全文获取类型
收费全文 | 256篇 |
免费 | 0篇 |
国内免费 | 1篇 |
专业分类
化学 | 190篇 |
力学 | 10篇 |
数学 | 42篇 |
物理学 | 15篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 4篇 |
2020年 | 1篇 |
2019年 | 6篇 |
2018年 | 1篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 5篇 |
2014年 | 2篇 |
2013年 | 10篇 |
2012年 | 10篇 |
2011年 | 9篇 |
2010年 | 7篇 |
2009年 | 6篇 |
2008年 | 19篇 |
2007年 | 13篇 |
2006年 | 14篇 |
2005年 | 19篇 |
2004年 | 8篇 |
2003年 | 4篇 |
2002年 | 4篇 |
2001年 | 2篇 |
2000年 | 9篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 2篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 7篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1974年 | 2篇 |
排序方式: 共有257条查询结果,搜索用时 15 毫秒
201.
Orazio A. Attanasi Graziano Baccolini Lucia De Crescentini Paolino Filippone 《Tetrahedron》2008,64(28):6724-6732
The reaction of 1,2-diaza-1,3-butadienes with dialkyl phenylphosphonites under solvent-free conditions proceeds via zwitterionic intermediate and gives, by precipitation, the stable ylidic α-phosphanylidene-hydrazones that, in turn, can be transformed into the corresponding 3-phenyl-2H-1,2,3λ5-diazaphospholes. The latter compounds are converted by hydrolytic cleavage in methanol-water (95:5) into E-hydrazonophosphonates that are useful for the preparation of the corresponding β-ketophosphonates and 4-[alkoxy(phenyl)phosphoryl]-1,2-diaza-1,3-butadienes. These peculiar 1,2-diaza-1,3-butadienes, bearing an alkoxy(phenyl)phosphoryl group on the carbon atom in position 4 are also able to add different nucleophiles, such as methanol or thiourea, giving 2-[alkoxy(phenyl)phosphoryl]-2-methoxyhydrazones and 5-phosphinate-substituted thiazol-4-ones, respectively. 相似文献
202.
203.
Graziano Fusini Davide Barsanti Gaetano Angelici Gianluca Casotti Angelo Canale Giovanni Benelli Andrea Lucchi Adriano Carpita 《Tetrahedron》2018,74(33):4381-4389
In the present study, eleven new sex-specific components extracted from female rectal gland of olive fruit flies were synthesized and identified. The quantitative determination of those components by GC and GC/EI-MS, at different moments of the insect life span, highlighted the growing trend of their secretion. While for the synthesis of saturated esters, conventional transesterification methods could be adopted, for the synthesis of unsaturated components, a Negishi cross-coupling between organozinc halides and (Z)-1-bromo-1-alkenes was developed. To the extent of our knowledge, this reaction represents the first example of supported-catalyst promoted Negishi coupling, between an alkylzinc reagent and an alkenyl halide. 相似文献
204.
In the last years, several studies have recently evaluated the beneficial effects of red orange juice (Citrus sinensis (L.) Osbeck) and its active components in weight management and obesity. Moro orange is a cultivar of red orange, particularly rich in active compounds such as anthocyanins, hydroxycinnamic acids, flavone glycosides and ascorbic acid, which displays anti-obesity effects in in vitro and in vivo studies. In this clinical study, the effect of a Moro juice extract (Morosil®, 400 mg/die) supplementation was evaluated in overweight healthy human volunteers for 12 weeks. Results showed that Moro juice extract intake was able to induce a significant reduction in body mass index (BMI) after 4 weeks of treatment (p < 0.05). Moreover, in subjects treated with Moro extract, body weight, BMI, waist and hip circumference were significantly different from the placebo group (p < 0.05). In conclusion, it could be suggested that the active compounds contained in Moro juice have a synergistic effect on fat accumulation in humans and Moro juice extract can be used in weight management and in the prevention of human obesity. 相似文献
205.
Graziano JJ Liu W Perera R Geierstanger BH Lesley SA Schultz PG 《Journal of the American Chemical Society》2008,130(1):176-185
A protein evolution strategy is described by which double-stranded DNA fragments encoding defined Escherichia coli protein secondary structural elements (alpha-helices, beta-strands, and loops) are assembled semirandomly into sequences comprised of as many as 800 amino acid residues. A library of novel polypeptides generated from this system was inserted into an enhanced green fluorescent protein (EGFP) fusion vector. Library members were screened by fluorescence activated cell sorting (FACS) to identify those polypeptides that fold into soluble, stable structures in vivo that comprised a subset of shorter sequences ( approximately 60 to 100 residues) from the semirandom sequence library. Approximately 108 clones were screened by FACS, a set of 1149 high fluorescence colonies were characterized by dPCR, and four soluble clones with varying amounts of secondary structure were identified. One of these is highly homologous to a domain of aspartate racemase from a marine bacterium (Polaromonas sp.) but is not homologous to any E. coli protein sequence. Several other selected polypeptides have no global sequence homology to any known protein but show significant alpha-helical content, limited dispersion in 1D nuclear magnetic resonance spectra, pH sensitive ANS binding and reversible folding into soluble structures. These results demonstrate that this strategy can generate novel polypeptide sequences containing secondary structure. 相似文献
206.
