Low-Loss Organic Hyperbolic Materials in the Visible Spectral Range: A Joint Experimental and First-Principles Study

Hyperbolic media strengthen numerous attractive applications in optics such as super-resolution imaging, enhanced spontaneous emission, and nanoscale waveguiding. Natural hyperbolic materials exist at visible frequencies; however, implementations of these materials suffer substantial compromises resulting from the high loss in the currently available candidates. Here, the first experimental and theoretical investigation of regioregular poly(3-alkylthiophenes) (rr-P3ATs), a naturally low-loss organic hyperbolic material (OHM) in the visible frequency range, is shown. These hyperbolic properties arise from a highly ordered structure of layered electron-rich conjugated thiophene ring backbones separated by insulating alkyl side chains. The optical and electronic properties of the rr-P3AT can be tuned by controlling the degree of crystallinity and alkyl side chain length. First-principles calculations support the experimental observations, which result from the rr-P3AT's structural and optical anisotropy. Conveniently, rr-P3AT-based OHMs are facile to fabricate, flexible, and biocompatible, which may lead to tremendous new opportunities in a wide range of applications.     

Incorporation of Ru(II) Polypyridyl Complexes into Nanomaterials for Cancer Therapy and Diagnosis

Ru(II) polypyridyl complexes are compounds of great interest in cancer therapy due to their unique photophysical, photochemical, and biological properties. For effective treatment, they must be able to penetrate tumor cells effectively and selectively. The development of nanoscale carriers capable of delivering Ru(II) polypyridyl complexes has the potential to passively or selectively enhance their cellular uptake in tumor cells. Many different strategies have been explored to incorporate Ru(II) polypyridyl complexes into a variety of nanosized constructs, ranging from organic to inorganic materials. Herein, recent developments in nanomaterials loaded with Ru(II) polypyridyl complexes are highlighted. Their rational design, preparation, and physicochemical properties are described, and their potential applications in cancer therapy are eventually discussed.     

Metal–Organic Frameworks Based on Group 3 and 4 Metals

Metal–organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status and future trends on the structural design of robust MOFs with high connectivity is provided. Cluster chemistry involving Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr is initially introduced. This is followed by a review of recently developed MOFs based on group 3 and 4 metals with their structures discussed based on the types of inorganic or organic building blocks. The novel properties and arising applications of these MOFs in catalysis, adsorption and separation, delivery, and sensing are highlighted. Overall, this review is expected to provide a timely summary on MOFs based on group 3 and 4 metals, which shall guide the future discovery and development of stable and functional MOFs for practical applications.     

Nitroxide Radicals with Cucurbit[n]urils and Other Cavitands

The interface of nitroxide radicals with cucurbit[n]urils (CB[n]) is covered in this review. Either used as spin probes, spin labels, or stoppers for paramagnetic rotaxanes, nitroxides offer new opportunities to investigate CB[n] and their inclusion complexes, especially thanks to EPR spectroscopy. On the other hand, CB[n] also offer interesting opportunities to modulate nitroxide properties such as protection or structuring. The multiple back and forth between the two well-established areas where nitroxides bring information about CB[n], and CB[n] modulate nitroxide properties, have enabled to shed some light at this new interesting interface.     

Precise Extraction of Charge Carrier Mobility for Organic Transistors

Unreliable mobility values, and particularly greatly overestimated values and severely distorted temperature dependences, have recently hampered the development of the organic transistor field. Given that organic field‐effect transistors (OFETs) have been routinely used to evaluate mobility, precise parameter extraction using the electrical properties of OFETs is thus of primary importance. This review examines the origins of the various mobilities that must be determined for OFET applications, the relevant extraction methods, and the data selection limitations, which help in avoiding conceptual errors during mobility extraction. For increased precision, the review also discusses device fabrication considerations, calibration of both the specific gate‐dielectric capacitance and the threshold voltage, the contact effects, and the bias and temperature dependences, which must actually be handled with great care but have mostly been overlooked to date. This review serves as a systematic overview of the OFET mobility extraction process to ensure high precision and will also aid in improving future research.     

