Au@CuO Core-Shell and Au@CuSe Yolk-Shell Nanocrystals as Promising Photocatalysts in Photoelectrochemical Water Splitting and Photocatalytic Hydrogen Production.

In this work, we demonstrated the practical use of Au@CuO core-shell and Au@CuSe yolk-shell nanocrystals as photocatalysts in photoelectrochemical (PEC) water splitting and photocatalytic hydrogen (H) production. The samples were prepared by conducting a sequential ion-exchange reaction on a Au@CuO core-shell nanocrystal template. Au@CuO and Au@CuSe displayed enhanced charge separation as the Au core and yolk can attract photoexcited electrons from the CuO and CuSe shells.

A novel galactose electrochemical biosensor intended for point-of-care measurement of quantitative liver function using galactose single-point test.

Liver disease has emerged as a healthcare burden because of high hospitalization rates attributed both to steatohepatitis and to severe hepatic toxicity associated with changes of drug exposure. Early detection of hepatic insufficiency is critical to preventing long-term liver damage. The galactose single-point test is recommended by the US FDA as a sensitive means to quantify liver function, yet the conventional method used for quantitation of circulating galactose still relies on the standard colorimetric method, requiring time-consuming and labor-intensive processes, and is confined to the medical laboratory, thus limiting prevalence.

Distinct Carrier Transport Properties Across Horizontally vs Vertically Oriented Heterostructures of 2D/3D Perovskites.

Two-dimensional-on-three-dimensional (2D/3D) halide perovskite heterostructures have been extensively utilized in optoelectronic devices. However, the labile nature of halide perovskites makes it difficult to form such heterostructures with well-defined compositions, orientations, and interfaces, which inhibits understanding of the carrier transfer properties across these heterostructures. Here, we report solution growth of both horizontally and vertically aligned 2D perovskite (PEA)PbBr (PEA = phenylethylammonium) microplates onto 3D CsPbBr single crystal thin films, with well-defined heterojunctions.

Rational design, engineer, and characterization of a novel pegylated single isomer human arginase for arginine depriving anti-cancer treatment.

Aims: Arginine depleting enzymes are found effective to treat arginine-auxotrophic cancers and therapy-resistant malignancies, alone or in combination with cytotoxic agents or immune checkpoint inhibitors. We aim to select and validate a long-lasting, safe and effective PEGylated and cobalt-chelated arginase conjugated at the selective cysteine residue as a therapeutic agent against cancers.

Main Methods: Exploring pharmacokinetic and pharmacodynamic properties of the three arginase conjugates with different PEG modality (20 kDa linear as A20L, 20 kDa branched as A20Y, and 40 kDa branched as A40Y) by cell-based and animal studies.

Immunogenicity and toxicokinetics assessment of the mono-PEGylated recombinant human interleukin-11 in cynomolgus monkeys.

Aim: Protein therapeutics have potential to elicit immune responses resulting in undesirable anti-drug antibodies (ADA) that might affect product efficacy and patient safety, and should be assessed in animals before applying the treatment to humans. In this paper, we aim to assess the immunogenicity and toxicokinetics of the mono-PEGylated recombinant human interleukin-11 (rhIL-11), a novel protein therapeutic for the treatment of chemotherapy-induced thrombocytopenia, in repeated administration to cynomolgus monkeys.

Main Methods: Enzyme-linked immunosorbent assay (ELISA) methods were developed to measure ADA responses and plasma PEGylated IL-11 (PEG-IL11) concentration in monkeys.

π-Extended Coumarins Derived with Nonhydrolyzable Iminophosphoranes as Two-Photon-Excited Fluorophores.

Novel coumarin-iminophosphorane (IPP) fluorophores that have stable resonance contributions from aza-ylides were formed by using the nonhydrolysis Staudinger reaction. The N═P formation reaction kinetics obey the conventional Staudinger reaction. The absorption and emission profiles of the coumarin-IPP derivatives can be fine-tuned: an electron-donating group at PPh enhances absorption and fluorescence, whereas an electron-withdrawing group at C-3 drives absorption and emission peaks toward blue-light wavelengths.

Discovery of T-1101 tosylate as a first-in-class clinical candidate for Hec1/Nek2 inhibition in cancer therapy.

Highly expressed in cancer 1 (Hec1) plays an essential role in mitosis and is correlated with cancer formation, progression, and survival. Phosphorylation of Hec1 by Nek2 kinase is essential for its mitotic function, thus any disruption of Hec1/Nek2 protein-protein interaction has potential for cancer therapy. We have developed T-1101 tosylate (9j tosylate, 9j formerly known as TAI-95), optimized from 4-aryl-N-pyridinylcarbonyl-2-aminothiazole of scaffold 9 by introducing various C-4' substituents to enhance potency and water solubility, as a first-in-class oral clinical candidate for Hec1 inhibition with potential for cancer therapy.

