Molecular engineering and solvent dependence of excitation energy hopping in self-assembled porphyrin boxes

It has been demonstrated that the direction and magnitude of transition dipole moments, and hence rates in the excitation energy hopping in the self-assembled porphyrin boxes can be tuned by insertion of ethynyl groups as well as the dielectric constant of solvent.     

High-energy 'composite' layered manganese-rich cathode materials via controlling Li2MnO3 phase activation for lithium-ion batteries

The 'composite' layered materials for lithium-ion batteries have recently attracted great attention owing to their large discharge capacities. Here, the 0.5Li(2)MnO(3)·0.5LiMn(0.42)Ni(0.42)Co(0.16)O(2)'composite' layered manganese-rich material is prepared and characterized by the synchrotron X-ray powder diffraction (SXPD). The relationship between its electrochemical performance and its 'composite' components, the Li(2)MnO(3) phase activation process during cycling and the cycle stability of this material at room temperature are elucidated based on its kinetic controlled electrochemical properties, dQ/dV curves and Raman scattering spectroscopies associated with different initial charge-discharge current densities (5 mA g(-1), 20 mA g(-1) and 50 mA g(-1)), cut-off voltages (4.6 V and 4.8 V) and cycle numbers (50 cycles and 150 cycles). Furthermore, its reaction pathways are tracked via a firstly introduced integrated compositional phase diagram of four components, Li(2)MnO(3), LiMn(0.42)Ni(0.42)Co(0.16)O(2), MO(2) (M = Mn(1-α-β)Ni(α)Co(β); 0 ≤α≤ 5/12, 0 ≤β≤ 1/6) and LiMnO(2), which turns out to be a very important guiding tool for understanding and utilizing this 'composite' material.     

Synthesis of silver nanoplates by two-dimensional oriented attachment

Synthesis of silver nanoplates was studied in the modified polyol method, where the nucleation and seed stage occurred in a poly(ethylene glycol) (PEG)-water mixture solution, and the growth stage happened in the PEG environment. The morphological evolution of nanoplates was characterized using UV, SEM, and TEM. Interestingly, plane nanostructures with unusual jagged edges were finally formed in our modified polyol method. Using TEM, we observed the medium state of fusion between two nanoplates, resulting in generating unusual jagged edges. Therefore, a novel two-dimensional oriented attachment occurred in our modified polyol method, which involves smaller nanoplates as the building blocks. Further control experiments showed that the presence of water could break this kinetic preferred reactivity, leading to the formation of nanoparticles.     

Cost-effective dye-sensitized solar cells consisting of two metal foils instead of transparent conductive oxide glass

A cost-effective structure for dye-sensitized solar cells (DSSCs) without using transparent conductive oxide (TCO) is reported. Instead of high-cost F/SnO(2) glass (FTO-glass) or woven metal mesh, a Ti foil and a perforation-patterned stainless steel (StSt) foil are introduced as the substrates for a counter-electrode and a photo-electrode, respectively.     

Interactive effects of pore size control and carbonization temperatures on supercapacitive behaviors of porous carbon/carbon nanotube composites

Porous carbon-based electrodes were prepared by carbonization with poly(vinylidene fluoride) (PVDF)/carbon nanotube (CNT) composites to further increase the specific capacitance for supercapacitors. The specific capacitance, pore size distribution, and surface area of the PVDF/CNT composites were measured, and the effect of the carbonization temperatures was examined. The electrochemical properties were examined by cyclic voltammetry, impedance spectroscopy, and galvanostatic charge-discharge performance using a two-electrode system in TEABF(4) (tetraethylammonium tetrafluoroborate)/acetonitrile as a non-aqueous electrolyte. The highest specific capacitance of ～101 Fg(-1) was obtained for the samples carbonized at 600 °C. The pore size of the samples could be controlled to below 7 nm through the carbonization process. This suggests that micropores make a significant contribution to the specific capacitance due to improved charge transfer between the pores of the electrode materials and the electrolyte.     

Pd-catalyzed sequential C-C bond formation and cleavage: evidence for an unexpected generation of arylpalladium(II) species

A Pd(II)-catalyzed reaction engaging alkenyl β-keto esters is reported that leads to the formation of 1-naphthols and an unexpected generation of arylpalladium(II) species. Interception of the in situ generated arylpalladium(II) species in a Mizoroki-Heck reaction, together with additional mechanistic studies, provided strong evidence in support of the first aromatization-driven β-carbon elimination process. A single Pd catalyst served to promote a series of both C-C bond forming and cleavage events in an unprecedented manner.     

Frequency response of the glucose sensor based on immobilized glucose oxidase membrane

Frequency response of the glucose sensor based on the immobilized glucose oxidase membrane was investigated experimentally by giving the sinusoidal change of glucose concentration to the glucose sensor and observing its output signal. Observed values of gains and phase lags of the frequency response of the glucose sensor followed the frequency response model of the first-order with dead time; The time constant and also the dead time were estimated and found to decrease as the amount of enzyme immobilized in the membrane increased and the thickness of the membrane decreased.

     

Formation of photo-functional spiroxazine monolayers and their dielectric constant determination using surface plasmon resonance

Spiroxazine are of considerable interest as photochromic materials because of their application. On the other hand, surface plasmon resonance (SPR) is a well-known optical method for measuring optical constants of thin film. In this study, photochromic materials were used as self-assembled monolayers (SAMs) of newly synthesized spiroxazine derivatives. We used Fresnel equation (four-layer model) to determine the precise dielectric constant () of the photochromic monolayers. Structure changes of spiroxazine derivatives under UV-light irradiation resulted in the change of optical constants, the dielectric constant and thickness. The obtained results indicated that the ring opening of photochromic spiroxazine can lead to the decrease in the dielectric constant and thickness.     

Mechanism and nanosize products of the sol-gel reaction using diphenylsilanediol and 3-methacryloxypropyltrimethoxysilane as precursors

We use a first-principles calculation and small-angle neutron scattering (SANS) to investigate the mechanism and the nanosize products of the sol-gel reaction with diphenylsilanediol (DPD) and 3-methacryloxypropyltrimethoxysilane (MEMO) precursors in synthesizing a hybrid waveguide material. It is predicted that switching between a DPD hydroxyl and a MEMO methoxy with a reaction rate of 6.8 x 10(-6) s(-1) at 300 K is the fastest process for the first reaction step, thus generating diphenylmethoxysilanol (DPM) and 3-methacryloxypropyldimethoxysilanol (MEDO) as products. However, we determine that this reaction pathway could be modified by the presence of the H2O released from a catalyst such as Ba(OH)2.H2O. Next, switching between the DPM hydroxyl and the MEDO methoxy is followed to generate diphenyldimethoxysilane (DPDM) and 3-methacryloxypropylmethoxysilanediol (MEMDO). However, condensation between a MEMDO hydroxyl and a DPDM methoxy is found to be most favorable for the third reaction step, which generates the DPDM-MEMDO dimer and CH3OH molecule as products. In a similar fashion, a DPDM methoxy of the DPDM-MEMDO dimer can condense with a MEMDO hydroxyl of the second DPDM-MEMDO dimer to increase the chain, but its reaction rate of 2.8 x 10(-11) s(-1) is predicted to be about 5 times smaller than that between a DPDM methoxy and a MEMDO hydroxyl. This implies that the reaction rate for the larger nanostructures becomes smaller. Additionally, our SANS measurements determine that the final products from our sol-gel reaction are on the nanometer scale, at sizes from 1.76 to 2.36 nm.