全文获取类型
收费全文 | 651篇 |
免费 | 17篇 |
国内免费 | 2篇 |
专业分类
化学 | 568篇 |
晶体学 | 2篇 |
力学 | 7篇 |
数学 | 55篇 |
物理学 | 38篇 |
出版年
2023年 | 3篇 |
2022年 | 23篇 |
2021年 | 28篇 |
2020年 | 21篇 |
2019年 | 19篇 |
2018年 | 6篇 |
2017年 | 9篇 |
2016年 | 15篇 |
2015年 | 18篇 |
2014年 | 26篇 |
2013年 | 46篇 |
2012年 | 34篇 |
2011年 | 41篇 |
2010年 | 38篇 |
2009年 | 25篇 |
2008年 | 38篇 |
2007年 | 35篇 |
2006年 | 40篇 |
2005年 | 41篇 |
2004年 | 31篇 |
2003年 | 33篇 |
2002年 | 28篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 2篇 |
1994年 | 8篇 |
1993年 | 5篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有670条查询结果,搜索用时 0 毫秒
31.
Dr. Jana Franke Dr. Martin Bock Dr. Richard Dehn Dr. Jörg Fohrer Dr. Santosh B. Mhaske Dr. Antonella Migliorini Dr. Argyrios A. Kanakis Dr. Rolf Jansen Dr. Jennifer Herrmann Prof. Dr. Rolf Müller Prof. Dr. Andreas Kirschning 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4272-4284
The total and semi‐synthesis of 13 new macrolactones derived from thuggacin, which is a secondary metabolite from the myxobacterium Sorangium cellulosum, are reported. The thuggacins have attracted much attention due to their strong antibacterial activity, particularly towards Mycobacterium tuberculosis. This study focuses on 1) thuggacin derivatives that cannot equilibrate by transacylation between the three natural thuggacins A–C, 2) the roles of the thiazole ring, and 3) the hexyl side chain at C2. Semi‐synthetic O‐methylation at C17 suppressed the transacylations without a substantial loss of antibacterial activity. Exchanging the C17–C25 side chain for simplified hydrophobic chains led to complete loss of antibacterial activity. Exchange of the thiazole by an oxazole ring or removal of the hexyl side chain at C2 had no substantial effect on the biological properties. 相似文献
32.
Rosaria Cozzolino Laura De Magistris Paola Saggese Matteo Stocchero Antonella Martignetti Michele Di Stasio Antonio Malorni Rosa Marotta Floriana Boscaino Livia Malorni 《Analytical and bioanalytical chemistry》2014,406(19):4649-4662
Autism spectrum disorders (ASDs) are a group of neurodevelopmental disorders which have a severe life-long effect on behavior and social functioning, and which are associated with metabolic abnormalities. Their diagnosis is on the basis of behavioral and developmental signs usually detected before three years of age, and there is no reliable biological marker. The objective of this study was to establish the volatile urinary metabolomic profiles of 24 autistic children and 21 healthy children (control group) to investigate volatile organic compounds (VOCs) as potential biomarkers for ASDs. Solid-phase microextraction (SPME) using DVB/CAR/PDMS sorbent coupled with gas chromatography–mass spectrometry was used to obtain the metabolomic information patterns. Urine samples were analyzed under both acid and alkaline pH, to profile a range of urinary components with different physicochemical properties. Multivariate statistics techniques were applied to bioanalytical data to visualize clusters of cases and to detect the VOCs able to differentiate autistic patients from healthy children. In particular, orthogonal projections to latent structures discriminant analysis (OPLS-DA) achieved very good separation between autistic and control groups under both acidic and alkaline pH, identifying discriminating metabolites. Among these, 3-methyl-cyclopentanone, 3-methyl-butanal, 2-methyl-butanal, and hexane under acid conditions, and 2-methyl-pyrazine, 2,3-dimethyl-pyrazine, and isoxazolo under alkaline pH had statistically higher levels in urine samples from autistic children than from the control group. Further investigation with a higher number of patients should be performed to outline the metabolic origins of these variables, define a possible association with ASDs, and verify the usefulness of these variables for early-stage diagnosis. Figure
? 相似文献
33.
34.
Curulli Antonella Montesperelli Giampiero Ronca Sara Cavalagli Nicola Ubertini Filippo Padeletti Giuseppina Vecchio Ciprioti Stefano 《Journal of Thermal Analysis and Calorimetry》2020,142(5):1721-1737
Journal of Thermal Analysis and Calorimetry - In the frame of the HERACLES (HEritage Resilience Against CLimate Events on Site) project, a set of cultural heritage sites was studied to improve... 相似文献
35.
Pitois A de las Heras LA Zampolli A Menichetti L Carlos R Lazzerini G Cionini L Salvatori PA Betti M 《Analytical and bioanalytical chemistry》2006,384(3):751-760
Boron neutron capture therapy (BNCT) is a bimodal radiotherapeutic treatment based on the irradiation of neoplastic tissues
with neutrons after the tissues have selectively accumulated molecules loaded with nuclides with large neutron capture cross-sections
(such boron-10). Boron-10 carriers have been tested to a limited extent, and clinical trials have been conducted on sulfhydryl
borane (10B-BSH) and boronophenylalanine (10B-BPA). However, precise and accurate measurements of boron-10 concentrations (0.1–100 μg/g) in specimens and samples of limited
size (μg scale) are needed in order to be able to biologically characterise new compounds in predictive tissue dosimetry,
toxicology and pharmacology studies as well as in clinical investigations. A new approach based on fast separation and detection
of 10B-BPA performed by coupling capillary electrophoresis to electrospray mass spectrometry is reported. This method allows the
quantitative analysis and characterisation of 10B-BPA in a short time with a high separation efficiency. Detection limits of 3 μM for 10B-BPA and 30 ng/mL for 10B were obtained with CE–ESI–MS. A quantification limit of 10 μM for 10B-BPA (100 ng/mL for 10B) was attained. The total boron-10 concentration was determined by high-resolution inductively coupled mass spectrometry
in order to validate the method. Boron-10 isotope measurements were carried out by HR–ICP–MS at medium resolution (R=4000)
due to the presence of an isobaric interference at mass 10. Good agreement was obtained between the values from CE–ESI–MS
and those from HR–ICP–MS. The method has been successfully used to determine the 10B-BPA in two lines of cultured cells. 相似文献
36.