Benzodipyrrole-2,6-dione-3,7-diylidenedimalononitrile Derivatives for Air-Stable -Type Organic Field-Effect Transistors: Critical Role of -Alkyl Substituent on Device Performance.

Benzodipyrrole-2,6-dione-3,7-diylidenedimalononitriles (BDPMs) were synthesized as active materials for the use in air-stable -type organic field-effect transistors (OFETs), whose optical and electrochemical properties were examined. BDPM-based small molecules exhibit deep lowest unoccupied molecular orbital levels, which are required in air-stable -type OFETs. An OFET device that was based on and fabricated by vapor deposition provided a maximum electron mobility of 0.

Benzophenanthrothiophenes: Syntheses, Crystal Structures, and Properties.

A new class of polycyclic heteroarenes based on benzo[3,4]phenanthro[1,2-]benzo[3,4]phenanthro[2,1-]thiophene () was prepared from polyaryl thiophenes via regioselective Scholl reactions. The molecular frameworks of these compounds exhibited twisted bridges and near-cofacial packing motifs with oppositely or parallel π-stacked structures depending on the substituents on the periphery. Theoretical calculation of electronic coupling and charge mobility was carried out on the basis of the single-crystal structures.

In Situ Analysis of Growth Behaviors of CuO Nanocubes in Liquid Cell Transmission Electron Microscopy.

Metal oxides have attracted substantial attention over the years and are commonly used in the semiconductor industry because of their excellent physical and chemical properties. Among the various metal oxides, cuprous oxide (CuO) is regarded as a promising material. It is inexpensive, earth-abundant, and nontoxic; therefore, it can be used in catalysis, sensors, solar cells, and p-type semiconductors.

In situ TEM observation of Au-CuO core-shell growth in liquids.

Heterogeneous nanoparticles are widely used in catalysis, sensors and biology due to their versatile functions. Among the various heterogeneous nanoparticles, Au-Cu2O core-shell nanoparticles show high stability and short response times for use as sensors and catalysts and have thus attracted much attention. Previous studies show that the properties of Au-Cu2O are mainly related to the shape and size of the Au-Cu2O nanoparticles.

Pharmacokinetic and Pharmacodynamic Evaluation of Different PEGylated Human Interleukin-11 Preparations in Animal Models.

Treating thrombocytopenia induced by chemotherapy remains an unmet-medical need. The use of recombinant human interleukin-11 (rhIL-11) requires repeated injections and induces significant fluid retention in some patients. Modification of human interleukin-11 with chemically inert polyethylene glycol polymer (PEG) may extend the peripheral circulation half-life leading to an improved pharmacokinetic and pharmadynamic profile.

Angular-Shaped Naphthalene Bis(1,5-diamide-2,6-diylidene)malononitrile for High-Performance, Air-Stable N-Type Organic Field-Effect Transistors.

The synthesis, characterization, and application of two angular-shaped naphthalene bis(1,5-diamide-2,6-diylidene)malononitriles (NBAMs) as high-performance air-stable n-type organic field effect transistor (OFET) materials are reported. NBAM derivatives exhibit deep lowest-unoccupied molecular orbital (LUMO) levels, suitable for air-stable n-type OFETs. The OFET device based on NBAM-EH fabricated by vapor deposition exhibits a maximum electron mobility of 0.

Efficient expression and isolation of recombinant human interleukin-11 (rhIL-11) in Pichia pastoris.

Current source of recombinant human interleukin-11 (rhIL-11) is isolated from a fusion protein expressed by E. coli that requires additional enterokinase to remove linked protein, resulting in product heterogeneity of N-terminal sequence. Due to lack of glycosylation, rhIL-11 is suitable to be expressed by yeast cells.

Preclinical evaluation of the mono-PEGylated recombinant human interleukin-11 in cynomolgus monkeys.

The mono-PEGylated recombinant human interleukin-11 (rhIL-11) was evaluated for its pharmacology and toxicology profile in non-human primates. This PEGylated IL-11 (PEG-IL11) showed a much prolonged circulating half-life of 67h in cynomolgus monkeys as compared to its un-PEGylated counterpart (~3h) through subcutaneous administration, implicating that a single injection of the recommended dose will effectively enhance thrombopoiesis in humans for a much longer period of time compared to rhIL-11 in humans (t=6.9h).

Di-2-(2-oxindolin-3-ylidene)malononitrile Derivatives for N-Type Air-Stable Organic Field-Effect Transistors.

