Improved Synthesis of Aliphatic Ketones by the Reaction of Alkylmercuric Bromides With Nickel Carbonyl in the Presence of Potassium Iodide

An improved and convenient procedure for symmetrical aliphatic ketone synthesis is described, which employs the reaction of alkylmercuric bromides with nickel carbonyl in the presence of potassium iodide.     

A structural remedy toward bright dipolar fluorophores in aqueous media

The donor–acceptor (D–A) type dipolar fluorophores, an important class of luminescent dyes with two-photon absorption behaviour, generally emit strongly in organic solvents but poorly in aqueous media. To understand and enhance the poor emission behaviour of dipolar dyes in aqueous media, we undertake a rational approach that includes a systematic structure variation of the donor, amino substituent of acedan, an important two-photon dye. We identify several factors that influence the emission behaviour of the dipolar dyes in aqueous media through computational and photophysical studies on new acedan derivatives. As a result, we can make acedan dyes emit bright fluorescence under one- and two-photon excitation in aqueous media by suppressing the liable factors for poor emission: 1,3-allylic strain, rotational freedom, and hydrogen bonding with water. We also validate that these findings can be generally extended to other dipolar fluorophores, as demonstrated for naphthalimide, coumarin and (4-nitro-2,1,3-benzoxadiazol-7-yl)amine (NBD) dyes. The new acedan and naphthalimide dyes thus allow us to obtain much brighter two-photon fluorescent images in cells and tissues than in their conventional forms. As an application of these findings, a thiol probe is synthesized based on a new naphthalimide dye, which shows greatly enhanced fluorescence from the widely used N,N-dimethyl analogue. The results disclosed here provide essential guidelines for the development of efficient dipolar dyes and fluorescence probes for studying biological systems, particularly by two-photon microscopy.     

Heat/Mass transfer in a two-pass rotating rectangular duct with and without 70°-angled ribs

The present study investigates convective heat/mass transfer and flow characteristics inside a cooling passage of rotating gas-turbine blades. The rotating duct with and without rib turbulators are used. The ribs of 70° attack angle are attached on leading and trailing surfaces in a staggered arrangement. A naphthalene sublimation technique is employed to determine detailed local heat transfer coefficients using the heat and mass transfer analogy. Additional numerical calculations are conducted to analyze the flow patterns in the cooling. The local heat/mass transfer and the flow pattern in the passage are changed significantly according to rib configurations, duct turning geometry and duct rotation speed. The results show that the duct rotation generates the heat transfer discrepancy between the leading and trailing walls due to the secondary flows induced by the Coriolis force. The heat/mass transfer on the ribbed duct shows 80% higher than the smooth duct because the ribs attached on the walls disturb the mainflow resulting in recirculation and secondary flows near the rib with the secondary flow generated by rotation. The overall heat transfer pattern on the leading and trailing walls for the first and second passes depend on the rotating speed and the turning geometry, but the local heat transfer trend is affected mainly by the rib arrangeements.     

Electrochemical capacitances of well-defined carbon surfaces

Reported is the capacitive behavior of homogeneous and well-defined surfaces of pristine carbon nanofibers (CNFs) and surface-modified CNFs. The capacitances of the well-defined CNFs were measured with cyclic voltammetry to correlate the surface structure with capacitance. Among the studied pristine CNFs, the edge surfaces of platelet CNFs (PCNF) and herringbone CNFs were more effective in capacitive charging than the basal plane surface of tubular CNF by a factor of 3-5. Graphitization of PCNF (GPCNF) changed the edge surface of PCNF into a domelike basal plane surface, and the corresponding capacitances decreased from 12.5 to 3.2 F/g. A chemical oxidation of the GPCNF, however, recovered a clear edge surface by removal of the curved basal planes to increase the capacitance to 5.6 F/g. The difference in the contribution of the edge surface and basal-plane surface to the capacitance of CNF was discussed in terms of the anisotropic conductivity of graphitic materials.     

