全文获取类型
收费全文 | 235篇 |
免费 | 26篇 |
国内免费 | 11篇 |
专业分类
化学 | 269篇 |
物理学 | 3篇 |
出版年
2024年 | 1篇 |
2023年 | 5篇 |
2022年 | 13篇 |
2021年 | 8篇 |
2020年 | 17篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2017年 | 4篇 |
2016年 | 13篇 |
2015年 | 15篇 |
2014年 | 7篇 |
2013年 | 16篇 |
2012年 | 10篇 |
2011年 | 14篇 |
2010年 | 8篇 |
2009年 | 13篇 |
2008年 | 15篇 |
2007年 | 16篇 |
2006年 | 17篇 |
2005年 | 19篇 |
2004年 | 16篇 |
2003年 | 15篇 |
2002年 | 6篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1995年 | 5篇 |
1994年 | 1篇 |
1990年 | 1篇 |
排序方式: 共有272条查询结果,搜索用时 15 毫秒
31.
32.
Gil Garrote Herminia Domínguez Juan C. Parajó 《Applied biochemistry and biotechnology》2001,95(3):195-207
Milled corncob samples were mixed with water and heated to obtain a liquid phase containing oligosaccharides, sugars, and
acetic acid as main reaction products (autohydrolysis reaction). To hydrolyze the sugar oligomers to the correspondent monomers,
sulfuric acid was added to the autohydrolysis liquors to reach 0.5–2 wt% of solution, and the reaction media were heated at
101.5–135°C. With this operational procedure, sugar solutions suitable as fermentation media (containing xylose as the major
component) were obtained. The kinetics of the posthydrolysis step was characterized on the basis of experimental data concerning
the time courses of the concentrations of xylooligosaccharides, xylose, furfural, and acetic acid. The concentrations of other
reaction byproducts (glucose or arabinose) were also measured. 相似文献
33.
《化学:亚洲杂志》2017,12(10):1027-1042
The importance of carbohydrates is evident by their essential role in all living systems. Their syntheses have attracted attention from chemists for over a century. Most chemical syntheses in this area focus on the preparation of carbohydrates from naturally occurring monosaccharides. De novo chemical synthesis of carbohydrates from feedstock starting materials has emerged as a complementary method for the preparation of diverse mono‐ and oligosaccharides. In this review, the history of de novo carbohydrate synthesis is briefly discussed and particular attention is given to methods that address the formation of glycosidic bonds for potential de novo synthesis of oligosaccharides. Almost all methods of this kind involve the formation of dihydropyran intermediates. Recent progress in forming dihydropyrans by Achmatowicz rearrangement, hetero‐Diels–Alder cycloaddition, ring‐closing metathesis, and other methods is also elaborated. 相似文献
34.
Erdélyi M d'Auvergne E Navarro-Vázquez A Leonov A Griesinger C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(34):9368-9376
The dynamics of the glycosidic bond of lactose was studied by a paramagnetic tagging‐based NMR technique, which allowed the collection of an unusually large series of NMR data for a single compound. By the use of distance‐ and orientation‐dependent residual dipolar couplings and pseudocontact shifts, the simultaneous fitting of the probabilities of computed conformations and the orientation of the magnetic susceptibility tensor of a series of lanthanide complexes of lactose show that its glycosidic bond samples syn/syn, anti/syn and syn/anti ?/ψ regions of the conformational space in water. The analysis indicates a higher reliability of pseudocontact shift data as compared to residual dipolar couplings with the presently available weakly orienting paramagnetic tagging technique. The method presented herein allows for an improved understanding of the dynamic behaviour of oligosaccharides. 相似文献
35.
Chang YL Liao SK Chen YC Hung WT Yu HM Yang WB Fang JM Chen CH Lee YC 《Journal of mass spectrometry : JMS》2011,46(3):247-255
MALDI-MS provides a rapid and sensitive analysis of large biomolecules such as proteins and nucleic acids. However, oligo- and polysaccharides are less sensitive in MS analysis partly due to their neutral and hydrophilic nature to cause low ionization efficiency. In this study, four types of oligosaccharides including aldoses, aminoaldoses, alduronic acids and α-keto acids were modified by appropriate tags at the reducing termini to improve their ionization efficiency. Bradykinin (BK), a vasoactive nonapeptide (RPPGFSPFR), containing two arginine and two phenylalanine residues turned out to be an excellent MS signal enhancer for maltoheptaose, GlcNAc oligomers and oligogalacturonic acids. In the MALDI-TOF-MS analysis using 2,5-dihydroxybenzoic acid (2,5-DHB) as the matrix, the GalA4-BK and GalA5-BK conjugates prepared by reductive amination showed the detection limit at 0.1 fmol, i.e. ~800-fold enhancement over the unmodified pentagalacturonic acids. The remarkable MS enhancement was attributable to the synergistic effect of the basic arginine residues for high proton affinity and the hydrophobic property phenylalanine residues for facile ionization. A tetrapeptide GFGR(OMe) and an arginine linked phenylenediamine (H(2) N)(2) Ph-R(OMe) were thus designed to act as potent tags of oligosaccharides in MS analysis. Interestingly, concurrent condensation and lactonization of α2,8-linked tetrasialic acid (SA4) was carried out with (H(2) N)(2) Ph-R(OMe) to obtain a quinoxalinone derivative, which showed > 200-fold enhancement over unmodified SA4 in the MALDI-TOF-MS analysis. 相似文献
36.
