全文获取类型
收费全文 | 4099篇 |
免费 | 358篇 |
国内免费 | 541篇 |
专业分类
化学 | 2912篇 |
晶体学 | 51篇 |
力学 | 234篇 |
综合类 | 49篇 |
数学 | 1386篇 |
物理学 | 366篇 |
出版年
2023年 | 65篇 |
2022年 | 81篇 |
2021年 | 119篇 |
2020年 | 160篇 |
2019年 | 166篇 |
2018年 | 115篇 |
2017年 | 142篇 |
2016年 | 176篇 |
2015年 | 106篇 |
2014年 | 191篇 |
2013年 | 308篇 |
2012年 | 184篇 |
2011年 | 182篇 |
2010年 | 176篇 |
2009年 | 227篇 |
2008年 | 213篇 |
2007年 | 278篇 |
2006年 | 249篇 |
2005年 | 223篇 |
2004年 | 224篇 |
2003年 | 241篇 |
2002年 | 173篇 |
2001年 | 148篇 |
2000年 | 108篇 |
1999年 | 96篇 |
1998年 | 84篇 |
1997年 | 83篇 |
1996年 | 66篇 |
1995年 | 88篇 |
1994年 | 59篇 |
1993年 | 37篇 |
1992年 | 38篇 |
1991年 | 33篇 |
1990年 | 25篇 |
1989年 | 18篇 |
1988年 | 18篇 |
1987年 | 15篇 |
1986年 | 11篇 |
1985年 | 13篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 7篇 |
1980年 | 2篇 |
1979年 | 7篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1972年 | 3篇 |
1971年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有4998条查询结果,搜索用时 109 毫秒
11.
Synthesis of polyphosphodiesters by ring‐opening polymerization of cyclic phosphates bearing allyl phosphoester protecting groups 下载免费PDF全文
Benoït Clément Daniel G. Molin Christine Jérôme Philippe Lecomte 《Journal of polymer science. Part A, Polymer chemistry》2015,53(22):2642-2648
The allyl phosphoester group is shown to be a protecting group for the synthesis of anionic polyphosphodiesters. Our strategy relies on the synthesis of a cyclic phosphate monomer bearing a pendant allyl phosphoester group, its easy purification by fractional distillation, its organocatalyzed ring‐opening polymerization by 1,8‐diazobicyclo[5.4.0]undec‐7‐ene (DBU) and 1‐[3,5‐bis(trifluoromethyl)phenyl]‐3‐cyclohexyl‐thiourea (TU). Finally, the deprotection of the allyl phosphoester group is carried out by reaction with sodium benzenethiolate in the absence of any detectable degradation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2642–2648 相似文献
12.
A New Concept for Obtaining SnO2 Fiber‐in‐Tube Nanostructures with Superior Electrochemical Properties 下载免费PDF全文
Young Jun Hong Ji‐Wook Yoon Prof. Jong‐Heun Lee Prof. Yun Chan Kang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):371-376
Tin oxide (SnO2) nanotubes with a fiber‐in‐tube structure have been prepared by electrospinning and the mechanism of their formation has been investigated. Tin oxide‐carbon composite nanofibers with a filled structure were formed as an intermediate product, which were then transformed into SnO2 nanotubes with a fiber‐in‐tube structure during heat treatment at 500 °C. Nanofibers with a diameter of 85 nm were found to be located inside hollow nanotubes with an outer diameter of 260 nm. The prepared SnO2 nanotubes had well‐developed mesopores. The discharge capacities of the SnO2 nanotubes at the 2nd and 300th cycles at a current density of 1 A g?1 were measured as 720 and 640 mA h g?1, respectively, and the corresponding capacity retention measured from the 2nd cycle was 88 %. The discharge capacities of the SnO2 nanotubes at incrementally increased current densities of 0.5, 1.5, 3, and 5 A g?1 were 774, 711, 652, and 591 mA h g?1, respectively. The SnO2 nanotubes with a fiber‐in‐tube structure showed superior cycling and rate performances compared to those of SnO2 nanopowder. The unique structure of the SnO2 nanotubes with a fiber@void@tube configuration improves their electrochemical properties by reducing the diffusion length of the lithium ions, and also imparts greater stability during electrochemical cycling. 相似文献
13.
Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport 下载免费PDF全文
B. Sc. Eduard Puig Prof. Dr. Beat Ernst Prof. Dr. Horst Kessler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8023-8027
Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (Papp) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature. 相似文献
14.
Giorgia Scetta Jianzhu Ju Nathan Selles Patrick Heuillet Matteo Ciccotti Costantino Creton 《Journal of polymer science. Part A, Polymer chemistry》2021,59(8):685-696
We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU. 相似文献
15.
Dr. Xiaoming Jie Dr. Qiu Sun Dr. Constantin G. Daniliuc Robert Knitsch Prof. Dr. Michael Ryan Hansen Prof. Dr. Hellmut Eckert Dr. Gerald Kehr Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1269-1273
The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)4 . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO2 molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions. 相似文献
16.
