全文获取类型
收费全文 | 11671篇 |
免费 | 1156篇 |
国内免费 | 1196篇 |
专业分类
化学 | 4173篇 |
晶体学 | 85篇 |
力学 | 1199篇 |
综合类 | 119篇 |
数学 | 853篇 |
物理学 | 1349篇 |
综合类 | 6245篇 |
出版年
2024年 | 29篇 |
2023年 | 144篇 |
2022年 | 278篇 |
2021年 | 306篇 |
2020年 | 374篇 |
2019年 | 359篇 |
2018年 | 301篇 |
2017年 | 395篇 |
2016年 | 466篇 |
2015年 | 451篇 |
2014年 | 643篇 |
2013年 | 724篇 |
2012年 | 661篇 |
2011年 | 695篇 |
2010年 | 503篇 |
2009年 | 665篇 |
2008年 | 574篇 |
2007年 | 687篇 |
2006年 | 679篇 |
2005年 | 608篇 |
2004年 | 568篇 |
2003年 | 602篇 |
2002年 | 439篇 |
2001年 | 345篇 |
2000年 | 313篇 |
1999年 | 327篇 |
1998年 | 244篇 |
1997年 | 267篇 |
1996年 | 197篇 |
1995年 | 199篇 |
1994年 | 183篇 |
1993年 | 128篇 |
1992年 | 134篇 |
1991年 | 117篇 |
1990年 | 99篇 |
1989年 | 90篇 |
1988年 | 64篇 |
1987年 | 57篇 |
1986年 | 33篇 |
1985年 | 16篇 |
1984年 | 8篇 |
1983年 | 9篇 |
1982年 | 10篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 12篇 |
1972年 | 3篇 |
1971年 | 1篇 |
1957年 | 2篇 |
1955年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
1.
《Mendeleev Communications》2022,32(5):597-600
Calorimetric monitoring of the autoclave reaction N2O4 + C2H4 at –85 to +10 °C under argon pressure 10–30 bar revealed that the exothermic chemical reaction started at temperatures above –52 °C at 10 bar, whereas an intensive exothermic reaction started at –85 °C and pressure of 30 bar. IR study showed that oligo/polynitroethylene was formed at 30 bar, while carbonyl and hydroxy compound as well as nitrate R–ONO2 formation occurred upon processing at 10 bar. 相似文献
2.
针对Exendin-4的螺旋结构特点, 采用去掉螺旋序列、 用3个连续Ala替换螺旋以及Gln13替换为Tyr13的方式对N端α-螺旋及C端α-螺旋进行改造, 设计出4个结构模拟物. 通过圆二光谱和荧光光谱进行结构分析, 结合模拟物生物活性实验, 分析Exendin-4螺旋结构与生物活性的关系. 结果表明: Exendin-4的N端螺旋比C端螺旋对生物活性影响更大; 在抗二肽基肽酶(DPPⅣ酶)的稳定性实验中, C端螺旋比N端螺旋具有更好维系Exendin-4稳定性的作用; 螺旋结构中Tyr13可作为提高Exendin-4生物活性的重要优化位点. 相似文献
3.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
4.
Dr. Ruijuan Yao Prof. Di Liu Dr. Huihui Wan Dr. Yongqiang Mei Jiahui Wang Dr. Rui Cai Dr. Huimin Zhang Dr. Yuzhen Zhao Dr. Zemin He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(71):e202202269
By linking the carbazole unit to the nitrogen atom of acridone through phenyl or pyridyl, two compounds, named 10-(4-(9H-carbazol-9-yl)phenyl)acridin-9(10H)-one (AC-Ph-Cz) and 10-(5-(9H-carbazol-9-yl)pyridin-2-yl)acridin-9(10H)-one (AC-Py-Cz) were designed and synthesized. These two materials, characterized with highly twisted and rigid structure, good thermal stability, and balanced carrier-transporting properties, were employed as host materials for green phosphorescent and thermally activated delayed fluorescent organic light-emitting diodes (OLEDs). The carbazole group, despite its small contribution to the highest occupied molecular orbitals (HOMOs) of these two materials, plays an essential role as an intramolecular host in energy delivering and improving the hole transporting ability of these two hosts. The incorporation of the electron-deficient pyridyl group as a linking group slightly improves the electron transporting capability of AC-Py-Cz. The green phosphorescent OLED (PhOLED) based on AC-Py-Cz exhibited excellent device performance with a turn-on voltage of 2.5 V, a maximum power efficiency and an external quantum efficiency (ηext) of 89.8 lm W−1 and 25.2 %, respectively, benefitting from the better charge-balancing ability of AC-Py-Cz host due to the presence of the pyridyl bridge. More importantly, all the devices based on these two hosts showed low efficiency roll-off at high brightness due to the suppressed non-radiative transition in the emitting layer. In particular, the AC-Py-Cz-hosted green PhOLED exhibited an efficiency roll-off of 1.6 % from the maximum next at a high brightness of 1000 cd m−2 and a roll-off of 15.9 % at an extremely high brightness of 10000 cd m−2. This study manifests that acridone-based host materials have great potential in fabricating OLEDs with low efficiency roll-off. 相似文献
5.
6.
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
7.
Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
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
8.
针对常规水压裂液会对页岩造成伤害,容易产生水锁,不易返排,还造成水资源消耗和污染环境等问题,制备了低伤害二氧化碳凝胶压裂液。将自备的F2EU和F4EU增稠剂加入到超临界CO2基液中,探究两种增稠剂的加入量对CO2凝胶压裂液黏度的影响,综合考虑成本与效果,优选了2%的F4EU增稠剂,可将CO2的黏度增至15.4 mPa·s。研究了温度、压力以及剪切速率对凝胶压裂液黏度的影响。实验结果表明,随着温度升高黏度总体降低,但中间出现一个短暂升高阶段;随着压力上升压裂液黏度增加;随着剪切速率的增加压裂液黏度下降,属于一种典型的剪切变稀的假塑性流体。F4EU超临界CO2凝胶压裂液的平均伤害率为1.39%,远远小于常规压裂液对岩芯的伤害率。实验表明,F4EU超临界CO2凝胶压裂液在页岩气压裂开采中具有良好的应用前景。 相似文献
9.
Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities
下载免费PDF全文
![点击此处可从《Journal of polymer science. Part A, Polymer chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Guillaume G. Hedir A. Pitto‐Barry Andrew P. Dove Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2015,53(23):2699-2710
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710 相似文献
10.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献