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1.
Nanotechnology ; 33(7)2021 Nov 25.
Article in English | MEDLINE | ID: mdl-34727538

ABSTRACT

Achieving an efficient and inexpensive bactericidal effect is a key point for the design of antibacterial agent. Recent advances have proved molybdenum disulfide (MoS2) as a promising platform for antimicrobial applications, while the combination of metal nanoparticle would promote the antibacterial efficiency. Nevertheless, the dispersivity, cheapness and safety of metal nanoparticle loaded on MoS2raised some concerns. In this paper, we successfully realized a uniform decoration of copper nanoparticles (CuNPs) on surface of MoS2nanosheets, and the size of CuNPs could be controlled below 5 nm. Under 5 min irradiation of 660 nm visible light, the synthesized CuNPs/MoS2composite demonstrated superior antibacterial performances (almost 100% bacterial killed) towards both Gram-negativeE. coliand Gram-positiveS. aureusover the single component (Cu or MoS2), while the bactericidal effect could last for at least 6 h. The synergism of photodynamic generated hydroxyl radical (·OH), oxidative stress without reactive oxygen species production and the release of Cu ions was considered as the mechanism for the antibacterial properties of CuNPs/MoS2. Our findings provided new insights into the development of two-dimensional antibacterial nanomaterials of high cost performance.


Subject(s)
Anti-Bacterial Agents , Bacteria/drug effects , Copper , Disulfides , Metal Nanoparticles , Molybdenum , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacokinetics , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/radiation effects , Copper/chemistry , Copper/pharmacokinetics , Copper/pharmacology , Copper/radiation effects , Disulfides/chemistry , Disulfides/pharmacology , Disulfides/radiation effects , Light , Metal Nanoparticles/chemistry , Metal Nanoparticles/radiation effects , Molybdenum/chemistry , Molybdenum/pharmacology , Molybdenum/radiation effects , Oxidative Stress/drug effects , Particle Size , Photochemical Processes
2.
ACS Appl Mater Interfaces ; 13(26): 31193-31205, 2021 Jul 07.
Article in English | MEDLINE | ID: mdl-34164984

ABSTRACT

Owing to the rise in prevalence of multidrug-resistant pathogens attributed to the overuse of antibiotics, infectious diseases caused by the transmission of microbes from contaminated surfaces to new hosts are an ever-increasing threat to public health. Thus, novel materials that can stem this crisis, while also functioning via multiple antimicrobial mechanisms so that pathogens are unable to develop resistance to them, are in urgent need. Toward this goal, in this work, we developed in situ grown bacterial cellulose/MoS2-chitosan nanocomposite materials (termed BC/MoS2-CS) that utilize synergistic membrane disruption and photodynamic and photothermal antibacterial activities to achieve more efficient bactericidal activity. The BC/MoS2-CS nanocomposite exhibited excellent antibacterial efficacy, achieving 99.998% (4.7 log units) and 99.988% (3.9 log units) photoinactivation of Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus, respectively, under visible-light illumination (xenon lamp, 500 W, λ ≥ 420 nm, and 30 min). Mechanistic studies revealed that the use of cationic chitosan likely facilitated bacterial membrane disruption and/or permeability, with hyperthermia (photothermal) and reactive oxygen species (photodynamic) leading to synergistic pathogen inactivation upon visible-light illumination. No mammalian cell cytotoxicity was observed for the BC/MoS2-CS membrane, suggesting that such composite nanomaterials are attractive as functional materials for infection control applications.


Subject(s)
Anti-Bacterial Agents/pharmacology , Disulfides/pharmacology , Molybdenum/pharmacology , Nanocomposites/chemistry , Photosensitizing Agents/pharmacology , Animals , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/radiation effects , Anti-Bacterial Agents/toxicity , Cell Line , Cellulose/chemistry , Cellulose/toxicity , Chitosan/chemistry , Chitosan/toxicity , Disulfides/chemistry , Disulfides/radiation effects , Disulfides/toxicity , Escherichia coli/drug effects , Heating , Light , Membranes, Artificial , Mice , Microbial Sensitivity Tests , Molybdenum/chemistry , Molybdenum/radiation effects , Molybdenum/toxicity , Nanocomposites/radiation effects , Nanocomposites/toxicity , Photosensitizing Agents/chemistry , Photosensitizing Agents/radiation effects , Photosensitizing Agents/toxicity , Reactive Oxygen Species/metabolism , Staphylococcus aureus/drug effects
3.
ACS Chem Biol ; 16(7): 1128-1141, 2021 07 16.
Article in English | MEDLINE | ID: mdl-34114796

ABSTRACT

Hydrogen sulfide (H2S) has gained significant attention as a potent bioregulator in the redox metabolome, but it is just one of many reactive sulfur species (RSS). Recently, small molecule persulfides (structure RSSH) have emerged as RSS of particular interest due to their enhanced antioxidant abilities compared to H2S and their ability to directly convert protein thiols into protein persulfides, suggesting that persulfides may have distinct physiological functions from H2S. However, persulfides exhibit instability and cross-reactivity that hampers the elucidation of their precise biological roles. As such, chemists have designed chemical tools and techniques to facilitate the study of persulfides under various conditions. These molecules and methods include persulfide trapping reagents and sensors, as well as compounds that degrade in response to various triggers to release persulfides, termed persulfide donors. There now exist a variety of persulfide donor classes, some of which possess tissue-targeting capabilities designed to mimic localized endogenous production of RSS. This Review briefly covers the physicochemical properties of persulfides, the endogenous production of small molecule persulfides, and their reactions with protein thiols and other reactive species. These introductory sections are followed by a discussion of chemical tools used in persulfide chemical biology, with critical analysis of recent advancements in the field and commentary on potential directions for future research.


