Ruthenium-Substituted Polyoxoanion Serves as Redox Shuttle and Intermediate Stabilizer in Selective Electrooxidation of Ethylene to Ethylene Glycol.

The high carbon intensity of present-day ethylene glycol (EG) production motivates interest in electrifying ethylene oxidation. Noting poor kinetics in prior reports of the organic electrooxidation of small hydrocarbons, we explored the design of mediators that activate and simultaneously stabilize light alkenes. A ruthenium-substituted polyoxometalate (Ru-POM, {Si[Ru(HO)WO]}) achieves 82% faradaic efficiency in EG production at 100 mA/cm under ambient conditions.

A study of structural effects on the focusing and imaging performance of hard X-rays with 20-30 nm zone plates.

Hard X-ray microscopes with 20-30 nm spatial resolution ranges are an advanced tool for the inspection of materials at the nanoscale. However, the limited efficiency of the focusing optics, for example, a Fresnel zone plate (ZP) lens, can significantly reduce the power of a nanoprobe. Despite several reports on ZP lenses that focus hard X-rays with 20 nm resolution - mainly constructed by zone-doubling techniques - a systematic investigation into the limiting factors has not been reported.

Near-Infrared Polarization-Sensitive Detection by All-Si Plasmonic Hot Electron Detectors.

Polarization-sensitive optoelectronic detection has been achieved by an all-Si detector in the NIR range, based on plasmon hot electron generation/internal photoemission effect. An advanced architecture with a specially designed anisotropic metasurface was developed and structurally optimized for maximizing the internal quantum efficiency (IQE). Assisted by finite difference time domain (FDTD) simulations, the well-designed device exhibits a maximum optical absorption of 80% around 1.

Dual layer chessboard metasurface sandwiched by a spin-on-carbon for spectral modulation.

Metasurfaces, composed by metals and dielectrics in periodical order with subwavelength pitches, are of great importance for their unique ability to abruptly manipulate optical fields. So far, all the reported metasurfaces are constructed by thermally deposited metals and dielectric films, based on semiconductor processes which are expensive and time-consuming. Inspired by the outstanding dry etch property of spin-on-carbon (SOC) as the interlayer material in CMOS technology, this paper proposes to utilize the SOC as the dielectric layer in a chessboard metasurface with dual layer of gold to form an array of local surface plasmonic resonators (localized surface plasmon resonance).

Interfacial Tuning of Electrocatalytic Ag Surfaces for Fragment-Based Electrophile Coupling.

Construction of C‒C bonds in medicinal chemistry frequently draws on the reductive coupling of organic halides with ketones or aldehydes. Catalytic C(sp)‒C(sp) bond formation, however, is constrained by the competitive side reactivity of radical intermediates following sp organic halide activation. Here, an alternative paradigm deploys catalytic Ag surfaces for reductive fragment-based electrophile coupling compatible with sp organic halides.

Traffic conflicts in the lane-switching sections at highway reconstruction zones.

Introduction: There are designated sections for lane-shifting in several highway reconstruction and expansion zones. Similar to the bottleneck sections of highways, these sections are characterized by poor pavement surface conditions, disorderly traffic flow, and high safety risk. This study examined the continuous track data of 1,297 vehicles collected using an area tracking radar.

A compound Kinoform/Fresnel zone plate lens with 15 nm resolution and high efficiency in soft x-ray.

X-ray microscope as an important nanoprobing tool plays a prevailing role in nano-inspections of materials. Despite the fast advances of high resolution focusing/imaging reported, the efficiency of existing high-resolution zone plates is mostly around 5% in soft x-ray and rapidly goes down to 1%-2% when the resolution approaches 10 nm. It is well known that the rectangular zone shape, beamstop, limited height/width ratios, material absorption of light and structural defects are likely responsible for the limited efficiency.

A chromophore-supported structural and functional model of dinuclear copper enzymes, for facilitating mechanism of action studies.

Type III dicopper centres are the heart of the reactive sites of enzymes that catalyze the oxidation of catechols. Numerous synthetic model complexes have been prepared to uncover the fundamental chemistry involved in these processes, but progress is still lagging much behind that for heme enzymes. One reason is that the latter gain very much from the informative spectroscopic features of their porphyrin-based metal-chelating ligand.

Protein-coated corrole nanoparticles for the treatment of prostate cancer cells.

Development of novel therapeutic strategies to eradicate malignant tumors is of paramount importance in cancer research. In a recent study, we have introduced a facile protocol for the preparation of corrole-protein nanoparticles (NPs). These NPs consist of a corrole-core coated with protein.

Clean Ar-Me conversion to Ar-aldehyde with the aid of carefully designed metallocorrole photocatalysts.

Toluene, p-xylene and mesitylene were cleanly converted to their corresponding monoaldehydes via mild photooxygenation utilizing transition metal and main group β-CF-substituted corroles. Aldehyde yield increased as more electron-donating CH groups are present on the substrate. 4-P was most efficient (TON ∼ 1072, mesitylene) via the singlet oxygen vis the superoxide mechanism.

Palladium Complexes of Corroles and Sapphyrins.

