全文获取类型
收费全文 | 592篇 |
免费 | 18篇 |
专业分类
化学 | 506篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 46篇 |
物理学 | 53篇 |
出版年
2023年 | 2篇 |
2022年 | 11篇 |
2021年 | 9篇 |
2020年 | 13篇 |
2019年 | 9篇 |
2018年 | 8篇 |
2017年 | 8篇 |
2016年 | 18篇 |
2015年 | 21篇 |
2014年 | 21篇 |
2013年 | 43篇 |
2012年 | 34篇 |
2011年 | 37篇 |
2010年 | 20篇 |
2009年 | 21篇 |
2008年 | 44篇 |
2007年 | 32篇 |
2006年 | 35篇 |
2005年 | 32篇 |
2004年 | 33篇 |
2003年 | 27篇 |
2002年 | 27篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 9篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 9篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1975年 | 4篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1935年 | 4篇 |
1934年 | 2篇 |
排序方式: 共有610条查询结果,搜索用时 15 毫秒
11.
12.
James O'Donnell Bruno Rusterholz Barbara Aebersold Denise Rüegg Wilhelm Simon Ernö Pretsch 《Mikrochimica acta》1994,113(1-2):45-52
In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992 相似文献
13.
We describe a simple method for the determination of phenobarbital, diphenylhydantoin, carbamazepine, and primidone in serum, by use of gas-liquid chromatography with temperature programming. The methylated derivatives of these anticonvulsants were well resolved, as was 5-(p-methylphenyl)-5-phenylhydantoin, the internal standard. In this procedure we used the jet tube for separation of the drug from the serum. The proposed procedure requires only 100 μl of serum and can be done in less than 30 min. The lower limit of detection for each of the drugs is 0.5 mg/liter. Analytical recoveries of drug from serum were excellent and peak height and concentration were linearly related up to twice the toxic concentration for serum. 相似文献
14.
We report here our findings on a new and highly efficient strategy for the synthesis of β-amino acids involving the addition of bis(O-silyl) ketene acetals on Mannich type iminium electrophiles. 相似文献
15.
Rafael Fogel Rafaela Rodrigues Garcia Rebeca da Silva Oliveira Denise Neves Menchero Palacio Luciana da Silva Madeira Nei Pereira Jr. 《Applied biochemistry and biotechnology》2005,122(1-3):741-752
The dilute-acid hydrolysis of sugarcane bagasse was optimized using a statistical experimental design resulting in hydrolysates
containing 57.25 g/L of xylose, which were fermented with a high inoculum concentration (10 g/L of the yeast Candida guilliermondii IM/UFRJ 50088). The addition of urea reduced the time of conversion (t
C) to 75 h (without nitrogen source addition t
C>127 h), and, consequently, improving the rates of xylitol bioproduction. Fermentator experiments, using the optimized conditions,
resulted in enhanced conversion rates, reducing t
C to 30 h. The stability of the yeast in the hydrolysate was also verified in a 480-h cultivation. 相似文献
16.
Denise Bohrer Uwe Heitmann Mao-dong Huang Helmut Becker-Ross Stefan Florek Bernhard Welz Denise Bertagnolli 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007
High-resolution continuum source atomic absorption spectrometry (HR-CS AAS) has been used to investigate spectral and non-spectral interferences found with a conventional line source atomic absorption spectrometer in the determination of aluminum in pharmaceutical products containing elevated iron and sugar concentrations. A transversely heated graphite furnace was used as the atomizer in both spectrometers. The two most sensitive aluminum lines at 309.3 nm and 396.2 nm were investigated and it was found that an iron absorption line at 309.278 nm, in the vicinity of the aluminum line at 309.271 nm, could be responsible for some spectral interference. The simultaneous presence of iron and the organic components of the matrix were responsible for radiation scattering, causing high continuous and also structured background absorption at both wavelengths. The aluminum and iron absorption could not be separated in time, i.e., the iron interference could not be eliminated by optimizing the graphite furnace temperature program. However, an interference-free determination of aluminum was possible carrying out the measurements with HR-CS AAS at 396.152 nm after applying least squares background correction for the elimination of the structured background. Analytical working range and other figures of merit were determined and are presented for both wavelengths using peak volume registration (center pixel ± 1) and the center pixel only. Limits of detection and characteristic masses ranged from 1.1 to 2.5 pg and 13 to 43 pg, respectively. The method was used for the determination of the aluminum contamination in pharmaceutical formulations for iron deficiency treatment, which present iron concentrations from 10 to 50 g l− 1. Spike recoveries from 89% to 105% show that the proposed method can be satisfactorily used for the quality control of these formulations. 相似文献
17.
In this work a laboratory polymerization scale process was studied for the production of polybutadiene with high content of cis-1,4 repeating units. A Ziegler-Natta catalytic system based on neodymium versatate (catalyst), diisobutylaluminium hydride (cocatalyst) and tert-butyl chloride (chlorinating agent) was used. The influence of solvent nature (pure grade) and possible contaminants (electron donors) in a recovered solvent from a butadiene-styrene anionic polymerization industrial plant on the stereoselectivity and catalytic activity, molecular weight and molecular weight distribution of the resultant polybutadienes was studied. The polymers were characterized by infrared spectroscopy and size exclusion chromatography. Polybutadienes with cis-1,4 units content in the range of 99-98% were produced. The polymers weight-average molecular weight, , varied from 2.23 × 105 to 4.47 × 105 and the molecular weight distribution, MWD, from 3.1 to 5.1. 相似文献
18.