Intramolecular and intermolecular energy transfers in donor-acceptor linear porphyrin arrays

We present highly time-resolved spontaneous fluorescence spectra of a porphyrin array system that consists of an energy donor and an acceptor linked by a phenyl group. The donors are meso-meso directly linked zinc(II) porphyrin arrays and the acceptor is a zinc(II) 5,15-di(phenylethynyl)porphyrin. The spectra over the entire Q (S1) emission band following the excitation of the donor B (S2) state have been measured directly without the conventional spectral reconstruction method. The time-resolved fluorescence spectra revealed detailed energy relaxation processes within the donor and subsequent energy transfer to the acceptor. The observed energy transfer rates to the acceptor are consistent with the Forster energy transfer rates calculated on the assumption that the energy is localized in the Q state of each porphyrin unit of the donor prior to the energy transfer. The passage of the energy deposited initially on one porphyrin unit of the donor to the acceptor illustrates a sequence of energy delocalization and localization processes before it finally reaches the acceptor.     

Very high third-order nonlinear optical activities of intrazeolite PbS quantum dots

Zeolite-intercalated semiconductor quantum dots (QDs) have long been proposed to give very high third-order nonlinear optical (3NLO) responses. However, measurements of their 3NLO responses have not been possible due to the lack of methods to prepare optically transparent QD-incorporating zeolite films supported on optically transparent substrates and to confine QDs only within zeolite interiors. We found that the zeolite-Y films grown on indium-tin-oxide-coated glass plates (Ygs) remain firmly bonded to the substrates during ion exchange with Pb2+ ions, drying, and formation of PbS QDs by treating Pb2+ ions with H2S. A series of Ygs encapsulating different numbers (n = 0, 8, 14, 23, and 33) of PbS in a unit cell [(PbS)n-Yg] were prepared. The PbS QDs were expelled by adsorbed moisture to the external surfaces, and the expelled QDs formed large QDs. Coating of the (PbS)n-Ygs with octadecyltrimethoxysilane results in effective confinement of the QDs within the internal pores. The zeolite-encapsulated PbS QDs showed remarkably high 3NLO activities at 532 and 1064 nm which are unparalleled by other PbS QDs dispersed in other matrixes.     

P4S10/dimethicone tandem: efficient reagent for thionation of various aromatic amides and esters

Organosulfur compounds are valuable because of their rich and varied chemistry especially in biological field. We report a new and efficient way for thionation of various aromatic amides and esters using P₄S₁₀/dimethicone tandem. The ease of handling and higher yield makes this protocol economical.     

Determination of the hyperpolarizability components of hemicyanine dyes by measuring the anisotropic fluorescence and second harmonic of the dyes uniformly aligned within zeolite channels

A unidirectional ensemble of hemicyanine molecules was prepared by inserting the molecules into the vertical channels of a uniformly oriented zeolite (silicalite-1) film grown on a glass substrate. Fluorescence from this sample excited with light polarized along the vertical channel was 50 times larger than that excited with light polarized orthogonal to the vertical channel direction. These vertically aligned hemicyanine dyes were used to determine the ratio of the molecular hyperpolarizability components beta(zxx)/beta(zzz) of hemicyanine.     

Controllable switching ratio in quantum dot/metal–metal oxide nanostructure based non-volatile memory device

In this paper, we report a facile quantum dot/In?CInOx(nanostructure)/quantum dot/In based non-volatile resistive memory device. The solution processed tri-layer structure exhibited bipolar resistive switching with a ratio of 100 between the high-resistance state and low-resistance state. The memory device was stable and functional even after 100,000 cycles of operation and it exhibited good retention characteristics. The ON/OFF switching ratio could be controlled by choosing appropriate metal in the structure. Memory operating mechanism is discussed based on charge trapping in quantum dots with InOx acting as barrier. A comparative study of memory devices consisting of aluminum and titanium in place of indium is presented. The possible reason for the variation in ON/OFF ratio is discussed on the size of the nano-sized grains of the middle metal layer.     

One-dimensional reaction coordinate and the corresponding potential of mean force from commitment probability distribution

In general, finding a one-dimensional representation of the kinetics of a high-dimensional system is a great simplification for the study of complex systems. Here, we propose a method to obtain a reaction coordinate whose potential of the mean force can reproduce the commitment probability distribution from the multidimensional surface. We prove that such a relevant one-dimensional representation can be readily calculated from the equilibrium distribution of commitment probabilities, which can be obtained with simulations. Also, it is shown that this representation is complementary to a previously proposed one-dimensional representation based on a quadratic approximation of the potential energy surface. The usefulness of the method is examined with dynamics in a two-dimensional system, showing that the one-dimensional surface thus obtained can predict the existence of an intermediate and the occurrence of path switching without a priori knowledge of the morphology of the original surface. The applicability of the method to more complex and realistic reactions such as protein folding is also discussed.