Subject(s)
Sulfides/analysis , Sulfides/pharmacology , Animals , Cell Line, Tumor , Chemistry Techniques, Analytical , Disulfides/chemistry , Disulfides/metabolism , Disulfides/radiation effects , Humans , Indicators and Reagents/chemistry , Light , Oxidation-Reduction , Prodrugs/chemistry , Prodrugs/metabolism , Prodrugs/pharmacology , Prodrugs/radiation effects , Sulfides/chemistry , Sulfides/metabolism
4.
Dalton Trans ; 50(19): 6598-6619, 2021 May 18.
Article in English | MEDLINE | ID: mdl-33899890

ABSTRACT

MoS2 nanosheets were developed by undertaking the liquid-phase exfoliation of bulk counterparts. In order to enhance its photocatalytic properties, the host material was doped with p-type transition metals (i.e., Ag, Co, Bi, and Zr). The hydrothermal technique was used to produce samples doped with 7.5 wt% transition metals (TM). X-ray diffraction detected the existence of 2H-phase by mirroring its reflection at 2θ ∼ 14°, while the peak distribution revealed the degree of exfoliation in samples. Low PL intensities indicated a lower recombination of electron-hole pairs, as corroborated by a high degree of photocatalytic action. Raman analysis was undertaken to identify molecular vibrations. The A1g mode in Raman spectra consistently showed a blueshift in all samples and the E12g mode was only slightly affected, which is evidence of the p-type doping in the MoS2 nanosheets. In the XPS spectrum, two characteristic peaks of Mo 3d appeared at 229.87 and 233.03 eV assigned to Mo-3d5/2 and Mo-3d3/2, respectively. Furthermore, a microstructural examination with HR-TEM and FESEM divulged a thin-layered structure of MoS2 consisting of flat, gently curved or twisted nanosheets. Diverse morphologies were observed with a non-uniform distribution of the dopant. Photocatalytic action of the TM-doped products effectively degraded methylene blue (MB) concentrations of up to 94 percent (for Ag-MoS2). The synergistic effect of doped MoS2 nanosheets against S. aureus in comparison to E. coli bacteria was also evaluated. The efficacy % age improved from (0-31.7%) and (23.5-55.2%) against E. coli, and (0-34.2%) and (8.3-69.23%) against S. aureus. Moreover, results from first principles calculations indicate that substitutional doping of TM atoms is indeed advantageous. Theoretical calculations confirmed that doping with Ag, Co, Bi, and Zr leads to a decrease in the band gap to a certain degree, in which the conduction band edge shifts toward lower energy, while the valence band shifts closer to the high energy end. It can be concluded that Ag, Co, and Bi impurities can lead to beneficial p-type doping in MoS2 monolayered structures. With regards to doping with Zr, the acceptor levels are formed above the edge of the valence band, revealing an introduction of the p-type character.


Subject(s)
Anti-Bacterial Agents , Disulfides , Nanostructures , Transition Elements , Anti-Bacterial Agents/administration & dosage , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/radiation effects , Catalysis , Disulfides/administration & dosage , Disulfides/chemistry , Disulfides/radiation effects , Escherichia coli/drug effects , Escherichia coli/growth & development , Light , Methylene Blue/chemistry , Microscopy, Electron, Scanning , Microscopy, Electron, Transmission , Nanostructures/administration & dosage , Nanostructures/chemistry , Nanostructures/radiation effects , Nanostructures/ultrastructure , Staphylococcus aureus/drug effects , Staphylococcus aureus/growth & development , Transition Elements/administration & dosage , Transition Elements/chemistry , Transition Elements/radiation effects
5.
Mikrochim Acta ; 187(8): 480, 2020 08 02.
Article in English | MEDLINE | ID: mdl-32743701

