Phase modulation and ellipticity of the light transmitted through a smectic C* layer with short helix pitch

A chiral ferroelectric smectic C* liquid crystal (FLC) with the helix pitch p ₀?=?330 nm was developed to avoid any scattering of visible light when the helix is not unwound over a certain limit. Planar cells with different FLC layer thickness (16 and 44 μm) have been assembled with helix axis parallel to the glass plates and aligned along the rubbing direction. The ellipticity of the light passing through the cells vs. the electric field was investigated, and a method for evaluating the electrically controlled birefringence via ellipticity measurements has been established. We have found that the FLC cell is an optical retardation layer driven by the electric field, the effective birefringence being proportional to the square electric field. The physical origin of the electrically controlled phase shift of the light passing through the FLC layer has been analysed.     

Trace formulas for additive and non-additive perturbations

Trace formulas for pairs of self-adjoint, maximal dissipative and accumulative as well as other types of resolvent comparable operators are obtained. In particular, the existence of a complex-valued spectral shift function for a pair {H^′,H}$\{H^{\prime },H\}$ of maximal accumulative operators has been proved. We investigate also the existence of a real-valued spectral shift function. Moreover, we treat in detail the case of additive trace class perturbations. Assuming that H   and H^′=H+V$H^{\prime }=H+V$ are maximal accumulative and V is trace class, we prove the existence of a summable   complex-valued spectral shift function. We also obtain trace formulas for pairs {H,H^?}$\{H,H^{?}\}$assuming only that H and  H^?$H^{?}$are resolvent comparable. In this case the determinant of the characteristic function of H is involved in trace formulas.     

Enhancement in the rate of conversion of peptide Cys-Pro esters to peptide thioesters by structural modification

We previously reported that the peptide containing a Cys-Pro ester (CPE) moiety is spontaneously transformed into a peptide thioester via an N to S acyl shift followed by diketopiperazine formation. In an attempt to identify more reactive structures for the formation of a peptide thioester, we modified the CPE structure, in which the Pro residue in the CPE moiety was replaced with N-substituted glycine derivatives. These peptides were transformed into a peptide thioester more rapidly. Alternatively, the addition of an amino acid residue at the C-terminus of the CPE moiety also accelerated thioester formation.     

Theoretical and photophysical investigation of biologically active fluorophore: 2-amino-6-chlorofluoren-9-one

The optimized geometric parameters of the 2-Amino-6-chlorofluoren-9-one (2A6CF9O) compound were estimated by employing density functional theory. The electronic characteristics of the molecule were explored using molecular frontier orbital energies and the MEP surface. Kamlet's and Catalan's multiple linear regression techniques along with different polarity functions were used to investigate the influence of pure solvents on spectral properties. In the system, both general solute-solvent and hydrogen bonding interactions are active. However, as compared to normal solute-solvent interactions, hydrogen bonding interactions have a smaller role. In addition, using computed ground state dipole moment, solvatochromic correlations were employed to infer excited state dipole moment.     

Analysis of drug interactions with serum proteins and related binding agents by affinity capillary electrophoresis: A review

Biomolecules such as serum proteins can interact with drugs in the body and influence their pharmaceutical effects. Specific and precise methods that analyze these interactions are critical for drug development or monitoring and for diagnostic purposes. Affinity capillary electrophoresis (ACE) is one technique that can be used to examine the binding between drugs and serum proteins, or other agents found in serum or blood. This article will review the basic principles of ACE, along with related affinity-based capillary electrophoresis (CE) methods, and examine recent developments that have occurred in this field as related to the characterization of drug–protein interactions. An overview will be given of the various formats that can be used in ACE and CE for such work, including the relative advantages or weaknesses of each approach. Various applications of ACE and affinity-based CE methods for the analysis of drug interactions with serum proteins and other binding agents will also be presented. Applications of ACE and related techniques that will be discussed include drug interaction studies with serum agents, chiral drug separations employing serum proteins, and the use of CE in hybrid methods to characterize drug binding with serum proteins.     

Beyond green with synthetic chlorophylls – Connecting structural features with spectral properties

The distinct features of chlorophylls in photosynthesis have led to the formation of numerous derivatives for applications encompassing solar energy conversion, molecular photonics, photodynamic therapy, and molecular imaging. Synthetic chlorins created de novo and bearing a geminal dimethyl group in the reduced ring have proved invaluable for fundamental studies. Four decades of research have led to accumulation of tabulated spectra for > 400 such synthetic chlorins with distinct structural frameworks (17-oxochlorins, 13¹-oxophorbines, chlorinimides) and substituents (alkyl, aryl, ethynyl, phenylethynyl, acetyl, formyl) located at specific (meso, β) positions. In this review, spectral traces (324 absorption, 247 fluorescence) are assembled along with photophysical data including the molar absorption coefficient (ε), fluorescence quantum yield (Φ_f) and singlet excited-state lifetime (τ_s). The review uses the accumulated spectral data derived from chlorins all containing a uniform molecular scaffold to (1) highlight the effects of molecular structure on spectral features, and (2) identify trends including how ε, Φ_f and τ_s vary with wavelength and other features. Use of a common geminal-dimethyl-substituted chlorin scaffold – beginning with no substituents, to one substituent at designated sites, and to 2 or more substituents – provides a systematic Aufbau approach for understanding the absorption spectra of chlorins on a path to and beyond the native chlorophylls. The review provides insights concerning the rational design of potent analogues of Nature’s preeminent red-region absorbers for potential utilization in diverse applications and is aimed at multiple audiences: those interested in spectral properties, tetrapyrrole photophysics, and the molecular design of new chromophores.     

