全文获取类型
收费全文 | 1228篇 |
免费 | 48篇 |
国内免费 | 5篇 |
专业分类
化学 | 1032篇 |
力学 | 19篇 |
数学 | 88篇 |
物理学 | 142篇 |
出版年
2024年 | 2篇 |
2023年 | 17篇 |
2022年 | 58篇 |
2021年 | 80篇 |
2020年 | 31篇 |
2019年 | 38篇 |
2018年 | 17篇 |
2017年 | 15篇 |
2016年 | 43篇 |
2015年 | 42篇 |
2014年 | 42篇 |
2013年 | 55篇 |
2012年 | 81篇 |
2011年 | 96篇 |
2010年 | 63篇 |
2009年 | 58篇 |
2008年 | 80篇 |
2007年 | 91篇 |
2006年 | 55篇 |
2005年 | 67篇 |
2004年 | 56篇 |
2003年 | 36篇 |
2002年 | 31篇 |
2001年 | 17篇 |
2000年 | 12篇 |
1999年 | 15篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 9篇 |
1993年 | 4篇 |
1992年 | 9篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 3篇 |
1973年 | 1篇 |
排序方式: 共有1281条查询结果,搜索用时 0 毫秒
11.
This survey critically discusses high-concentration-capacity (HCC) headspace (HS) techniques applied to sample the volatile fraction of matrices of interest in the flavors and fragrance fields. In particular, the advantages, limits, and fields of application of HS solid-phase microextraction (SPME), high-capacity HS sorptive extraction (HSSE) and HS solid-phase dynamic extraction (SPDE) are evaluated. These techniques are discussed in view of the peculiar characteristic of HCC-HS techniques, from the standpoint that these techniques are a bridge between static (S-HS) and dynamic HS (D-HS) because they are as simple, fast, easy to automate, and reliable as S-HS, yet afford analyte concentration factors comparable to those of D-HS. Moreover, the different degree of their development is a consequence of the different times in which they were introduced into the market, because the potential of HS-SPME is now well known, having been introduced approximately 12 years ago, but that of HSSE has still to be fully explored, and HS-SPDE still has to be investigated because it is very recent. 相似文献
12.
Quaglia M Carazzone C Sabella S Colombo R Giorgetti S Bellotti V De Lorenzi E 《Electrophoresis》2005,26(21):4055-4063
Beta2-microglobulin (beta2-m) is a small amyloidogenic protein normally present on the surface of most nucleated cells and responsible for dialysis-related amyloidosis, which represents a severe complication of long-term hemodialysis. A therapeutic approach for this amyloidosis could be based on the stabilization of beta2-m through the binding to a small molecule, and consequent inhibition of protein misfolding and amyloid fibril formation. A few compounds have been described to weakly bind beta2-m, including the drug suramin. The lack of a binding site for nonpolypeptidic ligands on the beta2-m structure makes it difficult for both the identification of functional groups responsible for the binding and the search of hits to be optimized. The characterization of the binding properties of suramin for beta2-m by using three different techniques (surface plasmon resonance, affinity CE (ACE), ultrafiltration) is here described and the results obtained are compared. The common features of the chemical structures of the compounds known to bind the protein led us to select 200 sulfonated/suramin-like molecules from a wider chemical library on the basis of similarity rules, so as to possibly single out some interesting hits and to gain more information on the functional groups involved in the binding. The development of screening methods to test the compounds by using ultrafiltration and ACE is described. 相似文献
13.
Mandrioli R Musenga A Ferranti A Lasaponara SS Fanali S Raggi MA 《Journal of separation science》2005,28(9-10):966-972
A micellar electrokinetic chromatographic method was developed and applied for the first time to the separation and quantification of the main components of cloves, namely eugenol and beta-caryophyllene. The analytes were separated in less than ten minutes in an unmodified fused silica capillary (effective length: 40.0 cm) using a background electrolyte composed of 25 mM carbonate buffer (pH 10.0) and 60 mM sodium dodecylsulfate. Analyte concentrations were determined in clove oil and in methanolic clove extracts after simple sequential dilution with methanol and background electrolyte, and the resulting electropherograms showed no interference due to other components. Precision assays gave satisfactory results, with mean standard deviation of peak areas lower than 4.7% (lower than 1.5% for migration times). The eugenol content of a commercial clove oil was about 70% (RSD% = 3.2), while that of beta-caryophyllene was about 15% (RSD% = 4.2); in clove extracts, on the other hand, eugenol was approximately 15% (RSD% = 4.7) and beta-caryophyllene 4% (RSD% = 5.1). Accuracy was also good (mean recovery >98%). 相似文献
14.