A collaborative study was conducted to compare a new enrichment procedure for the TECRA Salmonella Visual Immunoassay (TSVIA) with the reference method given in the U.S. Food and Drug Administration's Bacteriological Analytical Manual (7th Ed.). Three food types (milk powder, pepper, and soy flour) were analyzed in Australia and 3 food types (milk chocolate, dried egg, and raw turkey) were analyzed in the United States. Thirty-eight collaborators participated in the study. The TECRA method was evaluated using both Rappaport-Vassiliadis R10 (RV(R10)) and tetrathionate (TT) broths for selective enrichment. M broth cultures arising from each of the 2 selective enrichment broths were tested in the TSVIA using 2 individual wells, one for each selective broth, and a single well to test the pooled selective enrichment broths. The results for the pooled enrichment broths were reported elsewhere. This study presents the results for the use of single enrichment broths, i.e., RV(R10) only or TT only, with the TSVIA. No significant differences (p > 0.05) were observed for the pairwise comparison of the proportion of positive samples for either RV(R10) or TT used as a single enrichment broth for the TSVIA with that for the reference method. 相似文献
19.
Stefan Sahli Brian Frank W.Bernd Schweizer Franois Diederich Denise Blum‐Kaelin JohannesD. Aebi Hans‐Joachim Bhm Christian Oefner GlennE. Dale 《Helvetica chimica acta》2005,88(4):731-750
A new class of nonpeptidic inhibitors of the ZnII‐dependent metalloprotease neprilysin with IC50 values in the nanomolar activity range (0.034–0.30 μM ) were developed based on structure‐based de novo design (Figs. 1 and 2). The inhibitors feature benzimidazole and imidazo[4,5‐c]pyridine moieties as central scaffolds to undergo H‐bonding to Asn542 and Arg717 and to engage in favorable π‐π stacking interactions with the imidazole ring of His711. The platform is decorated with a thiol vector to coordinate to the ZnII ion and an aryl residue to occupy the hydrophobic S1′ pocket, but lack a substituent for binding in the S2′ pocket, which remains closed by the side chains of Phe106 and Arg110 when not occupied. The enantioselective syntheses of the active compounds (+)‐ 1 , (+)‐ 2 , (+)‐ 25 , and (+)‐ 26 were accomplished using Evans auxiliaries (Schemes 2, 4, and 5). The inhibitors (+)‐ 2 and (+)‐ 26 with an imidazo[4,5‐c]pyridine core are ca. 8 times more active than those with a benzimidazole core ((+)‐ 1 and (+)‐ 25 ) (Table 1). The predicted binding mode was established by X‐ray analysis of the complex of neprilysin with (+)‐ 2 at 2.25‐Å resolution (Fig. 4 and Table 2). The ligand coordinates with its sulfanyl residue to the ZnII ion, and the benzyl residue occupies the S1′ pocket. The 1H‐imidazole moiety of the central scaffold forms the required H‐bonds to the side chains of Asn542 and Arg717. The heterobicyclic platform additionally undergoes π‐π stacking with the side chain of His711 as well as edge‐to‐face‐type interactions with the side chain of Trp693. According to the X‐ray analysis, the substantial advantage in biological activity of the imidazo‐pyridine inhibitors over the benzimidazole ligands arises from favorable interactions of the pyridine N‐atom in the former with the side chain of Arg102. Unexpectedly, replacement of the phenyl group pointing into the deep S1′ pocket by a biphenyl group does not enhance the binding affinity for this class of inhibitors. 相似文献
20.
Robson Araújo de Freitas Junior Paloma Kênia de Moraes Berenguel Lossavaro Cndida Aparecida Leite Kassuya Edgar Julian Paredes-Gamero Nelson Carvalho Farias Júnior Maria Inês Lenz Souza Francielli Maria de Souza Silva-Comar Roberto Kenji Nakamura Cuman Denise Brentan Silva Mnica Cristina Toffoli-Kadri Saulo Euclides Silva-Filho 《Molecules (Basel, Switzerland)》2022,27(12)
The aim of this study is to evaluate the phytochemical profile, oral acute toxicity, and the effect of ylang-ylang (Cananga odorata Hook. F. & Thomson) essential oil (YEO) on acute inflammation. YEO was analyzed by gas chromatography/mass spectrometry. For in vitro tests, YEO was assessed using cytotoxicity, neutrophil chemotaxis induced by N-formyl methionyl leucyl phenylalanine (fMLP), and phagocytic activity tests. YEO was orally administered in zymosan-induced peritonitis, carrageenan-induced leukocyte rolling, and adhesion events in the in situ microcirculation model and in carrageenan-induced paw edema models. YEO (2000 mg/kg) was also tested using an acute toxicity test in Swiss mice. YEO showed a predominance of benzyl acetate, linalool, benzyl benzoate, and methyl benzoate. YEO did not present in vitro cytotoxicity. YEO reduced the in vitro neutrophil chemotaxis induced by fMLP and reduced the phagocytic activity. The oral treatment with YEO reduced the leukocyte recruitment and nitric oxide production in the zymosan-induced peritonitis model, reduced rolling and adherent leukocyte number induced by carrageenan in the in situ microcirculation model, and reduced carrageenan-induced edema and mechanical hyperalgesia. YEO did not present signs of toxicity in the acute toxicity test. In conclusion, YEO affected the leukocyte activation, and presented antiedematogenic, anti-hyperalgesic, and anti-inflammatory properties. 相似文献