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1.
Mikrochim Acta ; 191(6): 316, 2024 05 10.
Article En | MEDLINE | ID: mdl-38724679

An ultra-sensitive photoelectrochemical (PEC) sensor based on perovskite composite was developed for the determination of alkaline phosphatase (ALP) in human serum. In contrast to CsPbBr3 or Y6 that generated anodic current, the heterojunction of CsPbBr3/Y6 promoted photocarriers to separate and generated cathodic photocurrent. Ascorbic acid (AA) was produced by ALP hydrolyzing L-ascorbic acid 2-phosphate trisodium salt (AAP), which can combine with the holes on the photoelectrode surface, accelerating the transmission of photogenerated carriers, leading to enhanced photocurrent intensity. Thus, the enhancement of PEC current was linked to ALP activity. The PEC sensor exhibits good sensitivity for detection of ALP owing to the unique photoelectric properties of the CsPbBr3/Y6 heterojunction. The detection limit of the sensor was 0.012 U·L-1 with a linear dynamic range of 0.02-2000 U·L-1. Therefore, this PEC sensing platform shows great potential for the development of different PEC sensors.


Alkaline Phosphatase , Ascorbic Acid , Electrochemical Techniques , Electrodes , Limit of Detection , Oxides , Photochemical Processes , Titanium , Alkaline Phosphatase/chemistry , Alkaline Phosphatase/blood , Alkaline Phosphatase/metabolism , Humans , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Ascorbic Acid/chemistry , Ascorbic Acid/blood , Ascorbic Acid/analogs & derivatives , Titanium/chemistry , Oxides/chemistry , Calcium Compounds/chemistry , Biosensing Techniques/methods
2.
Molecules ; 29(9)2024 May 05.
Article En | MEDLINE | ID: mdl-38731639

The cyclometalated terpyridine complexes [Ru(η2-OAc)(NC-tpy)(PP)] (PP = dppb 1, (R,R)-Skewphos 4, (S,S)-Skewphos 5) are easily obtained from the acetate derivatives [Ru(η2-OAc)2(PP)] (PP = dppb, (R,R)-Skewphos 2, (S,S)-Skewphos 3) and tpy in methanol by elimination of AcOH. The precursors 2, 3 are prepared from [Ru(η2-OAc)2(PPh3)2] and Skewphos in cyclohexane. Conversely, the NNN complexes [Ru(η1-OAc)(NNN-tpy)(PP)]OAc (PP = (R,R)-Skewphos 6, (S,S)-Skewphos 7) are synthesized in a one pot reaction from [Ru(η2-OAc)2(PPh3)2], PP and tpy in methanol. The neutral NC-tpy 1, 4, 5 and cationic NNN-tpy 6, 7 complexes catalyze the transfer hydrogenation of acetophenone (S/C = 1000) in 2-propanol with NaOiPr under light irradiation at 30 °C. Formation of (S)-1-phenylethanol has been observed with 4, 6 in a MeOH/iPrOH mixture, whereas the R-enantiomer is obtained with 5, 7 (50-52% ee). The tpy complexes show cytotoxic activity against the anaplastic thyroid cancer 8505C and SW1736 cell lines (ED50 = 0.31-8.53 µM), with the cationic 7 displaying an ED50 of 0.31 µM, four times lower compared to the enantiomer 6.


Antineoplastic Agents , Pyridines , Ruthenium , Humans , Catalysis , Ruthenium/chemistry , Cell Line, Tumor , Pyridines/chemistry , Pyridines/pharmacology , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/chemical synthesis , Coordination Complexes/chemistry , Coordination Complexes/pharmacology , Coordination Complexes/chemical synthesis , Molecular Structure , Photochemical Processes
3.
Anal Chim Acta ; 1308: 342647, 2024 Jun 15.
Article En | MEDLINE | ID: mdl-38740456