The nitrogenization of phenyl rings on DIM derivatives not only enhances molecular coplanarity but also stabilizes molecular LUMO levels, favoring charge transfer and improving air stability. Therefore, n-type organic field-effect transistors (OFETs) that are based on DIM-N2C8 with nitrogen atoms on both sides of the phenyl rings exhibit a moderate electron mobility of 0.059 cm V s under ambient conditions.

Effect of Imidazole on the Electrochemistry of Zinc Porphyrins: An Electrochemical and Computational Study.

In this study, the electrochemical behavior of zinc meso-substituted porphyrins in the presence of imidazole is examined by using both cyclic voltammetry (CV) and density functional theory (DFT) methods. The results show that the first half-wave oxidation potentials (1st E) of zinc porphyrins complexed with imidazole all move to the negative side, while the second ones (2nd E) move to the positive side, resulting in larger half-wave oxidation potential splittings of the two oxidation states (ΔE = second E - first E) comparing with the zinc porphyrins. By employing DFT calculations, we have found that both sterically controlled inter π-conjugation between porphyrin rings and meso-substituted phenyl groups and deformation of porphyrin rings do play important roles in contributing to the half-wave oxidation potentials.

Electrochemical Behavior of meso-Substituted Porphyrins: The Role of Cation Radicals to the Half-Wave Oxidation Potential Splitting.

In this study, the electrochemical behavior of free base and zinc meso-substituted porphyrins is examined by cyclic voltammetry (CV) and density functional theory (DFT). The results show that the half-wave oxidation potential splitting of the two oxidation states (ΔE= second E1/2 - first E1/2) of tetraphenylporphyrin (H2TPP) and its zinc complex (ZnTPP) are higher than those of porphyrins and their zinc complexes with meso-substituted five-membered heterocylic rings. The ΔE values follow the trend of TPP > T(3'-thienyl)P > T(3'-furyl)P > T(2'-thienyl)P for both meso-porphyrins and their respective zinc complexes.

Hexaazatrinaphthylene Derivatives: Efficient Electron-Transporting Materials with Tunable Energy Levels for Inverted Perovskite Solar Cells.

Hexaazatrinaphthylene (HATNA) derivatives have been successfully shown to function as efficient electron-transporting materials (ETMs) for perovskite solar cells (PVSCs). The cells demonstrate a superior power conversion efficiency (PCE) of 17.6 % with negligible hysteresis.

Per-Substituted [8]Circulene and Its Non-Planar Fragments: Synthesis, Structural Analysis, and Properties.

The syntheses, structures, and physical properties of a full series of benzannulated tetraphenylenes are reported. The palladium-catalyzed annulation of tetraiodo-substituted 2,3,6,7,10,11,14,15-octamethyltetraphenylene with insufficient di(4-anisyl)ethyne yielded a mixture of per-substituted [8]circulene and its non-planar fragments, including mono-, para-di-, ortho-di-, and triannulated products. Their structures were unambiguously verified by X-ray crystallography.

Dinaphthozethrene and Diindenozethrene: Synthesis, Structural Analysis, and Properties.

Zethrene-based condensed arenes dinaphthozethrene and diindenozethrene were synthesized by oxidative cyclodehydrogenation and palladium-catalyzed cyclization of 7,14-diarylzethrenes, respectively. Their structures were analyzed by X-ray crystallography. The photophysical and electrochemical properties of these compounds were investigated.

An Unconventional Approach to Induce Liquid-Crystalline Phases of Triazine-Based Dendrons by Breaking Their Self-Assembly into Dimers.

Three triazine-based dendrons (1 a-c) were successfully prepared in 70-83 % yields. These newly prepared dendrons are found to be liquid crystalline (LC). Computational investigations on molecular conformations and dipoles of triazine-based dendrons reveal that the substituent on the central triazine unit interrupts strong dipole or H-bond interactions to avoid dimeric formation.

Pyromellitic dithioimides: thionation improves air-stability and electron mobility of N-type organic field-effect transistors.

Thionation and fluorination of pyromellitic diimides (PyDIs) increased the electron mobility and on/off ratio of the original diimides by two orders of magnitude and improved the threshold voltage and air-stability of diimide compounds.

Linear oligoarylamines: electrochemical, EPR, and computational studies of their oxidative states.

A series of straight-chain oligoarylamines were synthesized and examined by electrochemical, spectroelectrochemical, electron paramagnetic resonance techniques, and density functional theory (DFT) calculation. Depending on their electrochemical characteristics, these oligoarylamines were classified into two groups: one containing an odd number and the other an even number of redox centers. In the systems with odd redox centers (N1, N3, and N5), each oxidation was associated with the loss of one electron.

Zethrene and dibenzozethrene: masked biradical molecules?

The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel-catalyzed cyclodimerization of 9-ethynyl-1-iodoanthracenes.