Palladium complexes of corrole and sapphyrin were prepared in high yield and fully characterized. The corrole provides a tetradentate/trianionic square planar coordination sphere for Pd , charge balanced by pyridinium. Both one and two Pd ions may be accommodated by the pentapyrrolic skeleton of the sapphyrin, and in each case the macrocycle acts as bidentate/monoanionic ligand and the inner-sphere square planar geometry is completed by allyl anions coordinated in an η fashion.

Positive shift in corrole redox potentials leveraged by modest β-CF-substitution helps achieve efficient photocatalytic C-H bond functionalization by group 13 complexes.

Tris- and tetrakis-β-trifluoromethylated gallium (3CF-Ga, 4CF-Ga) and aluminum (3CF-Al, 4CF-Al) corrole systems were synthesized by a facile "one-pot" approach from the respective tri- and tetra-iodo starting compounds using the FSOCFCOMe reagent. The isolated 5,10,15-(tris-pentafluorophenyl)corrole-based compounds set the groundwork for another important β-substituent study in inorganic photocatalysis. As seen previously, -CF group substitution leads to red shifts in both the absorption and emission spectra compared to their unsubstituted counterparts (X.

Tuning Chemical and Physical Properties of Phosphorus Corroles for Advanced Applications.

Although the affinity of metallocorroles to axial ligands is quite low, this is not the case when the chelated element is phosphorus. This work is hence focused on the mechanism of ligand exchange of six-coordinate phosphorus corroles as a tool for affecting their chemical and physical properties. These fundamental investigations allowed for the development of facile methodologies for the synthesis of a large series of complexes and the establishment of several new structure/activity profiles that may be used to understand and predict spectroscopic features and for tailor-made modification of photophysical and electrochemical properties.

Maximizing Property Tuning of Phosphorus Corrole Photocatalysts through a Trifluoromethylation Approach.

An eight-member series of CF-substituted difluorophosphorus corroles was prepared for establishing a structure-activity profile of these high-potential photosensitizers. It consisted of preparing all four possible isomers of the monosubstituted corrole and complexes with 2-, 3-, 4-, and 5-CF groups on the macrocycle's periphery. The synthetic pathway to these CF-substituted derivatives, beginning with (tpfc)PF, involves two different initial routes: (i) direct electrophilic CF incorporation using FSOCFCOMe and copper iodide, or (ii) bromination to achieve the 2,3,8,17,18-pentabrominated compound using excess bromine in methanol.

Cell-Penetrating Protein/Corrole Nanoparticles.

Recent work has highlighted the potential of metallocorroles as versatile platforms for the development of drugs and imaging agents, since the bioavailability, physicochemical properties and therapeutic activity can be dramatically altered by metal ion substitution and/or functional group replacement. Significant advances in cancer treatment and imaging have been reported based on work with a water-soluble bis-sulfonated gallium corrole in both cellular and rodent-based models. We now show that cytotoxicities increase in the order Ga < Fe < Al < Mn < Sb < Au for bis-sulfonated corroles; and, importantly, that they correlate with metallocorrole affinities for very low density lipoprotein (VLDL), the main carrier of lipophilic drugs.

Rhodium Complexes of a New-Generation Sapphyrin: Unique Structures, Axial Chirality, and Catalysis.

Rhodium insertion into the new 5,10,15,20-tetrakis(trifluoromethyl)sapphyrin was found to be much more facile than for other analogues, owing to NH⋅⋅⋅F hydrogen-bonding interactions that stabilise the pyrrole-inverted structure characteristic of the metallated product. The thus-obtained rhodium(I) complexes have axial chirality, and the enantiomers were resolved. The latter were found to interconvert quite rapidly in a process that involves a tautomerisation-like movement of the metal fragment between the five N atoms.

One-Pot Synthesis of Contracted and Expanded Porphyrins with meso-CF Groups.

Corrole and sapphyrin with the smallest meso-substituents reported so far were prepared in a one-pot synthesis that relies on a non-aldehydic precursor for introducing CF groups. The substantial amounts of products obtained by this facile pathway allowed for the full characterization of 5,10,15-tris(trifluoromethyl)corrole, the access to a variety of stable chelates thereof and investigations that disclose the unique structural and chemical properties induced by the CF substituents. The novel 5,10,15,20-tetra(trifluoromethyl)sapphyrin undergoes only single protonation, which according to its crystal structure is stabilized by favorable non-bonding F/H interaction between the meso-CF and the inverted pyrrolic NH.

Ligand Induced Anionic Cuprous Cyanide Framework for Cupric Ion Turn on Luminescence Sensing and Photocatalytic Degradation of Organic Dyes.

A new microporous luminescent coordination polymer [(CH3)2NH2]·[Cu2(CN)3] (1) with channels occupied by dimethylamine cations was synthesized due to the inducing effect of 2-(2'-pyridyl)imidazole. Complex 1 exhibits bright-green emission in the solid state, and its emission intensity would be significantly enhanced, especially by DMAc and cupric ion after immersing the as-synthesized crystals of 1 into common organic solvents or methanol solutions of various metal ions. In addition, 1 exhibits photocatalytic activity for the degradation of RhB and MB under natural light and is stable during the photocatalysis process.