Structural and Functional Characterization of 4-Hydroxyphenylacetate 3-Hydroxylase from Escherichia coli

The hydroxylation of phenols into polyphenols, which are valuable chemicals and pharmaceutical products, is a challenging reaction. The search for green synthetic processes has led to considering microorganisms and pure hydroxylases as catalysts for phenol hydroxylation. Herein, we report the structural and functional characterization of the flavin adenine dinucleotide (FAD)-dependent 4-hydroxyphenylacetate 3-monooxygenase from Escherichia coli, named HpaB. It is shown that this enzyme enjoys a relatively broad substrate specificity, which allows the conversion of a number of non-natural phenolic compounds, such as tyrosol, hydroxymandelic acid, coumaric acid, hydroxybenzoic acid and its methyl ester, and phenol, into the corresponding catechols. The reaction can be performed by using a simple chemical assay based on formate as the electron donor and the organometallic complex [Rh(bpy)Cp*(H₂O)]²⁺ (Cp*: 1,2,3,4,5-pentamethylcyclopentadiene, bpy: 2,2′-bipyridyl) as the catalyst for FAD reduction. The availability of a crystal structure of HpaB in complex with FAD at 1.8 Å resolution opens up the possibility of the rational tuning of the substrate specificity and activity of this interesting class of phenol hydroxylases.     

Highly Stable COF‐Supported Co/Co(OH)2 Nanoparticles Heterogeneous Catalyst for Reduction of Nitrile/Nitro Compounds under Mild Conditions

Ordered nanoporosity in covalent organic framework (COF) offers excellent opportunity for property development. Loading nanoparticles (nPs) onto them is one approach to introducing tailor‐made properties into a COF. Here, a COF–Co/Co(OH)₂ composite containing about 16 wt% of <6 nm sized Co/Co(OH)₂ nPs is prepared on a N‐rich COF support that catalyzes the release of theoretical equivalence of H₂ from readily available, safe, and cheap NaBH₄. Furthermore, the released H₂ is utilized for the hydrogenation of nitrile and nitro compounds to amines under ambient conditions in a facile one‐pot reaction. The COF “by choice” is built from “methoxy” functionalized dialdehydes which is crucial in enabling the complete retention of the COF structure under the conditions of the catalysis, where the regular Schiff bonds would have hydrolyzed. The N‐rich binding pockets in the COF ensure strong nP–COF interactions, which provides stability and enables catalyst recycling. Modeling studies reveal the crucial role played by the COF in exposing the active facets and thereby in controlling the activation of the reducing agent. Additionally, via density functional theory, we provide a rational explanation for how these COFs can stabilize nanoparticles which grow beyond the limiting pore size of the COF and yet result in a truly stable heterogeneous catalyst – a ubiquitous observation. The study underscores the versatility of COF as a heterogeneous support for developing cheap and highly active nonnoble metal catalysts.     

A comparative thermodynamic analysis of Kalina and organic Rankine cycles for hot dry rock: a prospect study in the Gonghe Basin

Hot dry rock is a new type of geothermal resource which has a promising application prospect in China. This paper conducted a comparative research on performance evaluation of two eligible bottoming cycles for a hot dry rock power plant in the Gonghe Basin. Based on the given heat production conditions, a Kalina cycle and three organic Rankine cycles were tested respectively with different ammonia-water mixtures of seven ammonia mass fractions and nine eco-friendly working fluids. The results show that the optimal ammonia mass fraction is 82% for the proposed bottoming Kalina cycle in view of maximum net power output. Thermodynamic analysis suggests that wet fluids should be supercritical while dry fluids should be saturated at the inlet of turbine, respectively. The maximum net power output of the organic Rankine cycle with dry fluids expanding from saturated state is higher than that of the other organic Rankine cycle combinations, and is far higher than the maximum net power output in all tested Kalina cycle cases. Under the given heat production conditions of hot dry rock resource in the Gonghe Basin, the saturated organic Rankine cycle with the dry fluid butane as working fluid generates the largest amount of net power.