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1.
Org Lett ; 26(11): 2338-2342, 2024 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-38458971

RESUMEN

A mild, facile, and metal-free approach via the N-heterocyclic carbene-catalyzed SNAr reaction between aryl aldehydes with perfluoroarenes to obtain the coveted functional perfluorinated diarylmethanones is disclosed. This method accommodates a diverse substrate range and exhibits notable tolerance toward various functional groups. Our success in modifying biologically relevant molecules, crafting a fully fluorinated bioisosteric analogue of drug candidate D1, and highlighting the potential of these ketones as valuable electrolyte additives for lithium-ion batteries (LIBs) underscores the versatility of our methodology.

2.
Chem Commun (Camb) ; 60(22): 3079-3082, 2024 Mar 12.
Artículo en Inglés | MEDLINE | ID: mdl-38406884

RESUMEN

We present a novel, eco-friendly and one-pot approach for synthesizing unsymmetrical oxalamides with the aid of dichloroacetamide and amine/amides in the presence of CBr4 in a basic medium. The use of water as a potent supplement for the oxygen atom source and the detailed mechanism have been disclosed. Moreover, the protocol involves triple cleavage of CCl2Br and the formation of new C-O/C-N bonds, with the advantage of achieving selective bromination using CBr4 with good to excellent yield under mild conditions. The method also demonstrates promise for industrial use, as proven by its effective implementation in gram-scale synthesis conducted in a batch process, along with its utilization in a continuous-flow system.

3.
Anal Methods ; 16(8): 1261-1271, 2024 Feb 22.
Artículo en Inglés | MEDLINE | ID: mdl-38323472

RESUMEN

A fluorescence probe based on iron oxide quantum dots (IO-QDs) was synthesized using the hydrothermal method for the determination of tetracycline (TCy) and ciprofloxacin (CPx) in aqueous solution. The IO-QDs were characterized using high-resolution transmission electron microscopy (HR-TEM), powder X-ray diffraction (P-XRD), vibrating sample magnetometry (VSM), and Fourier-transform infrared spectroscopy (FTIR). The as-prepared IO-QDs are fluorescent, stable, and with a fluorescence quantum yield (QY) of 9.8 ± 0.12%. The fluorescence of IO-QDs was observed to be quenched and enhanced in the presence of TCy and CPx, respectively. The fluorescence intensity ratio shows linearity at concentrations from 1-100 µM and 5-100 µM for TCy and CPx, respectively; the detection limit for TCy and CPx was estimated to be 0.71 µM and 1.56 µM, respectively. The proposed method was also successfully utilized in the spiked samples of drinking water and honey with good recoveries. The method offered convenience, rapid detection, high sensitivity, selectivity, and cost-efficient alternative options for the determination of TCy and CPx in real samples.


Asunto(s)
Antibacterianos , Compuestos Férricos , Puntos Cuánticos , Ciprofloxacina , Puntos Cuánticos/química , Tetraciclina
4.
ACS Appl Mater Interfaces ; 14(39): 44969-44980, 2022 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-36150129

RESUMEN

Although N-heterocyclic carbenes (NHCs) are superior to thiol adsorbates in that they form remarkably stable bonds with gold, the generation of NHC-based self-assembled monolayers (SAMs) typically requires a strong base and an inert atmosphere, which limits the utility of such films in many applications. Herein, we report the development and use of bench-stable NHC adsorbates, benzimidazolium methanesulfonates, for the direct formation of NHC films on gold surfaces under an ambient atmosphere at room temperature without the need for extraordinary precautions. The generated NHC SAMs were fully characterized using ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS), and contact angle measurements, and they were compared to analogous SAMs generated from an NHC bicarbonate adsorbate. Based on these findings, a unique radical initiator α,ω-bidentate azo-terminated NHC adsorbate, NHC15AZO[OMs], was designed and synthesized for the preparation of SAMs on gold surfaces with both NHC headgroups bound to the surface. The adsorbate molecules in NHC15AZO SAMs can exist in a hairpin or a linear conformation depending on the concentration of the adsorbate solution used to prepare the SAM. These conformations were studied by a combination of ellipsometry, XPS, PM-IRRAS, and scanning electron microscopy using gold nanoparticles (AuNPs) as a tag material. Moreover, the potential utility of these unique radical-initiating NHC films as surface-initiated polymerization platforms was demonstrated by controlling the thickness of polystyrene brush films grown from azo-terminated NHC monolayer surfaces simply by adjusting the reaction time of the photoinitiated radical polymer growth process.

