全文获取类型
收费全文 | 730篇 |
免费 | 38篇 |
国内免费 | 2篇 |
专业分类
化学 | 608篇 |
晶体学 | 2篇 |
力学 | 7篇 |
数学 | 74篇 |
物理学 | 52篇 |
无线电 | 27篇 |
出版年
2024年 | 2篇 |
2023年 | 10篇 |
2022年 | 55篇 |
2021年 | 46篇 |
2020年 | 14篇 |
2019年 | 17篇 |
2018年 | 16篇 |
2017年 | 7篇 |
2016年 | 32篇 |
2015年 | 23篇 |
2014年 | 25篇 |
2013年 | 40篇 |
2012年 | 49篇 |
2011年 | 44篇 |
2010年 | 31篇 |
2009年 | 31篇 |
2008年 | 39篇 |
2007年 | 49篇 |
2006年 | 39篇 |
2005年 | 39篇 |
2004年 | 29篇 |
2003年 | 35篇 |
2002年 | 24篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 8篇 |
1997年 | 3篇 |
1996年 | 14篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有770条查询结果,搜索用时 0 毫秒
21.
Impellizzeri S McCaughan B Callan JF Raymo FM 《Journal of the American Chemical Society》2012,134(4):2276-2283
In search of strategies to photoactivate the luminescence of semiconductor quantum dots, we devised a synthetic approach to attach photocleavable 2-nitrobenzyl groups to CdSe-ZnS core-shell quantum dots coated with hydrophilic polymeric ligands. The emission intensity of the resulting nanostructured constructs increases by more than 60% with the photolysis of the 2-nitrobenzyl appendages. Indeed, the photoinduced separation of the organic chromophores from the inorganic nanoparticles suppresses an electron-transfer pathway from the latter to the former and is mostly responsible for the luminescence enhancement. However, the thiol groups anchoring the polymeric envelope to the ZnS shell also contribute to the photoinduced emission increase. Presumably, their photooxidation eliminates defects on the nanoparticle surface and promotes the radiative deactivation of the excited quantum dots. This effect is fully reversible but its magnitude is only a fraction of the change caused by the photocleavage of the 2-nitrobenzyl groups. In addition, these particular quantum dots can cross the membrane of model cells and their luminescence increases by ~80% after the intracellular photocleavage of the 2-nitrobenzyl quenchers. Thus, photoswitchable luminescent constructs with biocompatible character can be assembled combining the established photochemistry of the 2-nitrobenzyl photocage with the outstanding photophysical properties of semiconductor quantum dots and the hydrophilic character of appropriate polymeric ligands. 相似文献
22.
Sabrina Elkhanoufi Rachele Stefania Diego Alberti Simona Baroni Silvio Aime Prof. Simonetta Geninatti Crich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(17):e202104563
The assessment of unregulated level of enzyme activity is a crucial parameter for early diagnoses in a wide range of pathologies. In this study, we propose the use of electron paramagnetic resonance (EPR) as an easy method to probe carboxylesterase (CE) enzymatic activity in vitro. For this application, were synthesized two amphiphilic, nitroxide containing esters, namely Tempo-C12 (T-C12) and Tempo-2-C12 (T-2-C12). They exhibit low solubility in water and form stable micelles in which the radicals are EPR almost silent, but the hydrolysis of the ester bond yields narrows and intense EPR signals. The intensity of the EPR signals is proportional to the enzymatic activity. CEs1, CEs2 and esterase from porcine liver (PLE) were investigated. The obtained results show that T-C12 and T-2-C12-containing systems display a much higher selectivity toward the CEs2, with a Limit of Detection of the same order of those ones obtained with optical methods. 相似文献
23.
Americo Inglese Fabio Mavelli Rosario De Lisi Stefania Milioto 《Journal of solution chemistry》1997,26(3):319-336
Densities of binary mixtures of polar organic solvents with alcohols were measured at 25‡C. The solvents studied were N,N-dimethylformamide,
dimethylsulfoxide, and formamide while alcohols were butanol, pentanol, hexanol, and 1,4-butanediol. Density measurements
of hydrocarbons (from pentane to dodecane and some heptane isomers) + N,N-dimethylformamide were also performed. From these
data the apparent molar volumes of alcohols and hydrocarbons as functions of concentration were calculated. The standard partial
molar volumes were obtained by extrapolation to infinite dilution and are discussed in terms of group contributions. 相似文献
24.
Chakravarthi Simhadri Liting Bi Mathieu L. Lepage Mahdi Takaffoli Zhipeng Pei Stefania F. Musolino Abbas S. Milani Gino A. DiLabio Jeremy E. Wulff 《Chemical science》2021,12(11):4147
Motivated by a desire to develop flexible covalent adhesives that afford some of the same malleability in the adhesive layer as traditional polymer-based adhesives, we designed and synthesized two flexible, highly fluorinated bis-diazirines. Both molecules are shown to function as effective crosslinkers for polymer materials, and to act as strong adhesives when painted between two polymer objects of low surface energy, prior to thermal activation. Data obtained from lap-shear experiments suggests that greater molecular flexibility is correlated with improved mechanical compliance in the adhesive layer.Flexible, highly fluorinated covalent adhesives are synthesized, and are shown to afford comparable C–H insertion efficiency and adhesion strength relative to a rigid analogue, while providing improved mechanical compliance in the adhesion layer. 相似文献
25.
Prof. Gianlorenzo Bussetti Claudia Filoni Prof. Andrea Li Bassi Dr. Alberto Bossi Prof. Marcello Campione Prof. Alessio Orbelli Biroli Prof. Chiara Castiglioni Dr. Silvia Trabattoni Dr. Stefania De Rosa Prof. Luca Tortora Prof. Franco Ciccacci Prof. Lamberto Duò 《ChemistryOpen》2021,10(8):748-755
We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (ZnII) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential. 相似文献
26.