BACKGROUND: Presently, glyphosate (Gly) is the most extensively used herbicide globally, Nevertheless, its excessive usage has increased its accumulation in off-target locations, and aroused concerns for food and environmental safety. Commonly used detection methods, such as high-performance liquid chromatography and gas chromatography, have limitations due to expensive instruments, complex pre-processing steps, and inadequate sensitivity. Therefore, a facile, sensitive, and reliable Gly detection method should be developed. RESULTS: A photoelectrochemical (PEC) sensor consisting of a three-dimensional polymer phenylethnylcopper/nitrogen-doped graphene aerogel (PPhECu/3DNGA) electrode coupled with Fe3O4 NPs nanozyme was constructed for sensitive detection of Gly. The microscopic 3D network of electrodes offered fast transfer routes for photo-generated electrons and a large surface area for nanozyme loading, allowing high signal output and analytical sensitivity. Furthermore, the use of peroxidase-mimicking Fe3O4 NPs instead of natural enzyme improved the stability of the sensor against ambient temperature changes. Based on the inhibitory effect of Gly on the catalytic activity Fe3O4 NPs, the protocol achieved Gly detection in the range of 5 × 10-10 to 1 × 10-4 mol L-1. Additionally, feasibility of the detection was confirmed in real agricultural matrix including tea, maize seedlings, maize seeds and soil. SIGNIFICANCE: This work achieved facile, sensitive and reliable analysis towards Gly, and it was expected to inspire the design and utilization of 3D architectures in monitoring agricultural chemicals in food and environmental matrix.


Electrochemical Techniques , Electrodes , Glycine , Glyphosate , Graphite , Nitrogen , Photochemical Processes , Graphite/chemistry , Glycine/analogs & derivatives , Glycine/chemistry , Glycine/analysis , Nitrogen/chemistry , Polymers/chemistry , Copper/chemistry , Gels/chemistry , Herbicides/analysis , Limit of Detection , Magnetite Nanoparticles/chemistry , Magnetic Iron Oxide Nanoparticles/chemistry
4.
Int J Mol Sci ; 25(9)2024 May 01.
Article En | MEDLINE | ID: mdl-38732166

This current study assessed the impacts of morphology adjustment of perovskite BiFeO3 (BFO) on the construction and photocatalytic activity of P-infused g-C3N4/U-BiFeO3 (U-BFO/PCN) heterostructured composite photocatalysts. Favorable formation of U-BFO/PCN composites was attained via urea-aided morphology-controlled hydrothermal synthesis of BFO followed by solvosonication-mediated fusion with already synthesized P-g-C3N4 to form U-BFO/PCN composites. The prepared bare and composite photocatalysts' morphological, textural, structural, optical, and photocatalytic performance were meticulously examined through various analytical characterization techniques and photodegradation of aqueous rhodamine B (RhB). Ellipsoids and flakes morphological structures were obtained for U-BFO and BFO, and their effects on the successful fabrication of the heterojunctions were also established. The U-BFO/PCN composite exhibits 99.2% efficiency within 20 min of visible-light irradiation, surpassing BFO/PCN (88.5%), PCN (66.8%), and U-BFO (26.1%). The pseudo-first-order kinetics of U-BFO/PCN composites is 2.41 × 10-1 min-1, equivalent to 2.2 times, 57 times, and 4.3 times of BFO/PCN (1.08 × 10-1 min-1), U-BFO, (4.20 × 10-3 min-1), and PCN, (5.60 × 10-2 min-1), respectively. The recyclability test demonstrates an outstanding photostability for U-BFO/PCN after four cyclic runs. This improved photocatalytic activity exhibited by the composites can be attributed to enhanced visible-light utilization and additional accessible active sites due to surface and electronic band modification of CN via P-doping and effective charge separation achieved via successful composites formation.


Bismuth , Photolysis , Rhodamines , Catalysis , Bismuth/chemistry , Rhodamines/chemistry , Light , Ferric Compounds/chemistry , Nitrogen Compounds/chemistry , Titanium/chemistry , Photochemical Processes , Nitriles/chemistry , Kinetics , Graphite , Oxides , Calcium Compounds
5.
Luminescence ; 39(5): e4760, 2024 May.
Article En | MEDLINE | ID: mdl-38738510

The present communication reports on the synthesis of a novel methyl-pyridone azo fluorescent tag (MPAFT) were proven through 1H (NMR), FT-IR, UV-vis, and high-resolution mass spectrometry. The quantum chemical parameters of MPAFT were evaluated using density functional theory (DFT) analysis. It was further investigated for its latent fingerprint (LFPs) in various surfaces and anticounterfeiting applications. By exposing Level I-Level III, ridge features to UV light with a wavelength of 365 nm, a bioimaging investigation has also demonstrated the potential of MPAFT's emission behaviour. The cyclic voltammetry (CV) and linear sweep voltammetry (LSV) at MPAFT/MGCE (modified glassy carbon electrode) were used to explore the electrochemical sensitivity and reliable detection of dopamine (DA) in neutral PBS (pH 7) electrolyte solution, and the results show good sensitivity and detection. The lower detection limit for LSV was 0.81 µM under optimum conditions.


