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991.
Ureidopeptide‐Based Brønsted Bases: Design,Synthesis and Application to the Catalytic Enantioselective Synthesis of β‐Amino Nitriles from (Arylsulfonyl)acetonitriles
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Dr. Saioa Diosdado Dr. Rosa López Prof. Dr. Claudio Palomo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(21):6526-6531
The addition of cyanoalkyl moieties to imines is a very attractive method for the preparation of β‐amino nitriles. We present a highly efficient organocatalytic methodology for the stereoselective synthesis of β‐amino nitriles, in which the key to success is the use of ureidopeptide‐based Brønsted base catalysts in combination with (arylsulfonyl)acetonitriles as synthetic equivalents of the acetonitrile anion. The method gives access to a variety of β‐amino nitriles with good yields and excellent enantioselectivities, and broadens the stereoselective Mannich‐type methodologies available for their synthesis. 相似文献
992.
Characterization of New Specific Copper Chelators as Potential Drugs for the Treatment of Alzheimer’s Disease
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Dr. Michel Nguyen Dr. Anne Robert Dr. Alix Sournia‐Saquet Dr. Laure Vendier Dr. Bernard Meunier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6771-6785
The non‐controlled redox‐active metal ions, especially copper, in the brain of patients with Alzheimer disease (AD) should be considered at the origin of the intense oxidative damage in the AD brain. Several bis(8‐aminoquinoline) ligands, such as 1 and PA1637, are able to chelate Cu2+ with high affinity, and are specific chelators of copper with respect to iron and zinc. They are able to efficiently extract Cu2+ from a metal‐loaded amyloid. In addition, these tetradentate ligands are specific for the chelation of Cu2+ compared with Cu+. Consequently, the copper ion is easily released from the bis(8‐aminoquinoline) ligand under reductive conditions, and can be trapped again by a protein having some affinity for copper such as human serum albumin (HSA) proteins. In addition, the copper is not efficiently released from [Cu(CQ)2] in reductive conditions. The catalytic production of H2O2 by [Cu2+‐Aβ1?28]/ascorbate is inhibited in vitro by the bis(8‐aminoquinoline) 1 , suggesting that 1 should be able to play a protective role against oxidative damages induced by copper‐loaded amyloids. 相似文献
993.
Alex Sudakow Dr. Uli Papke Prof. Dr. Thomas Lindel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10223-10226
A novel photoarylation of amino acids and peptides is described, which tolerates the presence of water. Irradiation of Boc‐protected amino acids in the presence of N‐protected 2‐azidobenzimidazoles leads to selective arylation of carboxy termini or side chains. The new reaction also works for peptides. Irradiation of the nonapeptide H‐SPSYVYHQF‐OH also resulted in selective arylation of the tyrosine side chains, as indicated by ESI‐MS/MS fragmentation. Chemo‐ and regioselectivity could add the title reaction to the repertoire of photoaffinity labeling methods. 相似文献
994.
Peptide Conjugates for Directing the Morphology and Assembly of 1D Nanoparticle Superstructures
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Chen Zhang Dr. Chengyi Song Dr. H. Christopher Fry Prof. Nathaniel L. Rosi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):941-945
Designed peptide conjugates molecules are used to direct the synthesis and assembly of gold nanoparticles into complex 1D nanoparticle superstructures with various morphologies. Four peptide conjugates, each based on the gold‐binding peptide (AYSSGAPPMPPF; PEPAu), are prepared: C12H23O‐AYSSGAPPMPP ( 1 ), C12H23O‐AYSSGAPPMPPF ( 2 ), C12H23O‐AYSSGAPPMPPFF ( 3 ), and C12H23O‐AYSSGAPPMPPFFF ( 4 ). The affect that C‐terminal hydrophobic F residues have on both the soft‐assembly of the peptide conjugates and the resulting assembly of gold nanoparticle superstructures is examined. It is shown that the addition of two C‐terminal F residues ( 3 ) leads to thick, branched 1D gold nanoparticle superstructures, whereas the addition of three C‐terminal F residues ( 4 ) leads to bundling of thin 1D nanoparticle superstructures. 相似文献
995.
Rapid Total Synthesis of Cyclic Lipodepsipeptides as a Premise to Investigate their Self‐Assembly and Biological Activity
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Matthias De Vleeschouwer Dr. Davy Sinnaeve Jos Van den Begin Prof. Dr. Tom Coenye Prof. Dr. José C. Martins Prof. Dr. Annemieke Madder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7766-7775
A rapid and efficient total synthesis is reported for the cyclic lipodepsipeptide pseudodesmin A. This member of the Pseudomonas viscosin group is active against Gram‐positive bacteria and features self‐assembling properties. A conserved serine residue within the lactone macrocycle is exploited for initial immobilization on 2‐chlorotrityl chloride resin through ether formation with the side‐chain alcohol. Subsequent elongation proceeds through Fmoc solid‐phase peptide synthesis, including automated incorporation of the enantioselectively synthesized (R)‐3‐hydroxydecanoic acid lipid tail. Following esterification to generate the incipient lactone bond, the macrocycle is formed by on‐resin head‐to‐tail macrolactamization and cleaved from the resin to give the desired compound in good purity. The short and efficient synthesis route allows rapid generation of analogues by facile variation of both the peptide and lipid moieties with good control of epimerization while maximizing automation. Synthesis of the pseudodesmin A enantiomer yields identical self‐assembly and biological activity to that observed for the natural compound, showing that activity is not mediated by chiral interactions. A D ‐Asn8 analogue developed en route retains self‐assembly, but loses activity. The synthesis strategy should be generally applicable for the rapid generation of analogues from various cyclic lipodepsipeptide groups, allowing an investigation of their self‐assembling properties and structure–activity relationships. 相似文献
996.
