全文获取类型
收费全文 | 421篇 |
免费 | 38篇 |
国内免费 | 2篇 |
专业分类
化学 | 365篇 |
晶体学 | 7篇 |
力学 | 7篇 |
数学 | 36篇 |
物理学 | 46篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 16篇 |
2020年 | 15篇 |
2019年 | 9篇 |
2018年 | 12篇 |
2017年 | 7篇 |
2016年 | 18篇 |
2015年 | 15篇 |
2014年 | 20篇 |
2013年 | 34篇 |
2012年 | 26篇 |
2011年 | 40篇 |
2010年 | 25篇 |
2009年 | 17篇 |
2008年 | 25篇 |
2007年 | 23篇 |
2006年 | 29篇 |
2005年 | 17篇 |
2004年 | 28篇 |
2003年 | 16篇 |
2002年 | 11篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 6篇 |
1995年 | 1篇 |
1994年 | 6篇 |
1993年 | 1篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1896年 | 1篇 |
排序方式: 共有461条查询结果,搜索用时 15 毫秒
1.
Panpan Li Quanbin Liang Eugene Yau-Hin Hong Chin-Yiu Chan Yat-Hin Cheng Ming-Yi Leung Mei-Yee Chan Kam-Hung Low Hongbin Wu Vivian Wing-Wah Yam 《Chemical science》2020,11(42):11601
A class of acceptor–donor–acceptor chromophoric small-molecule non-fullerene acceptors, 1–4, with difluoroboron(iii) β-diketonate (BF2bdk) as the electron-accepting moiety has been developed. Through the variation of the central donor unit and the modification on the peripheral substituents of the terminal BF2bdk acceptor unit, their photophysical and electrochemical properties have been systematically studied. Taking advantage of their low-lying lowest unoccupied molecular orbital energy levels (from −3.65 to −3.72 eV) and relatively high electron mobility (7.49 × 10−4 cm2 V−1 s−1), these BF2bdk-based compounds have been employed as non-fullerene acceptors in organic solar cells with maximum power conversion efficiencies of up to 4.31%. Moreover, bistable resistive memory characteristics with charge-trapping mechanisms have been demonstrated in these BF2bdk-based compounds. This work not only demonstrates for the first time the use of a boron(iii) β-diketonate unit in constructing non-fullerene acceptors, but also provides more insights into designing organic materials with multi-functional properties.Boron(iii) β-diketonates have been demonstrated to serve as multi-functional materials in NFA-based OPVs and organic resistive memories. 相似文献
2.
From Spherical to Leaf‐Like Morphologies: Tunable Supramolecular Assembly of Alkynylgold(I) Complexes through Variations of the Alkyl Chain Length 下载免费PDF全文
Eugene Yau‐Hin Hong Dr. Hok‐Lai Wong Prof. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5732-5735
A series of luminescent polynuclear alkynylgold(I) complexes with different lengths of alkyl chains attached at the N‐heterocyclic carbene moieties has been synthesised and demonstrated to display intriguing self‐assembly behaviours through a cooperative growth mechanism. Variation of the alkyl chain length was found to cause drastic morphological differences in the aggregates and to strongly affect the thermodynamic parameters as revealed by the nucleation–elongation model. 相似文献
3.
This article proposes a global, chaos-based procedure for the discretization of functionals of Brownian motion into functionals of a Poisson process with intensity . Under this discretization we study the weak convergence, as the intensity of the underlying Poisson process goes to infinity, of Poisson functionals and their corresponding Malliavin-type derivatives to their Wiener counterparts. In addition, we derive a convergence rate of for the Poisson discretization of Wiener functionals by combining the multivariate Chen–Stein method with the Malliavin calculus. Our proposed sufficient condition for establishing the mentioned convergence rate involves the kernel functions in the Wiener chaos, yet we provide examples, especially the discretization of some common path dependent Wiener functionals, to which our results apply without committing the explicit computations of such kernels. To the best our knowledge, these are the first results in the literature on the universal convergence rate of a global discretization of general Wiener functionals. 相似文献
4.
