全文获取类型
收费全文 | 541篇 |
免费 | 22篇 |
专业分类
化学 | 444篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 50篇 |
物理学 | 57篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 48篇 |
2021年 | 39篇 |
2020年 | 18篇 |
2019年 | 23篇 |
2018年 | 6篇 |
2017年 | 9篇 |
2016年 | 23篇 |
2015年 | 26篇 |
2014年 | 20篇 |
2013年 | 32篇 |
2012年 | 35篇 |
2011年 | 56篇 |
2010年 | 35篇 |
2009年 | 22篇 |
2008年 | 23篇 |
2007年 | 28篇 |
2006年 | 22篇 |
2005年 | 25篇 |
2004年 | 20篇 |
2003年 | 13篇 |
2002年 | 19篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1996年 | 1篇 |
1992年 | 1篇 |
1985年 | 1篇 |
排序方式: 共有563条查询结果,搜索用时 0 毫秒
491.
The present study explores the application of the diffusion limited evaporation theory to the estimation of vapor pressure from TG experimental data. A simplified method was developed to calculate the apparent values of the vapor pressure of pure substances from TG data, based on isothermal TG runs with crucibles having different surface areas available for evaporation. Antoine parameters are estimated through a numerical procedure based on a non-linear least square algorithm. The procedure also evaluates the substance diffusivity in nitrogen. The methodology developed might be used for a preliminary screening of the vapor pressure of pure compounds, due to the limited amounts of sample that are necessary and to the limited time frame required for the experimental runs. However, the estimation of diffusivity and vapor pressures values by the TG technique is possible with limited accuracy. Possible sources of error were thoroughly investigated and discussed. 相似文献
492.
beta-lactamases confer resistance to beta-lactam antibiotics such as penicillins and cephalosporins. However, beta-lactams that form an acyl-intermediate with the enzyme but subsequently are hindered from forming a catalytically competent conformation seem to be inhibitors of beta-lactamases. This inhibition may be imparted by specific groups on the ubiquitous R(1) side chain of beta-lactams, such as the 2-amino-4-thiazolyl methoxyimino (ATMO) group common among third-generation cephalosporins. Using steric hindrance of deacylation as a design guide, penicillin and carbacephem substrates were converted into effective beta-lactamase inhibitors and antiresistance antibiotics. To investigate the structural bases of inhibition, the crystal structures of the acyl-adducts of the penicillin substrate amoxicillin and the new analogous inhibitor ATMO-penicillin were determined. ATMO-penicillin binds in a catalytically incompetent conformation resembling that adopted by third-generation cephalosporins, demonstrating the transferability of such sterically hindered groups in inhibitor design. 相似文献
493.
A set of 1‐(arylalkyl)quinolizidines, isosteric thioanalogues, and variously functionalized congeners were synthesized (see 1 – 25 ) and tested for affinity to sigma 1 and sigma 2 receptor subtypes, by displacing [3H]‐ (+)‐pentazocine and [3H]DTG from guinea pig brain and rat brain preparations, respectively. All compounds exhibited a good affinity for the σ1 subtype, with subnanomolar Ki values for the best of them, while only modest or poor affinity for the σ2 subtype was observed (Tables 1 and 2). Some structure? activity relationships were put forward. 相似文献
494.
Moison RM Rijnkels JM Podda E Righele F Tomasello F Caffieri S Beijersbergen van Henegouwen GM 《Photochemistry and photobiology》2003,77(4):343-348
Exposure of the nonsteroidal anti-inflammatory drug suprofen (SUP) to UV-radiation results in the formation of radicals, reactive oxygen species (ROS), photodecarboxylated products and photoadducts with biomacromolecules. Using an ex vivo pigskin explant model, we investigated whether topical coapplication of the water-soluble antioxidants vitamin C (Lascorbic acid, ASC), N-acetyl-L-cysteine (NAC) or L-cysteine ethylester (CYSET) with SUP reduced ultraviolet A (UVA)-induced decomposition of SUP. UVA-induced changes in antioxidant bioavailability in the stratum corneum and epidermis were also studied. Epidermal bioavailability of SUP in sham-irradiated pigskin increased 2.2- to 4.1-fold after the lowest antioxidant doses (P < 0.05). As compared with no applied antioxidant, increasing doses of all tested antioxidants resulted in increased levels of SUP and decreased levels of photoproducts (P < 0.05). A maximal protection against SUP photodegradation of 70% was found after an ASC dose of 1 micromol/cm2; these values were 60% for a NAC dose of 10 micromol/cm2 and 50% for a CYSET dose of 5 micromol/cm2. Skin antioxidant levels increased with increasing applied dose (P < 0.05); the bioavailability of CYSET was approximately three-fold lower than that of ASC and NAC. UVA exposure resulted in 30-50% consumption of the topically applied ASC or NAC in the stratum corneum, whereas CYSET was not consumed. In conclusion, the topically applied water-soluble antioxidants ASC, NAC and CYSET protect against UVA-induced decomposition of SUP by scavenging radicals and ROS. Coapplication of these antioxidants may therefore be an effective way to reduce or prevent the phototoxic effects of SUP in vivo. 相似文献
495.
Federica Colombo 《Tetrahedron letters》2007,48(15):2687-2690
The catalytic enantioselective addition of allyltributylstannane to N-protected α-iminoesters promoted by silver(I) trifluoromethanesulfonate in the presence of chiral imine ligands was studied. After testing several chiral imines derived from 1,2-diaminocyclohexane and binaphthyl diamine a very simple experimental procedure was developed that allowed us to obtain optically active homoallylic amines in very high yields and enantioselectivities up to 71%. 相似文献
496.
