Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
Novel heterocyclic azophotoswitches synthesized in a single step demonstrate sensitivity to visible light.
Язык: Английский
Langmuir, Год журнала: 2025, Номер unknown
Опубликована: Апрель 16, 2025
This study presents a novel, eco-friendly, and cost-effective magnetic hybrid photocatalyst, Fe3O4@SiO2/L-tryptophan, synthesized through scalable three-step green approach using natural agricultural waste. The Fe3O4@SiO2/L-tryptophan nanoparticle features core-shell structure with high surface area (63.14 m2/g), strong visible-light absorption (λ > 448 nm), narrow band gap (1.84 eV), superparamagnetic properties (22 emu/g), enabling efficient separation reusability. Characterization techniques (XRD, XPS, FT-IR, FE-SEM, HR-TEM, UV-vis DRS, TGA, BET, EIS) confirmed its structural stability, charge separation, interfacial transport. photocatalyst achieved 82.1% oxidative desulfurization of dibenzothiophene (DBT) conversion rates for toluene (85%) styrene (90%) under visible light O2 as an oxidant. It retained over 85% activity after five cycles, demonstrating excellent durability. For the first time, all components are derived from sources: Fe3O4 sorghum seed extract, SiO2 rice husk, L-tryptophan enhanced separation. sustainable synthesis reduces chemical waste energy consumption, setting new benchmark environmentally friendly photocatalysts.
Язык: Английский
Процитировано
0
Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Апрель 16, 2025
Comprehensive Summary The visible light‐driven photoswitches are attracting widespread attention, but it is challenging to leverage their phototriggered structural changes regulate dynamic bonds, assemblies, and materials. Herein, we incorporated reversible covalent sites of aldehyde ring‐chain tautomers into all‐visible‐light azobenzenes toward a versatile platform for light‐controlled formation/exchange C—N bonds from secondary amines. movement equilibrium was attained via manipulating intramolecular multiple hydrogen bonding E / Z configurational isomers. Such regulation further enabled photocontrolled kinetics the formation exchange reactions cyclic hemiaminal ethers amines exhibiting kinetic rate reversal varied capability isomers in engaging azo attached carboxylate with ammonium salt accounts difference. Moreover, photoswitching performance different solutions readily regulated by reactivity control light associated mechanistic foundation add collection photoswitchable chemistry would lay subsequent biological material applications.
Язык: Английский
Процитировано
0
bioRxiv (Cold Spring Harbor Laboratory), Год журнала: 2025, Номер unknown
Опубликована: Апрель 17, 2025
Abstract Photoswitchable unnatural amino acids (psUAAs) play a crucial role in the engineering of light-sensitivity enzymes, which holds significant promise for diverse applications such as biotherapy and biocatalysis. Besides near-quantitative photoconversion, success expediency psUAA certain application is defined by its interaction potential with enzyme, thermal stability effective wavelength irradiation. To establish high versatility current repertoire, we have designed synthesized six psUAAs based on azobenzene, arylazopyrazole, arylazothiazole, hemithioindigo spiropyran photoswitches. The resulting exhibit an enhanced within enzyme owing to their capacity hydrogen bonding, ionic interactions, metal ion coordination. Moreover, observed photochemical behaviors among psUAAs, four them reversibly switching between isomers purely visible light. Notably, identified orthogonal aminoacyl-tRNA synthetases that facilitate incorporation five co-translationally computationally analyzed synthetase-psUAA interactions. Finally, evaluated behavior enzymatic model tested photocontrol catalysis confirming diversity. Ultimately, our findings significantly expanded repertoire demonstrated feasibility studies.
Язык: Английский
Процитировано
0
Deleted Journal, Год журнала: 2025, Номер unknown
Опубликована: Апрель 25, 2025
Abstract In the era of precision medicine, photopharmacology that employs molecular photoswitches offers unique opportunities to control action bioactive molecules with high spatiotemporal resolution, while reducing drug side effects, systemic toxicity and emergence resistance. Over past two decades, field has witnessed great achievements in treating blindness, cancer, diabetes, antibiotic resistance, name but a few. Several challenges remain, however, particular fact most photopharmacological agents trigger their activity by Ultraviolet light, which is damaging normal cells poor tissue permeability. Visible light‐activated are hence highly desirable have captured keen recent research interest. This review highlights strategies for synthesis visible light‐responsive azobenzenes (ABs) applications emerging photopharmacology. Such photoswitchable drugs tremendously extend scope future vivo applications. Furthermore, we identify current discuss rational design switches at higher wavelength. We hope inspire further into photochemistry novel based on ABs or other photoswitches, triggered excitation light “phototherapeutic window” 650–900 nm, ultimately enabling full realization these “smart” clinical practice.
