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1.
Nano Lett ; 24(25): 7698-7705, 2024 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-38869496

RESUMO

Highly efficient recognition of cancer cells by immune cells is important for successful therapeutic-cell-based cancer immunotherapy. Herein, we present a facile NIR-II nanoadaptor [hyaluronic acid (HA)/dibenzocyclooctyne (DBCO)-Au:Ag2Te quantum dots (QDs)] for enhancing the tumor recognition and binding ability of natural killer (NK) cells via a bio-orthogonal click reaction in vivo. The Nanoadaptor possesses superior tumor-targeting capacity, facilitating the accumulation of the chemical receptor DBCO at the tumor sites. Subsequently, the enrichment of DBCO on tumor cell surfaces provides multivalent recognition sites for capturing pretreated azide engineered NK92 cells (NK92-N3) through an efficient click reaction, thereby significantly enhancing the therapeutical efficiency. The dynamic process of nanoadaptor-mediated recognition of NK cells to tumor cells could be vividly observed using multiplexed NIR-II fluorescence imaging in a mouse model of lung cancer. Such a nanoadaptor strategy can be extended to other therapeutic cellular systems and holds promise for future clinical applications.


Assuntos
Química Click , Células Matadoras Naturais , Células Matadoras Naturais/imunologia , Animais , Camundongos , Humanos , Pontos Quânticos/química , Ácido Hialurônico/química , Linhagem Celular Tumoral , Neoplasias Pulmonares/imunologia , Neoplasias Pulmonares/patologia , Ouro/química , Imunoterapia
2.
Nano Lett ; 2024 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-39036992

RESUMO

Extremely small iron oxide nanoparticle (ESIONP)-based stimuli-responsive switchable MRI contrast agents (CAs) show great promise for accurate detection of tumors due to their outstanding advantages of high specificity and low background signal. However, currently developed ESIONP-based switchable CAs often suffer single-biomarker-induced responses, which lack absolute specificity to pathological tissues, potentially diminishing diagnostic accuracy. In this study, weak acidity and hypoxia, two of the most remarkable characteristics of tumors, are introduced as dual biomarker stimuli to construct an ESIONP-based switchable MRI CA (DKL-CA), with its signal switch controlled by a "dual-key-and-lock" strategy. Only when DKL-CA is exposed to a coexisting weakly acidic and hypoxic environment can monodispersed ESIONPs form nanoclusters, thereby realizing a switch from the T1 to T2 contrast. Moreover, DKL-CA exhibits favorable biosafety and the capacity for precise tumor diagnosis in tumor-bearing mice. Overall, DKL-CA paves the way for designing highly accurate ESIONP-based MRI CAs for tumor diagnosis.

3.
J Lipid Res ; 65(7): 100570, 2024 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-38795858

RESUMO

Glycosphingolipids (GSLs) are abundant glycolipids on cells and essential for cell recognition, adhesion, signal transduction, and so on. However, their lipid anchors are not long enough to cross the membrane bilayer. To transduce transmembrane signals, GSLs must interact with other membrane components, whereas such interactions are difficult to investigate. To overcome this difficulty, bifunctional derivatives of II3-ß-N-acetyl-D-galactosamine-GA2 (GalNAc-GA2) and ß-N-acetyl-D-glucosamine-ceramide (GlcNAc-Cer) were synthesized as probes to explore GSL-interacting membrane proteins in live cells. Both probes contain photoreactive diazirine in the lipid moiety, which can crosslink with proximal membrane proteins upon photoactivation, and clickable alkyne in the glycan to facilitate affinity tag addition for crosslinked protein pull-down and characterization. The synthesis is highlighted by the efficient assembly of simple glycolipid precursors followed by on-site lipid remodeling. These probes were employed to profile GSL-interacting membrane proteins in HEK293 cells. The GalNAc-GA2 probe revealed 312 distinct proteins, with GlcNAc-Cer probe-crosslinked proteins as controls, suggesting the potential influence of the glycan on GSL functions. Many of the proteins identified with the GalNAc-GA2 probe are associated with GSLs, and some have been validated as being specific to this probe. The versatile probe design and experimental protocols are anticipated to be widely applicable to GSL research.

