Glucose oxidase: An emerging multidimensional treatment option for diabetic wound healing

Bioactive Materials, Год журнала: 2024, Номер 44, С. 131 - 151

Опубликована: Окт. 15, 2024

Язык: Английский

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Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet Gap

The Journal of Physical Chemistry Letters, Год журнала: 2023, Номер 14(49), С. 11069 - 11075

Опубликована: Дек. 4, 2023

Molecules that violate Hund's rule and exhibit an inverted gap between the lowest singlet S1 triplet T1 excited states have attracted considerable attention due to their potential applications in optoelectronics. Among these molecules, triangular-shaped heptazine, its derivatives, been limelight. However, conflicting reports arisen regarding relative energies of T1. Here, we employ highly accurate levels theory, such as CC3, not only resolve debate concerning sign but also quantify magnitude S1-T1 gap. We determined 0-0 evaluate significance vertical approximation. In addition, compute reference gaps for a series 10 related molecules. This enables us benchmark lower-order methods future larger systems within same family compounds. contribution can serve foundation design molecules with enhanced photophysical properties.

Язык: Английский

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Enhanced inverted singlet–triplet gaps in azaphenalenes and non-alternant hydrocarbons

Chemical Communications, Год журнала: 2024, Номер 60(15), С. 2070 - 2073

Опубликована: Янв. 1, 2024

A substituent-based design strategy induces and enhances inversions in the excited state singlet–triplet gaps a wide range of potential organic light-emitting molecules.

Язык: Английский

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Enhancing Photocatalytic Redox Activity of Polymeric Carbon Nitride for Valuable Fluorinated Heterocycles through Fast-Track Electron Highways

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11308 - 11317

Опубликована: Июль 15, 2024

The ionic structure of poly(heptazine imides) has a strong implication in photocatalytic hydrogen generation. From numerous reports, it is evident that these materials are also superior to covalent carbon nitrides various organic transformations. However, the reason been remaining vague. Herein, we report design molten-salt nitride (MCN) featuring represented by negatively charged polymeric scaffold and K+ counterions application this material as photocatalyst synthesis pharmaceutically relevant fluorinated heterocycles under visible light redox neutral conditions. ions serve sites for sorption ethyl bromodifluoroacetate, while electronically excited state MCN acts single electron transfer agent, enabling generation difluoroalkyl radicals from substrate. Combination two features endows outperforms homogeneous photocatalysts nitrides. Our protocol expands compounds with complex provides fresh perspectives on factors contributing enhanced efficiency imides).

Язык: Английский

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A Guide to Chemical Reactions Design in Carbon Nitride Photocatalysis

ChemPhotoChem, Год журнала: 2024, Номер 8(4)

Опубликована: Янв. 5, 2024

Abstract Graphitic carbon nitride semiconductors are inexpensive and reusable photocatalysts, which actively studied in organic synthesis. Successful design of photocatalytic reactions is based on the next considerations. i) Thermodynamic feasibility photoinduced processes, involve transfer electrons or electron‐proton couples. ii) Redox activity reagents. iii) Reactivity open‐shell intermediates generated from Herein, we summarize current understanding how local chemical structure graphitic nitrides their redox potentials used to reactions. This work intends serve as a guideline for materials scientists, who willing apply involving substrates, chemists, interested dive into heterogeneous photocatalysis.

Язык: Английский

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Regulation of oriented NO photooxidation to circumvent NO2 with high-coordinated M–N5 (M = Fe, Co, Mn, Ti) sites and far–carbon defects

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 350, С. 123948 - 123948

Опубликована: Апрель 24, 2024

Язык: Английский

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ΔDFT Predicts Inverted Singlet–Triplet Gaps with Chemical Accuracy at a Fraction of the Cost of Wave Function-Based Approaches

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(31), С. 8065 - 8077

Опубликована: Июль 31, 2024

Efficient OLEDs need to quickly convert singlet and triplet excitons into photons. Molecules with an inverted singlet–triplet energy gap (INVEST) are promising candidates for this task. However, typical INVEST molecules have drawbacks like too low oscillator strengths excitation energies. High-throughput screening could identify suitable molecules, but existing methods problematic: The workhorse method TD-DFT cannot reproduce inversion, while wave function-based slow. This study proposes a state-specific based on unrestricted Kohn–Sham DFT common hybrid functionals. Tuned the new INVEST15 benchmark set, achieves error of less than 1 kcal/mol, which is traced back cancellation between spin contamination dynamic correlation. Applied larger structurally diverse NAH159 set in black-box fashion, maintains small (1.2 kcal/mol) accurately predicts signs 83% cases, confirming its robustness suitability workflows.