ABSTRACT

MoS2 nanosheets were prepared by exfoliating MoS2 bulk crystals with ultrasonication in N-methylpyrrolidone and were integrated with gold nanostars (AuNS) to fabricate an AuNS/MoS2 nanocomposite. All nanomaterials were characterized by transmission electron microscope, scanning electron microscope, ultraviolet-visible spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. AuNS/MoS2 nanocomposites were coated onto a glassy carbon electrode (GCE) surface to construct a nanointerface for immobilizing neuron-specific enolase antibody (anti-NSE) thus forming a photoelectrochemical immunoassay system. AuNS can significantly promote the photoelectric conversion of MoS2 nanosheets improving the performance for a photoelectrochemical assay. Being illuminated with white light LED and controlling the potential at 0.05 V (vs. SCE), the photocurrent generated from anti-NSE(BSA)/AuNS/MoS2/GCE using 0.15 mol L-1 ascorbic acid as electron donor can be recorded with amperometry and used as an output signal for NSE quantitative assay. Under optimized experimental conditions, the photocurrent variation for the affinity-binding NSE is proportional to the logarithm of NSE concentration in the range 5.0 pg mL-1   to 1.5 ng mL-1 with a detection limit of 3.5 pg mL-1 (S/N = 3). The practicability of the PEC immunoassay system was evaluated by determining NSE in clinical serum samples. The recoveries ranged from 93.0 to 103% for the determination of NSE in serum samples with a standard addition method. The PEC immunoassay system possesses good accuracy for determining NSE in real samples. Graphical abstract.


Subject(s)
Disulfides/chemistry , Electrochemical Techniques/methods , Immunoassay/methods , Metal Nanoparticles/chemistry , Molybdenum/chemistry , Phosphopyruvate Hydratase/blood , Antibodies, Immobilized/immunology , Disulfides/radiation effects , Gold/chemistry , Humans , Light , Metal Nanoparticles/radiation effects , Molybdenum/radiation effects , Phosphopyruvate Hydratase/immunology , Photochemical Processes
6.
Braz J Anesthesiol ; 70(3): 233-239, 2020.
Article in Portuguese | MEDLINE | ID: mdl-32482354

ABSTRACT

BACKGROUND: The primary objective of this study was to investigate the effect of low dose ionizing radiation exposure on thiol/disulfide homeostasis and ischemia modified albumin levels. The secondary objective is to compare thiol/disulfide homeostasis and ischemia modified albumin levels among the personnel exposed to low dose ionizing radiation in anesthesia application areas, in and out of the Operation room. METHODS: The study included a total of 90 volunteers aged between 18 and 65 years old, with 45 personnel working in a setting with potential for radiation exposure (Exposed Group) and 45 personnel in a setting without radiation exposure (Control Group). Their native thiol, total thiol, disulphide, albumine and IMA levels were measured. Exposed group included personnel who were exposed to radiation outside the operating room - Operation room (-) Group and inside the Operating room - Operation room (+) Group. RESULTS: Albumin, native and total thiol levels were significantly lower in the participants exposed to radiation in the anesthesia application area, no statistically significant difference was found in terms of disulfide and ischemia modified albumin levels. In the Operation room (-) group exposed to radiation, native thiol and total thiol values were significantly lower compared to the Operation room (+) groups. CONCLUSION: Awareness of being in danger of oxidative stress should be established in personnel exposed to radiation in the anesthesia application area following low dose ionizing radiation exposure, and the necessary measures should be taken.


Subject(s)
Disulfides/blood , Disulfides/radiation effects , Homeostasis/radiation effects , Occupational Exposure , Radiation Dosage , Radiation Exposure , Radiation, Ionizing , Serum Albumin, Human/radiation effects , Sulfhydryl Compounds/blood , Sulfhydryl Compounds/radiation effects , Adolescent , Adult , Aged , Biomarkers/blood , Female , Humans , Male , Middle Aged , Operating Rooms , Prospective Studies , Young Adult
7.
Nat Chem ; 12(7): 603-607, 2020 07.
Article in English | MEDLINE | ID: mdl-32591744

ABSTRACT

Establishing how life can emerge from inanimate matter is among the grand challenges of contemporary science. Chemical systems that capture life's essential characteristics-replication, metabolism and compartmentalization-offer a route to understanding this momentous process. The synthesis of life, whether based on canonical biomolecules or fully synthetic molecules, requires the functional integration of these three characteristics. Here we show how a system of fully synthetic self-replicating molecules, on recruiting a cofactor, acquires the ability to transform thiols in its environment into disulfide precursors from which the molecules can replicate. The binding of replicator and cofactor enhances the activity of the latter in oxidizing thiols into disulfides through photoredox catalysis and thereby accelerates replication by increasing the availability of the disulfide precursors. This positive feedback marks the emergence of light-driven protometabolism in a system that bears no resemblance to canonical biochemistry and constitutes a major step towards the highly challenging aim of creating a new and completely synthetic form of life.


Subject(s)
Disulfides/chemistry , Light , Macrocyclic Compounds/chemistry , Sulfhydryl Compounds/chemistry , Catalysis , Disulfides/radiation effects , Evolution, Chemical , Kinetics , Macrocyclic Compounds/radiation effects , Models, Chemical , Origin of Life , Oxidation-Reduction , Photochemistry , Porphyrins/chemistry , Rose Bengal/chemistry , Sulfhydryl Compounds/radiation effects , Thermodynamics
8.
Rev. bras. anestesiol ; 70(3): 233-239, May-June 2020. tab, graf
Article in English, Portuguese | LILACS | ID: biblio-1137183