4.
Small ; 20(30): e2312112, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38409650

RESUMO

Harvesting freshwater from fog is one of the possible solutions to the global water scarcity crisis. Surfaces with both hydrophobic and hydrophilic regions are extensively employed for this purpose. Nevertheless, the longevity of these surfaces is still constrained by their delicate surface structures. The hydrophilic zones may become damaged or contaminated after repeated use, thereby compromising their effectiveness in fog collection. The preparation of generally applicable durable superhydrophobic coatings with self-generated Wenzel sites is reported here for long-term efficient and stable fog collection. The coatings are prepared by depositing the poly(tannic acid) coating as the primer layer on various substrates, self-assembly of trichlorovinylsilane into staggered silicone nanofilaments, and then thiol-ene click reaction with 1H,1H,2H,2H-perfluorodecanethiol. The coatings demonstrate remarkable static superhydrophobicity, robust impalement resistance, and stable self-generated Wenzel sites for water droplets. Therefore, the fog collection rate (FCR) of the coatings reaches 2.13 g cm-2 h-1 during 192 h continuous fog collection, which is triple that of bare substrate and outperforms most previous studies. Moreover, the systematic experiments and models have revealed that the key factors for achieving high FCR on superhydrophobic coatings are forming condensed droplets ≈1 mm in critical radius and a Wenzel site proportion of 0.3-0.4.

5.
Small ; : e2311351, 2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38453673

RESUMO

Supramolecular self-assembly has emerged as an efficient tool to construct well-organized nanostructures for biomedical applications by small organic molecules. However, the physicochemical properties of self-assembled nanoarchitectures are greatly influenced by their morphologies, mechanical properties, and working mechanisms, making it challenging to design and screen ideal building blocks. Herein, using a biocompatible firefly-sourced click reaction between the cyano group of 2-cyano-benzothiazole (CBT) and the 1,2-aminothiol group of cysteine (Cys), an amino-acid-encoded supramolecular self-assembly platform Cys(SEt)-X-CBT (X represents any amino acid) is developed to incorporate both covalent and noncovalent interactions for building diverse morphologies of nanostructures with bioinspired response mechanism, providing a convenient and rapid strategy to construct site-specific nanocarriers for drug delivery, cell imaging, and enzyme encapsulation. Additionally, it is worth noting that the biodegradation of Cys(SEt)-X-CBT generated nanocarriers can be easily tracked via bioluminescence imaging. By caging either the thiol or amino groups in Cys with other stimulus-responsive sites and modifying X with probes or drugs, a variety of multi-morphological and multifunctional nanomedicines can be readily prepared for a wide range of biomedical applications.

6.
Small ; 20(23): e2307309, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38150611

RESUMO

Ferroptosis is associated with the occurrence and development of many diseases, which is the result of an imbalance in cellular metabolism and oxidation-reduction balance. Therefore, it is an effective therapeutic strategy that simultaneously regulating the intracellular oxidation-reduction system. Herein, a click reaction of alkynylamide with thiol groups in the presence of amine or in PBS (pH = 7.4) is developed, which can react efficiently with thiol substances, such as cysteine (Cys), glutathione (GSH), and bovine serum albumin (BSA). Notably, MBTB-PA, an aggregation-induced emission (AIE) photosensitizer with an alkynylamide unit, is synthesized and its intracellular behavior is visualized in situ by fluorescence imaging, demonstrating its excellent ability to target the endoplasmic reticulum. Furthermore, MBTB-PA reacted with proteins in tumor cells, consumed reducing substances, and triggered intracellular oxidative stress, resulting in cell death. Based on this reaction therapy strategy, click reaction is combined with photodynamic therapy to achieve effective killing of tumor cells by simultaneously raising the intracellular oxidative state and reducing the reductive state. This work not only develops an application of click reaction of alkynamide with thiol in bioconjugation and anti-tumor therapy, but also provides feasible ideas for organic reactions in the exploration of organisms.