Shuo Zhang Prof. Dr. Peter H. Seeberger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(69):17444-17451
Acinetobacter baumannii is an opportunistic pathogen that causes serious nosocomial infections. One of the multidrug-resistant strains, AB5075, can result in bacteremia, pneumonia and wound infections associated with high morbidity and mortality. The structurally unique glycans on the surface of these bacteria are attractive targets for the development of glycoconjugate vaccines. Here, we report the first total synthesis of the densely functionalized trisaccharide repeating unit of A. baumannii AB5075 as well as two analogues. The construction of 1,2-cis linkages between the rare sugars relies on a double-serial inversion strategy. The judicious selection of building blocks and reaction conditions allowed for stereoselective glycosylations, the installation of acetamido groups and the (S)-3-hydroxybutanoyl chain. 相似文献
37.
Maaria Kortesniemi Tahereh Jafari Yumei Zhang Baoru Yang 《Molecules (Basel, Switzerland)》2022,27(17)
Human milk is an intricate, bioactive food promoting infant health. We studied the composition of human milk samples collected over an 8-month lactation using 1H NMR metabolomics. A total of 72 human breast milk samples were collected from ten Chinese mothers at eight different time points. The concentrations of ten human milk oligosaccharides (HMOs), fucose and lactose were quantified. Six of the mothers were classified as Lewis-positive secretors (Se+Le+) and four as Lewis-positive non-secretors (Se−Le+) based on the levels of 2′-fucosyllactose (2′-FL), lacto-N-fucopentaose (LNFP) II, lactodifucotetraose (LDFT) and lacto-N-neotetraose (LNnT). Acetate, citrate, short/medium-chain fatty acids, glutamine and urea showed a time-dependent trend in relation to the stage of lactation. The concentrations of 2′-FL, 3-FL (3-fucosyllactose), 3′-SL (3′-sialyllactose), LDFT, LNFP I, LNFP II, LNFP III, LNnT, LNT (lacto-N-tetraose), and fucose were statistically different between secretors and non-secretors. A temporal difference of approximately 1–2 months between the development of non-secretor and secretor HMO profiles was shown. The results highlighted the importance of long-term breastfeeding, especially among non-secretors. 相似文献
38.
离子色谱-脉冲安培检测白醋和豆腐水中单糖和大豆低聚糖 总被引:7,自引:0,他引:7
建立了测定白醋和豆腐水中常见的的3种单糖(半乳糖、葡萄糖、果糖),以及蔗糖、蜜二糖、棉子糖和水苏糖等大豆低聚糖的方法.以NaOH淋洗液梯度淋洗,7种糖在CarboPac PA10高效阴离子交换柱(HPAEC)上可以在30 min内完成分离.使用脉冲安培检测器(PAD)进行测定,7种糖的检出限(进样25 μL,S/N=3)分别为3、2、3、6、4、7和6 μg/L,且均具有较宽的线性范围(0.02~20 mg/L).白醋和豆腐水样品测定的相对标准偏差在0.15%~3.16%之间,7种糖的加标回收率在92%~104%之间; 本方法检测糖简便快捷、分离效果好、无需衍生、灵敏度高,适用于大豆及大豆制品中的常见糖组分的分析. 相似文献
39.
Rapid identification of common hexapyranose monosaccharide units by a simple TOCSY matching approach
Gheysen K Mihai C Conrath K Martins JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(29):8869-8878
Solution NMR spectroscopy is a well established technique for non-destructive characterization of the structures and conformations of complex oligo- and polysaccharides. One of the key experiments involves the use of 2D TOCSY to collect the 1H spins into groups that can be associated with the individual saccharide units that are present in the molecule under study. It is well known that the magnetization transfer rate through the 1H spin system during the TOCSY spin lock period is sensitive to the intervening 3J(H,H) scalar couplings, and therefore also to the saccharide stereochemistry. Here, we have investigated the potential to extract information on the stereochemistry of hexapyranose monosaccharide units directly from TOCSY spectra. Through a systematic experimental investigation of the magnetization transfer initiated from the anomeric 1H resonance in D-glucose, D-galactose and D-mannose it is shown that a 100 ms spin lock time provides optimal spectroscopic discrimination between these three commonly occurring building blocks. A simple matching scheme is proposed as a new tool for rapid attribution of the TOCSY traces originating from the anomeric 1H resonances towards the underlying monosaccharide type. The scheme appears robust with regard to structural variations and fairly tolerant to incidental overlap. Its application provides useful guidance during the subsequent NMR assignment process, as demonstrated with the PS7F polysaccharide from Streptococcus pneumonia. In addition, we show that our scheme affords a clear-cut distinction between the alpha- and beta-epimers of D-mannose-type units, which can be difficult to discriminate by NMR analysis. Application to the N-glycan 100.2 demonstrates the potential and wide applicability of this new discrimination approach. 相似文献
40.
Antonopoulos A Favetta P Jacquinet JC Lafosse M 《Journal of mass spectrometry : JMS》2005,40(12):1628-1636
Carbohydrate-protein linkage region of proteoglycans is a key oligosaccharide structure because their sulphated and/or phosphorylated analogues control the biosynthesis of glucosaminoglycans or galactosaminoglycans. Therefore, synthesised sulphated and/or phosphorylated analogues were characterised by tandem mass spectrometry in the negative-ion mode. Results demonstrated that the product ion profile was characterised by glycosidic and cross-ring cleavages depending on the position and the type of the charged group (sulphate, phosphate or carboxylate). When the above compounds were sulphated and phosphorylated, the ion found at m/z 79 was the only one that demonstrated a phosphate group on the structure. The data also suggested that when a sodium cation was present in a sulphated and phosphorylated structure, the phosphate group in most cases was neutralised by the sodium cation, and therefore cleaved off the molecule, while the sulphate group was carrying the negative charge. 相似文献