Cylindrical-sinc beam

Propagation of diffracted beams in free space has already been identified. One possible solution is derived from the Helmholtz wave equation and this solution is named as cylindrical-sinc beam. Therefore, cylindrical-sinc beam is a new beam type which can be obtained from Helmholtz equation. Diffraction properties of this new beam type were observed from an opaque aperture screen. Additionally, geometrical theory of diffraction is used to determine numerical values of diffracted fields. This new beam type which does not exist in the literature was observed by using these methods passing through an opaque aperture. The obtained expression was analyzed numerically. Simulation results of the beam depending on the length of aperture and distance to the observation point were added.     

Development of Kinetic Mechanism for the Esterification of Acrylic Acid with Hexanol Catalyzed by Ion‐Exchange Resin

The heterogeneous esterification reaction of acrylic acid with hexanol over three different cation‐exchange resins, Amberlyst 131, Amberlyst 15, and Dowex 50Wx‐400, was investigated. Surface area, pore volume, average pore diameter, and acid capacity analyses were carried out for these three catalysts. Amberlyst 131 gave the highest conversion, and therefore, further experiments were performed catalyzed by Amberlyst 131. The absence of external and internal mass transfer resistances was investigated for the esterification of acrylic acid with hexanol. Experiments showed that the reaction is controlled by chemical step rather than external and internal mass transfer steps. The effects of temperature, catalyst loading, and alcohol to acid molar ratio on the conversion of acrylic acid were determined. The activation energy and kinetic and adsorption constants were determined according to the Langmuir–Hinshelwood–Hougen–Watson mechanism.     

FT-IR Spectroscopic Study of M(1,2-Ethanedithiol)Ni(CN)4·Benzene (M=Co,Cd) Clathrates

New Hofmann-ethanedithiol-type clathrates, M(1,2-Ethanedithiol)Ni(CN)₄·Benzene (M=Cd,Co), have been obtained in the powdered form. By vibrational spectroscopy of these two new compounds, it is exhibited that their structures are similar to those of the other Hofmann-type clathrates.     

Unnatural amino acid mutagenesis of green fluorescent protein

Unnatural amino acid mutagenesis has been used to selectively substitute tyrosine 66 of green fluorescent protein (GFP) with five novel amino acids: p-amino-L-phenylalanine, p-methoxy-L-phenylalanine, p-iodo-L-phenylalanine, p-bromo-L-phenylalanine, and L-3-(2-naphthyl)alanine. The absorbance and emission maxima of the resulting mutant GFPs span the range from 375 to 435 nm and 428 to 498 nm, respectively. The spectral properties of the mutant GFPs, including the absorbance and fluorescence maxima and quantum yields, correlate with the structural and electronic properties of the substituents on the amino acids.     

Determination of antimony by using a quartz atom trap and electrochemical hydride generation atomic absorption spectrometry

The analytical performance of a miniature quartz trap coupled with electrochemical hydride generator for antimony determination is described. A portion of the inlet arm of the conventional quartz tube atomizer was used as an integrated trap medium for on-line preconcentration of electrochemically generated hydrides. This configuration minimizes transfer lines and connections. A thin-layer of electrochemical flow through cell was constructed. Lead and platinum foils were employed as cathode and anode materials, respectively. Experimental operation conditions for hydride generation as well as the collection and revolatilization conditions for the generated hydrides in the inlet arm of the quartz tube atomizer were optimized. Interferences of copper, nickel, iron, cobalt, arsenic, selenium, lead and tin were examined both with and without the trap. 3σ limit of detection was estimated as 0.053 μg l^− 1 for a sample size of 6.0 ml collected in 120 s. The trap has provided 18 fold sensitivity improvement as compared to electrochemical hydride generation alone. The accuracy of the proposed technique was evaluated with two standard reference materials; Trace Metals in Drinking Water, Cat # CRM-TMDW and Metals on Soil/Sediment #4, IRM-008.     

Close‐to‐convexity of normalized Dini functions

In this paper necessary and sufficient conditions are deduced for the close‐to‐convexity of some special combinations of Bessel functions of the first kind and their derivatives by using a result of Shah and Trimble about transcendental entire functions with univalent derivatives and some newly discovered Mittag–Leffler expansions for Bessel functions of the first kind.     