Assuntos
Química Click , Compostos de Sulfidrila , Compostos de Sulfidrila/química , Humanos , Linhagem Celular Tumoral , Animais , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/uso terapêutico
7.
Small ; 20(25): e2310799, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38213014

RESUMO

In the evolving landscape of water treatment, membrane technology has ascended to an instrumental role, underscored by its unmatched efficacy and ubiquity. Diverse synthesis and modification techniques are employed to fabricate state-of-the-art liquid separation membranes. Click reactions, distinguished by their rapid kinetics, minimal byproduct generation, and simple reaction condition, emerge as a potent paradigm for devising eco-functional materials. While the metal-free thiol-ene click reaction is acknowledged as a viable approach for membrane material innovation, a systematic elucidation of its applicability in liquid separation membrane development remains conspicuously absent. This review elucidates the pre-functionalization strategies of substrate materials tailored for thiol-ene reactions, notably highlighting thiolation and introducing unsaturated moieties. The consequential implications of thiol-ene reactions on membrane properties-including trade-off effect, surface wettability, and antifouling property-are discussed. The application of thiol-ene reaction in fabricating various liquid separation membranes for different water treatment processes, including wastewater treatment, oil/water separation, and ion separation, are reviewed. Finally, the prospects of thiol-ene reaction in designing novel liquid separation membrane, including pre-functionalization, products prediction, and solute-solute separation membrane, are proposed. This review endeavors to furnish invaluable insights, paving the way for expanding the horizons of thiol-ene reaction application in liquid separation membrane fabrication.

8.
Chemistry ; 30(40): e202400839, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38739300

RESUMO

1,2,4-triazines are a valuable class of heterodienes that can be employed in inverse electron-demand Diels-Alder reactions. However, their broader application in bioorthogonal chemistry is limited due to their low reactivity. This article focuses on 3-(trifluoromethyl)-1,2,4-triazines, which can be efficiently prepared in a one-pot reaction from NH-1,2,3-triazoles. These triazines are highly reactive in reactions with strained cyclooctenes, giving second-order rate constants as high as 230 M-1 s-1. Despite their high reactivity, the compounds remain sufficiently stable under biologically relevant conditions. We show that some of the compounds are fluorogenic, a property of potential use in bioimaging. In addition, we demonstrate the successful application of the triazines in labeling model biomolecules. Our work shows that the reactivity of 1,2,4-triazines can be enhanced by the 3-CF3-substitution, which we consider an important step toward the wider use of this promising class of reagents.

9.
Chemistry ; : e202401827, 2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-38989584

RESUMO

While rare earth elements (REEs) are essential for modern technology, their production methods raise concerns for agriculture. Researchers are now exploring ways to control and recycle REEs pollution, aiming to minimize agricultural impacts and potentially even develop methods to utilize these elements for improved crop yields. Regarding this issue, a new type of pillar[5]arene polymer (Pol-P[5]-BTZP) has been designed and synthesized by click reaction to enhance the efficiency of adsorption and recovery of rare earth metals. This polymer incorporates the unique structure of 2,6-di-1,2,3-triazolyl-pyridine. The results of various analyses revealed that Pol-P[5]-BTZP exhibits excellent thermal stability, a high specific surface area, and well-distributed networks of micropores and mesoporous structures. The adsorption capacity of Pol-P[5]-BTZP for Tm3+, a representative REE, was evaluated using the Langmuir and Freundlich isothermal adsorption models with a maximum adsorption capacity (Qmax) of 127.71 mg/g. Furthermore, the versatility of Pol-P[5]-BTZP in adsorption and recovering various REEs was tested. In addition to its adsorption capabilities, the potential of Pol-P[5]-BTZP for rare earth recovery and reuse was assessed through experiments on the impact of Tm3+ and La3+ on seed germination. These experiments demonstrated the wide-ranging applicability of Pol-P[5]-BTZP in recovering and reusing REEs for green agriculture.