5.
Spectrochim Acta A Mol Biomol Spectrosc ; 279: 121453, 2022 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-35667139

RESUMEN

In this work, a simple, easy and selective method for sensing lysine in an acidic medium was developed based on fluorescent iron oxide quantum dots (IO QDs). IO QDs using the hydrothermal method were prepared with different conditions (concentration of NPs, amount of citric acid, heating time, heating temperature, and total volume in the hydrothermal reactor) where iron oxide nanoparticles (IO NPs) were used as the starting materials. TEM, FTIR, UV-Vis Spectrometry, fluorescence spectrometry, Powder XRD, VSM were used to characterize the as-prepared IO QDs. The surface of the IO QDs contained -OH, -COO-, and other functional groups that acted as a bridge to bind the IO QDs nanoprobe with the surrounding analytes. Under acidic conditions (pH 3.0), IO QDs exhibited a rapid and interference-free fluorescence enhancement behavior after adding lysine within 2 min at room temperature, whereas other amino acids had no effect on IO QDs fluorescence. Therefore, the IO QDs prepared in this study have shown potential in lysine sensing applications. The results showed that the relative FL intensity was linear with lysine concentration in the range of 1-100 µM and had a detection limit of 0.66 µM. This proposed method has high selectivity for lysine over other amino acids, and the developed methods were used in real sample with good recoveries. Under relatively acidic conditions, a specific and fast lysine interaction was observed, resulting in the successful of IO QDs as the fluorescent probe for rapid and interference-free lysine assessment in dairy products.


Asunto(s)
Puntos Cuánticos , Productos Lácteos , Compuestos Férricos , Colorantes Fluorescentes/química , Lisina , Puntos Cuánticos/química , Espectrometría de Fluorescencia/métodos
6.
Comput Methods Programs Biomed ; 211: 106382, 2021 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-34555590

RESUMEN

BACKGROUND AND OBJECTIVE: Emergency physicians (EPs) frequently deal with abdominal pain, including that is caused by either gallstones or acute cholecystitis. Easy access and low cost justify point-of-care ultrasound (POCUS) use as a first-line test to detect these diseases; yet, the detection performance of POCUS by EPs is unreliable, causing misdiagnoses with serious impacts. This study aimed to develop a machine learning system to detect and localize gallstones and to detect acute cholecystitis by ultrasound (US) still images taken by physicians or technicians for preliminary diagnoses. METHODS: Abdominal US images (> 89,000) were collected from 2386 patients in a hospital database. We constructed training sets for gallstones with or without cholecystitis (N = 10,971) and cholecystitis with or without gallstones (N = 7348) as positives. Validation sets were also constructed for gallstones (N = 2664) and cholecystitis (N = 1919). We applied a single-shot multibox detector (SSD) and a feature pyramid network (FPN) to classify and localize objects using image features extracted by ResNet-50 for gallstones, and MobileNet V2 to classify cholecystitis. The deep learning models were pretrained using the COCO-2017 and ILSVRC-2012 datasets. RESULTS: Using the validation sets, the SSD-FPN-ResNet-50 and MobileNet V2 achieved areas under the receiver operating characteristics curve of 0.92 and 0.94, respectively. The inference speeds were 21 (47.6 frames per second, fps) and 7 ms (142.9 fps). CONCLUSIONS: A machine learning system was developed to detect and localize gallstones, and to detect cholecystitis, with acceptable discrimination and speed. This is the first study to develop this system for either gallstone or cholecystitis detection with absence or presence of each one. After clinical trials, this system may be used to assist EPs, including those in remote areas, for detecting these diseases.