Charge-exchange reactions involving benzene have been successfully exploited to increase the sensitivity of atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) towards hydrophobic compounds of significant environmental relevance which are not detectable with the ordinary APCI techniques. Among them, good sensitivity have been found for (a) highly chlorinated biphenyl derivatives such as dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethene (DDE); (b) cyclopentadienes such as Aldrin and its epoxy derivatives Dieldrin and Endrin; and (c) dibenzofurans and dibenzo-para-dioxins such as 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF) and 2,3,7,8-tetrachloro-dibenzo-para-dioxin (2,3,7,8-TCDD). The reactant benzene molecules were introduced into the source either through the nebulizer gas or by direct post-column addition of neat liquid, whereas the targeted compounds were analyzed using a high-performance liquid chromatography (HPLC) RP-18 column using methanol/water solutions as mobile phase. By using benzene as post-column reagent, positive ion mode detection was proven to be significantly enhanced as compared with APCI measurements carried out without benzene assistance. 相似文献
15.
Michele Sacerdoti Maria Chiara Dalconi Barbara Cavicchi Stefano Colonna 《Journal of solid state chemistry》2004,177(6):1781-1788
Sol-gel routes were used to prepare Ta 10 at% and Nb 5 at% and 10 at% doped titania nanosized powders. When fired between 410°C and 850°C the doped titania powders are in the anatase phase; further heating up to 1050°C is required to obtain the rutile phase. The presence of dopant atoms delays the rate of transformation as compared with pure titania powders. Doping also affects the rate of grain growth and increases the conductance response to gas. To better understand the role played by dopant atoms in inhibiting both phase transformation to rutile and grain growth, X-ray Absorption Spectroscopy measurements were performed at the LIII-LI absorption edges of Ta and Nb K absorption edge. Analysis was restricted to the anatase phase because the transformation to rutile phase, obtained by firing at 1050°C, is accompanied by the formation of undesired Ta and Nb oxides (Ta2O5 and Nb2TiO7, respectively). Extended X-ray Absorption Fine Structure and X-ray Absorption Near-Edge Spectroscopy analysis results indicate that in nanostructured anatase both tantalum and niobium atoms substitute Ti cations with +5 valence state. 相似文献
16.
Camera E Picardo M Presutti C Catarcini P Fanali S 《Journal of separation science》2004,27(12):971-976
We developed a simple and reliable analytical method for the quantification and the characterization of ceramides extracted from biological samples by high-performance liquid chromatography (HPLC) coupled to electrospray ionisation tandem mass spectrometry (ESI/MS/MS). The chromatographic separation of analytes was carried out in a RP8 column, eluting with a methanol-water mixture in gradient elution mode. The separated lipids were detected by total ion monitoring and characterised by MS/MS spectra; quantitative analysis was performed by integrating the extracted ion peaks obtained in the negative ion mode. Good repeatability was obtained for retention time (0.3-2%), peak area ratio (A(S)/A(IS), 2-8%), as well as limit of detection (LOD, 5-26 pg) and quantification (LOQ, 13-53 pg). The method was validated for the analysis of N-palmitoyl-D-erythro-sphingosine (Cer16), N-stearoyl-D-erythro-sphingosine (Cer18), N-tetracosanoyl-D-erythro-sphingosine (N24:0, lignoceric ceramide, Cer24:0), and N-tetracos-15'-enoyl-D-erythro-sphingosine (N24:1, nervonic ceramide, Cer24:1), giving good results. Lipid mixtures, extracted from skin and epidermal cells, were analysed for their content of the studied ceramides. 相似文献
17.
The catalytic (C/Pd) hydrogenation of 3-arylamino-2-nitro-2-enones ( 1 ) in the presence of carboxylic ortho esters ( 2 ) affords 4-acyl-1-arylimidazoles ( 3 ) in yields (20–70%) which depend on the degree of substitution of the imidazole ring. The spectral properties of compounds 3 , and particularly the 13C-nmr spectra, reflect both the electronic and steric effects of the substituents on the π-electron delocalization and planarity of the bicyclic system. 相似文献
18.