Monocyclic as well as fused bicyclic systems with a nitrogen 10 atom at the bridgehead, including indolizidines and quinolizidines, can be prepared in four steps from N-Boc β-lactams. These easily prepared, highly robust, and flexible building blocks allow the incorporation of chirality and structural diversity, rendering the method feasible for diversity- as well as target-oriented synthesis. 相似文献
37.
Conte P Mineo V Bubici S De Pasquale C Aboud F Maccotta A Planeta D Alonzo G 《Analytical and bioanalytical chemistry》2011,400(5):1443-1450
A number of pistachio oils were selected in order to test the efficacy of nuclear magnetic resonance relaxation dispersion (NMRD) technique in the evaluation of differences among oils (1) obtained from seeds subjected to different thermal desiccation processes, (2) retrieved from seeds belonging to the same cultivar grown in different geographical areas and (3) produced by using seed cultivars sampled in the same geographical region. NMRD measures relaxation rate values which are related to the dynamics of the chemical components of complex food systems. Results not only allowed to relate kinematic viscosity to relaxometry parameters but also were successful in the differentiation among the aforementioned oils. In fact, from the one hand, the larger the kinematic viscosity, the faster the rotational motions appeared as compared to the translational ones. On the other hand, relaxation rate curves (NMRD) varied according to the oxidative stresses and chemical composition of each sample. The present study showed for the first time that NMRD is a very promising technique for quick evaluations of pistachio oil quality without the need for time-consuming chemical manipulations. 相似文献
38.
Mauro Vaccaro Gaetano Mangiapia Antonella Accardo Diego Tesauro Eliana Gianolio Henrich Frielinghaus Giancarlo Morelli Luigi Paduano 《Colloid and polymer science》2008,286(14-15):1643-1652
Two novel amphiphilic unimers containing an aliphatic hydrophobic chain (PDA) with two C≡C triple bonds and hydrophilic heads presenting the chelating agent DTPAGlu and the CCK8 bioactive peptide, respectively, have been prepared by solid phase synthesis. Aggregates obtained by mixing together PDA-DTPAGlu, or its Gd(III) complex, and PDA-L2-CCK8 in 70/30 molar ratio before and after a polymerization process carried out by UV irradiation have been structurally characterized by means of small angle neutron scattering. The relaxivity properties of aggregates containing Gadolinium complexes have also been investigated. Elongated mixed micelles have been observed, in which the relaxivity value r 1p for each Gadolinium complex, measured at 20 MHz and 298 K, is around 12 mM–1 s–1. 相似文献
39.
De Maria P Fontana A Siani G D'Aurizio E Cerichelli G Chiarini M Angelini G Gasbarri C 《Colloids and surfaces. B, Biointerfaces》2011,87(1):73-78
The aggregation properties of a new sultaine surfactant have been studied in buffered aqueous solution at pH 7.4 under controlled condition of osmolarity. Spontaneously formed sultaine vesicles with a mean diameter of about 1 μm can be observed by optical microscopy. The phase behaviour of the surfactant has been investigated by differential scanning calorimetry (DSC) and Nile Red fluorescence. Two critical vesicular concentrations (CVC(1) and CVC(2)) have been fluorimetrically measured, by using pyrene and Nile Red as the fluorescent probes. The two populations of vesicles behave differently as a consequence of their size. The stability of extruded large unilamellar vesicles (LUV) formed slightly above the CVC(1) has been evaluated in the temperature range 25-75°C by following the rate of spontaneous release of entrapped 5(6)-carboxyfluorescein (CF). The stability of the same vesicles at 70°C has also been investigated under osmotic stress obtained by adding NaCl or sucrose to the bulk solution. At a sultaine concentration above the CVC(2) LUV tend to associate and form stable larger closely packed aggregates as suggested by Dynamic Laser Light Scattering and rheological measurements. 相似文献
40.
Tarallo R Accardo A Falanga A Guarnieri D Vitiello G Netti P D'Errico G Morelli G Galdiero S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12659-12668
Liposomes externally modified with the nineteen residues gH625 peptide, previously identified as a membrane‐perturbing domain in the gH glycoprotein of Herpes simplex virus type I, have been prepared in order to improve the intracellular uptake of an encapsulated drug. An easy and versatile synthetic strategy, based on click chemistry, has been used to bind, in a controlled way, several copies of the hydrophobic gH625 peptide on the external surface of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPG)‐based liposomes. Electron paramagnetic resonance studies, on liposomes derivatized with gH625 peptides, which are modified with the 2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐4‐amino‐4‐carboxylic acid (TOAC) spin label in several peptide positions, confirm the positioning of the coupled peptides on the liposome external surface, whereas dynamic light scattering measurements indicate an increase of the diameter of the liposomes of approximately 30 % after peptide introduction. Liposomes have been loaded with the cytotoxic drug doxorubicin and their ability to penetrate inside cells has been evaluated by confocal microscopy experiments. Results suggest that liposomes functionalized with gH625 may act as promising intracellular targeting carriers for efficient delivery of drugs, such as chemotherapeutic agents, into tumor cells. 相似文献