Язык: Английский
Процитировано
0
Coordination Chemistry Reviews, Год журнала: 2025, Номер 540, С. 216770 - 216770
Опубликована: Май 7, 2025
Язык: Английский
Процитировано
0
ChemElectroChem, Год журнала: 2025, Номер unknown
Опубликована: Май 12, 2025
Cyclic azobenzenes generally exhibit enhanced photophysical properties compared to conventional linear azobenzenes, such as visible‐light activation and exceptional thermal stability. However, their broader application has been hindered by synthetic challenges. Herein, the electrochemical synthesis of a ten‐membered cyclic azobenzene, 6,7‐dihydrodibenzo[e,i][1,4,7,8]dioxadiazecine (DDEI), is reported through reduction 1,2‐bis(2‐nitrophenoxy)ethane (BNPOE) in presence CO 2 . The mechanism, involving an irreversible eight‐electron process capture, elucidated using situ fourier transform infrared spectroscopy (FT‐IR) spectroelectrochemistry, complemented 13 C NMR, 1 H mass spectrometry analyzes. Both experimental results density functional theory calculations show that DDEI undergoes highly efficient trans ‐to‐ cis isomerization under green light (500 nm) irradiation, achieving remarkable yield 97%, with both isomers exhibiting excellent In contrast 8‐ 9‐membered line configuration more stable than configuration. This combination accessibility superior makes promising candidate for various applications, including those living systems.
Язык: Английский
Процитировано
0
ACS Nano, Год журнала: 2025, Номер unknown
Опубликована: Май 14, 2025
Stimuli engineering physical properties of transition metal dichalcogenides (TMDCs) have attracted intense interest due to the intriguing potential in future optoelectronics, valleytronics, and quantum information science. Azobenzene molecules provide an ideal platform manipulate optical monolayer TMDCs. Here, we employed reversibly photoswitchable mechanically cleavable solid azobenzene derivative polycrystal fabricate van der Waals heterostructure elucidated interface interaction between molecule WSe2 via visible laser-driven isomerization. The stronger coupling effect dipole reorientation induced by solid-liquid phase trans-to-cis conversion led significant variation electron doping WSe2. It is evidenced distinct photoluminescence (PL) quenching at room temperature pronounced shift from neutral exciton negative trion through temperature- gate-dependent PL surface potentials heterostructure. Our work thus provides a feasible approach selectively engineer 2D materials, which could lay versatile path development processing, functional photoresponsive devices, molecular probes.
Язык: Английский
Процитировано
0
The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Май 15, 2025
Azobenzenes are proven to be one of the most successful molecular photoswitches applied across different fields such as organic chemistry, material science, cosmetics, and pharmaceuticals. Such a widespread implementation is possible because their photochromic properties contingent upon substitution pattern aryl-core nature. In recent endeavors design, replacing or both phenyl rings with heteroaromatics turned out good strategy access compounds improved photoswitching properties, well expand diversity. One challenges related design new azobenzene that it often includes synthesis large libraries due limited methods for prediction properties. Herein, we present computationally driven workflow novel class photoswitches, heteroaryl azobenzenes N-bridgehead heterocycles─pyrazolo[1,5-a]pyrimidine 1,2,4-triazolo[1,5-a]pyrimidine. A small library was synthesized, photochemical were evaluated. Subsequently, these results used validate computational approach, which included in silico evaluation designed photoswitch candidates leading spectral red-shifted λmax values.
Язык: Английский
Процитировано
0
Advanced Materials, Год журнала: 2025, Номер unknown
Опубликована: Май 22, 2025
Abstract Obesity‐induced insulin resistance is a hallmark of metabolic syndrome, and chronic low‐grade inflammation links obesity to through the activation tissue‐infiltrating immune cells. Current treatments are lacking in efficacy immunosuppression. Therefore, novel therapies needed prevent alleviate obesity‐related resistance. In this work, red light‐responsive biomimetic nanoparticles (RSCP NPs) reported perform targeted delivery multiple drugs effectively reduce nonspecific enrichment. These results showed that dual‐targeting multiple‐signaling response (red light signaling different pH microenvironments) RSCP NPs enabled precise astaxanthin (Asta) rosiglitazone (Rosi) M1‐like macrophages white adipocytes, respectively, adipose tissue (WAT) promote adipocyte browning. Moreover, NPs‐mediated Asta Rosi treatment robustly alleviated other disorders obese animal models (high‐fat diet (HFD)‐induced or genetically mice). Overall, study provides theoretical practical basis for development application drug systems diseases by elucidating synergistic long‐term targeting mechanism target molecule stability light‐sensitive bionic nanodrug systems.
Язык: Английский
Процитировано
0
The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown
Опубликована: Май 31, 2025
Phenylazothiazole (PAT) is a novel heteroaryl azo photoswitch that undergoes trans (E) to cis (Z) photoisomerization under visible light, making it promising for biological applications. However, the quantum yield of E-to-Z isomerization significantly lower than Z-to-E process, limiting its practical utility. In this study, we employ nonadiabatic dynamics simulations investigate ultrafast photoisomerization. Through systematic analysis electronic structure methods, demonstrate spin-flip time-dependent density functional theory (SF-TDDFT) provides reliable description excited states, particularly at conical intersections, yielding results consistent with multireference methods. Based on two-dimensional potential energy surfaces, reveal E-PAT initially relaxes along torsional coordinate reach minimum S2 state, followed by two distinct pathways returning ground state. One pathway involves planar in S1 predominantly leading back E isomer rather Z isomer, which explains yield. Additionally, explore substituent effects optical properties and thermal PAT derivatives, showing substituents not only induce redshift absorption spectrum but also modulate activation barrier ground-state isomerization. These findings provide valuable theoretical insights into mechanism PATs offer guidance designing optoelectronic materials tunable properties.
Язык: Английский
Процитировано
0