Asunto(s)
Colecistitis , Cálculos Biliares , Colecistitis/diagnóstico por imagen , Cálculos Biliares/diagnóstico por imagen , Humanos , Redes Neurales de la Computación , Sistemas de Atención de Punto , Ultrasonografía
7.
J Chin Med Assoc ; 84(9): 842-850, 2021 09 01.
Artículo en Inglés | MEDLINE | ID: mdl-34282076

RESUMEN

BACKGROUND: The prevalence of nonalcoholic fatty liver disease is increasing over time worldwide, with similar trends to those of diabetes and obesity. A liver biopsy, the gold standard of diagnosis, is not favored due to its invasiveness. Meanwhile, noninvasive evaluation methods of fatty liver are still either very expensive or demonstrate poor diagnostic performances, thus, limiting their applications. We developed neural network-based models to assess fatty liver and classify the severity using B-mode ultrasound (US) images. METHODS: We followed standards for reporting of diagnostic accuracy guidelines to report this study. In this retrospective study, we utilized B-mode US images from a consecutive series of patients to develop four-class, two-class, and three-class diagnostic prediction models. The images were eligible if confirmed by at least two gastroenterologists. We compared pretrained convolutional neural network models, consisting of visual geometry group (VGG)19, ResNet-50 v2, MobileNet v2, Xception, and Inception v2. For validation, we utilized 20% of the dataset resulting in >100 images for each severity category. RESULTS: There were 21,855 images from 2,070 patients classified as normal (N = 11,307), mild (N = 4,467), moderate (N = 3,155), or severe steatosis (N = 2,926). We used ResNet-50 v2 for the final model as the best ones. The areas under the receiver operating characteristic curves were 0.974 (mild steatosis vs others), 0.971 (moderate steatosis vs others), 0.981 (severe steatosis vs others), 0.985 (any severity vs normal), and 0.996 (moderate-to-severe steatosis/clinically abnormal vs normal-to-mild steatosis/clinically normal). CONCLUSION: Our deep learning models achieved comparable predictive performances to the most accurate, yet expensive, noninvasive diagnostic methods for fatty liver. Because of the discriminative ability, including for mild steatosis, significant impacts on clinical applications for fatty liver are expected. However, we need to overcome machine-dependent variation, motion artifacts, lacking of second confirmation from any other tools, and hospital-dependent regional bias.


Asunto(s)
Abdomen/diagnóstico por imagen , Aprendizaje Profundo , Enfermedad del Hígado Graso no Alcohólico/diagnóstico por imagen , Enfermedad del Hígado Graso no Alcohólico/fisiopatología , Ultrasonografía , Humanos , Gravedad del Paciente , Estudios Retrospectivos , Estados Unidos
8.
JMIR Med Inform ; 8(11): e23472, 2020 Nov 26.
Artículo en Inglés | MEDLINE | ID: mdl-33139242

RESUMEN

BACKGROUND: Retinal imaging has been applied for detecting eye diseases and cardiovascular risks using deep learning-based methods. Furthermore, retinal microvascular and structural changes were found in renal function impairments. However, a deep learning-based method using retinal images for detecting early renal function impairment has not yet been well studied. OBJECTIVE: This study aimed to develop and evaluate a deep learning model for detecting early renal function impairment using retinal fundus images. METHODS: This retrospective study enrolled patients who underwent renal function tests with color fundus images captured at any time between January 1, 2001, and August 31, 2019. A deep learning model was constructed to detect impaired renal function from the images. Early renal function impairment was defined as estimated glomerular filtration rate <90 mL/min/1.73 m2. Model performance was evaluated with respect to the receiver operating characteristic curve and area under the curve (AUC). RESULTS: In total, 25,706 retinal fundus images were obtained from 6212 patients for the study period. The images were divided at an 8:1:1 ratio. The training, validation, and testing data sets respectively contained 20,787, 2189, and 2730 images from 4970, 621, and 621 patients. There were 10,686 and 15,020 images determined to indicate normal and impaired renal function, respectively. The AUC of the model was 0.81 in the overall population. In subgroups stratified by serum hemoglobin A1c (HbA1c) level, the AUCs were 0.81, 0.84, 0.85, and 0.87 for the HbA1c levels of ≤6.5%, >6.5%, >7.5%, and >10%, respectively. CONCLUSIONS: The deep learning model in this study enables the detection of early renal function impairment using retinal fundus images. The model was more accurate for patients with elevated serum HbA1c levels.