Dopamine , Electrochemical Techniques , Fluorescent Dyes , Pyrazoles , Pyridones , Pyridones/chemistry , Dopamine/analysis , Dopamine/chemistry , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Pyrazoles/chemistry , Humans , Molecular Structure , Density Functional Theory , Optical Imaging , Photochemical Processes
6.
Colloids Surf B Biointerfaces ; 238: 113923, 2024 Jun.
Article En | MEDLINE | ID: mdl-38692173

The rapid advancement of photodynamic therapy (PDT) antibacterial materials has led to promising alternatives to antibiotics for treating bacterial infections. However, antibacterial drugs have poor light absorption and utilization rates, which limits their practical application. Constructing two-dimensional (2D) heterojunctions from materials with matching photophysical properties has emerged as a highly effective strategy for achieving high-efficiency photo-antibacterial performance. Here, we designed and prepared an atom co-sharing Bi/Bi4O5Br2 nanosheet heterojunction by a simple in situ reduction. This heterojunction material combines outstanding biocompatibility with excellent bactericidal efficiency, which exceeded 90 % against Escherichia coli (a Gram-negative bacterium) and Staphylococcus aureus (a Gram-positive bacterium) under visible light irradiation, around nine-fold higher than that with pure Bi4O5Br2 nanosheets. The results suggest that localized surface plasmon resonance (LSPR) of shared Bi atoms on the Bi4O5Br2 nanosheets promotes light utilization and the separation and transfer of photo-generated charges, thus producing more abundant reactive oxygen species (ROS), which can partake in the PDT antibacterial effect. Our study underscores the potential utility of LSPR-enhanced Bi-based nanosheet heterojunctions for safe and efficient PDT to combat bacterial infections.


Anti-Bacterial Agents , Bismuth , Escherichia coli , Light , Nanostructures , Staphylococcus aureus , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Escherichia coli/drug effects , Staphylococcus aureus/drug effects , Nanostructures/chemistry , Bismuth/chemistry , Bismuth/pharmacology , Catalysis , Microbial Sensitivity Tests , Photochemical Processes , Reactive Oxygen Species/metabolism , Surface Plasmon Resonance , Photochemotherapy , Particle Size
7.
J Am Chem Soc ; 146(20): 13754-13759, 2024 May 22.
Article En | MEDLINE | ID: mdl-38739748

a-Tertiary amino acids are essential components of drugs and agrochemicals, yet traditional syntheses are step-intensive and provide access to a limited range of structures with varying levels of enantioselectivity. Here, we report the α-alkylation of unprotected alanine and glycine by pyridinium salts using pyridoxal (PLP)-dependent threonine aldolases with a Rose Bengal photoredox catalyst. The strategy efficiently prepares various a-tertiary amino acids in a single chemical step as a single enantiomer. UV-vis spectroscopy studies reveal a ternary interaction between the pyridinium salt, protein, and photocatalyst, which we hypothesize is responsible for localizing radical formation to the active site. This method highlights the opportunity for combining photoredox catalysts with enzymes to reveal new catalytic functions for known enzymes.


Amino Acids , Amino Acids/chemistry , Glycine Hydroxymethyltransferase/metabolism , Glycine Hydroxymethyltransferase/chemistry , Photochemical Processes , Biocatalysis , Catalysis , Alkylation , Glycine/chemistry , Glycine/analogs & derivatives , Stereoisomerism , Molecular Structure , Oxidation-Reduction
8.
Nature ; 629(8010): 98-104, 2024 May.
Article En | MEDLINE | ID: mdl-38693411

