Carbene Functionalization of Monolayer Tungsten Disulfide for Enhanced Quantum Emission.

Semiconducting two-dimensional (2D) transition metal dichalcogenides (TMDs) are promising materials for an array of applications, ranging from conventional field-effect transistors, photodetectors, and light-emitting diodes to their more recent use in quantum photonic technologies. Chemical functionalization of 2D TMDs with organic ligands and adlayers provides an additional means for customizing their electronic and optical properties. While many pathways have been reported for the chemical functionalization of 2D TMDs, their frequent reliance on solution-based methods results in limited control over adlayer thickness and coverage, thus hindering utility in high-performance applications.

Interface Size-Dependent Changes in Activity of Water Splitting Electrocatalysts.

The traditional method of reporting electrocatalytic activity by normalizing current to the geometric area (mA cm) often results in exaggerated activity for electrodes smaller than 1 cm. Using stainless steel 304 (SS-304) and Ni foam electrodes of varying sizes (0.3-2.

Molecular Simulation Insights into Acid Gas Interactions within Ni-Based Fluorinated Square-Pillared Metal-Organic Framework.

The increasing prominence of metal-organic frameworks (MOFs) in gas separation technologies has sparked significant interest in their application in flue gas treatment. Nevertheless, the adsorption of acidic gases in MOFs presents significant challenges owing to their complex interactions with the framework. The adsorption interactions of acidic gases and their mixtures with [Ni(1,4-pyrazine)(AlF)] (ALFFIVE-Ni-Pyr) are explored while considering the flexibility of the framework.

Ferrocene conjugated Os(II) complex for photo-catalytic cancer therapy of triple-negative breast cancer cells.

A novel ferrocene-conjugated bimetallic Os(II) photocatalyst (OsFe) showed micromolar photocatalytic anticancer activity against triple-negative breast cancer cells NADH oxidation and caspase 3 activation under visible light.

Achieving the optimal Ni(OH) : Pt ratio for enhancing electrocatalytic water-dissociation and H delivery in proton-deficient environments.

Despite the availability of abundant, inexpensive non-noble metal-based anode catalysts for alkaline water electrolysis, the cathodic hydrogen evolution reaction (HER) continues to be a challenge, even in the case of state-of-the-art Pt catalysts. In such proton-deficient environments, a metal hydroxide-/oxide-based co-catalyst that can help polarize the H-O bond in water has been found to promote proton abstraction and subsequent reduction into H on Pt and Ru surfaces. In this regard, the Ni(OH) : Pt co-catalyst is one of the best.

Dinuclear Tridentate Ru(II) Complex with Strong Near-Infrared Light-Triggered Anticancer Activity.

The design of the dinuclear Ru(II) complex () with strong near-infrared (NIR) absorption properties has been reported for efficient anticancer phototherapy. Under 700 nm LED light excitation, exhibited remarkable synergistic type I/II photosensitization ability and photocatalytic activity toward intracellular biomolecules. showed impressive 700 nm light-triggered anticancer activity under normoxia and hypoxia compared with the clinically used photosensitizer Chlorin e6.

Visible and Red Light-Triggered Anticancer Profile of a Ferrocene-Re(I)-Tricarbonyl Conjugate: Experimental and Theoretical Studies.

We have red-shifted the light absorbance property of a Re(I)-tricarbonyl complex via distant conjugation of a ferrocene moiety and developed a novel complex , [Re(Fctp)(CO)Cl], where Fctp = 4'-ferrocenyl-2,2':6',2″-terpyridine. showed green to red light absorption ability and blue emission, indicating its potential for photodynamic therapy (PDT) application. The conjugation of ferrocene introduced ferrocene-based transitions, which lie at a higher wavelength within the PDT therapeutic window.

Comparative Study of Sonodynamic and Photoactivated Cancer Therapies with Re(I)-Tricarbonyl Complexes Comprising Phenanthroline Ligands.

Herein, we have compared the effectivity of light-based photoactivated cancer therapy and ultrasound-based sonodynamic therapy with Re(I)-tricarbonyl complexes (-) against cancer cells. The observed photophysical and TD-DFT calculations indicated the potential of - to act as good anticancer agents under visible light/ultrasound exposure. did not display any dark- or light- or ultrasound-triggered anticancer activity.