ABSTRACT

Abstract Background: The primary objective of this study was to investigate the effect of low dose ionizing radiation exposure on thiol/disulfide homeostasis and ischemia modified albumin levels. The secondary objective is to compare thiol/disulfide homeostasis and ischemia modified albumin levels among the personnel exposed to low dose ionizing radiation in anesthesia application areas, in and out of the operation room. Methods: The study included a total of 90 volunteers aged between 18 and 65 years old, with 45 personnel working in a setting with potential for radiation exposure (Exposed Group) and 45 personnel in a setting without radiation exposure (Control Group). Their native thiol, total thiol, disulphide, albumine and IMA levels were measured. Exposed group included personnel who were exposed to radiation outside the operating room - Operation room (−) Group and inside the operating room - Operation room (+) Group. Results: Albumin, native and total thiol levels were significantly lower in the participants exposed to radiation in the anesthesia application area; no statistically significant difference was found in terms of disulfide and ischemia modified albumin levels. In the Operation room (−) Group exposed to radiation, native thiol and total thiol values were significantly lower compared to the Operation room (+) Group. Conclusion: Awareness of being in danger of oxidative stress should be established in personnel exposed to radiation in the anesthesia application area following low dose ionizing radiation exposure, and the necessary measures should be taken.


Resumo Justificativa: O objetivo principal do estudo foi investigar o efeito de exposição à radiação ionizante de baixa dose nos níveis de homeostase tiol/dissulfeto e de albumina modificada por isquemia. O objetivo secundário foi comparar os níveis de homeostase tiol/dissulfeto e albumina modificada por isquemia entre indivíduos expostos à radiação ionizante de baixa dose nas áreas de procedimentos anestésicos, dentro e fora da sala de cirurgia. Método: O estudo incluiu um total de 90 voluntários com idades entre 18 e 65 anos, 45 profissionais que trabalhavam em ambiente de exposição potencial a radiação (Grupo Exposto) e 45 profissionais que trabalhavam em ambiente sem exposição à radiação (Grupo Controle). Foram medidos os níveis de tiol nativo, tiol total, dissulfeto, albumina e albumina modificada por isquemia. O Grupo Exposto era constituído por profissionais expostos a radiação fora da sala de cirurgia - Grupo sala de cirurgia (-) e na sala de cirurgia - Grupo sala de cirurgia (+). Resultados: Os níveis de albumina, tiol nativo e total foram significantemente mais baixos nos participantes expostos à radiação em área de realização de anestesia, e nenhuma diferença estatisticamente significante foi encontrada para os níveis de dissulfeto e albumina modificada por isquemia. No Grupo exposto sala de cirurgia (-), os valores de tiol nativo e tiol total foram significantemente mais baixos quando comparados ao Grupo sala de cirurgia (+). Conclusões: Os profissionais expostos à radiação em área de realização de anestesia devem ser conscientizados quanto ao perigo do estresse oxidativo após exposição à radiação ionizante de baixa dose e medidas cabíveis devem ser instituídas.


Subject(s)
Humans , Male , Female , Adolescent , Adult , Aged , Young Adult , Radiation Dosage , Radiation, Ionizing , Sulfhydryl Compounds/radiation effects , Sulfhydryl Compounds/blood , Occupational Exposure , Radiation Exposure , Disulfides/radiation effects , Disulfides/blood , Serum Albumin, Human/radiation effects , Homeostasis/radiation effects , Operating Rooms , Biomarkers/blood , Prospective Studies , Middle Aged
9.
J Phys Chem Lett ; 11(12): 4591-4596, 2020 Jun 18.
Article in English | MEDLINE | ID: mdl-32412762

ABSTRACT

After decades of speculation without material proof, the yellow-orange luminescence of scapolite is definitely assigned to (S2)- activators trapped in [Na4] square cages. Synthetic sulfur-doped scapolites confirm the implication of sulfur species in luminescence. Formally, the emission and excitation spectra of various polysulfide species were calculated. The excellent match between theory and experiments for (S2)- dimers provides definitive proof that it is the cause of the yellow-orange luminescence in scapolite.


Subject(s)
Luminescent Agents/chemistry , Minerals/chemistry , Color , Disulfides/chemistry , Disulfides/radiation effects , Light , Luminescence , Luminescent Agents/radiation effects , Minerals/radiation effects , Sodium/chemistry , Sodium/radiation effects
10.
Proc Natl Acad Sci U S A ; 117(24): 13329-13338, 2020 06 16.
Article in English | MEDLINE | ID: mdl-32461372

ABSTRACT

Two-dimensional (2D) molybdenum disulfide (MoS2) nanomaterials are an emerging class of biomaterials that are photoresponsive at near-infrared wavelengths (NIR). Here, we demonstrate the ability of 2D MoS2 to modulate cellular functions of human stem cells through photothermal mechanisms. The interaction of MoS2 and NIR stimulation of MoS2 with human stem cells is investigated using whole-transcriptome sequencing (RNA-seq). Global gene expression profile of stem cells reveals significant influence of MoS2 and NIR stimulation of MoS2 on integrins, cellular migration, and wound healing. The combination of MoS2 and NIR light may provide new approaches to regulate and direct these cellular functions for the purposes of regenerative medicine as well as cancer therapy.