Asymmetric Modulation of Protein Order–Disorder Transitions by Phosphorylation and Partner Binding

As for many intrinsically disordered proteins, order–disorder transitions in the N‐terminal oligomerization domain of the multifunctional nucleolar protein nucleophosmin (Npm‐N) are central to its function, with phosphorylation and partner binding acting as regulatory switches. However, the mechanism of this transition and its regulation remain poorly understood. In this study, single‐molecule and ensemble experiments revealed pathways with alternative sequences of folding and assembly steps for Npm‐N. Pathways could be switched by altering the ionic strength. Phosphorylation resulted in pathway‐specific effects, and decoupled folding and assembly steps to facilitate disorder. Conversely, binding to a physiological partner locked Npm‐N in ordered pentamers and counteracted the effects of phosphorylation. The mechanistic plasticity found in the Npm‐N order–disorder transition enabled a complex interplay of phosphorylation and partner‐binding steps to modulate its folding landscape.     

A panchromatic boradiazaindacene (BODIPY) sensitizer for dye-sensitized solar cells

A novel distyryl-substituted boradiazaindacene (BODIPY) dye displays interesting properties as a sensitizer in DSSC systems, opening the way to further exploration of structure-efficiency correlation within this class of dyes.     

Parametrization, molecular dynamics simulation, and calculation of electron spin resonance spectra of a nitroxide spin label on a polyalanine alpha-helix

The nitroxide spin label 1-oxyl-2,2,5,5-tetramethylpyrroline-3-methyl-methanethiosulfonate (MTSSL), commonly used in site-directed spin labeling of proteins, is studied with molecular dynamics (MD) simulations. After developing force field parameters for the nitroxide moiety and the spin label linker, we simulate MTSSL attached to a polyalanine alpha-helix in explicit solvent to elucidate the factors affecting its conformational dynamics. Electron spin resonance spectra at 9 and 250 GHz are simulated in the time domain using the MD trajectories and including global rotational diffusion appropriate for the tumbling of T4 Lysozyme in solution. Analysis of the MD simulations reveals the presence of significant hydrophobic interactions of the spin label with the alanine side chains.     

Insights into the Ultrafast Photodissociation Dynamics of Isoprene-Derived Criegee Intermediates

Isoprene is the most abundant nonmethane volatile organic compound emitted into the troposphere by terrestrial vegetation. Reaction with ozone represents an important isoprene removal process from the troposphere and is a well-known source of Criegee intermediates (CIs), which are reactive carbonyl oxides. Three CIs, formaldehyde oxide (CH₂OO), methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide) are formed during isoprene ozonolysis. All three CIs contain strongly absorbing ππ* states, electronic excitation, which leads to dissociation to form aldehyde/ketone + oxygen products. Here, we compare the excited state chemistry of CH₂OO, MVK-oxide and MACR-oxide in order to ascertain how increasing molecular complexity affects their photodynamics. In CH₂OO, vertical excitation to the S₂ state leads to prompt O-O bond fission with a unity quantum yield. Branching into both the O (¹D) + H₂CO (S₀) and O (³P) + H₂CO (T₁) product channels is predicted, with 80% of trajectories dissociating to form the former product pair. Analogous vertical excitation of the lowest energy conformers of MVK-oxide and MACR-oxide also undergoes O-O bond fission to form O + MVK/MACR products—albeit with a nonunity quantum yield. In the latter case, ca. 10% and 25% of trajectories remain as the parent MVK-oxide and MACR-oxide molecules, respectively. Additionally, at most only 5% of the dissociating trajectories form O (³P) + MVK/MACR (T₁) products, with a greater fraction forming O (¹D) + MVK/MACR (S₀) products (cf. CH₂OO). This latter observation coupled with the greater fraction of undissociated trajectories aligns with the bathochromic shift in the electronic absorption of the MACR-oxide and MVK-oxide (cf. CH₂OO). We discuss the implications of the results in a broader context, including those that are relevant to the atmosphere.