9.
ACS Omega ; 5(37): 23769-23777, 2020 Sep 22.
Artículo en Inglés | MEDLINE | ID: mdl-32984696

RESUMEN

Core@shell metal nanoparticles have emerged as promising photocatalysts because of their strong and tunable plasmonic properties; however, marked improvements in photocatalytic efficiency are needed if these materials are to be widely used in practical applications. Accordingly, the design of new and functional light-responsive nanostructures remains a central focus of nanomaterial research. To this end, we report the synthesis of nanorattles comprising hollow gold-silver nanoshells encapsulated within vacuous tin oxide shells of adjustable thicknesses (∼10 and ∼30 nm for the two examples prepared in this initial report). These composite nanorattles exhibited broad tunable optical extinctions ranging from ultraviolet to near-infrared spectral regions (i.e., 300-745 nm). Zeta potential measurements showed a large negative surface charge of approximately -35 mV, which afforded colloidal stability to the nanorattles in aqueous solution. We also characterized the nanorattles structurally and compositionally using scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Futhermore, finite-difference time-domain simulation and photoluminescence properties of the composited nanoparticles were investigated. Collectively, these studies indicate that our tin oxide-coated hollow gold-silver nanorattles are promising candidates for use in solar-driven applications.

10.
ACS Appl Mater Interfaces ; 12(42): 47368-47376, 2020 Oct 21.
Artículo en Inglés | MEDLINE | ID: mdl-32930564

RESUMEN

Lithium-sulfur batteries have shown great promise as next-generation high energy density power sources, but their commercial applications are hindered by short battery cycle life arising from the dissolution and shuttling of polysulfides. To address this shortcoming, we prepared two types of semihollow core-shell nanoparticles in which (1) elemental sulfur is encapsulated within a porous silica shell (S@SiO2) and (2) elemental sulfur is encapsulated within a porous silica shell where the inner surface of the shell is decorated with small Au nanoparticles (S@Au@SiO2). These core-shell nanoparticles, both ∼300 nm in diameter, were generated from analogous zinc sulfide-based core-shell nanoparticles (ZnS@SiO2 and ZnS@Au@SiO2, respectively) by converting the ZnS cores to elemental sulfur upon treatment with Fe(NO3)3. With a high surface area and strong host-polysulfide interaction, the SiO2 shells effectively trap the polysulfides; moreover, the internal void space of these nanostructures accommodates the volume expansion of the sulfur core upon lithiation. By decorating ∼5-7 nm Au nanoparticles evenly on the inner surface of the porous SiO2 shells (i.e., S@Au@SiO2), electron transport is enhanced, with consequently enhanced sulfur conversion kinetics at high current rates. Studies of battery performance showed that the S@SiO2 cathode can deliver an initial capacity of 1153 mA h g-1 under 0.2 C and retain 816 mA h g-1 after 100 cycles. More importantly, the Au-decorated S@Au@SiO2 cathode can deliver a high capacity of 500 mA h g-1 under 5 C.

11.
Chem Rev ; 119(8): 4986-5056, 2019 04 24.
Artículo en Inglés | MEDLINE | ID: mdl-30938514

RESUMEN

N-Heterocyclic carbenes (NHCs) have become one of the most widely studied class of ligands in molecular chemistry and have found applications in fields as varied as catalysis, the stabilization of reactive molecular fragments, and biochemistry. More recently, NHCs have found applications in materials chemistry and have allowed for the functionalization of surfaces, polymers, nanoparticles, and discrete, well-defined clusters. In this review, we provide an in-depth look at recent advances in the use of NHCs for the development of functional materials.

12.
J Am Chem Soc ; 140(5): 1576-1579, 2018 02 07.
Artículo en Inglés | MEDLINE | ID: mdl-29211456

RESUMEN

Highly stable gold nanoparticles (Au NPs) functionalized by bidentate N-heterocyclic carbene (NHC) ligands have been synthesized by top-down and bottom-up approaches. A detailed study of the effect of alkylation, denticity, and method of synthesis has led to the production of NHC-stabilized nanoparticles with higher thermal stability than bi- and tridentate thiol-protected Au NPs and than monodentate NHC-stabilized NPs. Importantly, bidentate NHC-protected NPs also displayed unprecedented stability to external thiol, which has been an unsolved problem to date with all nanoparticles. Thus, multidentate NHC ligands are an important, and as yet unrecognized, step forward for the preparation of high stability nanomaterials.

