Optoelectronic Properties of Carbon-Bound Boron Difluoride Hydrazone Dimers

The creation of dimeric boron difluoride complexes of chelating N-donor ligands is a proven strategy for the enhancement of the optoelectronic properties of fluorescent dyes. We report dimers based on the boron difluoride hydrazone (BODIHY) framework, which offer unique and sometimes unexpected substituent-dependent absorption, emission, and electrochemical properties. BODIHY dimers have low-energy absorption bands (λ_max=421 to 479 nm, ϵ=17 200 to 39 900 m ⁻¹ cm⁻¹) that are red-shifted relative to monomeric analogues. THF solutions of these dimers exhibit aggregation-induced emission upon addition of water, with emission enhancement factors ranging from 5 to 18. Thin films of BODIHY dimers are weakly emissive as a result of the inner-filter effect, attributed to intermolecular π-type interactions. BODIHY dimers are redox-active and display two one-electron oxidation and two one-electron reduction waves that strongly depend on the N-aryl substituents. These properties are rationalized using density-functional theory calculations and X-ray crystallography experiments.     

Platinum Oxide Nanoparticles for Electrochemical Hydrogen Evolution: Influence of Platinum Valence State

Electrochemical hydrogen generation is a rising prospect for future renewable energy storage and conversion. Platinum remains a leading choice of catalyst, but because of its high cost and low natural abundance, it is critical to optimize its use. In the present study, platinum oxide nanoparticles of approximately 2 nm in diameter are deposited on carbon nitride (C3N4) nanosheets by thermal refluxing of C3N4 and PtCl₂ or PtCl₄ in water. These nanoparticles exhibit apparent electrocatalytic activity toward the hydrogen evolution reaction (HER) in acid. Interestingly, the HER activity increases with increasing Pt⁴⁺ concentration in the nanoparticles, and the optimized catalyst even outperforms commercial Pt/C, exhibiting an overpotential of only −7.7 mV to reach the current density of 10 mA cm⁻² and a Tafel slope of −26.3 mV dec⁻¹. The results from this study suggest that the future design of platinum oxide catalysts should strive to maximize the Pt⁴⁺ sites and minimize the formation of the less active Pt²⁺ species.     

Benchtop NMR analysis of piperazine-based drugs hyperpolarised by SABRE

Piperazine-based drugs, such as N-benzylpiperazine (BZP), became attractive in the 2000s due to possessing effects similar to amphetamines. Herein, BZP, in addition to its pyridyl analogues, 2-, 3-, and 4-pyridylmethylpiperidine (2-PMP, 3-PMP, and 4-PMP respectively) was subjected to the hyperpolarisation technique Signal Amplification By Reversible Exchange (SABRE) in order to demonstrate the use of this technique to detect these piperazine-based drugs. Although BZP was not hyperpolarised via SABRE, 2-PMP, 3-PMP, and 4-PMP were, with the ortho- and meta-pyridyl protons of 4-PMP showing the largest enhancement of 313-fold and 267-fold, respectively, in a 1.4-T detection field, following polarisation transfer at Earth's magnetic field. In addition to the freebase, 4-PMP.3HCl was also appraised by SABRE and was found not to polarise, however, the addition of increasing equivalents of triethylamine (TEA) produced the freebase, with a maximum enhancement observed upon the addition of 3 equivalents of TEA. Further addition of TEA led to a reduction in the observed enhancement. SABRE was also employed to polarise 4-PMP.3HCl (~20% w/w) in a simulated tablet to demonstrate the forensic application of the technique (138-fold enhancement for the ortho-pyridyl protons). The amount of 4-PMP.3HCl present in the simulated tablet was quantified via NMR using D₂O as a solvent and compared well to complimentary gas chromatography–mass spectrometry data. Exchanging D₂O for CD₃OD as the solvent utilised for analysis resulted in a significantly lower amount of 4-PMP.3HCl being determined, thus highlighting safeguarding issues linked to drug abuse in relation to determining the amount of active pharmaceutical ingredient present.     

Cycloaddition Reactions of an Active Cyclic Phosphane/Borane Pair with Alkenes,Alkynes, and Carbon Dioxide

The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)₄ . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO₂ molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions.     