Turrio-Baldassarri L Battistelli CL Iamiceli AL 《Analytical and bioanalytical chemistry》2003,375(4):589-595
Pressurized Fluid Extraction (PFE) was evaluated for the extraction of polycyclic aromatic hydrocarbons (PAHs) and nitro-derivatives from diesel particulate matter. Extraction conditions were set up by performing several tests in which temperature, solvent strength, pressure, and static time were gradually increased. The results obtained on a laboratory test material made of a "lean" (low content of soluble fraction) Diesel particulate matter indicate that very severe conditions were needed in order to obtain better recoveries of the higher molecular weight molecules. Moreover, extraction efficiency seems to be influenced by the amount of soluble matter in the particulate, so that a "lean" particulate appears more difficult to extract. Recoveries of the deuterated standards of certain PAHs (i.e. indeno[1,2,3- cd]pyrene) were incomplete even with the toughest conditions tested. Experiments carried out on a certified material (SRM 1650 from NIST) also indicate that PFE can perform a better extraction of some of the PAHs than the method used for certification, but still incomplete. Comparison of results obtained on the SRM with different extraction techniques suggests that the composition of the extract varies considerably with the extraction technique and conditions. It is relevant to notice that recent Diesel engines produce leaner particulate: for future materials more drastic extraction conditions will be required. 相似文献
19.
On-line combination of partial filling capillary electrophoresis and electrospray ionization mass spectrometry was demonstrated for the simultaneous enantioseparation of tramadol and its main phase I metabolites. The partial filling technique was efficient at avoiding MS contamination by the chiral selector. Different experimental factors were investigated, including the chiral selector nature and concentration, plug length as well as the separation temperature. The best enantioseparation of the investigated compounds was achieved with a coated polyvinyl alcohol capillary and a 40 mM ammonium acetate buffer, pH 4.0, adding sulfobutyl ether beta-cyclodextrin (2.5 mg/ml) as the chiral selector. The charged cyclodextrin not only allowed enantioseparation of tramadol and its metabolites, but also improved the selectivity of compounds with the same molecular mass. Finally, CE-electrospray ionisation-MS was successfully applied to the stereoselective analysis of tramadol and its main metabolites in plasma after a simple liquid-liquid extraction. 相似文献
20.
Wu J Zaleski TJ Valenzano C Khosla C Cane DE 《Journal of the American Chemical Society》2005,127(49):17393-17404
Picromycin/methymycin synthase (PICS) is a modular polyketide synthase (PKS) that is responsible for the biosynthesis of both 10-deoxymethynolide (1) and narbonolide (2), the parent 12- and 14-membered aglycone precursors of the macrolide antibiotics methymycin and picromycin, respectively. PICS module 2 is a dehydratase (DH)-containing module that catalyzes the formation of the unsaturated triketide intermediate using malonyl-CoA as the chain extension substrate. Recombinant PICS module 2+TE, with the PICS thioesterase domain appended to the C-terminus to allow release of polyketide products, was expressed in Escherichia coli. Purified PICS module 2+TE converted malonyl-CoA and 4, the N-acetylcysteamine thioester of (2S,3R)-2-methyl-3-hydroxypentanoic acid, to a 1:2 mixture of the triketide acid (4S,5R)-4-methyl-5-hydroxy-2-heptenoic acid (5) and (3S,4S,5R)-3,5-dihydroxy-4-methyl-n-heptanoic acid-delta-lactone (10) with a combined kcat of 0.6 min(-1). The triketide lactone 10 is formed by thioesterase-catalyzed cyclization of the corresponding d-3-hydroxyacyl-SACP intermediate, a reaction which competes with dehydration catalyzed by the dehydratase domain. PICS module 2+TE showed a strong preference for the syn-diketide-SNAC 4, with a 20-fold greater kcat/K(m) than the anti-(2S,3S)-diketide-SNAC 14, and a 40-fold advantage over the syn-(2R,3S)-diketide-SNAC 13. PICS module 2(DH(0))+TE, with an inactivated DH domain, produced exclusively 10, while three PICS module 2(KR(0))+TE mutants, with inactivated KR domains, produced exclusively or predominantly the unreduced triketide ketolactone, (4S,5R)-3-oxo-4-methyl-5-hydroxy-n-heptanoic acid-delta-lactone (7). These studies establish for the first time the structure and stereochemistry of the intermediates of a polyketide chain elongation cycle catalyzed by a DH-containing module, while confirming the importance of key active site residues in both KR and DH domains. 相似文献