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111.
Optimization of Experimental Parameters to Explore Small‐Ligand/Aptamer Interactions through Use of 1H NMR Spectroscopy and Molecular Modeling 下载免费PDF全文
Dr. Florence Souard Dr. Sandrine Perrier Dr. Vincent Noël Dr. Claire Fave Emmanuelle Fiore Prof. Eric Peyrin Prof. Julian Garcia Dr. Cécile Vanhaverbeke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15740-15748
Aptamers constitute an emerging class of molecules designed and selected to recognize any given target that ranges from small compounds to large biomolecules, and even cells. However, the underlying physicochemical principles that govern the ligand‐binding process still have to be clarified. A major issue when dealing with short oligonucleotides is their intrinsic flexibility that renders their active conformation highly sensitive to experimental conditions. To overcome this problem and determine the best experimental parameters, an approach based on the design‐of‐experiments methodology has been developed. Here, the focus is on DNA aptamers that possess high specificity and affinity for small molecules, L ‐tyrosinamide, and adenosine monophosphate. Factors such as buffer, pH value, ionic strength, Mg2+‐ion concentration, and ligand/aptamer ratio have been considered to find the optimal experimental conditions. It was then possible to gain new insight into the conformational features of the two ligands by using ligand‐observed NMR spectroscopic techniques and molecular mechanics. 相似文献
112.
Self-organization of 3,5-dihydroxybenzylalcohol (DHBA) based dendrimers of generations 0-3 (G0-G3) on bare and functionalized single crystal silicon (Si/SiO2) surfaces has been examined. The underlying monolayer plays a significant role in the supramolecular assembly leading to ordered structures of DHBA (G0) and generation 1-3 (G1-G3) dendrimers at interfaces. Ordered hyperbranched structures are formed on surfaces containing self-assembled monolayers with complimentary features to the assembling molecules, whereas no such organized assemblies are observed on unfunctionalized surfaces. 相似文献
113.
Kai Huang Dr. Florence Duclairoir Dr. Tiziana Pro Dr. Julien Buckley Dr. Gilles Marchand Dr. Eugénie Martinez Dr. Jean‐Claude Marchon Dr. Barbara De Salvo Dr. Guillaume Delapierre Dr. Françoise Vinet Dr. 《Chemphyschem》2009,10(6):963-971
The missing link : Ferrocene and porphyrin monolayers are tethered on silicon surfaces with short (see picture, left) or long (right) linkers. Electron transfer to the silicon substrate is faster for monolayers with a short linker.
114.
This paper focuses on the analytical performance improvement of the coupled technique HPLC-ICPMS using on-line collision/reaction cell technology for selenium elemental and speciation analyses at the ng (Se) l(-1) level in aquatic environment. Collision/reaction cell operating parameters were optimised, resulting in selected conditions of 5.5 ml min(-1) H(2) and 0.5 ml min(-1) He mixture. The detection limits obtained were around 5 ng (Se) l(-1) for total analysis, and between 7 and 15 ng (Se) l(-1) depending on the species for speciation analysis. The capability of UV irradiation-hydride generation interfacing to increase detector sensitivity was also evaluated for speciation analysis. The detection limits obtained were in the range 2-8 ng (Se) l(-1) depending on the species. Moreover, such interface allowed to prevent bromine introduction to the ICPMS which is particularly convenient for selenium trace analysis in natural waters as (80)Se is preserved free from BrH interferences. The developed method was validated using certified water with low selenium content (TM Rain 95, NWRI, Canada) and applied to the analysis of different waters. 相似文献
115.
Marcellino S Attar H Lièvremont D Lett MC Barbier F Lagarde F 《Analytica chimica acta》2008,629(1-2):73-83
An analytical method was developed for antimony speciation and antimony(III) preconcentration in water samples. The method is based on the selective retention of Sb(III) by modified Saccharomyces cerevisiae in the presence of Sb(V). Heat, caustic and solvent pretreatments of the biomass were investigated to improve the kinetics and thermodynamics of Sb(III) uptake process at room temperature. Heating for 30 min at 80 degrees C was defined as the optimal treatment. Antimony accumulation by the cells was independent of pH (5-10) and ionic strength (0.01-0.1 mol L(-1)). 140 mg of yeast and 2h of contact were necessary to ensure quantitative sequestration of Sb(III) up to 750 microg L(-1). In these conditions, Sb(V) was not retained. Sb(V) was quantified in sorption supernatant by inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma optical emission spectrometry (ICP-OES). Sb(III) was determined after elution with 40 mmol L(-1) thioglycolic acid at pH 10. A preconcentration factor close to nine was achieved for Sb(III) when 100mL of sample was processed. After preconcentration, the detection limits for Sb(III) and Sb(V) were 2 and 5 ng L(-1), respectively, using ICP-MS, 7 and 0.9 microg L(-1) using ICP-OES. The proposed method was successfully applied to the determination of Sb(III) and Sb(V) in spiked river and mineral water samples. The relative standard deviations (n=3) were in the 2-5% range at the tenth microg L(-1) level and less than 10% at the lowest Sb(III) and Sb(V) tested concentration (0.1 microg L(-1)). Corrected recoveries were in all cases close to 100%. 相似文献
116.