Marco Verona Sara Rubagotti Stefania Croci Sophia Sarpaki Francesca Borgna Marianna Tosato Elisa Vettorato Giovanni Marzaro Francesca Mastrotto Mattia Asti 《Molecules (Basel, Switzerland)》2021,26(4)
The cholecystokinin-2 receptor (CCK-2R) is overexpressed in several human cancers but displays limited expression in normal tissues. For this reason, it is a suitable target for developing specific radiotracers. In this study, a nastorazepide-based ligand functionalized with a 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelator (IP-001) was synthesized and labelled with indium-111. The radiolabeling process yielded >95% with a molar activity of 10 MBq/nmol and a radiochemical purity of >98%. Stability studies have shown a remarkable resistance to degradation (>93%) within 120 h of incubation in human blood. The in vitro uptake of [111In]In-IP-001 was assessed for up to 24 h on a high CCK-2R-expressing tumor cell line (A549) showing maximal accumulation after 4 h of incubation. Biodistribution and single photon emission tomography (SPECT)/CT imaging were evaluated on BALB/c nude mice bearing A549 xenograft tumors. Implanted tumors could be clearly visualized after only 4 h post injection (2.36 ± 0.26% ID/cc), although a high amount of radiotracer was also found in the liver, kidneys, and spleen (8.25 ± 2.21%, 6.99 ± 0.97%, and 3.88 ± 0.36% ID/cc, respectively). Clearance was slow by both hepatobiliary and renal excretion. Tumor retention persisted for up to 24 h, with the tumor to organs ratio increasing over-time and ending with a tumor uptake (1.52 ± 0.71% ID/cc) comparable to liver and kidneys. 相似文献
27.
Lucia De Crescentini Gianfranco Favi Giacomo Mari Gianluca Ciancaleoni Marcello Costamagna Stefania Santeusanio Fabio Mantellini 《Molecules (Basel, Switzerland)》2021,26(21)
Here we report the synthesis of interesting 3-alkyl-4-hydroxy-1-aryl-4-(propa-1,2-dienyl)1H-pyrazol-5(4H)-ones and 9-alkyl-7-aryl-1-oxa-7,8-diazaspiro[4.4]nona-3,8-dien-6-ones, starting from 1,2-diaza-1,3-dienes (DDs) and propargyl alcohol. The reaction proceeds through a sequence Michael-type nucleophilic attack/cyclization/[2,3]-Wittig rearrangement. In the same way, the reaction between the aforementioned DDs and allyl alcohol furnished 4-allyl-4-hydroxy-3-alkyl-1-aryl-1H-pyrazol-5(4H)-ones. A DFT study was also carried out, in order to have decisive clarifications about the mechanism. 相似文献
28.
Dr. Anna Troiani Prof. Dr. Giulia de Petris Prof. Dr. Federico Pepi Dr. Stefania Garzoli Dr. Chiara Salvitti Prof. Dr. Marzio Rosi Prof. Dr. Andreina Ricci 《ChemistryOpen》2019,8(9):1190-1198
A gas-phase investigation of the D -fructose dehydration reaction in the presence of base has been performed by the joint application of mass spectrometric techniques and theoretical calculations. Protonated addition products of D -fructose and base were generated in the gas phase by electrospray ionization using several bases of different proton affinity. The intermediates, products and decomposition channels were investigated by ion trap mass spectrometry. Electronic structure calculations allowed the identification of the ionic intermediates and products of a selected system containing NH3, helping to rationalize the observed reaction pathways. The obtained results show that the final product, the protonated 5-hydroxymethyl-2-furaldheyde [5-HMF]H+, is better formed using selected bases and only if these remain clustered until the end of the dehydration process. 相似文献
29.
Luca Scrivano Ortensia Ilaria Parisi Domenico Iacopetta Mariarosa Ruffo Jessica Ceramella Maria Stefania Sinicropi Francesco Puoci 《先进技术聚合物》2019,30(3):743-748
The present work reports on the synthesis of a molecularly imprinted polymer (MIP) based on methacrylic acid and ethylene glycol dimethacrylate for sunitinib delivery. Sunitinib (SUT) is a tyrosine kinase inhibitor used in many cancer diseases. Like the majority of the anticancer drugs, SUT suffers of a low bioavailability, and at the same time, it is characterized by a narrow therapeutic window. In order to reduce drug systemic toxicity, we synthesized a MIP‐based drug delivery system for SUT‐controlled release. MIP was obtained by bulk polymerization through the so‐called noncovalent approach. Rebinding experiments were performed to evaluate the success of the imprinting process and the ability of MIP to bind in a specific and selective fashion the template molecule. Resulting data showed that sunitinib rebinding percentage was 70%, while nonimprinted polymer (NIP) rebinding percentage was 46%. A not significant difference was observed between MIP and NIP in semaxanib binding experiments. Moreover, the drug release profiles were studied for both MIP and NIP. A sustained release was observed from sunitinib‐loaded MIP during 24 hours, reaching 58% after 6 hours and 76% at the end‐point. NIP, on the contrary, released almost 90% of the loaded drug within 6 hours. Furthermore, the drug carrier was tested in vitro against MCF‐7 cells, in which the cytotoxic effect of sunitinib released from MIP reached the maximum after 72 hours, while NIP completed its effect within 48 hours. These results demonstrated that molecularly imprinted polymers are suitable systems for SUT release. 相似文献