Zwitterionic chiral stationary phases based on cinchona and chiral sulfonic acids for the direct stereoselective separation of amino acids and other amphoteric compounds
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Tong Zhang Emilie Holder Pilar Franco Wolfgang Lindner 《Journal of separation science》2014,37(11):1237-1247
An extensive series of free amino acids and analogs were directly resolved into enantiomers (and stereoisomers where appropriate) by HPLC on zwitterionic chiral stationary phases (Chiralpak ZWIX(+) and Chiralpak ZWIX(?)). The interaction and chiral recognition mechanisms were based on the synergistic double ion‐paring process between the analyte and the chiral selectors. The chiral separation and elution order were found to be predictable for primary α‐amino acids with apolar aliphatic side chains. A systematic investigation was undertaken to gain an insight into the influence of the structural features on the enantiorecognition. The presence of polar and/or aromatic groups in the analyte structure is believed to tune the double ion‐paring equilibrium by the involvement of the secondary interaction forces such as hydrogen bonding, Van der Waals forces and π–π stacking in concert with steric parameters. The ZWIX chiral columns were able to separate enantiomers and stereoisomers of various amphoteric compounds with no need for precolumn derivatization. Column switching between ZWIX(+) and ZWIX(?) is believed to be an instrumental tool to reverse or control the enantiomers elution order, due to the complementarity of the applied chiral selectors. 相似文献
997.
分别从中药成分分析、活性筛选和代谢组学三方面对质谱技术在中药研究中的应用进展进行了全面综述.在中药成分分析方面,重点介绍了寡糖异构体的分析方法,以及质谱指纹图谱技术在中药成分分析及质量控制中的应用;在活性筛选方面,分别介绍了超滤-质谱、细胞膜色谱-质谱、微透析-质谱、亲和色谱-质谱、强度衰减质谱、修饰琼脂糖珠-质谱和直接分析质谱等技术及其应用;在代谢组学研究方面,对中药治疗肝损伤、肾虚、心肌梗死和糖尿病等疾病方面的研究进展进行了阐述.上述内容充分反映了质谱技术在中药创新性研究中的重要性. 相似文献
998.
In our work,a new extraction tip with gold-modified polymer is developed.The simple,self-made and extremely economical tips were successfully applied to capture cysteine-containing peptides.The loading capacity of a tip(column bed:0.3 mm diameter,5 mm length)is 2–4μg peptides.We can make one tip in 30 s and each costs less than 0.1 cent.The use of these tips can achieve a stable analysis with less background interference,even for 10 ng target peptides.Compared with other separation techniques,our method can save much time and energy while providing a means to selectively capture cysteine-containing peptides from complex analyte due to the strong interaction.All results showed that our new extraction tips have minimal cost and perfect selectivity;thus they have great potential in sample pretreatment systems for proteomics. 相似文献
999.
Yuan‐Yuan Li Ping Liu Yang Tang Hong‐Mei Li Ya‐Ling Tang Xin‐Hua Liang Ya‐Jie Tang 《Helvetica chimica acta》2013,96(4):702-709
The four new cerebrosides 1 – 4 possessing a unique C18 9‐methylsphinga‐4,8‐dienine‐related moiety and a cyclic octapeptide, 5 , possessing alternating proline and glycine moietes were isolated from the Tuber indicum fermentation mycelium. Their structures were established on the basis of a spectroscopic analysis including NMR and HR‐ESI‐MS, as well as an acidic methanolysis experiment. To the best of our knowledge, the cerebrosides identified in the present study are quite different from those isolated from Tuber indicum fruiting bodies. Additionally, it was the first time that a cyclic peptide was isolated from the Tuber genus. 相似文献
1000.
The aim of this study was to evaluate physico-chemical properties and the healing capacity of surface treated titanium. Surface
treatment combining sand-blasting, acid etching and alkaline etching (BIO surface) was evaluated together with machined titanium
as a reference surface. Hydration, wetting angle, surface area and roughness parameters were evaluated for both surfaces.
Stability of dental implants with both surfaces implanted in the tibia of dog was measured during the healing of twelve weeks.
BIO surface exhibited lower wetting angle, larger surface area, higher degree of hydration and higher average roughness compared
to machined titanium. Implants with the BIO surface maintained their stability during the whole healing period in contrast
to those with machined titanium surface, which showed a statistically significant decrease in stability three and nine weeks
after implantation. 相似文献