Green Light-Triggered Photocatalytic Anticancer Activity of Terpyridine-Based Ru(II) Photocatalysts.

The relentless increase in drug resistance of platinum-based chemotherapeutics has opened the scope for other new cancer therapies with novel mechanisms of action (MoA). Recently, photocatalytic cancer therapy, an intrusive catalytic treatment, is receiving significant interest due to its multitargeting cell death mechanism with high selectivity. Here, we report the synthesis and characterization of three photoresponsive Ru(II) complexes, viz.

CuNi sulphidation maximizes MOR activity by expanding the accessibility of active sites!

Sulphidation of a CuNi alloy of Cu : Ni ratio 81 : 19 led to an exponential activity enhancement in the alkaline methanol oxidation reaction (MOR) by four fold due to an order of magnitude increase in the number of active Cu and Ni sites and improved charge transfer properties.

Trifluoromethylation of 2D Transition Metal Dichalcogenides: A Mild Functionalization and Tunable p-Type Doping Method.

Chemical modification is a powerful strategy for tuning the electronic properties of 2D semiconductors. Here we report the electrophilic trifluoromethylation of 2D WSe and MoS under mild conditions using the reagent trifluoromethyl thianthrenium triflate (TTT). Chemical characterization and density functional theory calculations reveal that the trifluoromethyl groups bind covalently to surface chalcogen atoms as well as oxygen substitution sites.

Experimental and theoretical insights into the supercapacitive performance of interconnected WS nanosheets.

Transition metal dichalcogenides (TMDs) are fascinating and prodigious considerations in the electrochemical energy storage sector because of their two dimensional chemistry as well as heterogeneous characteristics. Herein, we synthesized interconnected WS nanosheets by a hydrothermal method followed by sulphuration at 850 °C in an argon atmosphere. The ultrathin WS nanosheet array is endowed with an excellent specific capacitance of 74 F g at the current density of 3 A g up 7000 cycles.

Anomalously enhanced ion transport and uptake in functionalized angstrom-scale two-dimensional channels.

Emulating angstrom-scale dynamics of the highly selective biological ion channels is a challenging task. Recent work on angstrom-scale artificial channels has expanded our understanding of ion transport and uptake mechanisms under confinement. However, the role of chemical environment in such channels is still not well understood.

Density Functional Theory-Guided Photo-Triggered Anticancer Activity of Curcumin-Based Zinc(II) Complexes.

Photodynamic therapy (PDT) has evolved as a new therapeutic modality for cancer treatment with fewer side effects and drug resistance. Curcumin exhibits PDT activity, but its low bioavailability restricts its clinical application. Here, the bioavailability of curcumin was increased by its complex formation with the Zn(II) center.

Triplet States of Cyanostar and Its Anion Complexes.

The design of advanced optical materials based on triplet states requires knowledge of the triplet energies of the molecular building blocks. To this end, we report the triplet energy of cyanostar () macrocycles, which are the key structure-directing units of small-molecule ionic isolation lattices (SMILES) that have emerged as programmable optical materials. Cyanostar is a cyclic pentamer of covalently linked cyanostilbene units that form π-stacked dimers when binding anions as 2:1 complexes.

Chemomechanical modification of quantum emission in monolayer WSe.

Two-dimensional (2D) materials have attracted attention for quantum information science due to their ability to host single-photon emitters (SPEs). Although the properties of atomically thin materials are highly sensitive to surface modification, chemical functionalization remains unexplored in the design and control of 2D material SPEs. Here, we report a chemomechanical approach to modify SPEs in monolayer WSe through the synergistic combination of localized mechanical strain and noncovalent surface functionalization with aryl diazonium chemistry.

Localized π Surface States on 2D Molybdenum Disulfide from Carbene-Functionalization as a Qubit Design Strategy.

Surface chemistry is increasingly important for a number of applications, from catalysis to molecular qubits. For the qubit application, it is imperative that the energy levels of surface species involved in the process of interest are energetically distinct-that is addressable and not buried below or coincident with the substrate energy levels. One way to afford this is through chemical functionalization with derivatives that impart the property of choice to the interface.