Subject(s)
Disulfides/radiation effects , Mesenchymal Stem Cells/radiation effects , Molybdenum/radiation effects , Nanostructures/radiation effects , Cell Adhesion/radiation effects , Cell Movement/radiation effects , Cell Survival , Disulfides/chemistry , Disulfides/metabolism , Gene Expression Profiling , Humans , Infrared Rays , Integrins/genetics , Integrins/metabolism , Mesenchymal Stem Cells/cytology , Mesenchymal Stem Cells/metabolism , Molybdenum/chemistry , Molybdenum/metabolism , Nanostructures/chemistry , Photosensitizing Agents , Signal Transduction/radiation effects
11.
J Hazard Mater ; 390: 122158, 2020 05 15.
Article in English | MEDLINE | ID: mdl-32004762

ABSTRACT

In this study, MoS2/ZnSnO3 (MS-ZSO) composite photocatalyst with loading MS nanosheets onto the surface of porous ZSO microcubes was synthesized using a simple hydrothermal route. The prepared MS-ZSO composite can be easily excited under visible light, and 3 % MS-ZSO exhibits an outstanding photo-degradation (>80 % in 60 min) and mineralization performance (>42 % in 60 min) of the tetracycline. A remarkable improvement in the photocatalytic activity of MS-ZSO composite derived from a positive synergistic effect of well-matched energy level positions, increasement the absorption of visible light, prolonged life time decay and improved interfacial charge transfer between MS and ZSO. In-depth investigation on charge carrier separation mechanism toward MS/ZSO composite under visible light was proposed, which was further evidenced by capture experiments and electron spin resonance (ESR) techniques. Furthermore, the corresponding intermediates of tetracycline degradation over MS-ZSO composites were inspected by liquid chromatography-mass spectrometry (LC-MS) analysis, and the possible degradation paths were proposed.


Subject(s)
Anti-Bacterial Agents/chemistry , Disulfides/radiation effects , Light , Molybdenum/radiation effects , Nanostructures/radiation effects , Oxides/radiation effects , Tetracycline/chemistry , Tin Compounds/radiation effects , Zinc Compounds/radiation effects , Catalysis , Disulfides/chemistry , Molybdenum/chemistry , Nanostructures/chemistry , Oxides/chemistry , Photochemical Processes , Tin Compounds/chemistry , Zinc Compounds/chemistry
12.
J Hazard Mater ; 385: 121553, 2020 03 05.
Article in English | MEDLINE | ID: mdl-31818659

ABSTRACT

MoS2/α-NiMoO4 ultra-thin nanoneedle composite was synthesized by microwave hydrothermal process in one step. The nanocomposite revealed the complete destruction of multidrug resistant Staphylococcus aureus (S. aureus) within 150 min under visible light irradiation. According to electron spin resonance measurement and radical trapping experiment, it has been established that O2¯ acts as a major active species for bacterial inactivation in visible light. The bacterial inactivation was further proved by membrane deformities in bacterial cell membrane, DNA fragmentation, and protein destruction. TEM- elemental mapping confirms the inactivation of S. aureus by reactive oxygen species (ROS) but not the toxicity of photocatalyst. Transient photocurrent responses, electrochemical impedance spectroscopy, and cyclic voltammetry measurements reveal the efficient separation of electron-hole pairs in the composite photocatalyst. The composite photocatalyst shows greater ROS production, higher degree of DNA fragmentation and protein degradation, detrimental effects on the morphology of the bacterial cell wall, outstanding transient photocurrent responses, reduction of interfacial charge transfer resistance, superb oxidation/reduction potential, strong visible light absorption, and adequate separation of photogenerated electron-hole pairs as compared to host photocatalyst. The photocatalytic inactivation mechanism was explained. So, this promising composite photocatalyst can be applied for inactivation of multidrug resistant bacteria in biological waste water.


Subject(s)
Anti-Bacterial Agents/pharmacology , Disulfides/pharmacology , Methicillin-Resistant Staphylococcus aureus/drug effects , Molybdenum/pharmacology , Nanocomposites/chemistry , Nanofibers/chemistry , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/radiation effects , Catalysis , Cell Membrane/drug effects , DNA/drug effects , DNA Fragmentation/drug effects , Disulfides/chemistry , Disulfides/radiation effects , Light , Molybdenum/chemistry , Molybdenum/radiation effects , Nanocomposites/radiation effects , Nanofibers/radiation effects , Reactive Oxygen Species/metabolism
13.
Analyst ; 144(23): 6871-6880, 2019 Nov 18.
Article in English | MEDLINE | ID: mdl-31686068