Olfa Labidi Florence Porcher Rose-Noëlle Vannier 《Journal of solid state chemistry》2008,181(9):2260-2267
Reinvestigation of PbBiOVO4 thermal behaviour revealed a phase transition. As shown by single-crystal X-ray diffraction and high-resolution neutron powder diffraction, α-PbBiOVO4 transforms to β-PbBiOVO4 at 550 °C. At 25 °C, α-PbBiOVO4 is triclinic, S.G. P-1, Z=2, with a=5.6088(3), b=7.1109(3), c=7.2978(3) Å, α=108.957(2), β=111.889(2), and γ=94.833(2)°. Above 550 °C, β-PbBiOVO4 is monoclinic, S.G. C2/m, Z=4, with a=13.61(1), b=5.64(1), c=7.18(1) Å, and β=113.75(1)°. Both structures are built upon (O2Bi2Pb2)∞ chains parallel to the [100] direction in the α polymorph and [001] in the β-polymorph. These chains are undulated in α and linear in β. In both structures, VO4 tetrahedra are organized in two sets of rows parallel to (O2Bi2Pb2)∞ chains, thus building layers of (OBiPb) sandwiched by two layers of VO4 oriented head to tail; VO4 displays different orientations in α- and β-PbBiOVO4. 相似文献
117.
118.
Florence Bally Christophe A. Serra Cyril Brochon Georges Hadziioannou 《Macromolecular rapid communications》2011,32(22):1820-1825
Polymerization reactions can benefit from continuous‐flow microprocess in terms of kinetics control, reactants mixing or simply efficiency when high‐throughput screening experiments are carried out. In this work, we perform for the first time the synthesis of branched macromolecular architecture through a controlled/‘living' polymerization technique, in tubular microreactor. Just by tuning process parameters, such as flow rates of the reactants, we manage to generate a library of polymers with various macromolecular characteristics. Compared to conventional batch process, polymerization kinetics shows a faster initiation step and more interestingly an improved branching efficiency. Due to reduced diffusion pathway, a characteristic of microsystems, it is thus possible to reach branched polymers exhibiting a denser architecture, and potentially a higher functionality for later applications. 相似文献
119.
Using concentration measurements based on high performance liquid chromatography, we have investigated the kinetics of reaction between single-stranded oligonucleotides containing a d(GpG) sequence, i.e., d(GG), d(TGG), d(TTGG), and d(CTGGCTCA), and the platinum complexes cis-[Pt(NH(3))(2)(H(2)O)(2)](2+) (1) and [Pt(NH(3))(3)(H(2)O)](2+) (2). The rate constants for the substitution of one aqua ligand of platinum in 1 or 2 by each guanine of the oligonucleotides were individually measured, as well as, for 1, those for the subsequent conversion of the monoadducts to the diadduct. For the platination of d(GG) and d(TGG), the rate constants are similar for the 5'- and 3'-guanines. The longer oligonucleotides d(TTGG) and d(CTGGCTCA) are platinated slightly faster on the 5'-G than on the 3'-G. 2 shows a similar slight preference for the 5'-guanine, but it reacts by a factor of 4-10 more slowly than 1. For both complexes, the platination rate constants increase with increasing oligonucleotide length. Platination of the 5'-G by 1 is 1 order of magnitude faster on d(CTGGCTCA) than on d(GG). Concerning the chelation step giving the GG diadduct of 1, the longer the oligonucleotide, the larger is the ratio between the rates of the cyclization of the 3'- and 5'-monoadducts k(3)(')(c) and k(5)(')(c): k(3)(')(c)/k(5)(')(c) equals 1.4 for d(GG) and 3.3 for d(CTGGCTCA). 相似文献
120.
Aresta M Tommasi I Quaranta E Fragale C Mascetti J Tranquille M Galan F Fouassier M 《Inorganic chemistry》1996,35(14):4254-4260
Extended labeling experiments have shown that formation of rhodium peroxocarbonate from CO(2) and [RhCl(eta(2)-O(2))(P)(3)] (P is PEt(2)Ph or PEtPh(2)) proceeds through O-O bond cleavage and CO(2) insertion. O-transfer to ancillary phosphine ligand to give R(3)P=O selectively (>85%) involves the Rh-linked O atom of the peroxo group of RhCl(CO(4))(P)(3). 相似文献