Franceschi P Vrhovsek U Guella G 《Rapid communications in mass spectrometry : RCM》2011,25(7):827-833
Mass spectrometry is an established analytical technique in high-throughput metabolomics, often coupled with ultra-performance liquid chromatographic separation (UPLC). Since ion formation under 'soft' conditions is a complex phenomenon resulting in fragmentation, clustering and adduct formation, the extraction of meaningful information from holistic metabolomic profiling of biological samples requires the understanding of the physicochemical phenomena occurring inside an ionization source. In this paper we investigate the ionization dynamics of two ellagitannins (sanguiin H6 and lambertianin C) by combining state of the art mass spectrometric techniques (MALDI, ESI, APCI), ion mobility (IMS) and NMR. These compounds can be used as prototype of an important class of bio-active compound present in relevant concentrations in some food matrices. 相似文献
207.
Frassanito R Cantonati M Flaim G Mancini I Guella G 《Rapid communications in mass spectrometry : RCM》2008,22(22):3531-3539
Liquid chromatography/electrospray ionisation mass spectrometry (LC/ESI-MS) has been employed to identify carotenoid esters present in raw organic extracts of pigmented freshwater microalgae and to gain structural information on these compounds. In particular, acyl carotenoid derivatives of Haematococcus pluvialis and Euglena sanguinea have been characterised by tandem mass spectrometry (MS/MS) in a quadrupole ion trap. ESI-MS/MS allows recognition of the presence of carotenoid esters in complicated mixtures without any initial chromatographic work-up and without the need to use UV-Vis photo-diode array (PDA) detectors. Product ion scans of the [M + Na]+ ion lead to known neutral losses of the C7H8 and C8H10 residues from the conjugated polyene moiety of the carotenoid unit, that permit the unambiguous identification of the carotenoid itself. These structurally relevant ions are not observed in positive or negative ion APCI (atmospheric pressure chemical ionisation) mass spectra. Moreover, the several product ions observed in positive and/or negative ion ESI-MS/MS not only are a diagnostic signature of the main structural features of the acyl chains such as length, position and unsaturation, but also display the nominal mass of the parent xanthophyll. Our methodology has been validated (i) by using esters of astaxanthin obtained from off-line purification of the H. pluvialis extracts and structurally elucidated through proton nuclear magnetic resonance (1H-NMR) spectroscopy and (ii) by product analysis of esters by alkaline hydrolysis. The characterisation of the unknown carotenoid esters of E. sanguinea is a demonstration of the capabilities of this methodology. 相似文献
208.
Graziano Guella Fernando Dini Francesco Pietra 《Angewandte Chemie (International ed. in English)》1999,38(8):1134-1136
Challenging questions are raised about the biosynthetic origin of vannusal A ( 1 ), a metabolite that is isolated from the tropical marine ciliate Euplotes vannus and contains an unusual C30 backbone. 相似文献
209.
4-Bromodiazaphosphole-3-oxides or sulfides can be obtained by reaction of the corresponding unsubstituted derivative with appropriate reagents. PTAB was demonstrated to be very regio- and stereoselective, allowing bromination exclusively at the 4-position of the ring with prevalent or exclusive formation of one of the two possible isomers. However, when regioselectivity is not required, cheaper and more available bromine or NBS can be used conveniently. 4-Chlorodiazaphosphole-3-oxides can be obtained by reaction of the corresponding unsubstituted derivative with NCS. 4-Bromodiazaphosphole-3-oxides undergo stereoselective methanolysis as well as parent unsubstituted oxides. 相似文献
210.
New polyhalogenated, twelve‐membered, O‐bridged cyclic C15‐ethers, having in common oxygenation at C(6) and a bromoallene side chain at C(4) (where C(1) is the bromoallene‐chain terminus), were isolated from the red seaweed Laurencia obtusa from the Turkish Mediterranean Sea, i.e., the 9,12‐O‐bridged obtusallene VII ( 5 ), the 6,9 : 9,12‐bis‐O‐bridged obtusallene V ( 3 ) and obtusallene VI ( 4 ), as well as the 6,9‐O‐bridged obtusallene VIII ( 8 ) and obtusallene IX ( 9 ). The behavior of portions of the macrocycle involved in fast motions and their equilibrium position depend on the particular compound, revealing a subtle conformational behavior of these macrocycles, while 8 and 9 show an unprecedented solvolytic reactivity at the masked furfuryl (=2‐furylmethyl) C‐atom. 相似文献