10.
Chemistry ; 30(15): e202303596, 2024 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-38133633

RESUMO

Water-soluble organic cages are attractive targets for their molecular recognition and sensing features of biologically relevant molecules. Here, we have successfully designed and synthesized a pair of water-soluble cationic cages employing click reaction as the fundamental step followed by the N-methylation of the triazole rings. The rigid and shape-persistent 3D hydrophobic cavity, positively charged surface, H-bonding triazolium rings, and excellent water solubility empower both cages to exhibit a superior affinity and selectivity for binding with adenosine-5'-triphosphate (ATP) compared to cyclophanes and other macrocyclic receptors. Both cage molecules (PCC⋅Cl and BCC⋅Cl) can bind a highly emissive dye HPTS (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt) to form non-fluorescent complexes. The addition of ATP resulted in the stronger cage⊂ATP complexes with the retention of HPTS emission upon its displacement. The resultant indicator-displacement assay system can efficiently sense and quantify ATP in nanomolar detection limits in buffer solutions and human serum matrix. Spectroscopic and theoretical studies revealed the synergistic effect of π⋅⋅⋅π stacking interaction between the aromatic moiety of the cationic cages and the adenine moiety of ATP, as well as the electrostatic and hydrogen bonding interaction between the phosphate anion of ATP and triazole protons of cages, played the pivotal roles in the sensing process.


Assuntos
Adenina , Trifosfato de Adenosina , Humanos , Bioensaio , Ciclofanos , Prótons , Triazóis
11.
Chemistry ; 30(14): e202400092, 2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38311590

RESUMO

Fluorescent polymeric materials have been exploited in the fields of aesthetical purposes, biomedical engineering, and three-dimensional printing applications. While the fluorescent materials are prepared by the polymerization of fluorescent monomer or the blending a fluorescent dye with common polymer, the covalent immobilization of fluorescent dye onto common polymers is not the practical technique. In this paper, dansylated nitrile N-oxide (Dansyl-NO) has been designed and synthesized to be a stable nitrile N-oxide as the derivative of 2-hydroxy-1-naphthaldehyde. While Dansyl-NO shows good reactivity to an alkene and an alkyne to give fluorescent Dansyl-Ene and Dansyl-Yne, respectively, it hardly reacts to a nitrile. The results indicate that Dansyl-NO serves as a fluorescent dye clickable to alkenes and alkynes. To know the effects of solvent on the fluorescent properties, the UV-vis and fluorescence spectra of Dansyl-Ene are measured in three solvents. Dansyl-Ene shows fluorescent solvatochromism, which appears to be red-shifted along with the increase in solvent polarity. Poly(styrene-co-butadiene) directly reacts with Dansyl-NO to give fluorescent modified SB. The emission spectrum of modified SB is blue-shifted compared with that of Dansyl-Ene. The blue-shift could be possibly attributed to the presence of less polar polymer skeleton around the dansyl moieties of modified SB.

12.
Bioorg Chem ; 146: 107262, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38467092

RESUMO

Modern classes of antimicrobials are crucial because most drugs in development today are basically antibiotic derivatives. Even though a large number of metal-based compounds have been studied as antimicrobial agents, relatively few studies have examined the antimicrobial properties of Pd(II) and Pt(II) compounds. The [3+2] cycloaddition reactions of [M(N3)L]PF6 (M = Pd(II) and Pt(II); L = 4'-(2-pyridyl)-2,2':6',2″-terpyridine) with 4,4,4-trifluoro-2-butynoic acid ethyl ester gave the corresponding triazolate complexes. The reaction products were fully characterized with a variety of analytical and spectroscopic tools including X-ray crystallographic analysis. The crystal structure of [Pd(triazolatoCF3,COOCH2CH3)L]PF6 provided cut-off evidence that the kinetically formed N1-triazolato isomer favoured the isomerization to the thermodynamically stable N2-analogue. The experimental work was complemented with computational work to get an insight into the nature of the predominant triazolate isomer. The lysozyme binding affinity of the triazolate complexes was examined by mass spectrometry. An analysis of the lysozyme Pd(II) adducts suggests a coordinative covalent mode of binding via the loss of the triazolato ligand. The free ligand and its triazolate complexes displayed selective toxicity against Candida albicans and Cryptococcus neoformans, while no cytotoxicity was observed against the normal human embryonic kidney cell line.