Photobiocatalysis-where light is used to expand the reactivity of an enzyme-has recently emerged as a powerful strategy to develop chemistries that are new to nature. These systems have shown potential in asymmetric radical reactions that have long eluded small-molecule catalysts1. So far, unnatural photobiocatalytic reactions are limited to overall reductive and redox-neutral processes2-9. Here we report photobiocatalytic asymmetric sp3-sp3 oxidative cross-coupling between organoboron reagents and amino acids. This reaction requires the cooperative use of engineered pyridoxal biocatalysts, photoredox catalysts and an oxidizing agent. We repurpose a family of pyridoxal-5'-phosphate-dependent enzymes, threonine aldolases10-12, for the α-C-H functionalization of glycine and α-branched amino acid substrates by a radical mechanism, giving rise to a range of α-tri- and tetrasubstituted non-canonical amino acids 13-15 possessing up to two contiguous stereocentres. Directed evolution of pyridoxal radical enzymes allowed primary and secondary radical precursors, including benzyl, allyl and alkylboron reagents, to be coupled in an enantio- and diastereocontrolled fashion. Cooperative photoredox-pyridoxal biocatalysis provides a platform for sp3-sp3 oxidative coupling16, permitting the stereoselective, intermolecular free-radical transformations that are unknown to chemistry or biology.


Amino Acids , Biocatalysis , Oxidative Coupling , Photochemical Processes , Amino Acids/biosynthesis , Amino Acids/chemistry , Amino Acids/metabolism , Biocatalysis/radiation effects , Directed Molecular Evolution , Free Radicals/chemistry , Free Radicals/metabolism , Glycine/chemistry , Glycine/metabolism , Glycine Hydroxymethyltransferase/metabolism , Glycine Hydroxymethyltransferase/chemistry , Indicators and Reagents , Light , Oxidative Coupling/radiation effects , Pyridoxal Phosphate/metabolism , Stereoisomerism , Amino Acids, Branched-Chain/chemistry , Amino Acids, Branched-Chain/metabolism
9.
ACS Appl Bio Mater ; 7(5): 3431-3440, 2024 May 20.
Article En | MEDLINE | ID: mdl-38697834

Light-induced release of cisplatin from Pt(IV) prodrugs represents a promising approach for precise control over the antiproliferative activity of Pt-based chemotherapeutic drugs. This method has the potential to overcome crucial drawbacks of conventional cisplatin therapy, such as high general toxicity toward healthy organs and tissues. Herein, we report two Pt(IV) prodrugs with BODIPY-based photoactive ligands Pt-1 and Pt-2, which were designed using carbamate and triazole linkers, respectively. Both prodrugs demonstrated the ability to release cisplatin under blue light irradiation without the requirement of an external reducing agent. Dicarboxylated Pt-2 prodrug turned out to be more stable in the dark and more sensitive to light than its monocarbamate Pt-1 counterpart; these observations were explained using DFT calculations. The investigation of the photoreduction mechanism of Pt-1 and Pt-2 prodrugs using DFT modeling and ΔG0 PET estimation suggests that the photoinduced electron transfer from the singlet excited state of the BODIPY axial ligand to the Pt(IV) center is the key step in the light-induced release of cisplatin from the complexes. Cytotoxicity studies demonstrated that both prodrugs were nontoxic in the dark and toxic to MCF-7 cells under low-dose irradiation with blue light, and the observed effect was solely due to the cisplatin release from the Pt(IV) prodrugs. Our research presents an elegant synthetic approach to light-activated Pt(IV) prodrugs and presents findings that may contribute to the future rational design of photoactivatable Pt(IV) prodrugs.


Antineoplastic Agents , Drug Screening Assays, Antitumor , Light , Prodrugs , Prodrugs/chemistry , Prodrugs/pharmacology , Prodrugs/chemical synthesis , Humans , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemical synthesis , Molecular Structure , Materials Testing , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology , Biocompatible Materials/chemical synthesis , Cell Survival/drug effects , Cell Proliferation/drug effects , Cisplatin/pharmacology , Cisplatin/chemistry , Particle Size , Boron Compounds/chemistry , Boron Compounds/pharmacology , Boron Compounds/chemical synthesis , Photochemical Processes , Density Functional Theory
10.
Bioorg Chem ; 147: 107418, 2024 Jun.
Article En | MEDLINE | ID: mdl-38703441