Serum transferrin (Tf) comprises several isoforms with up to two complex oligosaccharide chains containing zero to eight sialic acid residues and neutral sugars. The major glycoform, known as tetrasialo-Tf, contains four sialic acid residues and accounts for about 80% of whole Tf in human serum. Carbohydrate-deficient transferrin (CDT) encompasses isoforms that are deficient in carbohydrate chains and consequently in sialic acid residues (including asialo-, monosialo- and disialo-Tf) and is a well known marker for chronic alcohol abuse. Recently capillary zone electrophoresis (CZE) has been reported as a tool extremely effective for the simultaneous, individual, quantitative determination of CDT isoforms. Three CZE methods that feature different dynamic capillary coatings were evaluated and optimized for CDT determination in human serum of alcohol abusers and control subjects. CZE separation was performed in alkaline borate buffers after serum sample saturation with iron, electropherograms were detected at 200 nm, data were evaluated as % area of disialo-Tf in relation to tetrasialo-Tf and peak identification was accomplished via relative migration times to tetrasialo-Tf, immunosubtraction and enzymatic sequential cleavage of sialic acid residues. Dynamic capillary coatings with diaminobutane, spermine and a double coating produced by commercially available proprietary agents were investigated and found to be suitable for determination of CDT in human serum. For all three approaches, best results were obtained in 50 microm I.D. fused-silica capillaries of 50 cm effective length and a capillary cartridge temperature of 20-25 degrees C. Using 3 mM 1,4-diaminobutane or 0.02 mM spermine in a borate-based running buffer of pH 8.3 provided data of remarkable similarity with resolution of di-, tri-, tetra- and pentasialo-Tf within 15-18 min. With the double coating, asialo-Tf and Tf isoforms with two to six sialic acid residues were baseline separated. Compared to the two amine-based procedures, the run times were found to be somewhat shorter, the detector signals higher, the applied power level significantly lower and the reproducibility better. 相似文献
497.
Stanislaw Miertus Vladimir Frecer Emo Chiellini Federica Chiellini Roberto Solaro Jacopo Tomasi 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(1):23-46
Using a simple molecular mechanics approach interaction energy profiles of simple probes (C, CH4, C6H6, H2O, NH4
+, and HCOO-) passing through the center of the -CD ring cavity along the main molecular symmetry axis were first evaluated. Molecular Electrostatic Potential (MEP) values along the same path were also evaluated. The effect of the flexibility of the host -CD molecule together with solute-solvent (H2O) interactions have been represented by averaging structures of MD calculations for -CD alone and -CD surrounded by 133 H2O molecules. The effect of various substitutions of -CD has also been evaluated. Small symmetric hydrophobic probes (such as C, CH4, C6H6) are predicted to form stable inclusion complexes with non-substituted and substituted -CDs, the probe position typically being near the cavity center. The stability of the inclusion complexes will increase with increasing size and aliphatic character of the probe. Small polar and charged probes (such as H2O, NH4
+, HCOO-) are predicted to prefer the interaction with the solvent (water) in the bulk phase rather than the formation of inclusion complexes with non-substituted and substituted -CDs. Guest–host interactions in the stable inclusion complexes with hydrophobic probes are almost entirely dominated by dispersion interactions. The MEP reaches magnitudes close to zero in the center of the non-substituted -CD ring cavity and in most of the studied substituted -CDs and shows maximum positive or negative values outside of the cavity, near the ring faces. Substitution of -CD by neutral substituents leads to enhanced binding of hydrophobic probes and significant changes in the MEP profile along the -CD symmetry axis. 相似文献
498.
499.
500.
Federica Pellati Renato Bruni Maria Grazia Bellardi Assunta Bertaccini Stefania Benvenuti 《Journal of chromatography. A》2009,1216(15):3260-3269
In this study, a simple and reliable HPLC method for the qualitative and quantitative analysis of cardiac glycosides in Digitalis lanata Ehrh. raw material was developed and applied to healthy and phytoplasma-infected plants. The target analytes cover a broad range of secondary metabolites, including primary, secondary and tertiary glycosides and the corresponding aglycones. The sample preparation was carried out by sonication of the plant material with 70% (v/v) aqueous methanol at room temperature, followed by reversed-phase solid-phase extraction purification from interfering pigments. The HPLC analyses were performed on a Symmetry C18 column (75 mm × 4.6 mm I.D., 3.5 μm), with a gradient elution composed of water and acetonitrile, at a flow rate of 1.0 mL/min. The column temperature was set at 20 °C and the photodiode array detector monitored the eluent at 220 nm. The method was validated with respect to ICH guidelines and the validation parameters were found to be highly satisfactory. The application of the method to the analysis of D. lanata leaves indicated that air-drying was the optimum method for raw material processing when compared with freeze-drying. The analysis of healthy and phytoplasma-infected plants demonstrated that the secondary metabolite mainly affected by the pathogen presence was lanatoside C (153.2 μg/100 mg versus 76.1 μg/100 mg). Considering the importance of D. lanata plant material as source of cardiac glycosides, the developed method can be considered suitable for the phytochemical analysis and for the quality assurance of D. lanata used for pharmaceutical purpose. 相似文献