Assuntos
Anti-Infecciosos , Muramidase , Humanos , Anti-Infecciosos/farmacologia , Reação de Cicloadição , Isomerismo , Ligantes , Platina/química , Chumbo/química
13.
Mikrochim Acta ; 191(3): 151, 2024 02 22.
Artigo em Inglês | MEDLINE | ID: mdl-38386184

RESUMO

A novel luminol derivative of N-(1,4-dioxo-1,2,3,4-tetrahydrophthalazin-5-yl)acrylamide (DTA) with excellent luminescence efficiency was designed and synthesized. Furthermore, a molecularly imprinted electrochemiluminescence sensor (MIECLS) was fabricated to detect ultratrace levels of human serum albumin (HSA) with high sensitivity and selectivity via a click reaction. The molecularly imprinted polymers (MIPs) were formed on the electrode surface via electropolymerization with HSA as a template molecule and catechol as a monomer. In the detection process, the -SH group of HSA on the electrode and the C = C bond of acryloyl group in DTA formed a new C-S bond via the Michael addition reaction to construct the MIECLS. The higher the concentration of HSA, the greater electrochemiluminescence (ECL) intensity measured. Taking advantage of MIECLS for ECL detection (scanning potential, - 0.4 to 0.5 V), there was a good linear relationship between ECL intensity and the logarithm of HSA concentration in the range 5 × 10-9 to 1 × 10-13 mg mL-1. The limit of detection (LOD) of the sensor was 1.05 × 10-15 mg mL-1. The sensor exhibited outstanding selectivity and stability. The sensor was applied to detect HSA in human serum with good recoveries of 97.7-105.2%. The concentration of HSA was detected by electrochemical method using the gating effect of MIP.


Assuntos
Acrilamida , Luminol , Humanos , Técnicas Eletroquímicas , Eletrodos , Albumina Sérica Humana
14.
Arch Pharm (Weinheim) ; 357(4): e2300673, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38247229

RESUMO

In the face of escalating challenges of microbial resistance strains, this study describes the design and synthesis of 5-({1-[(1H-1,2,3-triazol-4-yl)methyl]-1H-indol-3-yl}methylene)thiazolidine-2,4-dione derivatives, which have demonstrated significant antimicrobial properties. Compared with the minimum inhibitory concentrations (MIC) values of ciprofloxacin on the respective strains, compounds 5a, 5d, 5g, 5l, and 5m exhibited potent antibacterial activity with MIC values ranging from 16 to 25 µM. Almost all the synthesized compounds showed lower MIC compared to standards against vancomycin-resistant enterococcus and methicillin-resistant Staphylococcus aureus strains. Additionally, the majority of the synthesized compounds demonstrated remarkable antifungal activity, against Candida albicans and Aspergillus niger, as compared to nystatin, griseofulvin, and fluconazole. Furthermore, the majority of compounds exhibited notable inhibitory effects against the Plasmodium falciparum strain, having IC50 values ranging from 1.31 to 2.79 µM as compared to standard quinine (2.71 µM). Cytotoxicity evaluation of compounds 5a-q on SHSY-5Y cells at up to 100 µg/mL showed no adverse effects. Comparison with control groups highlights their noncytotoxic characteristics. Molecular docking confirmed compound binding to target active sites, with stable protein-ligand complexes displaying drug-like molecules. Molecular dynamics simulations revealed dynamic stability and interactions. Rigorous tests and molecular modeling unveil the effectiveness of the compounds against drug-resistant microbes, providing hope for new antimicrobial compounds with potential safety.


