An Oxysulfide Photocatalyst Evolving Hydrogen with an Apparent Quantum Efficiency of 30 % under Visible Light

Photocatalytic water splitting is a simple means of converting solar energy into storable hydrogen energy. Narrow-band gap oxysulfide photocatalysts have attracted much attention in this regard owing to the significant visible-light absorption and relatively high stability of these compounds. However, existing materials suffer from low efficiencies due to difficulties in synthesizing these oxysulfides with suitable degrees of crystallinity and particle sizes, and in constructing effective reaction sites. The present work demonstrates the production of a Gd₂Ti₂O₅S₂ (λ<650 nm) photocatalyst capable of efficiently driving photocatalytic reactions. Single-crystalline, plate-like Gd₂Ti₂O₅S₂ particles with atomically ordered surfaces were synthesized by flux and chemical etching methods. Ultrafine Pt-IrO₂ cocatalyst particles that promoted hydrogen (H₂) and oxygen (O₂) evolution reactions were subsequently loaded on the Gd₂Ti₂O₅S₂ while ensuring an intimate contact by employing a microwave-heating technique. The optimized Gd₂Ti₂O₅S₂ was found to evolve H₂ from an aqueous methanol solution with a remarkable apparent quantum efficiency of 30 % at 420 nm. This material was also stable during O₂ evolution in the presence of a sacrificial reagent. The results presented herein demonstrates a highly efficient narrow-band gap oxysulfide photocatalyst with potential applications in practical solar hydrogen production.     

Thermally actuated shape-memory polymers: Experiments, theory, and numerical simulations

With the aim of developing a thermo-mechanically coupled large-deformation constitutive theory and a numerical-simulation capability for modeling the response of thermally actuated shape-memory polymers, we have (i) conducted large strain compression experiments on a representative shape-memory polymer to strains of approximately unity at strain rates of 10⁻³ and 10⁻¹ s⁻¹, and at temperatures ranging from room temperature to approximately 30 °C above the glass transition temperature of the polymer; (ii) formulated a thermo-mechanically coupled large-deformation constitutive theory; (iii) calibrated the material parameters appearing in the theory using the stress-strain data from the compression experiments; (iv) numerically implemented the theory by writing a user-material subroutine for a widely used finite element program; and (v) conducted representative experiments to validate the predictive capability of our theory and its numerical implementation in complex three-dimensional geometries. By comparing the numerically predicted response in these validation simulations against measurements from corresponding experiments, we show that our theory is capable of reasonably accurately reproducing the experimental results. As a demonstration of the robustness of the three-dimensional numerical capability, we also show results from a simulation of the shape-recovery response of a stent made from the polymer when it is inserted in an artery modeled as a compliant elastomeric tube.     

Understanding the influence of structural hierarchy and its coupling with chemical environment on the strength of idealized tropocollagen–hydroxyapatite biomaterials

Hard biomaterials such as bone, dentin, and nacre have primarily an organic phase (e.g. tropocollagen (TC)) and a mineral phase (e.g. hydroxyapatite (HAP) or aragonite) arranged in a staggered arrangement at the nanoscopic length scale. Interfacial interactions between the organic phase and the mineral phase as well as the structural effects arising due to the staggered arrangement significantly affect the strength of such biomaterials. The effect of such factors is intricately intertwined with the chemical environment of such materials. In the present investigation, an idealized TC–HAP composite system under tensile loading is analyzed using explicit three-dimensional (3-D) molecular dynamics (MD) simulations to develop an understanding of these factors. The material system is analyzed in three different environments: (1) in the absence of water molecules (non-hydrated), (2) in the presence of water molecules (hydrated), and (3) in the presence of water molecules with calcium ions (ionized water). The analyses focus on understanding the correlations among factors such as the structural arrangement, the peak stress during deformation, Young's modulus, the peak interfacial strength, and the length scale of the localization of peak stress during deformation. Analyses show that maximizing the contact area between the TC and HAP phases results in higher interfacial strength as well as higher fracture strength. Due to the staggered arrangement, the orientation of HAP crystals has insignificant effect on the biomaterial strength. Analyses based on strength scaling as a function of structural hierarchy level reveal that while peak strength follows a multiscaling relation, the fracture strength does not. The peak strain for failure was found to be independent of the changes in levels of structural hierarchy. Overall, the analyses, being limited in size due to the computational time constraint, point out important correlations between the mechanical strength and chemically influenced structural hierarchy of biomaterials.     

Iterative Arylation of Amino Acids and Aliphatic Amines via δ‐C(sp3)−H Activation: Experimental and Computational Exploration

Directed C?H functionalization has been realized as a complementary tool to the traditional approaches for a straightforward access of non‐proteinogenic amino acids; albeit such a process is restricted mostly up to the γ‐position. In the present work, we demonstrate the diverse (hetero)arylation of amino acids and analogous aliphatic amines selectively at the remote δ‐position by tuning the reactivity controlled by ligands. An organopalladium δ‐C(sp³)?H activated intermediate has been isolated and crystallographically characterized. Mechanistic investigations carried out experimentally in conjunction with computational studies shed light on the difference in the mechanistic picture depending on the substrate structure.     

Facile Synthesis,Antimicrobial Activity and Molecular Docking of Novel 2,4,5‐Trisubstituted‐1H‐Imidazole–Triazole Hybrid Compounds

In the present work, a series of 18 imidazole–triazole hybrids ( 4a–r ) has been synthesized in good yield from substituted naphthaldehydes and 1,2‐diketones in the presence of ammonium acetate. The synthesized imidazole–triazole hybrid compounds were characterized by spectral techniques and screened in vitro for their antimicrobial activity. Compound 4h was found to be most active against Staphylococcus epidermidis, and compound 4e exhibited promising activity against Escherichia coli. In the fungal species under test, compound 4q was most potent against Aspergillus niger, even better than the fluconazole. Further, compound 4e was docked in the binding site of DNA gyrase topoisomerase II of E. coli.     

Application of ring-rearrangement metathesis in organic synthesis: A grand design

In this report, we compiled various strategies involving a ring-rearrangement metathesis as a key step to assemble diverse molecules. Popular name reactions such as Grignard reaction, Overman rearrangement, Fischer indolization, Beckmann rearrangement and Diels–Alder reaction were used in combination with ring-rearrangement metathesis to construct complex targets. Additionally, CH activation and RRM strategy has been used to assemble azacycles. In some instances, the ring-rearrangement metathesis was expected to occur; however, ring-opening metathesis products were realized. These methods were included in the miscellaneous section. We anticipate that the lessons learned here are useful in designing complex polycyclic and heterocyclic targets suitable for biological and material science applications. Beside our work, we have also included others work as a background information.     

Correction to: Biosynthesized Zinc Oxide Nanoparticles as Efficient Photocatalytic and Antimicrobial Agent

Journal of Cluster Science - The authors claimed that acknowledgement in published article is not same as provided in revised/accepted paper.     

One-pot synthesis of carbazoles from indoles via a metal free benzannulation

We report a simple, one-pot, and metal free benzannulation protocol to carbazoles starting with indoles, carbonyl compounds and an appropriate dienophiles. Mechanistically, this strategy generates an in situ diene by condensation between indole and carbonyl compound succeed and subsequent dehydration. Later, Diels–Alder reaction of this diene with a suitable dienophile followed by oxidation delivers the carbazole derivative. This methodology provide an easy access to carbazoles containing 1,4-naphthoquinone moiety.