ABSTRACT

Surface functionalization is a key step in biosensing since it is the basis of an effective analyte recognition. Among all the bioreceptors, antibodies (Abs) play a key role thanks to their superior specificity, although the available immobilization strategies suffer from several drawbacks. When gold is the interacting surface, the recently introduced Photochemical Immobilization Technique (PIT) has been shown to be a quick, easy-to-use and very effective method to tether Abs oriented upright by means of thiols produced via tryptophan mediated disulphide bridge reduction. Although the molecular mechanism of this process is quite well identified, the detailed morphology of the immobilized antibodies is still elusive due to inherent difficulties related to the microscopy imaging of Abs. The combination of Mass Spectrometry, Surface-Enhanced Raman Spectroscopy and Ellman's assay demonstrates that Abs irradiated under the conditions in which PIT is realized show only two effective disulphide bridges available for binding. They are located in the constant region of the immunoglobulin light chain so that the most likely position Ab assumes is side-on, i.e. with one Fab (i.e. the antigen binding portion of the antibody) exposed to the solution. This is not a limitation of the recognition efficiency in view of the intrinsic flexibility of the Ab structure, which makes the free Fab able to sway in the solution, a feature of great importance in many biosensing applications.


Subject(s)
Antibodies, Immobilized/chemistry , Antibodies, Monoclonal, Murine-Derived/chemistry , Immunoglobulin Constant Regions/chemistry , Amino Acid Sequence , Antibodies, Immobilized/radiation effects , Antibodies, Monoclonal, Murine-Derived/radiation effects , Biosensing Techniques/instrumentation , Disulfides/radiation effects , Immunoglobulin Constant Regions/radiation effects , Metal Nanoparticles/chemistry , Protein Conformation , Silver/chemistry , Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization , Spectrum Analysis, Raman , Surface Properties , Ultraviolet Rays
14.
Carbohydr Polym ; 222: 115039, 2019 Oct 15.
Article in English | MEDLINE | ID: mdl-31320053

ABSTRACT

The purpose of this study was to design an injectable hydrogel with temperature-sensitive property for safe and high efficient in vivo colon cancer hyperthermia and chemotherapy. Chitosan (CS) solution was injected into the tumor at room temperature and automatically gelled after warming to body temperature in the present of ß-glycerophosphate (ß-GP). Combined localized tumor photothermal and chemotherapy were achieved by dissolving photothermal material MoS2/Bi2S3-PEG (MBP) nanosheets and drug molecule doxorubicin (DOX) into the hydrogel, and the gel system could encapsulate DOX and MBP nanosheets and prevent them from entering the blood circulation and damaging normal tissues and cells. More importantly, the CS/MBP/DOX (CMD) hydrogel exhibited a photothermal efficiency of 22.18% and 31.42% in the first and second near infrared light (NIR I and NIR II) biowindows respectively at a low MBP concentration (0.5 mg/mL). Besides, the release of the DOX from CMD hydrogel was controllable since the gel temperature could be governed by NIR laser irradiation. Moreover, the chitosan-based hydrogel had antibacterial effects. The designed composite hydrogel is anticipated to act as a platform for the high efficient treatment of tumors owing to the different penetration depths of NIR I and NIR II.


Subject(s)
Antineoplastic Agents/therapeutic use , Chitosan/chemistry , Colonic Neoplasms/drug therapy , Doxorubicin/therapeutic use , Drug Carriers/chemistry , Hydrogels/chemistry , Animals , Anti-Bacterial Agents/administration & dosage , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Antineoplastic Agents/administration & dosage , Bismuth/administration & dosage , Cell Line , Chitosan/administration & dosage , Chitosan/pharmacology , Disulfides/administration & dosage , Disulfides/radiation effects , Doxorubicin/administration & dosage , Drug Carriers/administration & dosage , Drug Carriers/pharmacology , Drug Liberation , Escherichia coli/drug effects , Hydrogels/administration & dosage , Hydrogels/pharmacology , Hyperthermia, Induced/methods , Infrared Rays , Injections , Mice, Inbred BALB C , Molybdenum/administration & dosage , Molybdenum/radiation effects , Polyethylene Glycols/administration & dosage , Polyethylene Glycols/chemistry , Sulfides/administration & dosage , Sulfides/radiation effects , Temperature , Xenograft Model Antitumor Assays
15.
Mikrochim Acta ; 186(8): 490, 2019 07 02.
Article in English | MEDLINE | ID: mdl-31267219

ABSTRACT

A photoelectrochemical (PEC) method has been developed for sensitive detection of trypsin. It is based on the use of a composite consisting of MoS2 nanosheets and TiO2 nanorods (MoS2-TiO2). The material has a high specific surface area, superior electrical conductivity, excellent biocompatibility and good band gap matching. The composite was synthesized by a one-pot method using TiO2 as a template. This results in a uniform distribution of the MoS2 nanosheets (<5 layers) in the composite. If the composite, placed on an indium tin oxide (ITO) electrode, is coupled to apoferritin, the photocurrent response decreases due to the insulating effect of the protein. Trypsin, in acting as an alkaline protease, decomposes the apoferritin. This results in the recovery of the PEC signal. Attractive features of this PEC method include (a) a superior PEC signal, (b) sensor stability, (c) simple operation, and (d) the lack of any additional modifications of the biosensor. This warrants high sensitivity, reproducibility, repeatability and practicality. The ITO sensor has a linear response in the 1 to 1000 ng·mL-1 trypsin concentration range and a 0.82 ng·mL-1 detection limit. The assay was applied to the determination of trypsin in spiked serum samples and gave satisfactory results. Graphical abstract Schematic presentation of an indium tin oxide (ITO)/MoS2-TiO2 sensor for detecting trypsin. The PEC signal was decreased after immobilization of apoferritin (APO) on the modified ITO. Trypsin catalytically hydrolyzes APO specifically and induces the PEC signal to recover.