Bonding,Aromaticity and Isomerization of Furfuraldehyde through Off-Nucleus Isotropic Magnetic Shielding

Off-nucleus isotropic magnetic shielding (σ_iso(r)) and multi-points nucleus independent chemical shift (NICS(0-2 Å)) index were utilized to find the impacts of the isomerization of gas-phase furfuraldehyde (FD) on bonding and aromaticity of FD. Multidimensional (1D to 3D) grids of ghost atoms (bqs) were used as local magnetic probes to evaluate σ_iso(r) through gauge-including atomic orbitals (GIAO) at density functional theory (DFT) and B3LYP functional/6-311+G(d,p) basis set level of theory. 1D σ_iso(r) responses along each bond of FD were examined. Also, a σ_iso(r) 2D-scan was performed to obtain σ_iso(r) behavior at vertical heights of 0–1 Å above the FD plane in its cis, transition state (TS) and trans forms. New techniques for evaluating 2D σ_iso(r) cross-sections are also included. Our findings showed that bonds in cyclic and acyclic parts of FD are dissimilar. Unlike the C−O bond of furanyl, the C=O bond of the formyl group is magnetically different. C−C and C−H bonds in furanyl are found similar to those in aromatic rings. A unique σ_iso(r) trend was observed for the C₂−C₆ bond during FD isomerization. Based on NICS(0-2 Å) values, the degree of aromaticity follows the order of cis FD<trans FD<furan<TS FD.     

Enhanced Oral Absorption of Icaritin by Using Mixed Polymeric Micelles Prepared with a Creative Acid-Base Shift Method

The purpose of this study was to develop mixed polymeric micelles with high drug loading capacity to improve the oral bioavailability of icaritin with Soluplus^® and Poloxamer 407 using a creative acid-base shift (ABS) method, which exhibits the advantages of exclusion of organic solvents, high drug loading and ease of scaling-up. The feasibility of the ABS method was successfully demonstrated by studies of icaritin-loaded polymeric micelles (IPMs). The prepared IPMs were characterized to have a spherical shape with a size of 72.74 ± 0.51 nm, and 13.18% drug loading content. In vitro release tests confirmed the faster release of icaritin from IPMs compared to an oil suspension. Furthermore, bioavailability of icaritin in IPMs in beagle dogs displayed a 14.9-fold increase when compared with the oil suspension. Transcellular transport studies of IPMs across Caco-2 cell monolayers confirmed that the IPMs were endocytosed in their intact forms through macropinocytosis, clathrin-, and caveolae-mediated pathways. In conclusion, the results suggested that the mixed micelles of Soluplus^® and Poloxamer 407 could be a feasible drug delivery system to enhance oral bioavailability of icaritin, and the ABS method might be a promising technology for the preparation of polymeric micelles to encapsulate poorly water-soluble weakly acidic and alkaline drugs.     

Evaluation of Multi-Objective Optimization Algorithms for NMR Chemical Shift Assignment

An automated NMR chemical shift assignment algorithm was developed using multi-objective optimization techniques. The problem is modeled as a combinatorial optimization problem and its objective parameters are defined separately in different score functions. Some of the heuristic approaches of evolutionary optimization are employed in this problem model. Both, a conventional genetic algorithm and multi-objective methods, i.e., the non-dominated sorting genetic algorithms II and III (NSGA2 and NSGA3), are applied to the problem. The multi-objective approaches consider each objective parameter separately, whereas the genetic algorithm followed a conventional way, where all objectives are combined in one score function. Several improvement steps and repetitions on these algorithms are performed and their combinations are also created as a hyper-heuristic approach to the problem. Additionally, a hill-climbing algorithm is also applied after the evolutionary algorithm steps. The algorithms are tested on several different datasets with a set of 11 commonly used spectra. The test results showed that our algorithm could assign both sidechain and backbone atoms fully automatically without any manual interactions. Our approaches could provide around a 65% success rate and could assign some of the atoms that could not be assigned by other methods.     

The Influence of Water Vapor on the Electrochemical Shift of an Ionic Liquid Measured by Ambient Pressure X-ray Photoelectron Spectroscopy

Ionic liquids (ILs) are considered to be one of the steppingstones to fabricate next generation electrochemical devices given their unique physical and chemical properties. The addition of water to ILs significantly impact electrochemical related properties including viscosity, density, conductivity, and electrochemical window. Herein we utilize ambient pressure X-ray photoelectron spectroscopy (APXPS) to examine the impact of water on values of the electrochemical shift (S), which is determined by measuring changes in binding energy shifts as a function of an external bias. APXPS spectra of C 1s, O 1s and N 1s regions are examined for the IL 1-butyl-3-methylimidazolium acetate, [C₄mim][OAc], at the IL/gas interface as a function of both water vapor pressure and external bias. Results reveal that in the absence of water vapor there is an IL ohmic drop between the working electrode and quasi reference electrode, giving rise to chemical specific S values of less than one. Upon introducing water vapor, S values approach one as a function of increasing water vapor pressure, indicating a decrease in the IL ohmic drop as the IL/water mixture becomes more conductive and the potential drop is driven by the electric double layer at the electrode/IL interface.