Synthesis,Electrochemistry, and Photophysical Studies of Ruthenium(II) Polypyridine Complexes with D–π–A–π–D Type Ligands and Their Application Studies as Organic Memories 下载免费PDF全文
Ming‐Yi Leung Dr. Sammual Yu‐Lut Leung Dr. Di Wu Dr. Tao Yu Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):14013-14021
A new class of ruthenium(II) polypyridine complexes with a series of D–π–A–π–D type (D=donor, A=acceptor) ligands was synthesized and characterized by 1H NMR spectroscopy, mass spectrometry, and elemental analysis. The photophysical and electrochemical properties of the complexes were also investigated. The newly synthesized ruthenium(II) polypyridine complexes were found to exhibit two intense absorption bands at both high‐energy (λ=333–369 nm) and low‐energy (λ=520–535 nm) regions. They are assigned as intraligand (IL) π→π* transitions of the bipyridine (bpy) and π‐conjugated bpy ligands, and IL charge‐transfer (CT) transitions from the donor to the acceptor moiety with mixing of dπ(RuII)→π*(bpy) and dπ(RuII)→π*(L) MLCT characters, respectively. In addition, all complexes were demonstrated to exhibit intense red emissions at approximately λ=727–744 nm in degassed dichloromethane at 298 K or in n‐butyronitrile glass at 77 K. Nanosecond transient absorption (TA) spectroscopy has also been carried out, establishing the presence of the charge‐separated state. In order to understand the electrochemical properties of the complexes, cyclic voltammetry has also been performed. Two quasi‐reversible oxidation couples and three quasi‐reversible reduction couples were observed. One of the ruthenium(II) complexes has been utilized in the fabrication of memory devices, in which an ON/OFF current ratio of over 104 was obtained. 相似文献
5.
Highly Phosphorescent Crystals of Square‐Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements,Induced Circular Dichroism,and TD‐DFT Calculations 下载免费PDF全文
Dr. Hugo Sesolis Dr. Julien Dubarle‐Offner Dr. Carmen K. M. Chan Emmanuel Puig Geoffrey Gontard Pierre Winter Prof. Andrew L. Cooksy Prof. Vivian W. W. Yam Dr. Hani Amouri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8032-8037
A novel class of chiral luminescent square‐planar platinum complexes with a π‐bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls the aggregation of this square planar luminophor and imposes a homo‐ or hetero‐chiral arrangement at the supramolecular level, displaying non‐covalent Pt–Pt and π–π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD‐DFT calculation is obtained to rationalize this unique behavior. 相似文献
6.
Robert D. Bradley Brennan D. McManus Jessalyn G. Yam Dr. Veronica Carta Dr. Ana Bahamonde 《Angewandte Chemie (International ed. in English)》2023,62(43):e202310753
This work demonstrates the dominance of a Ni(0/II/III) cycle for Ni-photoredox amide arylation, which contrasts with other Ni-photoredox C-heteroatom couplings that operate via Ni(I/III) self-sustained cycles. The kinetic data gathered when using different Ni precatalysts supports an initial Ni(0)-mediated oxidative addition into the aryl bromide. Using NiCl2 as the precatalyst resulted in an observable induction period, which was found to arise from a photochemical activation event to generate Ni(0) and to be prolonged by unproductive comproportionation between the Ni(II) precatalyst and the in situ generated Ni(0) active species. Ligand exchange after oxidative addition yields a Ni(II) aryl amido complex, which was identified as the catalyst resting state for the reaction. Stoichiometric experiments showed that oxidation of this Ni(II) aryl amido intermediate was required to yield functionalized amide products. The kinetic data presented supports a rate-limiting photochemically-mediated Ni(II/III) oxidation to enable C−N reductive elimination. An alternative Ni(I/III) self-sustained manifold was discarded based on EPR and kinetic measurements. The mechanistic insights uncovered herein will inform the community on how subtle changes in Ni-photoredox reaction conditions may impact the reaction pathway, and have enabled us to include aryl chlorides as coupling partners and to reduce the Ni loading by 20-fold without any reactivity loss. 相似文献
7.
Vivian E. Cornelio Mariele M. Pedroso André S. Afonso João B. Fernandes M.Fátima G.F. da Silva Ronaldo C. Faria Paulo C. Vieira 《Analytica chimica acta》2015
The hemoglobin (Hb) released from erythrocytes is a primary nutritive component for many blood-feeding parasites. The aspartic protease cathepsin D is a hemoglobinase that is involved in the Hb degradation process and is considered an interesting target for chemotherapy intervention. However, traditional enzymatic assays for studying Hb degradation utilize spectrophotometric techniques, which do not allow real-time monitoring and can present serious interference problems. Herein, we describe a biosensor using simple approach for the real-time monitoring of Hb hydrolysis as well as an efficient screening method for natural products as enzymatic inhibitors using a quartz crystal microbalance (QCM) technique. Hemoglobin was anchored on the quartz crystal surface using mixed self-assembled monolayers. The addition of the enzyme caused a mass change (frequency shift) due to Hb hydrolysis, which was monitored in real time. From the frequency change patterns of the Hb-functionalized QCM, we evaluated the enzymatic reaction by determining the kinetic parameters of product formation (kcat). The QCM enzymatic assay using immobilized human Hb was shown to be an excellent approach for screening possible inhibitors in complex mixtures, opening up a new avenue for the discovery of novel inhibitors. 相似文献
8.