13.
J Colloid Interface Sci ; 513: 715-725, 2018 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-29220686

RESUMEN

Titanium dioxide (TiO2) has gained increasing interest in materials research due to its outstanding properties and promising applications in a wide range of fields. From this perspective, we report the synthesis of custom-designed anatase TiO2 submicrometer particles coated with partial Au shells (ATiO2-AuShl). The synthetic strategy used herein yields uniformly shaped monodisperse particles. Amorphous TiO2 core particles were synthesized using template-free oxidation and hydrolysis of titanium nitride (TiN); subsequent hydrothermal treatment generated anatase TiO2 (ATiO2) particles. Coating ATiO2 particles with partial Au shells was accomplished using a simple seeded-growth method. Evaluation of the optical properties of these ATiO2-AuShl particles showed that these submicrometer composites exhibited an intense absorption peak for TiO2 in the UV region (∼326 nm) and a broad extinction band in the visible range (∼650 nm) arising from the incomplete Au shell. These ATiO2-AuShl composite particles provide a unique and effective means for broadening the optical response of TiO2-based nano- and micron-scale materials. The simplicity of our synthetic method should broaden the application of ATiO2-AuShl particles in various visible light-driven technologies.

14.
Langmuir ; 33(50): 14211-14219, 2017 12 19.
Artículo en Inglés | MEDLINE | ID: mdl-29148789

RESUMEN

Soft matter-directed self-assembly of amphiphilic inorganic nanoparticles (NPs) has recently emerged as a promising approach to access NP ensembles with superior collective properties. While thiol-terminated molecules are primarily employed to tether the amphiphilic ligand to the metal, concerns remain regarding the stabilities of the resulting NPs and their corresponding aggregates. As an alternative, we report amphiphilic N-heterocyclic carbene (NHC)-functionalized gold nanoparticles (AuNPs). To accomplish this, an amphiphilic NHC-AuI complex based on an asymmetric triethylene glycol-/dodecyl-functionalized benzimidazole was first synthesized and used to prepare the corresponding stable amphiphilic NHC-decorated AuNPs. The resulting NPs were comprehensively characterized using both solution- and solid-state-based techniques such as proton nuclear magnetic resonance spectroscopy, dynamic light scattering, transmission electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. By optimizing the self-assembly behavior of these amphiphilic AuNPs in deionized water, ethanol, and their mixtures, we were able to fine-tune the plasmonic properties of the AuNPs in the wide range of 525-640 nm. Furthermore, when treated with thiols, the ensembles showed greater stability compared to their parent discrete AuNP counterparts at room temperature.

15.
Adv Mater ; 29(31)2017 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-28612952

RESUMEN

To meet the increasing demands for ultrasensitivity in monitoring trace amounts of low-abundance early biomarkers or environmental toxins, the development of a robust sensing system is urgently needed. Here, a novel signal cascade strategy is reported via an ultrasensitive polymeric sensing system (UPSS) composed of gold nanoparticle (gNP)-decorated polymer, which enables gNP aggregation in polymeric network and electrical conductance change upon specific aptamer-based biomolecular recognition. Ultralow concentrations of thrombin (10-18 m) as well as a low molecular weight anatoxin (165 Da, 10-14 m) are detected selectively and reproducibly. The biomolecular recognition induced polymeric network shrinkage responses as well as dose-dependent responses of the UPSS are validated using in situ real-time atomic-force microscopy, representing the first instance of real-time detection of biomolecular binding-induced polymer shrinkage in soft matter. Furthermore, in situ real-time confocal laser scanning microscopy imaging reveals the dynamic process of gNP aggregation responses upon biomolecular binding.


Asunto(s)
Nanopartículas del Metal , Aptámeros de Nucleótidos , Técnicas Biosensibles , Oro , Polímeros , Trombina
16.
Angew Chem Int Ed Engl ; 56(22): 6198-6202, 2017 05 22.
Artículo en Inglés | MEDLINE | ID: mdl-28407403

RESUMEN

NHC-AuI complexes were used to prepare stable, water-soluble, NHC-protected gold nanoparticles. The water-soluble, charged nature of the nanoparticles permitted analysis by polyacrylamide gel electrophoresis (PAGE), which showed that the nanoparticles were highly monodisperse, with tunable core diameters between 2.0 and 3.3 nm depending on the synthesis conditions. Temporal, thermal, and chemical stability of the nanoparticles were determined to be high. Treatment with thiols caused etching of the particles after 24 h; however larger plasmonic particles showed greater resistance to thiol treatment. These water-soluble, bio-compatible nanoparticles are promising candidates for use in photoacoustic imaging, with even the smallest nanoparticles giving reliable photoacoustic signals.

