Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation

The replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications.     

Catalytic Stereoinversion of L‐Alanine to Deuterated D‐Alanine

A combination of an achiral pyridoxal analogue and a chiral base has been developed for catalytic deuteration of L ‐alanine with inversion of stereochemistry to give deuterated D ‐alanine under mild conditions (neutral pD and 25 °C) without the use of any protecting groups. This system can also be used for catalytic deuteration of D ‐alanine with retention of stereochemistry to give deuterated D ‐alanine. Thus a racemic mixture of alanine can be catalytically deuterated to give an enantiomeric excess of deuterated D ‐alanine. While catalytic deracemization of alanine is forbidden by the second law of thermodynamics, this system can be used for catalytic deracemization of alanine with deuteration. Such green and biomimetic approach to catalytic stereocontrol provides insights into efficient amino acid transformations.     

Cloning and Expression of Che a 1, the Major Allergen of <Emphasis Type="Italic">Chenopodium album</Emphasis> in <Emphasis Type="Italic">Escherichia coli</Emphasis>

Chenopodium album is a weedy annual plant in the genus Chenopodium. C. album pollen represents a predominant allergen source in Iran. The main C. album pollen allergens have been described as Che a 1, Che a 2, and Che a 3. The aim of this work was to clone the Che a 1 in Escherichia coli to establish a system for overproduction of the recombinant Che a 1 (rChe a 1). In order to clone this allergen, the pollens were subjected to RNA extraction. A full-length fragment encoding Che a 1 was prepared by polymerase chain reaction amplification of the first-strand cDNA synthesized from extracted RNA. Cloning was carried out by inserting the cDNA into the pET21b (+) vector, thereafter the construct was transformed into E. coli Top10 cells and expression of the protein was induced by IPTG. The rChe a 1 was purified using histidine tag in recombinant protein by means of Ni–NTA affinity chromatography. IgE immunoblotting, ELISA, and inhibition ELISA were done to evaluate IgE binding of the purified protein. In conclusion, the cDNA for the major allergen of the C. album pollen, Che a 1, was successfully cloned and rChe a 1 was purified. Inhibition assays demonstrated allergic subjects sera reacted with rChe a 1 similar to natural Che a 1 in crude extract of C. album pollen. This study is the first report of using the E. coli as a prokaryotic system for Che a 1 cloning and production of rChe a 1.     

Device characteristics and tight binding based modeling of bilayer graphene field-effect transistor

In this work the device characteristic of bilayer graphene MOSFET is investigated by calculation of transmission coefficient using tight-binding method. The real shape of applied potential on the bilayer graphene was included in the tight binding calculation. As obtained transmission coefficient is used to explore the current–voltage characteristics of the device in both on and off regimes. Electrical behavior of the device was obtained for different gate and drains voltages and channel length.     

Optimization of Circular Ring Microstrip Antenna Using Genetic Algorithm

Circular ring microstrip antennas have several interesting properties that make it attractive in wireless applications. Although several analysis techniques such as cavity model, generalized transmission line model, Fourier-Hankel transform domain and the method of matched asymptotic expansion have been studied by researchers, there is no efficient design tool that has been incorporated with a suitable optimization algorithm. In this paper, the cavity model analysis along with the genetic optimization algorithm is presented for the design of circular ring microstrip antennas. The method studied here is based on the well-known cavity model and the optimization of the dimensions and feed point location of the circular ring antenna is performed via the genetic optimization algorithm, to achieve an acceptable antenna operation around a desired resonance frequency. The antennas designed by this efficient design procedure were realized experimentally, and the results are compared. In addition, these results are also compared to the results obtained by the commercial electromagnetic simulation tool, the FEM based software, HFSS by ANSOFT.     

Robust inverse optimization

Given an observation of a decision-maker’s uncertain behavior, we develop a robust inverse optimization model for imputing an objective function that is robust against mis-specifications of the behavior. We characterize the inversely optimized cost vectors for uncertainty sets that may or may not intersect the feasible region, and propose tractable solution methods for special cases. We demonstrate the proposed model in the context of diet recommendation.     

Spectroscopic Characterization of Thiazole Orange-3 DNA Interaction

The interaction of a new derivative of thiazole orange (TO-3) with calf thymus DNA (ctDNA) has been investigated by fluorescence and absorption spectroscopy. When TO-3 binds to ctDNA, absorption bands exhibit significant hypochromicity at low base pair/dye ratio (BP/D ratio), and high BP/D show hyperchromicity with red shift. The spectral changes are attributed to the different species formed between TO-3 and ctDNA in the titration course of the dye molecule with DNA. Multivariate curve resolutions–alternating least squares (MCR–ALS) is applied to the absorption measurements recorded to recover the concentration profiles and the pure spectra of the DNA/TO-3 complexes involved in the process. The binding constant and size of the binding site have been determined spectrophotometrically using the McGhee von Hippel equation. MCR–ALS has been used to reveal the precise concentration profiles of all detectable species formed between ctDNA and TO-3 and their pure spectral profiles.     

Electrospun superhydrophobic polystyrene hollow fiber as a probe for liquid–liquid microextraction with gas chromatography‐mass spectrometry

A superhydrophobic polystyrene hollow fiber was electrospun around a copper spring collector. This approach led to the construction of a hollow fiber membrane, and the copper spring acted as a scaffold. The characteristic properties of the hollow fiber were studied by scanning electron microscopy. The membrane was used as a probe to transfer the extracting solvent from aquatic media to a gas chromatograph. After performing the liquid–liquid microextraction procedure on 10 mL of water sample by octanol, the whole solution was passed through the prepared polystyrene hollow fiber. Propanol, containing 2 mg/L lindane as the internal standard, was used for desorption and an aliquot of 2 μL of the desorbing solvent was subsequently injected into gas chromatography with mass spectrometry. Effects of different parameters influencing the extraction efficiency were optimized. The limits of detection and quantification were 2 and 6 ng/L, respectively. The relative standard deviations at a concentration level of 100 ng/L were between 2 and 6% (n = 3) while the method linearity ranged from 6 to 200 ng/L. Some real water samples were analyzed by the developed method and relative recoveries were in the range of 76–107%.     

Enhanced optical and hydrophilic properties of V and La co-doped ZnO thin films

V and La co-doped and undoped ZnO thin films were deposited on a glass substrate via the sol–gel method to investigate the structural, optical, and wettability of ZnO thin film by changing the V-doping concentration. Microstructure and water contact angles of the films were measured by SEM and contact angle goniometer, respectively. SEM studies revealed that the grain size and surface roughness of the film were changed by doping concentration. In addition, the contact angles were studied to find the possible effects of doping on the hydrophilicity of the film, indicating that the ZnO films were hydrophobic in nature. Finally, a good correlation was observed between the SEM micrographs and contact angle results, and the nature of ZnO film was found to be changed from hydrophobic to hydrophilic.