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131.
Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties 下载免费PDF全文
Dr. Mehdi El Sayed Moussa Dr. Hui Chen Zuoyong Wang Dr. Monika Srebro‐Hooper Dr. Nicolas Vanthuyne Dr. Soizic Chevance Prof. Christian Roussel Prof. J. A. Gareth Williams Prof. Jochen Autschbach Prof. Régis Réau Prof. Zheng Duan Dr. Christophe Lescop Dr. Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):6075-6086
Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the AuI d10 metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of AuI–AuI interactions in 2 a , b . 相似文献
132.
Host–Guest Assembly of a Molecular Reporter with Chiral Cyanohydrins for Assignment of Absolute Stereochemistry 下载免费PDF全文
Hadi Gholami Dr. Mercy Anyika Jun Zhang Dr. Chrysoula Vasileiou Prof. Dr. Babak Borhan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9235-9239
The absolute stereochemistry of cyanohydrins, derived from ketones and aldehydes, is obtained routinely, in a microscale and derivatization‐free manner, upon their complexation with Zn‐MAPOL, a zincated porphyrin host with a binding pocket comprised of a biphenol core. The host–guest complex leads to observable exciton‐coupled circular dichroism (ECCD), the sign of which is easily correlated to the absolute stereochemistry of the bound cyanohydrin. A working model, based on the ECCD signal of cyanohydrins with known configuration, is proposed. 相似文献
133.
134.
Lok P. Singh Sriman K. BhattacharyyaRahul Kumar Geetika MishraUsha Sharma Garima SinghSaurabh Ahalawat 《Advances in colloid and interface science》2014
Recently, silica nanoparticles (SNPs) have drawn widespread attention due to their applications in many emerging areas because of their tailorable morphology. During the last decade, remarkable efforts have been made on the investigations for novel processing methodologies to prepare SNPs, resulting in better control of the size, shape, porosity and significant improvements in the physio-chemical properties. A number of techniques available for preparing SNPs namely, flame spray pyrolysis, chemical vapour deposition, micro-emulsion, ball milling, sol-gel etc. have resulted, a number of publications. Among these, preparation by sol-gel has been the focus of research as the synthesis is straightforward, scalable and controllable. Therefore, this review focuses on the recent progress in the field of synthesis of SNPs exhibiting ordered mesoporous structure, their distribution pattern, morphological attributes and applications. The mesoporous silica nanoparticles (MSNPs) with good dispersion, varying morphology, narrow size distribution and homogeneous porous structure have been successfully prepared using organic and inorganic templates. The soft template assisted synthesis using surfactants for obtaining desirable shapes, pores, morphology and mechanisms proposed has been reviewed. Apart from single template, double and mixed surfactants, electrolytes, polymers etc. as templates have also been intensively discussed. The influence of reaction conditions such as temperature, pH, concentration of reagents, drying techniques, solvents, precursor, aging time etc. have also been deliberated. These MSNPs are suitable for a variety of applications viz., in the drug delivery systems, high performance liquid chromatography (HPLC), biosensors, cosmetics as well as construction materials. The applications of these SNPs have also been briefly summarized. 相似文献
135.
Synthesis,Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems 下载免费PDF全文
Prof. Dr. Tetsuo Okujima Dr. John Mack Dr. Jun Nakamura Gugu Kubheka Prof. Dr. Tebello Nyokong Dr. Hua Zhu Naoki Komobuchi Prof. Dr. Noboru Ono Prof. Dr. Hiroko Yamada Prof. Dr. Hidemitsu Uno Prof. Dr. Nagao Kobayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14730-14738
A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro‐Diels–Alder reaction of bicyclo[2.2.2]octadiene‐fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time‐dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π‐molecular orbitals. 相似文献
136.
Tom Miclot Dr. Camille Corbier Prof. Alessio Terenzi Cécilia Hognon Prof. Stéphanie Grandemange Prof. Giampaolo Barone Prof. Antonio Monari 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(34):8865-8874
Human telomeric DNA, in G-quadruplex (G4) conformation, is characterized by a remarkable structural stability that confers it the capacity to resist to oxidative stress producing one or even clustered 8-oxoguanine (8oxoG) lesions. We present a combined experimental/computational investigation, by using circular dichroism in aqueous solutions, cellular immunofluorescence assays and molecular dynamics simulations, that identifies the crucial role of the stability of G4s to oxidative lesions, related also to their biological role as inhibitors of telomerase, an enzyme overexpressed in most cancers associated to oxidative stress. 相似文献
137.
Dr. Adam A. Sobczuk Dr. Youichi Tsuchiya Dr. Tomohiro Shiraki Dr. Shun‐ichi Tamaru Prof. Seiji Shinkai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):2832-2838
A unique class of oligothiophene‐based organogelator bearing two crown ethers at both ends was synthesized. This compound could gelatinize several organic solvents, forming one‐dimensional fibrous aggregates. From the observation of circular dichroism, it was confirmed that the helical handedness of the fibrous assembly is controllable by the chirality of 1,2bisammonium guests, thus suggesting that one guest molecule bridges two gelator molecules through the crown–ammonium interaction. Interestingly, we have found that such chirality is created by thermal gelation, whereas it disappears by thixotropic gelation. The new finding implies that the present organogel system is applicable as a reversible switching memory device, featuring memory creation by a heat mode and memory erasing by a mechanical mode. 相似文献
138.
The paper describes the validation of a newly developed very LES (VLES) method for the simulation of turbulent separated flow. The new VLES method is a unified simulation approach that can change seamlessly from Reynolds‐averaged Navier–Stokes to DNS depending on the numerical resolution. Four complex test cases are selected to validate the performance of the new method, that is, the flow past a square cylinder at Re = 3000 confined in a channel (with a blockage ratio of 20%), the turbulent flow over a circular cylinder at Re = 3900 as well as Re = 140,000, and a turbulent backward‐facing step flow with a thick incoming boundary layer at Re = 40,000. The simulation results are compared with available experimental, LES, and detached eddy simulation‐type results. The new VLES model performs well overall, and the predictions are satisfactory compared with previous experimental and numerical results. It is observed that the new VLES method is quite efficient for the turbulent flow simulations; that is, good predictions can be obtained using a quite coarse mesh compared with the previous LES method. Discussions of the implementation of the present VLES modeling are also conducted on the basis of the simulations of turbulent channel flow up to high Reynolds number of Reτ = 4000. The efficiency of the present VLES modeling is also observed in the channel flow simulation. From a practical point of view, this new method has considerable potential for more complex turbulent flow simulations at relative high Reynolds numbers. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
139.
Hanna Ayoub Virginie LAIR Sophie Griveau Philippe Brunswick Fethi Bedioui Michel Cassir 《Electroanalysis》2012,24(6):1324-1333
An electrochemical sensor detects the risk of diabetes and prediabetes; low potentials are applied to nickel electrodes and electrical responses are measured. Although the contact of nickel with skin is short, the risk of allergical reactions cannot be discarded. SS 304L, with lower Ni content, was tested in carbonate buffer solutions containing chloride, lactate and urea to investigate its sensitivity to different parameters in sweat and compare it to nickel. The results show that SS 304L is a suitable material for the assessment of sudomotor dysfunction due to its high capacity to detect the deviation in Cl? concentration. Sensitivity of SS 304L to Cl? is much higher than for nickel. 相似文献
140.