17.
Colloids Surf B Biointerfaces ; 145: 291-300, 2016 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-27208443

RESUMEN

Nanoparticles decorated with biocompatible coatings have received considerable attention in recent years for their potential biomedical applications. However, the desirable properties of nanoparticles for in vivo uses, such as colloidal stability, biodistribution, and pharmacokinetics, require further research. In this work, we report a bio-derived zwitterionic surface ligand, cysteine betaine (Cys-b) for the modification of hollow gold-silver nanoshells, giving rise to hyperthermia applications. Cys-b coatings on planar substrates and nanoshells were compared to conventional (11-mercaptoundecyl)tri(ethylene glycol) (OEG-thiol) to investigate their effects on the fouling resistance, colloidal stability, environmental tolerance, and photothermal properties. The results found that Cys-b and OEG-thiol coatings exhibited comparable antifouling properties against bacteria of gram-negative Pseudomonas aeruginosa (P. aeruginosa) and gram-positive Staphylococcus epidermidis (S. epidermidis), NIH-3T3 fibroblasts, and bovine serum albumin. However, when the modified nanoshells were suspended at a temperature of 50°C in aqueous 3M NaCl solutions, shifts in the extinction maximum of the OEG-capped nanoshells with time were observed, while the corresponding spectra of nanoshells capped with Cys-b generally remained unchanged. In addition, when the nanoshells were continuously exposed to NIR irradiation, the temperature of the solution containing nanoshells capped with Cys-b increased to a plateau of 54°C, while that of the OEG-capped nanoshells gradually decreased after reaching a peak temperature. Accordingly, the Cys-b nanoshells were conjugated with anti-HER2 antibodies for targeted delivery to HER2-positive MDA-MB-453 breast cancer cells for hyperthermia treatment. The results showed the selective delivery and effective photothermal cell ablation with the antibody-conjugated Cys-b nanoshells. Therefore, this work demonstrated the promise of bio-derived zwitterionic Cys-b as a stable and biocompatible surface coating for materials in nanomedicine.


Asunto(s)
Betaína/farmacología , Cisteína/análogos & derivados , Hipertermia Inducida , Rayos Infrarrojos , Nanocáscaras/química , Compuestos de Amonio Cuaternario/farmacología , Adsorción , Animales , Bovinos , Adhesión Celular/efectos de los fármacos , Línea Celular Tumoral , Cisteína/farmacología , Fibroblastos/citología , Fibroblastos/efectos de los fármacos , Oro/farmacología , Ratones , Células 3T3 NIH , Espectroscopía de Fotoelectrones , Plata/farmacología , Propiedades de Superficie , Factores de Tiempo
18.
ACS Appl Mater Interfaces ; 8(14): 9152-61, 2016 Apr 13.
Artículo en Inglés | MEDLINE | ID: mdl-26973998

RESUMEN

Gold-silver nanoshells (GS-NSs) having a tunable surface plasmon resonance (SPR) were employed to facilitate charge separation of photoexcited carriers in the photocalytic production of hydrogen from water. Zinc indium sulfide (ZnIn2S4; ZIS), a visible-light-active photocatalyst, where the band gap varies with the [Zn]/[In] ratio, was used as a model ZIS system (E(g) = 2.25 eV) to investigate the mechanisms of plasmonic enhancement associated with the nanoshells. Three types of GS-NS cores with intense absorptions centered roughly at 500, 700, and 900 nm were used as seeds for preparing GS-NS@ZIS core-shell structures via a microwave-assisted hydrothermal reaction, yielding core-shell particles with composite diameters of ∼200 nm. Notably, an interlayer of dielectric silica (SiO2) between the GS-NSs and the ZIS photocatalyst provided another parameter to enhance the production of hydrogen and to distinguish the charge-transfer mechanisms. In particular, the direct transfer of hot electrons from the GS-NSs to the ZIS photocatalyst was blocked by this layer. Of the 10 particle samples examined in this study, the greatest hydrogen gas evolution rate was observed for GS-NSs having a SiO2 interlayer thickness of ∼17 nm and an SPR absorption centered at ∼700 nm, yielding a rate 2.6 times higher than that of the ZIS without GS-NSs. The apparent quantum efficiencies for these core-shell particles were recorded and compared to the absorption spectra. Analyses of the charge-transfer mechanisms were evaluated and are discussed based on the experimental findings.