Assuntos
Antimaláricos , Staphylococcus aureus Resistente à Meticilina , Tiazolidinedionas , Antibacterianos/química , Antimaláricos/farmacologia , Triazóis/farmacologia , Simulação de Acoplamento Molecular , Relação Estrutura-Atividade , Indóis/farmacologia , Testes de Sensibilidade Microbiana , Estrutura Molecular
15.
Nano Lett ; 23(13): 6178-6183, 2023 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-37363812

RESUMO

Apoptosis, with a hallmark of upregulated protease Caspase-3, has been frequently imaged with various probes to reveal the therapeutic efficiencies of different drugs. However, activatable molecular probes with programmable self-assembling behaviors that enable enhanced T1-weighted magnetic resonance imaging (MRI) of apoptosis remain scarce. Herein, taking advantage of a CBT-Cys click reaction, we rationally designed a Caspase-3-activatable self-assembling probe Ac-Asp-Glu-Val-Asp-Cys(StBu)-Lys(DOTA(Gd))-CBT (DEVDCS-Gd-CBT) for apoptosis imaging in vivo. After Caspase-3 cleavage in apoptotic cells, DEVDCS-Gd-CBT underwent CBT-Cys click reaction to form a cyclic dimer, which self-assembled into Gd nanoparticles. With this probe, enhanced T1-weighted MR images of apoptosis were achieved at low magnetic fields in vitro, in cis-dichlorodiamineplatinum-induced apoptotic cells and in tail-amputation-simulated apoptotic zebrafish. We anticipate that the smart probe DEVDCS-Gd-CBT could be applied for T1-weighted MRI of apoptosis-related diseases in the clinic in the future.


Assuntos
Gadolínio , Nanopartículas , Animais , Caspase 3 , Peixe-Zebra , Imageamento por Ressonância Magnética/métodos , Apoptose , Meios de Contraste
16.
Molecules ; 29(13)2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38998962

RESUMO

Cancer is one of the deadliest diseases to humanity. There is significant progress in treating this disease, but developing some drugs that can fight this disease remains a challenge in the field of medical research. Thirteen new 1,2,3-triazole linked tetrahydrocurcumin derivatives were synthesized by click reaction, including a 1,3-dipolar cycloaddition reaction of tetrahydrocurcumin baring mono-alkyne with azides in good yields, and their in vitro anticancer activity against four cancer cell lines, including human cervical carcinoma (HeLa), human lung adenocarcinoma (A549), human hepatoma carcinoma (HepG2), and human colon carcinoma (HCT-116) were investigated using MTT(3-(4,5-dimethylthiazole-2-yl)-2,5-diphenyltetraz-olium bromide) assay. The newly synthesized compounds had their structures identified using NMR HRMS and IR techniques. Some of prepared compounds, including compounds 4g and 4k, showed potent cytotoxic activity against four cancer cell lines compared to the positive control of cisplatin and tetrahydrocurcumin. Compound 4g exhibited anticancer activity with a IC50 value of 1.09 ± 0.17 µM against human colon carcinoma HCT-116 and 45.16 ± 0.92 µM against A549 cell lines compared to the positive controls of tetrahydrocurcumin and cisplatin. Moreover, further biological examination in HCT-116 cells showed that compound 4g can arrest the cell cycle at the G1 phase. A docking study revealed that the potential mechanism by which 4g exerts its anti-colon cancer effect may be through inhabiting the binding of APC-Asef. Compound 4g can be used as a promising lead for further exploration of potential anticancer agents.


Assuntos
Antineoplásicos , Curcumina , Simulação de Acoplamento Molecular , Triazóis , Humanos , Curcumina/farmacologia , Curcumina/análogos & derivados , Curcumina/química , Curcumina/síntese química , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Triazóis/química , Triazóis/farmacologia , Triazóis/síntese química , Linhagem Celular Tumoral , Ensaios de Seleção de Medicamentos Antitumorais , Relação Estrutura-Atividade , Proliferação de Células/efeitos dos fármacos , Estrutura Molecular , Células A549 , Células HCT116 , Células Hep G2
17.
Molecules ; 29(6)2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38542827

RESUMO

Incorporation of a trifluoromethyl group with 1,2,3-triazoles motifs was described. We explored a click reaction approach for regioselective synthesis of 1-susbstituted-4-trifluoromethyl-1,2,3-triazoles in which 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) reacts with commercial 2-bromo-3,3,3-trifluoropropene (BTP) to form 3,3,3-trifloropropyne (TFP) in situ. Arising from merits associated with the availability and stability of BTP, and the high efficiencies of CuI/1,10-Phenanthroline (Phen)-catalyzed cycloaddition reactions of azides with alkynes, this readily performed click process takes place to form the target 1,2,3-triazoles in high yields, and with a wide azide substrate scope. The potential value of this protocol was demonstrated by its application to a gram-scale reaction.