A key approach in developing green chemistry involves converting solar energy into chemical energy of biomolecules through photocatalysis. Photocatalysis can facilitate the regeneration of nicotinamide cofactors during redox processes. Nicotinamide cofactor biomimetics (NCBs) are economical substitutes for natural cofactors. Here, photocatalytic regeneration of NADH and reduced NCBs (NCBsred) using graphitic carbon nitride (g-C3N4) was developed. The process involves g-C3N4 as the photocatalyst, Cp*Rh(bpy)H2O2+ as the electron mediator, and Triethanolamine as the electron donor, facilitating the reduction of NAD+ and various oxidative NCBs (NCBsox) under light irradiation. Notably, the highest reduction yield of 48.32 % was achieved with BANA+, outperforming the natural cofactor NAD+. Electrochemical analysis reveals that the reduction efficiency and capacity of cofactors relies on their redox potentials. Additionally, a coupled photo-enzymatic catalysis system was explored for the reduction of 4-Ketoisophorone by Old Yellow Enzyme XenA. Among all the NCBsox and NAD+, the highest conversion ratio of over 99 % was obtained with BANA+. After recycled for 8 times, g-C3N4 maintained over 93.6 % catalytic efficiency. The photocatalytic cofactor regeneration showcases its outstanding performance with NAD+ as well as NCBsox. This work significantly advances the development of photocatalytic cofactor regeneration for artificial cofactors and its potential application.


Biocatalysis , Oxidation-Reduction , Photochemical Processes , Biomimetic Materials/chemistry , Biomimetic Materials/metabolism , Molecular Structure , NAD/chemistry , NAD/metabolism , Biomimetics , Niacinamide/chemistry , Niacinamide/metabolism , Nitrogen Compounds/chemistry , Graphite
11.
Chemosphere ; 358: 142158, 2024 Jun.
Article En | MEDLINE | ID: mdl-38697561

A novel dual Photo-Fenton photocatalyst Fe2O3-Fe-CN with excellent Fe(III)/Fe(II) conversion efficiency and trace metal ion leaching rate has been fabricated by in-situ deposition of α-Fe2O3 quantum dots on ultrathin porous Fe-doped carbon nitride (Fe-CN) nanosheets. The iron species in Fe-CN and α-Fe2O3 QDs constitute a mutually reinforcing dual Photo-Fenton effect. The 4% Fe2O3-Fe-CN showed superior performance with kobs values 8.60 and 4.80 folders greater than pure CN and Fe-CN, respectively. The synergistic effect between α-Fe2O3 QDs and the ultrathin porous structure of Fe-CN is the primary reason for the outstanding catalytic performance exhibited by α-Fe2O3/Fe-CN. On one hand, the ultrathin porous structure of Fe-CN promotes the rapid transfer of photogenerated electrons. On the other hand, the efficient photogenerated charge separation at the α-Fe2O3/Fe-CN interface enables more photogenerated electrons to participate in the Fe3+/Fe2+ conversion and H2O2 activation. The trapping experiments demonstrate that •OH and •O2- are the primary active species in TC degradation. This work presents novel insights into the design of efficient heterogeneous Fenton catalysts for practical applications.


Ferric Compounds , Hydrogen Peroxide , Iron , Quantum Dots , Catalysis , Ferric Compounds/chemistry , Iron/chemistry , Hydrogen Peroxide/chemistry , Quantum Dots/chemistry , Photochemical Processes , Nitriles/chemistry , Porosity , Graphite , Nitrogen Compounds
12.
Langmuir ; 40(20): 10718-10725, 2024 May 21.
Article En | MEDLINE | ID: mdl-38728259

For accurate in vivo detection, nonspecific adsorption of biomacromolecules such as proteins and cells is a severe issue. The adsorption leads to electrode passivation, significantly compromising both the sensitivity and precision of sensing. Meanwhile, common antibiofouling modifications, such as polymer coatings, still grapple with issues related to biocompatibility, electrode passivation, and miniaturization. Herein, we propose a composite antibiofouling coating strategy based on zwitterionic metal-organic frameworks (Z-MOFs) and a combination of acrylamide hydrogels. On a well-designed TiO2/Z-MOF/hydrogel photoelectrode, we achieve highly sensitive and selective detection of dopamine in complex biological environments. The hydrogel's three-dimensional porous structure combined with unique microporous architecture of Z-MOF ensures effective sieving of interfering macromolecules while preserving efficient small molecules and electron transport. This innovative approach paves the way for constructing miniature, in vivo antibiofouling sensors for molecule monitoring in living organisms with complicated chemical environments.


