Intramolecular orbital engineered hetero bimetallic Ce-Fe MOF with reduced transition energy and enhanced visible light property

A structurally stable, 3d-4f heterometallic coordination polymer has been solvothermally synthesised and evaluated for its accomplished materials properties. The light absorption activity in the visible band was higher for unique Ce-Fe MOF than that of the homometallic Ce-MOF or Fe- MOF. The intimate overlap of two different metal clusters in heterometallic environmental induced the formation of low line conduction orbital, which ultimately lowered the transition energy. The heterometallic acquired an additional sensitisation from a Fe-μ3-oxo cluster that had vibrantly enhanced the light uptake activity. The vacancy created in the 6s, 5d orbital of Ce in Ce-Fe MOF contributed to the photo-excitation of electrons and reduced the recombination time. This distinct intramolecular arrangement assisted the exciton trapping characteristic. Also, the presence of multiple metal cores in the framework aided to confine the increased number of excitons for a redox reaction. The solar photocatalysis study with acetaminophen revealed these improved materialistic features by degrading it 94.6% with a rate constant of 0.0137 min⁻¹. The recycle studies confirmed the robust stability of the synthesised MOF.     

Electrochemical Signal Enhancer Fabricated Using Lysine‐rich Peptide for Ultrasensitive Electrochemical DNA Biosensor Analysis

Here we present a novel design of electrochemical signal enhancer to increase the detection sensitivity of electrochemical DNA biosensors. The key element of this enhancer is a lysine‐rich peptide (LRP). Its C‐terminal is conjugated with a planer molecule, being able to intercalate into the base pairs of probe‐target duplexes. The lysine residues of LRP are covalently linked with electrochemical signal indicators, acting as an assembly of electrochemical signal indicators. Experimental results proved the feasibility of the novel design. We have examined the effects of the numbers of lysine residues and the hybridization conditions on the detection sensitivity. The optimization procedures have led to significant sensitivity enhancement, and the LOD (limit of detection) has been determined to be 1.4 amol. This enhancer demonstrates advantages of easy operation, simple instrumentation, and high exemption from environmental influence.     

Surface modification of polyamide 12 angioplasty balloons by photochemical reaction with an aromatic azide

Polyamide 12 (PA12) is used in a variety of applications when low moisture absorption, good dimensional stability, and toughness are required. Polyamide 12 is one of the polymers most frequently employed to fabricate angioplasty balloon catheters; however, its high hydrophobicity and chemical inertness require the application of coatings to make its surface more hydrophilic and biocompatible. In this work, an alternative method, based on the photochemical reaction of PA12 with a hydrophilic aromatic azide, was developed. Static and dynamic contact angle measurements evidenced that the surface modification process was able to improve PA12 wettability and that the effects were retained even after 12 months from surface treatment. Polyamide 12 modification resulted in an increase of its surface free energy, as evaluated by the van Oss, Good, and Chaudhury method. X‐ray photoelectron spectroscopy confirmed the presence of the aromatic azide on PA12 surface. Finally, compliance tests showed that the modification process did not reduce the mechanical performance of balloons.     

Recent advances of organometallic complexes in emerging photovoltaics

Organometallic complexes (OMCs) consisting of organic and metal active moieties have shown immense potential for application in solar cells. The diverse structure, rich porosity, and unique charge centers of OMCs enable them to be functional in solar cells. In this review, we introduced four types of OMCs, such as crown organometallic complexes, β-diketone metal complexes, cyclometallic complexes, and main chain metal-containing polymers, providing an in-depth analysis of the structure-performance relationship. OMCs could serve as active or interlayer materials in a variety of solar cell systems such as organic solar cells, perovskite solar cells, and dye-sensitized solar cells, especially some metals to improve the photoelectric performance of the device as dopants. In the end, perspectives on the opportunities and challenges of OMCs are given.     

On Electrostatics,Covalency, and Chemical Dashes: Physical Interactions versus Chemical Bonds

The increasing availability of real-space interaction energies between quantum atoms or fragments that provide a chemically intuitive decomposition of intrinsic bond energies into electrostatic and covalent terms [see, for instance, Chem. Eur. J. 2018 , 24, 9101] provides evidence for differences between the physicist's concept of interaction and the chemist's concept of a bond. Herein, it is argued that, for the former, all types of interactions are treated equally, whereas, for the latter, only the covalent short-range interactions have actually been used to build intuition about chemical graphs and chemical bonds. This has led to the bonding role of long-range Coulombic terms in molecular chemistry being overlooked. Simultaneously, blind consideration of electrostatic terms in chemical bonding parlance may lead to confusion. The relationship between these concepts is examined herein, and some notes of caution on how to merge them are proposed.     

The thermophysical properties of low‐temperature Pb plasma

The thermophysical properties of low‐temperature Pb plasma are calculated at temperatures 10–100 kK and densities below 0.2 of the solid‐state value. The thermodynamic values (pressure and internal energy) and transport coefficients (electrical conductivity, thermal conductivity, and thermal power) are considered. The plasma composition and thermodynamic parameters are obtained within the chemical approach, namely by means of the solution of the corresponding system of the coupled mass action law equations. Atom ionization up to +4 is taken into consideration. The electronic transport coefficients are calculated within the relaxation time approximation. The results obtained by means of the present model are compared with the available data of other models and experiments.     

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

Electrochemical sensors for environmental gas analysis

The application of electrochemical sensors for measurement of concentration of pollutant gases in air in the part-per-billion (10⁹) range is reviewed. Performance-limiting factors, particularly the effects of extremes and of relatively rapid changes in ambient temperature and humidity, are noted. Variations in composition of the electrolyte in the meniscus at the electrode–gas interface and instability of the solid–liquid–gas contact line, causing important variations in current due to background electrode reactions, are deduced and suggested as the reason for the performance limitations. Suggestions are made for mitigation through instrument design.