Functionalized Alkynylplatinum(II) Polypyridyl Complexes for Use as Sensitizers in Dye‐Sensitized Solar Cells

A series of platinum(II) alkynyl‐based sensitizers has been synthesized and found to show light‐to‐electricity conversion properties. These dyes were developed as sensitizers for the application in nanocrystalline TiO₂ dye‐sensitized solar cells (DSSCs). Their photophysical and electrochemical properties were studied. The excited‐state property was probed using nanosecond transient absorption spectroscopy, which showed the formation of a charge‐separated state that arises from the intramolecular photoinduced charge transfer from the platinum(II) alkynylbithienylbenzothiadiazole moiety (donor) to the polypyridyl ligand (acceptor). A lifetime of 3.4 μs was observed for the charge‐separated state. A dye‐sensitized solar cell based on one of the complexes showed a short‐circuit photocurrent of 7.12 mA cm^?2, an open circuit voltage of 780 mV, and a fill factor of 0.65, thus giving an overall power conversion efficiency of 3.6 %.     

Isotope dilution gas chromatography/mass spectrometry method for determination of pyrethroids in apple juice

This paper presents the development of a highly precise and accurate analytical method for the determination of three matrix-bound pyrethroids, namely, cypermethrin, permethrin, and bifenthrin, using an isotope dilution gas chromatography/mass spectrometry technique. Identification of the analytes was confirmed under selective ion monitoring mode by the presence of two dominant ion fragments within specific time windows and matching of relative ion intensities of the ions concerned in samples and calibration standards. Quantitation was based on the measurement of concentration ratios of the natural and isotope analogues in the sample and calibration blends. Intraday and interday repeatabilities of replicate analyses of the pyethroids in an apple juice sample were below 0.5%. The expanded relative uncertainty ranged from 3 to 6%, which was significantly lower than the range obtained using internal or external calibration methods. As a labeled analogue is not available for bifenthrin, bifenthrin was determined using labeled cis-permethrin as the internal standard. The results were counterchecked by a gas chromatography-electron capture detection technique using PCB 209 as the internal standard. The method developed was applied to a recent pilot study organized by CCQM and the results were consistent with those of other participants.     

A Journey to the Total Synthesis of Daptomycin

Daptomycin, the first antibiotic of its class, provides a new structural motif for the development of new antibiotics. Recently, we have completed the total synthesis of daptomycin. The development of the successful synthetic strategy is described here, including the application of serine/threonine ligation mediated peptide cyclization to the daptomycin macrocyclization.     

Aeroacoustics of duct junction flows merging at different angles

This paper reports an exploratory study of the aeroacoustics of a merging flow at a duct junction with the same width in all branches and different merging angles. The focus is put on the acoustic generation due to the flow unsteadiness. The study is carried out by the direct aeroacoustic simulation (DAS) approach, which solves the unsteady compressible Navier–Stokes equations and the perfect gas equation of state simultaneously using the conservation element and solution element (CE/SE) method. The Mach number based on the maximum inlet velocity of side branch is 0.1 and the Reynolds number of the flow based on duct width and this velocity is 2.3×10⁵. The numerical simulations are performed in two dimensions and the aeroacoustics at different merging angles (30°, 45°, 60° and 90°) are studied. Both the levels of unsteady interactions of merging flow structures and the efficiency of the acoustic generation are observed to increase with the merging angles, where the increase in acoustic efficiency can be up to three orders of magnitude. The major acoustic source is found to be the fluctuating wall pressure induced by the flow unsteadiness in the downstream branch. A scaling law between the wall fluctuating force and the acoustic efficiency is also derived.     

Dynamics of viscous fingers in Hele-Shaw cells of liquid crystals Theory and experiment

The theoretical and experimental developments in the interfacial dynamics and the formation of viscous fingering patterns in Hele-Shaw cells of liquid crystal-air systems are summarized and discussed. These include radial and linear cells with or without grooves engraved on the cell plates. Instabilities of fingers, the role of intrinsic and extrinsic anisotropies, etc., are emphasized. In a linear cell, when the injected air is kept at constant pressure, a whole sequence of successive instabilities of fingers (hump, tip-splitting, sidewrinkling, sidebranching and DLA-like structure) is observed in a single run of the experiment. In our theory, the equations of motion of nematic flows in Hele-Shaw cells are derived from the Ericksen-Leslie equations. In the linear approximation, the equations resemble those of isotropic liquids with the presence of effective viscosities and anisotropic surface tension. Experimental observations are interpreted with the introduction of an effective control parameter which may be time dependent. Special features of viscous fingers in liquid crystals in contrast to those in isotropic liquids, such as asymmetric dendritics, displacement of the finger from the central axis of the linear cell, and reentrant sequence of patterns, are pointed out. Plausible explanations of these phenomena are given. In this newly developed field, a large number of interesting problems remain to be solved.     

Improved Stabilities of Labeling Probes for the Selective Modification of Endogenous Proteins in Living Cells and In Vivo

To date, various affinity-based protein labeling probes have been developed and applied in biological research to modify endogenous proteins in cell lysates and on the cell surface. However, the reactive groups on the labeling probes are also the cause of probe instability and nonselective labeling in a more complex environment, e. g., intracellular and in vivo. Here, we show that labeling probes composed of a sterically stabilized difluorophenyl pivalate can achieve efficient and selective labeling of endogenous proteins on the cell surface, inside living cells and in vivo. As compared with the existing protein labeling probes, probes with the difluorophenyl pivalate exhibit several advantages, including long-term stability in stock solutions, resistance to enzymatic hydrolysis and can be customized easily with diverse fluorophores and protein ligands. With this probe design, endogenous hypoxia biomarker in living cells and nude mice were successfully labeled and validated by in vivo, ex vivo, and immunohistochemistry imaging.     

Nonlinear spectral-spatial control and localization of supercontinuum radiation

We present the first observation of spatiospectral control and localization of supercontinuum light through the nonlinear interaction of spectral components in extended periodic structures. We use an array of optical waveguides in a LiNbO3 crystal and employ the interplay between diffraction and nonlinearity to dynamically control the output spectrum of the supercontinuum radiation. This effect presents an efficient scheme for optically tunable spectral filtering of supercontinua.     

Synthesis of Two‐Dimensional Transition‐Metal Phosphates with Highly Ordered Mesoporous Structures for Lithium‐Ion Battery Applications

Materials with ordered mesoporous structures have shown great potential in a wide range of applications. In particular, the combination of mesoporosity, low dimensionality, and well‐defined morphology in nanostructures may exhibit even more attractive features. However, the synthesis of such structures is still challenging in polar solvents. Herein, we report the preparation of ultrathin two‐dimensional (2D) nanoflakes of transition‐metal phosphates, including FePO₄, Mn₃(PO₄)₂, and Co₃(PO₄)₂, with highly ordered mesoporous structures in a nonpolar solvent. The as‐obtained nanoflakes with thicknesses of about 3.7 nm are constructed from a single layer of parallel‐packed pore channels. These uniquely ordered mesoporous 2D nanostructures may originate from the 2D assembly of cylindrical micelles formed by the amphiphilic precursors in the nonpolar solvent. The 2D mesoporous FePO₄ nanoflakes were used as the cathode for a lithium‐ion battery, which exhibits excellent stability and high rate capabilities.