Biosensing Techniques , Dopamine , Hydrogels , Titanium , Hydrogels/chemistry , Dopamine/analysis , Dopamine/chemistry , Biosensing Techniques/methods , Titanium/chemistry , Biofouling/prevention & control , Electrochemical Techniques/methods , Photochemical Processes , Metal-Organic Frameworks/chemistry , Biocompatible Materials/chemistry , Electrodes
13.
Anal Chim Acta ; 1306: 342585, 2024 Jun 01.
Article En | MEDLINE | ID: mdl-38692786

Herein, we developed a convenient and versatile dual-mode electrochemiluminescence (ECL) and photoelectrochemistry (PEC) sensing radar for the detection of Prostate-specific antigen (PSA), which has important implications for detection of low-abundance disease-associated proteins. Cerium-based metal-organic framework (Ce-MOFs) were firstly modified on the electrode, showing well ECL and PEC property. In particular, a unique multifunctional Au@CdS quantum dots (QDs) probe loaded numerous QDs and antibody was fabricated, not only displaying strong ECL and PEC signals, but also having specific recognition to PSA. After the signal probe was linked to the electrode by immune reaction, much amplified signals of ECL and PEC were generated for double-mode detection of PSA. Therefore, this work proposed a multifunctional Au@CdS QDs signal probe with excellent ECL and PEC performance, and developed an ultrasensitive photoelectric biosensing platform for dual-mode detection, which provides an effective method for health monitoring of cancer patients.


Cadmium Compounds , Electrochemical Techniques , Metal-Organic Frameworks , Prostate-Specific Antigen , Quantum Dots , Sulfides , Quantum Dots/chemistry , Cadmium Compounds/chemistry , Sulfides/chemistry , Humans , Prostate-Specific Antigen/analysis , Prostate-Specific Antigen/blood , Metal-Organic Frameworks/chemistry , Gold/chemistry , Cerium/chemistry , Biosensing Techniques , Photochemical Processes , Limit of Detection , Electrodes , Luminescent Measurements
14.
Sci Rep ; 14(1): 10406, 2024 05 06.
Article En | MEDLINE | ID: mdl-38710736

Active pharmaceutical ingredients have emerged as an environmentally undesirable element because of their widespread exploitation and consequent pollution, which has deleterious effects on living things. In the pursuit of sustainable environmental remediation, biomedical applications, and energy production, there has been a significant focus on two-dimensional materials (2D materials) owing to their unique electrical, optical, and structural properties. Herein, we have synthesized 2D zinc oxide nanosheets (ZnO NSs) using a facile and practicable hydrothermal method and characterized them thoroughly using spectroscopic and microscopic techniques. The 2D nanosheets are used as an efficient photocatalyst for antibiotic (herein, end-user ciprofloxacin (CIP) was used as a model antibiotic) degradation under sunlight. It is observed that ZnO NSs photodegrade ~ 90% of CIP within two hours of sunlight illumination. The molecular mechanism of CIP degradation is proposed based on ex-situ IR analysis. Moreover, the 2D ZNO NSs are used as an antimicrobial agent and exhibit antibacterial qualities against a range of bacterial species, including Escherichia coli, Staphylococcus aureus, and MIC of the bacteria are found to be 5 µg/l and 10 µg/l, respectively. Despite having the biocompatible nature of ZnO, as-synthesized nanosheets have also shown cytotoxicity against two types of cancer cells, i.e. A549 and A375. Thus, ZnO nanosheets showed a nontoxic nature, which can be exploited as promising alternatives in different biomedical applications.


Anti-Bacterial Agents , Antineoplastic Agents , Nanostructures , Zinc Oxide , Zinc Oxide/chemistry , Zinc Oxide/pharmacology , Humans , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Catalysis , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Nanostructures/chemistry , Escherichia coli/drug effects , Ciprofloxacin/pharmacology , Ciprofloxacin/chemistry , Staphylococcus aureus/drug effects , Microbial Sensitivity Tests , Cell Line, Tumor , Photochemical Processes , Photolysis
15.
Luminescence ; 39(5): e4758, 2024 May.
Article En | MEDLINE | ID: mdl-38712530