Subject(s)
Biosensing Techniques , Trypsin/analysis , Catalysis , Disulfides/chemistry , Disulfides/radiation effects , Electrochemical Techniques , Electrodes , Humans , Light , Molybdenum/chemistry , Molybdenum/radiation effects , Nanostructures/chemistry , Nanostructures/radiation effects , Photochemical Processes , Tin Compounds/chemistry , Titanium/chemistry , Titanium/radiation effects , Trypsin/blood , Trypsin/chemistry
16.
Phys Chem Chem Phys ; 21(8): 4176-4183, 2019 Feb 20.
Article in English | MEDLINE | ID: mdl-30724277

ABSTRACT

The disulfide bond is prone to ultraviolet light-induced cleavage, but the microscopic details of the light-activated bond breakage remain elusive. Here, we carry out quantum chemical calculations and the first TSH simulation of the excited state dynamics of disulfides at the MS-CASPT2 level. We demonstrate that during relaxation of the S1 state, IC to the S2 state is the predominant relaxation pathway and efficient ISC to the T2 state is geometry-dependent. Moreover, the bond cleavage leads to a strong coupling region of singlet-triplet quasidegeneracy and enlarged SOC, from which both returning to the S0 state and effective triplet formation happen. On the basis of the simulation results, the proposed electronic relaxation mechanism of light-activated disulfides is S1 → S2(T2) → region of singlet-triplet quasidegeneracy → S0, which emphasizes the competitive participation of the triplet states in the relaxation dynamics of disulfides. This theoretical work provides insights into the intrinsic excited-state properties of disulfide molecules.


Subject(s)
Disulfides/chemistry , Disulfides/radiation effects , Photolysis , Kinetics , Models, Molecular , Molecular Structure , Protein Conformation , Protein Stability , Quantum Theory , Structure-Activity Relationship , Thermodynamics , Ultraviolet Rays
17.
Langmuir ; 35(5): 1919-1926, 2019 02 05.
Article in English | MEDLINE | ID: mdl-30204452

ABSTRACT

An adamantane-containing zwitterionic copolymer poly(2-(methacryloyloxy)ethyl phosphorylcholine)- co-poly(2-(methacryloyloxy)ethyl adamantane-1-carboxylate) (poly(MPC- co-MAda)) was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. The hydrophobic photosensitizer chlorin e6 (Ce6) was conjugated to ß-cyclodextrin (ß-CD) by glutathione (GSH)-sensitive disulfide bonds. The Ce6 conjugated supramolecular prodrug nanocarriers were fabricated due to the host-guest interaction between adamantane and ß-CD, which was confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The Ce6 conjugated prodrug nanocarriers showed reduction-responsive release of Ce6, which could result in the activation of Ce6. The generation of cytotoxic reactive oxygen species (ROS) was significantly enhanced due to the activation of Ce6. In additiona, the Ce6 conjugated prodrug nanocarriers could effectively inhibit the proliferation of cancer cells upon light irradiation.


Subject(s)
Drug Carriers/chemistry , Nanoparticles/chemistry , Photosensitizing Agents/pharmacology , Porphyrins/pharmacology , Prodrugs/pharmacology , Adamantane/analogs & derivatives , Adamantane/chemical synthesis , Antineoplastic Agents/chemical synthesis , Antineoplastic Agents/pharmacology , Antineoplastic Agents/radiation effects , Chlorophyllides , Cyclodextrins/chemical synthesis , Cyclodextrins/pharmacology , Cyclodextrins/radiation effects , Disulfides/chemical synthesis , Disulfides/pharmacology , Disulfides/radiation effects , Drug Carriers/chemical synthesis , Drug Liberation , Humans , Light , MCF-7 Cells , Phosphorylcholine/analogs & derivatives , Phosphorylcholine/chemical synthesis , Photochemotherapy , Photosensitizing Agents/chemical synthesis , Photosensitizing Agents/radiation effects , Polymethacrylic Acids/chemical synthesis , Polymethacrylic Acids/chemistry , Porphyrins/chemical synthesis , Porphyrins/radiation effects , Prodrugs/chemical synthesis , Prodrugs/radiation effects , Reactive Oxygen Species/metabolism
18.
J Phys Chem B ; 122(38): 8783-8795, 2018 09 27.
Article in English | MEDLINE | ID: mdl-30040900

ABSTRACT

Over the past two decades, two-dimensional infrared (2D IR) spectroscopy has evolved from the theoretical underpinnings of nonlinear spectroscopy as a means of investigating detailed molecular structure on an ultrafast time scale. The combined time and spectral resolution over which spectra can be collected on complex molecular systems has led to the precise structural resolution of dynamic species that have previously been impossible to directly observe through traditional methods. The adoption of 2D IR spectroscopy for the study of protein folding and peptide interactions has provided key details of how small changes in conformations can exert major influences on the activities of these complex molecular systems. Traditional 2D IR experiments are limited to molecules under equilibrium conditions, where small motions and fluctuations of these larger molecules often still lead to functionality. Utilizing techniques that allow the rapid initiation of chemical or structural changes in conjunction with 2D IR spectroscopy, i.e., transient 2D IR, a vast dynamic range becomes available to the spectroscopist uncovering structural content far from equilibrium. Furthermore, this allows the observation of reaction pathways of these macromolecules under quasi- and nonequilibrium conditions.