Martín Calvelo Alejandro Lamas Dr. Arcadio Guerra Dr. Manuel Amorín Dr. Rebeca Garcia-Fandino Prof. Dr. Juan R. Granja 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5846-5858
Cyclic peptides with disc-shaped structures have emerged as potent building blocks for the preparation of new biomaterials in fields ranging from biological to material science. In this work, we analyze in depth the self-assembling properties of a new type of cyclic peptides based on the alternation of α-residues and cyclic δ-amino acids (α,δ-CPs). To examine the preferred stacking properties adopted by cyclic peptides bearing this type of amino acids, we carried out a synergistic in vitro/in silico approximation by using simple dimeric models and then extended to nanotubes. Although these new cyclic peptides (α,δ-CPs) can interact either in a parallel or antiparallel fashion, our results confirm that although the parallel β-sheet is more stable, it can be switched to the antiparallel stacking by choosing residues that can establish favorable cross-strand interactions. Moreover, the subsequent comparison by using the same methodology but applied to α,γ-CPs models, up to the moment assumed as antiparallel-like d,l -α-CPs, led to unforeseen conclusions that put into question preliminary conjectures about these systems. Surprisingly, they tend to adopt a parallel β-sheet directed by the skeleton interactions. These results imply a change of paradigm with respect to cyclic peptide designs that should be considered for dimers and nanotubes. 相似文献
17.
Daniela Cappello Dr. Ryan R. Maar Prof. Dr. Viktor N. Staroverov Prof. Dr. Joe B. Gilroy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5522-5529
The creation of dimeric boron difluoride complexes of chelating N-donor ligands is a proven strategy for the enhancement of the optoelectronic properties of fluorescent dyes. We report dimers based on the boron difluoride hydrazone (BODIHY) framework, which offer unique and sometimes unexpected substituent-dependent absorption, emission, and electrochemical properties. BODIHY dimers have low-energy absorption bands (λmax=421 to 479 nm, ϵ=17 200 to 39 900 m −1 cm−1) that are red-shifted relative to monomeric analogues. THF solutions of these dimers exhibit aggregation-induced emission upon addition of water, with emission enhancement factors ranging from 5 to 18. Thin films of BODIHY dimers are weakly emissive as a result of the inner-filter effect, attributed to intermolecular π-type interactions. BODIHY dimers are redox-active and display two one-electron oxidation and two one-electron reduction waves that strongly depend on the N-aryl substituents. These properties are rationalized using density-functional theory calculations and X-ray crystallography experiments. 相似文献
18.
Dr. Mateusz Janeta Prof. Tadeusz Lis Prof. Sławomir Szafert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13686-13697
In the present research, the synthesis, spectroscopic characterization, and structural investigations of a unique ZnII complex of imine-functionalized polyhedral oligomeric silsesquioxane (POSS) is designed, and hereby described, as a catalyst for the synthesis of cyclic carbonates from epoxides and CO2. The uncommon features of the designed catalytic system is the elimination of the need for a high pressure of CO2 and the significant shortening of reaction times commonly associated with such difficult transformations like that of styrene oxide to styrene carbonate. Our studies have shown that imine-POSS is able to chelate metal ions like ZnII to form a unique coordination complex. The silsesquioxane core and the hindrance of the side arms (their steric effect) influence the construction process of the homoleptic Zn4@POSS-1 complex. The compound was characterized in solution by NMR (1H, 13C, 29Si), ESI-MS, UV/Vis spectroscopy and in the solid state by thermogravimetric/differential thermal analysis (TG-DTA), elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), cross-polarization magic angle spinning (CP MAS) NMR (13C, 29Si) spectroscopy, and X-ray crystallography. 相似文献
19.
Dr. Yongliang Zhang Botao Wu Dr. Mingdong Zhong Prof. Dr. Wen-Xiong Zhang Prof. Dr. Zhenfeng Xi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16472-16479
Transition-metal alkylidenes have exhibited wide applications in organometallic chemistry and synthetic organic chemistry, however, cyclic Schrock-carbene-like bis-alkylidenes of group 4 metals with a four-electron donor from an alkylidene have not been reported. Herein, the synthesis and characterization of five-membered cyclic bis-alkylidenes of titanium ( 4 a , b ) and zirconium ( 5 a , b ) are reported, as the first well-defined group 4 metallacyclopentatrienes, by two-electron reduction of their corresponding titana- and zirconacyclopentadienes. DFT analyses of 4 a show a four-electron donor (σ-donation and π-donation) from an alkylidene carbon to the metal center. The reaction of 4 a with N,N′-diisopropylcarbodiimide (DIC) leads to the [2+2]-cycloaddition product 6 . Compound 4 a reacted with CO, affording the oxycyclopentadienyl titanium complex 7 . These reactivities demonstrate the multiple metal–carbon bond character. The reactions of 4 a or 5 a with cyclooctatetraene (COT) or azobenzene afforded sandwich titanium complex 8 or diphenylhydrazine-coordinated zirconacyclopentadiene 9 , respectively, which exhibit two-electron reductive ability. 相似文献
20.