The ability of heterogeneous photocatalysis to effectively remove organic pollutants from wastewater has shown great promise as a tool for environmental remediation. Pure zinc ferrites (ZnFe2O4) and magnesium-doped zinc ferrites (Mg@ZnFe2O4) with variable percentages of Mg (0.5, 1, 3, 5, 7, and 9 mol%) were synthesized via hydrothermal route and their photocatalytic activity was checked against methylene blue (MB) taken as a model dye. FTIR, XPS, BET, PL, XRD, TEM, and UV-Vis spectroscopy were used for the identification and morphological characterization of the prepared nanoparticles (NPs) and nanocomposites (NCs). The 7% Mg@ZnFe2O4 NPs demonstrated excellent degradation against MB under sunlight. The 7% Mg@ZnFe2O4 NPs were integrated with diverse contents (10, 50, 30, and 70 wt.%) of S@g-C3N4 to develop NCs with better activity. When the NCs were tested to degrade MB dye, it was revealed that the 7%Mg@ZnFe2O4/S@g-C3N4 NCs were more effective at utilizing solar energy than the other NPs and NCs. The synergistic effect of the interface formed between Mg@ZnFe2O4 and S@g-C3N4 was primarily responsible for the boosted photocatalytic capability of the NCs. The fabricated NCs may function as an effective new photocatalyst to remove organic dyes from wastewater.


Ferric Compounds , Methylene Blue , Nitrogen Compounds , Solar Energy , Water Pollutants, Chemical , Zinc , Catalysis , Water Pollutants, Chemical/chemistry , Ferric Compounds/chemistry , Methylene Blue/chemistry , Zinc/chemistry , Magnesium/chemistry , Photolysis , Photochemical Processes , Coloring Agents/chemistry , Nanocomposites/chemistry , Graphite/chemistry , Wastewater/chemistry , Nitriles/chemistry
16.
J Am Chem Soc ; 146(19): 13598-13606, 2024 May 15.
Article En | MEDLINE | ID: mdl-38691811

Nucleic acid-binding dyes (NuABDs) are fluorogenic probes that light up after binding to nucleic acids. Taking advantage of their fluorogenicity, NuABDs have been widely utilized in the fields of nanotechnology and biotechnology for diagnostic and analytical applications. We demonstrate the potential of NuABDs together with an appropriate nucleic acid scaffold as an intriguing photocatalyst for precisely controlled atom-transfer radical polymerization (ATRP). Additionally, we systematically investigated the thermodynamic and electrochemical properties of the dyes, providing insights into the mechanism that drives the photopolymerization. The versatility of the NuABD-based platform was also demonstrated through successful polymerizations using several NuABDs in conjunction with diverse nucleic acid scaffolds, such as G-quadruplex DNA or DNA nanoflowers. This study not only extends the horizons of controlled photopolymerization but also broadens opportunities for nucleic acid-based materials and technologies, including nucleic acid-polymer biohybrids and stimuli-responsive ATRP platforms.


Fluorescent Dyes , Photochemical Processes , Polymerization , Catalysis , Fluorescent Dyes/chemistry , Free Radicals/chemistry , DNA/chemistry , Nucleic Acids/chemistry , G-Quadruplexes
17.
J Am Chem Soc ; 146(19): 13617-13628, 2024 May 15.
Article En | MEDLINE | ID: mdl-38695163

Here, we present a cross-linking approach to covalently functionalize and stabilize DNA origami structures in a one-pot reaction. Our strategy involves adding nucleotide sequences to adjacent staple strands, so that, upon assembly of the origami structure, the extensions form short hairpin duplexes targetable by psoralen-labeled triplex-forming oligonucleotides bearing other functional groups (pso-TFOs). Subsequent irradiation with UVA light generates psoralen adducts with one or both hairpin staples leading to site-specific attachment of the pso-TFO (and attached group) to the origami with ca. 80% efficiency. Bis-adduct formation between strands in proximal hairpins further tethers the TFO to the structure and generates "superstaples" that improve the structural integrity of the functionalized complex. We show that directing cross-linking to regions outside of the origami core dramatically reduces sensitivity of the structures to thermal denaturation and disassembly by T7 RNA polymerase. We also show that the underlying duplex regions of the origami core are digested by DNase I and thus remain accessible to read-out by DNA-binding proteins. Our strategy is scalable and cost-effective, as it works with existing DNA origami structures, does not require scaffold redesign, and can be achieved with just one psoralen-modified oligonucleotide.