18.
Angew Chem Int Ed Engl ; : e202408918, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39013139

RESUMO

The excessive and prolonged use of antibiotics contributes to the emergence of drug-resistant S. aureus strains and potential dysbacteriosis-related diseases, necessitating the exploration of alternative therapeutic approaches. Herein, we present a light-activated nanocatalyst for synthesizing in-situ antimicrobials through photoredox-catalytic click reaction, achieving precise, site-directed elimination of S. aureus skin infections. Methylene blue (MB), a commercially available photosensitizer, was encapsulated within the CuII-based metal-organic framework, MOF-199, and further enveloped with Pluronic F-127 to create the light-responsive nanocatalyst MB@PMOF. Upon exposure to red light, MB participates in a photoredox-catalytic cycle, driven by the 1,3,5-benzenetricarboxylic carboxylate salts (BTC-) ligand presented in the structure of MOF-199. This light-activated MB then catalyzes the reduction of CuII to CuI through a single-electron transfer (SET) process, efficiently initiating the click reaction to form active antimicrobial agents under physiological conditions. Both in vitro and in vivo results demonstrated the effectiveness of MB@PMOF-catalyzed drug synthesis in inhibiting S. aureus, including their methicillin-resistant strains, thereby accelerating skin healing in severe bacterial infections. This study introduces a novel design paradigm for controlled, on-site drug synthesis, offering a promising alternative to realize precise treatment of bacterial infections without undesirable side effects.

19.
Angew Chem Int Ed Engl ; 63(12): e202318898, 2024 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-38284482

RESUMO

Developing reversible-deactivation radical polymerization (RDRP) methods that could directly control the thiyl radical propagation is highly desirable yet remains challenging in modern polymer chemistry. Here, we reported the first reversible thiyl radical addition-fragmentation chain transfer (SRAFT) polymerization strategy, which utilizes allyl sulfides as chain transfer agents for reversibly deactivating the propagating thiyl radicals, thus allowing us to directly control a challenging thiyl radical chain polymerization to afford polymers with well-defined architectures. A linear dependence of molecular weight on conversion, high chain-end fidelity, and efficient chain extension proved good controllability of the polymerization. In addition, density functional theory calculations provided insight into the reversible deactivation ability of allyl sulfides. The SRAFT strategy developed in this work represents a promising platform for discovering new controlled polymerizations based on thiyl radical chemistry.

20.
Angew Chem Int Ed Engl ; 63(19): e202400511, 2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38488202

RESUMO

As ferroelectrics hold significance and application prospects in wearable devices, the elastification of ferroelectrics becomes more and more important. Nevertheless, achieving elastic ferroelectrics requires stringent synthesis conditions, while the elastification of relaxor ferroelectric materials remains unexplored, presenting an untapped potential for utilization in energy storage and actuation for wearable electronics. The thiol-ene click reaction offers a mild and rapid reaction platform to prepare functional polymers. Therefore, we employed this approach to obtain an elastic relaxor ferroelectric by crosslinking an intramolecular carbon-carbon double bonds (CF=CH) polymer matrix with multiple thiol groups via a thiol-ene click reaction. The resulting elastic relaxor ferroelectric demonstrates pronounced relaxor-type ferroelectric behaviour. This material exhibits low modulus, excellent resilience, and fatigue resistance, maintaining a stable ferroelectric response even under strains up to 70 %. This study introduces a straightforward and efficient approach for the construction of elastic relaxor ferroelectrics, thereby expanding the application possibilities in wearable electronics.

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