Язык: Английский

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Simultaneous Photocatalytic Production of H₂ and Acetal from Ethanol with Quantum Efficiency over 73% by Protonated Poly(heptazine imide) under Visible Light

ACS Catalysis, Год журнала: 2024, Номер 14(19), С. 14836 - 14854

Опубликована: Сен. 23, 2024

In this work, protonated poly(heptazine imide) (H-PHI) was obtained by adding acid to the suspension of potassium PHI (K-PHI) in ethanol. It established that H-PHI demonstrates very high photocatalytic activity reaction hydrogen formation from ethanol presence Pt nanoparticles under visible light irradiation comparison with K-PHI. This enhancement can be attributed improved efficiency photogenerated charge transfer photocatalyst's surface, where redox processes occur. Various factors influencing system's were evaluated. Notably, it discovered conditions introduction into system significantly affect size (cocatalyst metal) deposition on thereby enhancing stability producing molecular hydrogen. operate efficiently air without additional components photocatalyst surface block access. Under optimal conditions, apparent quantum yield production at 410 nm is around 73%, highest reported value for carbon nitride materials date. The addition not only increases reduction part but also leads a value-added product ethanol-1,1-diethoxyethane (acetal) selectivity.

Язык: Английский

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The Role of Theoretical Calculations for INVEST Systems: Complementarity Between Theory and Experiments and Rationalization of the Results

Advanced Optical Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

Abstract Here, the key role played by theoretical calculations for molecules presenting an inverted singlet‐triplet excited state (e.g. S 1 and T ) energy difference, or Δ E ST < 0, whose interest has steadily raised in recent years fostered experimental advances showing negative values a collection of real‐world systems is reviewed. The evolution computational efforts from pioneering on reduced set prototypical covered, to high‐throughput virtual screenings thousands identify new molecular scaffolds tune properties other than excitation energies, describe necessary benchmarking methods done parallel along years. Overall, complementarity prompted discovery more displaying 0 values, basic design principles are rationalized thus reviewed here too, while allowing at same time find which offer reasonable trade‐off between accuracy cost.

Язык: Английский

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Computational Design of Molecules Having Less Overlapping HOMO and LUMO in the Same Plane

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Апрель 3, 2025

The negative energy difference between singlet and triplet excited states (ΔEST) is currently attracting significant attention; however, molecular designs remain largely confined to azaphenalene structures, as reported by Leupin Wirz in 1980. To show ΔEST, a maximally separated highest occupied orbital (HOMO) lowest unoccupied (LUMO) arrangement crucial minimizing the exchange interaction state. We revisited electronic structure of cyclazine, consisting cyclododecahexaene ([12]annulene) central nitrogen atom. 12 π-electrons peripheral cyclic oligoene play an important role achieving less overlapping HOMO LUMO arrangement, bridging atom inside produces while maintaining stable planar structure. Based on these insights, we designed set 10 molecules which number (N) 16, 20, 24, satisfying N = 4·n (n 4, 5, 6), further 11 extended 14, 18, 22, 26, + 2 3, 6). HOMO, LUMO, (K), ΔEST were calculated using configuration singles, TD-DFT, equation motion coupled-cluster singles doubles (EOM-CCSD), with optimized without any symmetry constraint. Among structures 4·n, only bond alternation exhibit small K ΔEST. In contrast, among 2, none arrangement. both no EOM-CCSD calculation. findings this study will pave way for broader exhibiting where overlap essential.

Язык: Английский

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