Single-Cell Quantification of a Highly Biocompatible Dinuclear Iridium(III) Complex for Photocatalytic Cancer Therapy.

Quantifying the content of metal-based anticancer drugs within single cancer cells remains a challenge. Here, we used single-cell inductively coupled plasma mass spectrometry to study the uptake and retention of mononuclear (Ir1) and dinuclear (Ir2) Ir photoredox catalysts. This method allowed rapid and precise quantification of the drug in individual cancer cells.

Highly Efficient Ir(III)-Coumarin Photo-Redox Catalyst for Synergetic Multi-Mode Cancer Photo-Therapy.

Four photo-catalysts of the general formula [Ir(CO6/ppy) (L)]Cl where CO6=coumarin 6 (Ir1-Ir3), ppy=2-phenylpyridine (Ir4), L=4'-(3,5-di-tert-butylphenyl)-2,2' : 6',2''-terpyridine (Ir1), 4'-(3,5-bis(trifluoromethyl)phenyl)-2,2' : 6',2''-terpyridine (Ir2 and Ir4), and 4-([2,2' : 6',2''-terpyridin]-4'-yl)-N,N-dimethylaniline (Ir3) were synthesized and characterized. These photostable photo-catalysts (Ir1-Ir3) showed strong visible light absorption between 400-550 nm. Upon light irradiation (465 and 525 nm), Ir1-Ir3 generated singlet oxygen and induced rapidly photo-catalytic oxidation of cellular coenzymes NAD(P)H.

In-vitro and In-vivo Photocatalytic Cancer Therapy with Biocompatible Iridium(III) Photocatalysts.

Photocatalytic anticancer profile of a Ir photocatalyst (Ir3) with strong light absorption, high turnover frequency, and excellent biocompatibility is reported. Ir3 showed selective photo-cytotoxicity against cisplatin- and sorafenib-resistant cell lines while remaining dormant to normal cell lines in the dark. Ir3 exhibited excellent photo-catalytic oxidation of cellular co-enzyme, the reduced nicotinamide adenine dinucleotide phosphate (NADPH), and amino acids via a single electron transfer mechanism.

Zero-Overlap Fluorophores for Fluorescent Studies at Any Concentration.

Fluorophores are powerful tools for the study of chemistry, biology, and physics. However, fluorescence is severely impaired when concentrations climb above 5 μM as a result of effects like self-absorption and chromatic shifts in the emitted light. Herein, we report the creation of a charge-transfer (CT) fluorophore and the discovery that its emission color seen at low concentrations is unchanged even at 5 mM, some 3 orders of magnitude beyond typical limits.

Multi-state amine sensing by electron transfers in a BODIPY probe.

Amines are ubiquitous in the chemical industry and are present in a wide range of biological processes, motivating the development of amine-sensitive sensors. There are many turn-on amine sensors, however there are no examples of turn-on sensors that utilize the amine's ability to react by single electron transfer (SET). We investigated a new turn-on amine probe with a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorophore.

Coupling Constants, High Spin, and Broken Symmetry States of Organic Radicals: an Assessment of the Molecules-in-Molecules Fragmentation-Based Method.

We extend the application of our multilayer molecules-in-molecules (MIM) fragmentation-based method to the study of open-shell systems, particularly organic radicals. A test set of organic mono-, di- and polyradicals with a wide range in size, containing up to 360 atoms, was investigated. Total energies computed with MIM using density functional theory (DFT) were compared with full, unfragmented energies to assess the performance of MIM and to develop a systematic protocol for the treatment of large radical systems.

Fenton's Reagent Catalyzed Release of Carbon Monooxide from 1,3-Dihydroxy Acetone.

Triose sugar, 1,3-dihydroxy acetone (DHA) on treatment with Fenton's reagent releases CO under physiological conditions. The release of CO has been demonstrated by myoglobin assay and quantum chemical studies. The mechanistic study has been carried out using B3LYP/6-311++G(d,p), M06-2X/6-311++G(d,p) and CCSD(T)//M06-2X/6-311++G(d,p) level of theories in aqueous medium with dielectric constant of 78.