Subject(s)
Peptides/chemistry , Azo Compounds/chemistry , Azo Compounds/radiation effects , Disulfides/chemistry , Disulfides/radiation effects , Heterocyclic Compounds, 1-Ring/chemistry , Heterocyclic Compounds, 1-Ring/radiation effects , Peptides/radiation effects , Protein Conformation , Protein Folding , Spectrophotometry, Infrared/methods , Temperature
19.
Phys Chem Chem Phys ; 20(24): 16501-16509, 2018 Jun 20.
Article in English | MEDLINE | ID: mdl-29878021

ABSTRACT

In this study, we demonstrated a prompt and sensitive detection technique for cardiac troponin T (cTnT) in buffer and biological fluid (serum) using an NIR-active fluorescent anti-cTnT-labelled carbon dot (CD) and molybdenum disulfide (MoS2)-based nano-couple. Exfoliated MoS2 nanosheets strongly grasp the anti-cTnT-labelled CDs over their surface, and an excited-state non-radiative energy transfer mechanism takes place from CDs to MoS2, thereby quenching the upconversion fluorescence. The nonlinear and upward Stern-Volmer relationship is observed, which indicates a combined static and dynamic quenching. Static and time-resolved fluorescence measurements predict distance-dependent Förster resonance energy transfer (FRET) dynamics, which control the detection process. In the presence of cTnT, the energy transfer process gets hindered due to strong antibody/antigen (anti-cTnT/cTnT) interaction. The cTnT molecules affect the positions of the nano-couple and cause effective detachment of CDs from the MoS2 surface. This results hindrance in the energy transfer process with consequent restoration of upconversion intensity. A linear response is observed between the cTnT concentration and the restored fluorescence intensity in the concentration range of 0.1-50 ng mL-1 with a limit of detection of 0.12 ng mL-1 and a limit of quantification of 0.38 ng mL-1. Statistical analysis shows that the present assay possesses an accuracy of 101.4 ± 3.76 with a co-relation co-efficient of 0.99. Thus, CD/MoS2 provides a promising platform for the sensitive detection of cTnT.


Subject(s)
Carbon/radiation effects , Disulfides/radiation effects , Molybdenum/radiation effects , Quantum Dots/radiation effects , Troponin T/blood , Antibodies/immunology , Biosensing Techniques/methods , Carbon/chemistry , Disulfides/chemistry , Fluorescence , Fluorescence Resonance Energy Transfer/methods , Humans , Immunologic Techniques/methods , Light , Limit of Detection , Molybdenum/chemistry , Quantum Dots/chemistry , Troponin T/immunology
20.
J Hazard Mater ; 341: 10-19, 2018 Jan 05.
Article in English | MEDLINE | ID: mdl-28763632

ABSTRACT

The development of efficient solar driven catalytic system for the degradation of antibiotics has become increasingly important in environmental protection and remediation. Non-noble-metal NiS and MoS2 nanosheet co-modified graphitic C3N4 ternary heterostructure has been synthesized via a facile combination of hydrothermal and ultrasound method, and the ternary heterostructure has been utilized for photocatalytic degradation of antibiotic agents. The antibiotics of ciprofloxacin (CIP) and tetracycline hydrochloride (TC) were photodegraded by the hybrid under the visible light. The optimal photodegradation rate of the ternary heterostructure reaches about 96% after 2h irradiation, which is 2.1 times higher than that of pure g-C3N4 for TC degradation. The photocatalytic degradation rates of the ternary heterostructure for both CIP and TC obey the pseudo-first-order kinetic model. The enhanced visible light adsorption and charge separation efficiency contribute to the photocatalytic performance of the ternary heterostructure. This work provides new insights and pathways by which efficient degradation of antibiotics can be achieved and will stimulate further studies in this important field.


Subject(s)
Anti-Bacterial Agents/chemistry , Disulfides , Graphite , Light , Molybdenum , Nanocomposites , Nickel , Nitriles , Azo Compounds/chemistry , Ciprofloxacin/chemistry , Coloring Agents/chemistry , Disulfides/chemistry , Disulfides/radiation effects , Graphite/chemistry , Graphite/radiation effects , Molybdenum/chemistry , Molybdenum/radiation effects , Nanocomposites/chemistry , Nanocomposites/radiation effects , Nickel/chemistry , Nickel/radiation effects , Nitriles/chemistry , Nitriles/radiation effects , Photolysis , Tetracycline/chemistry
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