Wound Healing Attributes of Polyelectrolyte Multilayers Prepared with Multi‐l‐arginyl‐poly‐l‐aspartate Pairing with Hyaluronic Acid and γ‐Polyglutamic Acid

Biodegradable multi‐l ‐arginyl‐poly‐l ‐aspartate (MAPA), more commonly cyanophycin, prepared with recombinant Escherichia coli contains a polyaspartate backbone with lysine and arginine as side chains. Two assemblies of polyelectrolyte multilayers (PEMs) are fabricated at three different concentration ratios of insoluble MAPA (iMAPA) with hyaluronic acid (iMAPA/HA) and with γ‐polyglutamic acid (iMAPA/γ‐PGA), respectively, utilizing a layer‐by‐layer approach. Both films with iMAPA and its counterpart, HA or γ‐PGA, as the terminal layer are prepared to assess the effect on film roughness, cell growth, and cell migration. iMAPA incorporation is higher for a higher concentration of the anionic polymer due to better charge interaction. The iMAPA/HA films when compared to iMAPA/γ‐PGA multilayers show least roughness. The growth rates of L929 fibroblast cells on the PEMs are similar to those on glass substrate, with no supplementary effect of the terminal layer. However, the migration rates of L929 cells increase for all PEMs. γ‐PGA incorporated films impart 50% enhancement to the cell migration after 12 h of culture as compared to the untreated glass, and the smooth films containing HA display a maximum 82% improvement. The results present the use of iMAPA to construct a new layer‐by‐layer system of polyelectrolyte biopolymers with a potential application in wound dressing.     

Oxidopyrylium [5+2] cycloaddition chemistry: Historical perspective and recent advances (2008–2018)

The following review article provides an overview of oxidopyrylium [5+2] cycloaddition chemistry, with a particular emphasis placed on seminal historical developments and advancements made over the last decade. It is our hope this review serves as a valuable resource to those interested in the oxidopyrylium cycloaddition chemistry, and helps inspire future advancements.     

Solving a multi-objective simulation model using a hybrid response surface method and lexicographical goal programming approach—a case study on integrated circuit ink-marking machines

In an integrated circuit (IC) packaging plant, the ink-marking machine has a significantly higher throughput than the other processing machines. When periodic demand surges result in backlog orders or in lost customers, there is a need to increase system throughput. To resolve this problem, the purchase of a new machine often results in excess capacity in addition to added operation and acquisition costs. Therefore, the productivity improvement effort has priority over the machine purchase decision. This paper seeks to optimize both throughput and cycle time performance for IC ink-marking machines. While throughput increase is the primary objective, there is an acceptable cycle time limit for a feasible solution. It is a multi-objective problem. The proposed solution methodology constructed a simulation metamodel for the ink-marking operation by using a fractional factorial experimental design and regression analysis. It is then solved by a hybrid response surface method and lexicographical goal programming approach. Solution results illustrated a successful application.     

New inequalities for subspace arrangements

For each positive integer n?4, we give an inequality satisfied by rank functions of arrangements of n subspaces. When n=4 we recover Ingleton's inequality; for higher n the inequalities are all new. These inequalities can be thought of as a hierarchy of necessary conditions for a (poly)matroid to be realizable. Some related open questions about the “cone of realizable polymatroids” are also presented.     

Boundaries of weak peak points in noncommutative algebras of Lipschitz functions

It has been shown that any Banach algebra satisfying ‖f ²‖ = ‖f‖² has a representation as an algebra of quaternion-valued continuous functions. Whereas some of the classical theory of algebras of continuous complex-valued functions extends immediately to algebras of quaternion-valued functions, similar work has not been done to analyze how the theory of algebras of complex-valued Lipschitz functions extends to algebras of quaternion-valued Lipschitz functions. Denote by Lip(X, \mathbbF\mathbb{F}) the algebra over R of F-valued Lipschitz functions on a compact metric space (X, d), where \mathbbF\mathbb{F} = ℝ, ℂ, or ℍ, the non-commutative division ring of quaternions. In this work, we analyze a class of subalgebras of Lip(X, \mathbbF\mathbb{F}) in which the closure of the weak peak points is the Shilov boundary, and we show that algebras of functions taking values in the quaternions are the most general objects to which the theory of weak peak points extends naturally. This is done by generalizing a classical result for uniform algebras, due to Bishop, which ensures the existence of the Shilov boundary. While the result of Bishop need not hold in general algebras of quaternion-valued Lipschitz functions, we give sufficient conditions on such an algebra for it to hold and to guarantee the existence of the Shilov boundary.