19.
ACS Appl Mater Interfaces ; 7(42): 23776-86, 2015 Oct 28.
Artículo en Inglés | MEDLINE | ID: mdl-26452141

RESUMEN

Great care has been paid to the biointerface between a bulk material and the biological environment, which plays a key role in the optimized performance of medical devices. In this work, we report a new superhydrophilic adsorbate, called L-cysteine betaine (Cys-b), having branched zwitterionic groups that give rise to surfaces and nanoparticles with enhanced chemical stability, biofouling resistance, and inertness to environmental changes. Cys-b was synthesized from the amphoteric sulfur-containing amino acid, L-cysteine (Cys), by quaternization of its amino group. Gold surfaces modified with Cys-b exhibited prominent repellence against the nonspecific adsorption of proteins, bacteria, and fibroblast cells. In addition, Cys-b existed in zwitterionic form over a wide pH range (i.e., pH 3.4 to 10.8), and showed excellent suppression in photoinduced oxidation on gold substrates. Furthermore, the modification of hollow Ag@Au nanoshells with Cys-b gave rise to nanoparticles with excellent colloidal stability and resistance to coordinative interaction with Cu(2+). Taken together, the unique features of Cys-b offer a new nanoscale coating for use in a wide spectrum of applications.


Asunto(s)
Adsorción/efectos de los fármacos , Betaína/farmacología , Incrustaciones Biológicas , Cisteína/farmacología , Aminoácidos/química , Betaína/síntesis química , Betaína/química , Cisteína/síntesis química , Cisteína/química , Equipos y Suministros , Oro/química , Interacciones Hidrofóbicas e Hidrofílicas , Polímeros/química , Albúmina Sérica Bovina/química , Albúmina Sérica Bovina/efectos de los fármacos , Propiedades de Superficie/efectos de los fármacos
20.
ACS Appl Mater Interfaces ; 7(7): 3981-93, 2015 Feb 25.
Artículo en Inglés | MEDLINE | ID: mdl-25611157

RESUMEN

Catheter-related infections (CRIs) are associated with the formation of pathogenic biofilms on the surfaces of silicone catheters, which are ubiquitous in medicine. These biofilms provide protection against antimicrobial agents and facilitate the development of bacterial resistance to antibiotics. The application of photothermal agents on catheter surfaces is an innovative approach to overcoming biofilm-generated CRIs. Gold nanoshells (AuNSs) represent a promising photothermal tool, because they can be used to generate heat upon exposure to near-infrared (NIR) radiation, are biologically inert at physiological temperatures, and can be engineered for the photothermal ablation of cells and tissue. In this study, AuNSs functionalized with carboxylate-terminated organosulfur ligands were attached to model catheter surfaces and tested for their effectiveness at killing adhered Enterococcus faecalis (E. faecalis) bacteria. The morphology of the AuNSs was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), while the elemental composition was characterized by energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Furthermore, optical and photothermal properties were acquired by ultraviolet-visible (UV-vis) spectroscopy and thermographic imaging with an infrared camera, respectively. Bacterial survival studies on AuNS-modified surfaces irradiated with and without NIR light were evaluated using a colony-formation assay. These studies demonstrated that AuNS-modified surfaces, when illuminated with NIR light, can effectively kill E. faecalis on silicone surfaces.


Asunto(s)
Enterococcus faecalis/efectos de la radiación , Oro/química , Nanocáscaras/química , Siliconas/química , Biopelículas/efectos de la radiación , Infecciones Relacionadas con Catéteres/microbiología , Infecciones Relacionadas con Catéteres/prevención & control , Enterococcus faecalis/crecimiento & desarrollo , Enterococcus faecalis/fisiología , Humanos , Rayos Infrarrojos , Temperatura
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