Investigation of excited states of BODIPY derivatives and non-orthogonal dimers from the perspective of singlet fission.

We report state of the art electronic structure calculations RICC2 and XMCQDPT of BODIPY nonorthogonal dimers to understand the photophysical processes from the intramolecular singlet fission (iSF) perspective. We have calculated singlet, triplet and quintet states at the XMCQDPT(8,8)/cc-pVDZ level of theory and diabatic singlet states at the XMCQDPT(4,4)/cc-pVDZ level of theory. In all the systems studied, charge transfer states ((CA) and (AC)) couple strongly with locally excited ((SS)) and multiexcitonic ((TT)) states.

Catalytic asymmetric fragmentation of cyclopropanes.

The stereoselective activation of alkanes constitutes a long-standing and grand challenge for chemistry. Although metal-containing enzymes oxidize alkanes with remarkable ease and selectivity, chemical approaches have largely been limited to transition metal-based catalytic carbon-hydrogen functionalizations. Alkanes can be protonated to form pentacoordinated carbonium ions and fragmented into smaller hydrocarbons in the presence of strong Brønsted acids.

-Substituted Iminothiolane (NIT): A Promising Strategy for Protecting Lysine Side Chains for Solid-Phase Peptide Chemistry.

In this study, we introduce -substituted iminothiolane (NIT) as a robust protecting group for lysine side chains. NIT is compatible with Fmoc-SPPS and can be efficiently removed under mild nucleophilic conditions. Notably, NIT offers enhanced hydrophilicity compared to traditional orthogonal lysine-protecting groups and does not undergo intramolecular migration.

External photocatalyst-free photocycloaddition between triplet vinylnitrenes with 1,3-biradical character and activated olefins under 420 nm LEDs.

Herein, we report that triplet vinylnitrenes with 1,3-biradical character can directly participate in photocycloaddition reactions with olefins to produce single diastereomers of the corresponding 1-pyrrolines under 420 nm LEDs in acetonitrile solvent. Moreover, a one-pot method has been developed to produce pyrroles directly through photocycloaddition and oxidation sequences. The excited state of the substrate olefin can sensitize vinyl azide energy transfer, eliminating the need for an external photocatalyst or sensitizer.

A Dual Action Platinum(IV) Complex with Self-assembly Property Inhibits Prostate Cancer through Mitochondrial Stress Pathway.

Platinum(IV) prodrugs are highly promising anticancer agents because they can selectively target tumors and minimize the adverse effects associated with their Pt congeners. In this study, we synthesized dual action Pt complexes by linking oxoplatin with lithocholic acid. The synthesized compounds, designated as PL-I, PL-II, and PL-III, can spontaneously self-assemble in water, resulting in the formation of spherical shape nanoparticles.

Advanced AIE Materials for Environmental Monitoring: Selective Sensing of Thorium(IV) in Aquatic Systems.

Thorium (Th) is commonly used in various applications, but its long-term exposure poses health risks, necessitating its detection in aqueous environments. Traditional methods such as inductively coupled plasma mass spectrometry are sensitive but require complex instrumentation. Optical sensors, particularly fluorometry-based methods, are simpler, cost-effective, and selective.

Photocatalytic CO reduction to CO catalysed by lanthanide complexes.

Here we demonstrate the efficient CO reduction to CO catalysed by lanthanide-based complexes under light irradiation, by which the highest CO evolution rate can reach 78 ± 8 μmol g h in 4 h. This work provides an economic and environmentally friendly route for CO conversion.

Ortho-Para Conversion for H + H Collision in Low Temperature: A Fully Close-Coupled Time-Dependent Wave Packet Study.

The collision-induced rate coefficients of ortho-para conversion for the H + H reaction provide accurate information to probe the lifetime of cold environments in interstellar media. Rotationally resolved reaction probabilities are calculated at the low collision energy regime (0 < ≤ 0.3 eV) by employing the coupled three-dimensional (3D) time-dependent wave packet (TDWP) formalism in hyperspherical coordinates on a recently constructed ab initio ground adiabatic potential energy surface of H [ , , 204306] for the process H + H ( = 0, = 0-5) → H + H (' = 0, ').

Fabrication of Thermo-Responsive Polymer-MOF@cellulase Composites with Improved Catalytic Performance for Hydrolysis of Cellulose.

Metal-organic frameworks (MOFs) are considered as an ideal enzyme support because of their porous structural superiority. However, MOFs@enzyme composites have usually compromised their hydrolysis efficiency due to the narrow space inducing unfavourable enzyme conformations. Herein, a thermo-responsive poly(N,N-dimethylacrylamide) (PD) was fixed onto the surface of UiO-66-NH (UiO) through a post-synthetic modification protocol.

Light-Promoted Extraction of Precious Metals Using a Porphyrin-Integrated One-Dimensional Covalent Organic Framework.

Precious metals are valuable materials for the chemical industry, but they are scarce and pose a risk of supply disruption. Recycling precious metals from waste is a promising strategy, here we tactfully utilize light irradiation as an environmental-friendly and energy-saving adjunctive strategy to promote the reduction of precious metal ions, thereby improving the adsorption capacity and kinetics. A newly light-sensitive covalent organic framework (PP-COF) was synthesized to illustrate the effectiveness and feasibility of this light auxiliary strategy.

Dicarbatriphyrin(2.1.1) and its Carbacalix[1]Phyrin Analogue: Structure-Property Relationships and Application as a Fe(III) Chemosensor.