Cross-Linking Reagents , DNA , Nucleic Acid Conformation , Ultraviolet Rays , DNA/chemistry , Cross-Linking Reagents/chemistry , Photochemical Processes , Ficusin/chemistry
18.
Org Lett ; 26(19): 4065-4070, 2024 May 17.
Article En | MEDLINE | ID: mdl-38696591

We introduce a novel and straightforward methodology for photoredox arylation of an indole scaffold using aryldiazonium salts under mild and metal-free conditions. Our approach enables the regioselective and chemoselective introduction of several aryl groups to the C(2) position of indoles and tryptophan, even in competition with other amino acids. This approach extends to the late-stage functionalization of peptides and lysozyme, heralding the unprecedented arylation of tryptophan residues in wild-type proteins and offering broad utility in chemical biology.


Indoles , Oxidation-Reduction , Tryptophan , Tryptophan/chemistry , Indoles/chemistry , Molecular Structure , Photochemical Processes , Muramidase/chemistry , Peptides/chemistry , Stereoisomerism , Catalysis
19.
Nat Commun ; 15(1): 4025, 2024 May 13.
Article En | MEDLINE | ID: mdl-38740804

Intracellular membranes composing organelles of eukaryotes include membrane proteins playing crucial roles in physiological functions. However, a comprehensive understanding of the cellular responses triggered by intracellular membrane-focused oxidative stress remains elusive. Herein, we report an amphiphilic photocatalyst localised in intracellular membranes to damage membrane proteins oxidatively, resulting in non-canonical pyroptosis. Our developed photocatalysis generates hydroxyl radicals and hydrogen peroxides via water oxidation, which is accelerated under hypoxia. Single-molecule magnetic tweezers reveal that photocatalysis-induced oxidation markedly destabilised membrane protein folding. In cell environment, label-free quantification reveals that oxidative damage occurs primarily in membrane proteins related to protein quality control, thereby aggravating mitochondrial and endoplasmic reticulum stress and inducing lytic cell death. Notably, the photocatalysis activates non-canonical inflammasome caspases, resulting in gasdermin D cleavage to its pore-forming fragment and subsequent pyroptosis. These findings suggest that the oxidation of intracellular membrane proteins triggers non-canonical pyroptosis.


Inflammasomes , Membrane Proteins , Oxidation-Reduction , Pyroptosis , Humans , Inflammasomes/metabolism , Membrane Proteins/metabolism , Oxidative Stress , Catalysis , Endoplasmic Reticulum Stress , Hydrogen Peroxide/metabolism , Phosphate-Binding Proteins/metabolism , Hydroxyl Radical/metabolism , Mitochondria/metabolism , Intracellular Membranes/metabolism , Intracellular Signaling Peptides and Proteins/metabolism , Mice , Animals , Photochemical Processes , Protein Folding , Caspases/metabolism , Gasdermins
20.
Int J Mol Sci ; 25(9)2024 Apr 26.
Article En | MEDLINE | ID: mdl-38731960

Due to a large number of harmful chemicals flowing into the water source in production and life, the water quality deteriorates, and the use value of water is reduced or lost. Biochar has a strong physical adsorption effect, but it can only separate pollutants from water and cannot eliminate pollutants fundamentally. Photocatalytic degradation technology using photocatalysts uses chemical methods to degrade or mineralize organic pollutants, but it is difficult to recover and reuse. Woody biomass has the advantages of huge reserves, convenient access and a low price. Processing woody biomass into biochar and then combining it with photocatalysts has played a complementary role. In this paper, the shortcomings of a photocatalyst and biochar in water treatment are introduced, respectively, and the advantages of a woody biochar-based photocatalyst made by combining them are summarized. The preparation and assembly methods of the woody biochar-based photocatalyst starting from the preparation of biochar are listed, and the water treatment efficiency of the woody biochar-based photocatalyst using different photocatalysts is listed. Finally, the future development of the woody biochar-based photocatalyst is summarized and prospected.


Carbon , Charcoal , Water Purification , Wood , Water Purification/methods , Charcoal/chemistry , Catalysis , Wood/chemistry , Carbon/chemistry , Water Pollutants, Chemical/chemistry , Photochemical Processes , Adsorption
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