Toxicologically Relevant Compounds database (ca 50 500 compounds and phase I and phase II metabolites) consisting of a subset of PubChem compounds and a list of candidates was retrieved. Then, starting from the mass of unknown, mass shifts corresponding to pre‐defined biotransformations (e.g. demethylation, glucuronidation, etc.) were calculated and corresponding mass chromatograms were extracted from the total ion current (TIC) in order to search for metabolite peaks. For each candidate, the number of different functional groups in the molecule was automatically calculated using E‐Dragon software (Talete srl, Milan, Italy). Then, the presence of metabolites in the TIC was matched with functional groups data in order to exclude candidates with structures not compatible with observed biotransformations (e.g. loss of methyl from a structure not bearing methyls). The procedure was tested on 108 pharmaco‐toxicologically relevant compounds (PTRC) and their phase I metabolites were detected in real positive samples. The mean list length (MLL) of candidates retrieved from the database was 7.01 ± 4.77 (median, 7; range, 1–28) before the application of the ‘metabolomic’ approach, and after the application it was reduced to 4.08 ± 3.11 (median 3, range 1–17). HRMS allows a much broader screening for PTRC than other screening approaches (e.g. library search on mass spectra databases). The ‘metabolomic’ approach enables the reduction of the list of candidate isomers. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
45.
Bortolo L. Vanzetti 《Monatshefte für Chemie / Chemical Monthly》1929,52(1):163-168
Ohne Zusammenfassung 相似文献
46.
Rossella Dorati 《Polymer Degradation and Stability》2007,92(9):1660-1668
The aim was to investigate the degradation behaviour of poly(ethylene glycol-co-d,l-lactide) (PEG-d,l-PLA) multiblock copolymer, in bulk and as microspheres, in aqueous medium. The degradation behaviour of PLA homopolymers in bulk and microspheres was evaluated as comparison.Microsphere preparation was performed by the double emulsion solvent evaporation method. Physical-chemical characterization of the raw polymers and the microspheres was performed by nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry (MDSC). Polymer molecular weight, before and after incubation in aqueous environment, was evaluated by GPC; water uptake and mass loss were determined gravimetrically.The presence of PEG segments inside PLA chains gave a characteristic spongy structure to the microspheres. A significant increase in polymer Tg values was found for the microsphere formulations compared to polymer in bulk. After 63 days of incubation in the aqueous environment, the PEG-d,l-PLA microspheres achieved an average Mw reduction of 47% compared to 20% for PLA microspheres. The corresponding Mw decrease of the polymers in bulk was significantly higher: 72% and 41% for PEG-d,l-PLA and PLA, respectively.The data show how the degradation behaviour of polymer in bulk in an aqueous environment is significantly different from the behaviour of the corresponding microspheres. These results highlight the importance of performing a thorough physical-chemical characterization on microsphere formulations. 相似文献
47.
González-Núñez ME Mello R Royo J Asensio G Monzó I Tomás F López JG Ortiz FL 《The Journal of organic chemistry》2004,69(26):9090-9099
The detailed study of the oxidation of thianthrene 5-oxide (1) with methyl(trifluoromethyl)dioxirane (5b) in different solvents and in the presence of (18)O isotopic tracers is reported. Thianthrene 5-oxide (1) is a flexible molecule in solution, and this property allows for transannular interaction of the sulfoxide group with the expected zwitterionic 7 and hypervalent 10-S-4 sulfurane 9 intermediates formed in the oxidation and biases the course of the reaction toward the monooxygenation pathway. 相似文献
48.
An inversion procedure for converting linear viscoelastic properties of polymer melts into molecular weight distribution (MWD) described by the generalized exponential function (GEX) has been implemented and applied in a previous work (Cocchini F, Nobile MR. Rheol Acta 42:232–242, 2003). It is based on the elegant relationship between the relaxation spectrum and the MWD function proposed by Thimm W, Friedrich C, Marth M. J Rheol 43:1663–1672 (1999). In the present paper, such a methodology has been generalized to properly account for sharp MWDs, in particular, nearly monodisperse or blends of nearly monodisperse polymer samples. The generalized relationship has been verified and calibrated using the BSW kernel (Baumgaertel M, Schausberger A, Winter HH. Rheol Acta 29:400–408, 1990) to describe the rheological behavior of some Polystyrene samples from the literature, in terms of the known MWD. Then, it has been successfully applied to the inversion problem for a wider set of samples, with both broad and sharp distributions. The Rouse contribution at high frequencies and the accelerating effect on the relaxation times due to polydispersion have been also addressed. 相似文献
49.
Andrea Salvo Giovanna Loredana La Torre Rossella Vadalà Antonio Francesco Mottese Emanuele Saija 《Natural product research》2016,30(13):1517-1525
Considering that the determination of authenticity and of the geographical origin of food is a very challenging issue, in this study we studied by means of histological and histochemical analyses the famous Sicilian lemon known as ‘Interdonato Lemon of Messina PGI’. Since the protected geographical indication Interdonato lemon of Messina possesses high organoleptic properties, the composition of the hexane extract of lemon peel was determined by HRGC and HRGC–MS analyses and compared with that of lemon of different cultivars. The results obtained are informative of the oil’s quality and explain the variation of the lemon essential oil composition. Given the fundamental economic implications of any fraud, the aim of this study was to determine a fingerprint able to evaluate the authentication of the geographic origin in such way to prevent frauds in national and international markets. 相似文献
50.
Rossella Basilotta Deborah Mannino Alessia Filippone Giovanna Casili Angela Prestifilippo Lorenzo Colarossi Gabriele Raciti Emanuela Esposito Michela Campolo 《Molecules (Basel, Switzerland)》2021,26(13)
Since cancer is a multifactorial disease with a high mortality rate, the study of new therapeutic strategies is one of the main objectives in modern research. Numerous chemotherapeutic agents, although widely used, have the disadvantage of being not very soluble in water or selective towards cancerous cells, with consequent side effects. Therefore, in recent years, a greater interest has emerged in innovative drug delivery systems (DDSs) such as calixarene, a third-generation supramolecular compound. Calixarene and its water-soluble derivatives show good biocompatibility and have low cytotoxicity. Thanks to their chemical–physical characteristics, calixarenes can be easily functionalized, and by itself can encapsulate host molecules forming nanostructures capable of releasing drugs in a controlled way. The encapsulation of anticancer drugs in a calixarene derivate improves their bioavailability and efficacy. Thus, the use of calixarenes as carriers of anticancer drugs could reduce their side effects and increase their affinity towards the target. This review summarizes the numerous research advances regarding the development of calixarene nanoparticles capable of encapsulating various anticancer drugs. 相似文献