The investigation of unsaturated or π-conjugated hydrocarbons, particularly within the macrocyclic framework, has garnered significant interest due to their fundamental properties and practical applications. This research focuses on the synthesis and characterization of a novel stable dicarbatriphyrin(2.1.

Electrochemical and imaging evaluations of electrochemically activated screen-printed gold electrodes.

Sulfuric acid is commonly used to electrochemically activate gold electrodes in a variety of electrochemical applications. This work provides the first evaluations of the electrochemical behaviors and a 3D image of an activated screen-printed gold electrode (SPGE, purchased commercially) through electrochemical and imaging analyses. The activated SPGE surface appears rougher than the unactivated SPGE surface when viewed through microtopography images using scanning electron microscopy (SEM) and atomic force microscopy (AFM).

Enhancing Phototoxicity in BODIPY-Perylene Charge Transfer Dyads by Combined Iodination and Mesylation.

The uptake and phototoxicity of a family of BODIPY-perylene charge transfer dyads are compared in live cancer and non-cancer cell lines to evaluate their performance in imaging and photodynamic therapy (PDT). The impact of iodination and mesylation of the meso position of the compounds on their optical properties, cell uptake and toxicity are compared. Notably, across all derivatives the probes were minimally dark toxic up to 50 μM, (the maximum concentration tested), but exhibited outstanding phototoxicity with nanomolar IC values and impressive phototoxic indices (PI, ratio of dark IC to light IC), with best performance for the mesylated iodinated derivative MB2PI, which had a PI of >218 and >8.

Photosensitizer-Free Photoinduced Ground-State Triplet Carbene-Assisted Persistent Aryloxy Radical Generation via Hydrogen Atom Transfer.

The traditional intermolecular O-H insertion strategy is typically associated with the reactivity exhibited by the singlet spin state, or it can alter the spin state from triplet to singlet by hydrogen bonding. Herein, we report diazoarylidene succinimide that generates a persistent ground-state triplet carbene under visible light (Blue LED, 456 nm) without a photosensitizer. This triplet carbene undergoes an intramolecular O-H insertion via hydrogen atom transfer, forming a persistent aryloxy radical without altering its spin state and leading to biologically relevant 2-chromenes.

O,S-Chelated bis(pentafluorophenyl)boron and diphenylboron-β-thioketonates: synthesis, photophysical, electrochemical and NLO properties.

Boron-β-diketonates are classical emissive materials that have been utilized in various fields, however, boron monothio-β-thioketonates, where one oxygen atom is exchanged for a sulphur atom, have not been explored in detail. To gain a better understanding of this class of materials, we synthesised various aryl substituted monothio-β-diketonate boron complexes with two different aryl substitutions on the boron center and studied their structural, optical and electrochemical properties. Single crystal X-ray analysis revealed that there is considerable deviation in B-O and B-S bond lengths for bis(pentafluorophenyl)boron complexes against diphenyl boron complexes.

Integrative approach to assessing bioactivity from hempseed protein isolate extracted and dehydrated by different methods: Synergising in silico prediction and in vitro validation.

This study demonstrated a comprehensive workflow combining in silico screening and prediction with in vitro validation to investigate the bioactivity of hempseed protein isolate (HPI) extracted and dehydrated using different methods. By adopting an in silico approach, 13 major proteins of HPI were hydrolysed by 20 selected enzymes, leading to the prediction of 20 potential bioactivities. With papain hydrolysis, dipeptidyl peptidase-IV (DPP4) and angiotensin-converting enzyme (ACE) inhibitory activities emerged as having the highest potential.

D-π-A Type [7]Helicene-like Imide Derivatives with Tunable Photophysical Properties and Circularly Polarized Luminescence.

Helicenes and their derivatives show great application prospects as circularly polarized luminescence (CPL) materials, but their fluorescence quantum yields (Φs) need a breakthrough urgently. Herein, we reported a series of D-π-A type helical luminescent emitters by combining the [7]helicene-like imide acceptor with five different donors. The obtained five emitters display blue-to-orange luminescence and markedly enhanced Φ.

Deciphering Electrocatalytic Hydrogen Production in Water Through a Bioinspired Water-Stable Copper(II) Complex Adorned with (NS)-Donor Sites.

Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase-like active sites in sustainable H generation, a meticulously designed and water-stable copper(II) complex, [Cl-Cu-L]ClO, featuring the N,S-type ligand, L (2,2'-((butane-2,3-diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes -Cl substitution by HO during electrochemical conditions yielding [HO-Cu-L] as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.

Upgrading of nitrate to hydrazine through cascading electrocatalytic ammonia production with controllable N-N coupling.

Nitrogen oxides (NO) play important roles in the nitrogen cycle system and serve as renewable nitrogen sources for the synthesis of value-added chemicals driven by clean electricity. However, it is challenging to achieve selective conversion of NO to multi-nitrogen products (e.g.

Asymmetric Synthesis of Benzofuranones with a C3 Quaternary Center via an Addition/Cyclization Cascade Using Noncovalent N-Heterocyclic Carbene Catalysis.

An asymmetric addition/cyclization cascade of amidoesters and iminoquinones is developed using noncovalent N-heterocyclic carbene (NHC) catalysis. The process enables access to various functionalized benzofuranones with an all-carbon quaternary stereocenter with high yields and ee values. The reaction displays a broad substrate scope.