Cleavage of a PN Bond in a Urea‐Containing (Ph2P(R)PPh2)‐Bridged Dinuclear Gold(I) Thiolate Complex by Fluoride and a Mechanistic Insight 下载免费PDF全文
Dr. Xiaoming He Dr. Wai Han Lam Dr. Eddie Chung‐Chin Cheng Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(23):8447-8454
A urea‐containing, (Ph2P(R)PPh2)‐bridged, dinuclear, gold(I) thiolate complex, [Au2{Ph2PN(C6H4OMe‐4)PPh2}(SC6H4NHCONHC6H5)2] ( 1 ) was designed and synthesized and its photophysical and anion recognition properties studied. The results show that 1 has a high selectivity toward F?. Upon addition of F?, the yellow solution was decolorized, and drastic changes of emission and 1H and 31P{1H} NMR signals were observed. Interestingly, these changes are attributed to fluoride‐assisted P?N bond hydrolysis, instead of the expected hydrogen‐bonding interactions with the urea receptor. Similar changes were observed for two other basic anions, AcO? and H2PO4?, but to a much lesser extent; and these anions were found to bind to the urea receptor at the same time. On the other hand, Cl? was found to only bind to the urea moiety through hydrogen‐bonding interactions. Further studies with the control complex [Au2{Ph2PN(C6H4OMe‐4)PPh2}Cl2] ( 2 ) indicate that F? assists the hydrolysis process via cleavage of the P?N bond. DFT calculations were performed to study the reaction mechanism for the fluoride‐assisted P?N bond hydrolysis of 2 ; these provide a better insight into the role of fluoride in the hydrolysis. 相似文献
9.
Dual Esterase‐ and Steroid‐Responsive Energy Transfer Modulation of Ruthenium(II) and Rhenium(I) Complex Functionalized Gold Nanoparticles 下载免费PDF全文
Dr. Frankie Chi‐Ming Leung Dr. Vonika Ka‐Man Au Dr. Hai‐Ou Song Prof. Dr. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16448-16454
A number of adamantane‐containing ruthenium(II) and rhenium(I) complexes have been synthesized, characterized, and noncovalently functionalized with β‐cyclodextrin‐capped gold nanoparticles (β‐CD–GNPs) through the host–guest interaction between cyclodextrin and adamantane. The resultant nanoconjugates have been characterized by transmission electron microscopy (TEM), energy‐dispersive X‐ray analysis (EDX), and 2D ROESY 1H NMR experiments. The Förster resonance energy transfer (FRET) properties of the nanoconjugates can be modulated by both esterase‐accelerated hydrolysis and competitive displacement of steroid, by monitoring the emission intensity and luminescence lifetime. The FRET efficiencies are found to vary with the nature of the chromophores and the length of the spacer between the transition metal complexes and the GNPs. This work constitutes a “proof‐of‐principle” assay method for the dual‐functional detection of important classes of biomolecules, such as enzymes and steroids. 相似文献
10.
Yanping Guan Bilian Li Wei Wei Siyi Wang Vivian‐min Yuen Yao Liu Zheng Ao Shan Zhou Hang Tian Min Huang Xingrong Song Guoping Zhong 《Biomedical chromatography : BMC》2019,33(12)
Dexmedetomidine is an important sedative agent administered as premedication to achieve procedural sedation in children. To describe the correlation between the genetic state and the concentration of dexmedetomidine, it is necessary to develop a specific, time‐saving and economical method for detection of dexmedetomidine in plasma samples. In this work, an ultra‐high‐performance liquid chromatography (UHPLC)–tandem mass spectrometry method has been established and validated for detection of dexmedetomidine in plasma from pediatric population. After a simple liquid–liquid extraction with an organic solution, the analytes were separated on an ACQUITY BEH C18 column (2.1 mm × 50 mm, 1.7 μm particle size) by gradient elution with the mobile phase of acetonitrile and 1‰ aqueous formic acid (flow rate 0.3 mL min?1). Mass spectrometry measurements were performed under the positive selected reaction monitoring and the mass transitions monitored were m/z 201.3 → 95.1, 204.2 → 98.0 for dexmedetomidine and deuterated medetomidine (internal standard), respectively. Validation of the method based on China Food and Drug Administration guidelines showed acceptable selectivity. The UHPLC method employed a stable isotope‐labeled internal standard, showed good specificity and was successfully used to detect dexmedetomidine in plasma samples from 260 pediatric patients. A subsequent application of this method to a pharmacogenetic study was also described. Importantly, this is the first study to report the correlation between CYP2A6 rs835309 activity and concentration of dexmedetomidine. 相似文献