Antibiofilm Activity of Eugenol-Loaded Chitosan Coatings against Common Medical-Device-Contaminating Bacteria.

The formation of pathogenic biofilms on medical devices is a major public health concern accounting for over 65% of healthcare-associated infections and causing high infection morbidity, mortality, and a great burden to patients and the healthcare system due to its resistance to treatment. In this study, we developed a chitosan-based antimicrobial coating with embedded mesoporous silica nanoparticles (MSNs) to load and deliver eugenol, an essential oil component, to inhibit the biofilm formation of common bacteria in medical-device-related infections. The eugenol-loaded MSNs were dispersed in a chitosan solution, which was then cross-linked with glutaraldehyde and drop-casted to obtain coatings. The MSNs and coatings were characterized by dynamic light scattering, Brunauer-Emmett-Teller analysis, attenuated-total-reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, 3D optical profilometry, and scanning electron microscopy. The release behavior of eugenol-loaded MSNs and coatings and the antibiofilm and antimicrobial activity of the coatings against adherent Staphylococcus aureus, methicillin-resistant S. aureus, and Pseudomonas aeruginosa were investigated. Eugenol was released from the MSNs and coatings in aqueous conditions in a controlled manner with an initial low release, followed by a peak release, a decrease, and a plateau. While the chitosan coatings alone or with unloaded MSNs demonstrated limited antimicrobial effects and still supported biofilm formation after 24 h, the coating containing eugenol not only reduced biofilm formation but also killed the majority of the attached bacteria. It also showed biocompatibility in indirect contact with NIH/3T3 fibroblasts and a high percentage of live cells in direct contact. However, further investigations into cell proliferation in direct contact are recommended. The findings indicated that the chitosan-based coating with eugenol-loaded MSNs could be developed into an effective strategy to inhibit biofilm formation on medical devices.

Facile Synthesis of Platinum Nanoparticle-Embedded Reduced Graphene Oxide for the Detection of Carbendazim.

In recent years, there has been a significant interest in the advancement of electrochemical sensing platforms to detect pesticides with high sensitivity and selectivity. Current research presents a novel approach utilising platinum nanoparticles (NPs) and reduced graphene oxide deposited on a glassy carbon electrode (Pt-rGO/GCE) for direct electrochemical measurement of carbendazim (CBZ). A straightforward one-step electrodeposition process was applied to prepare the Pt-rGO sensing platform. The incorporation of conductive rGO nanosheets along with distinctive structured Pt NPs significantly enhanced the effective electrode surface area and electron transfer of CBZ. Additionally, when exposed to 50 µM CBZ, Pt-rGO/GCE exhibited a higher current response compared to the bare electrode. Further investigations were performed to analyse and optimise the experimental parameters that could influence pesticide detection. Under the optimised conditions of pH 7 and 5 min of accumulation time, the Pt-rGO/GCE sensor showed a linear concentration detection range from 0.1 µM to 50 µM, with a detection limit of 3.46 nM. The fabricated sensor was successfully employed for CBZ detection in milk and tap water with 98.88% and 98.57% recovery, respectively. The fabricated sensor showed higher sensitivity and reproducibility, thus indicating the potential of this technology in the development of reliable sensors for the detection of CBZ or similar pesticides in forthcoming applications.

Clinical Analysis of Supraclavicular Flaps for the Repair of the Pharyngeal Fistula.

Objectives: We explored the value of supraclavicular flaps in repairing pharyngeal fistula. Methods: Patients treated with supraclavicular flaps were included. Data on preoperative radiotherapy, surgical modality, flap size, postoperative healing, and other clinical outcomes were collected. Techniques, indications, and postoperative complications after repairing with supraclavicular flaps were described. A total of 16 male patients aged 58 to 79 years were involved, including 10 cases of postoperative pharyngeal fistula after hypopharyngeal cancer, 5 cases of postoperative pharyngeal fistula after laryngeal cancer, and 1 case of postoperative pharyngeal fistula after laryngeal and esophageal cancer. In 12 patients, the pharyngeal fistula was repaired by double island folding of the supraclavicular flap; in the remaining 4 patients, the pharyngeal fistula was repaired by the supraclavicular flaps combined with the pectoralis major flaps. The supraclavicular flap was 6 to 8 cm in width and 6 to 15 cm in length. Results: One patient developed partial necrosis at the distal end of the flap, which was successfully treated with debridement and dressing. The flaps grew well in the remaining 15 patients. Among them, a patient with a postoperative pharyngeal fistula after hypopharyngeal carcinoma was implanted with radioactive particles for tumor recurrence at the esophageal entrance, and died in the 11th month after surgery. Conclusions: The supraclavicular flap can achieve excellent results in the repair of pharyngeal fistula.

Investigation of Antimicrobial Effects of Polydopamine-Based Composite Coatings.

Herein, polydopamine (PDA)-based antimicrobial coatings loaded with silver nanoparticles (Ag NPs) and gentamicin were designed and prepared on glass slides using two different approaches. To our knowledge, this study was performed for the first time with the aim to compare these methods (viz., in situ loading and physical adsorption method) regarding the loading and release behavior of payloads. In one method, gentamicin was in situ loaded on PDA-coated substrates during PDA polymerization followed by Ag NPs immobilization (named as Ag@Gen/PDA); for the second method, Ag NPs and gentamicin were simultaneously loaded onto PDA via physical adsorption by immersing pre-formed PDA coatings into a mixed solution of Ag NPs and gentamicin (named as Ag/Gen@PDA). The loading and release characteristics of these antimicrobial coatings were compared, and both gave variable outcomes. The in situ loading method consequently provided a relatively slow release of loaded antimicrobials, i.e., approx. 46% for Ag@Gen/PDA as compared to 92% from physically adsorbed Ag/GenPDA in an immersion period of 30 days. A similar trend was observed for gentamicin release, i.e., ~0.006 µg/mL from Ag@Gen/PDA and 0.02 µg/mL from Ag/Gen@PDA each day. The slower antimicrobial release from Ag@Gen/PDA coatings would ultimately provide an effective long-term antimicrobial property as compared to Ag/Gen@PDA. Finally, the synergistic antimicrobial activities of these composite coatings were assessed against two microbial species, namely, Staphylococcus aureus and Escherichia coli, hence providing evidence in the prevention of bacterial colonization.

Multifunctional Fe3O4 Nanoparticles Filled Polydopamine Hollow Rods for Antibacterial Biofilm Treatment.

This work reports the use of mesoporous silica rods as templates for the step-wise preparation of multifunctional Fe3O4 NPs filled polydopamine hollow rods (Fe3O4@PDA HR). The capacity of as-synthesized Fe3O4@PDA HR as a new drug carrier platform was assessed by its loading and the triggered release of fosfomycin under various stimulations. It was found that the release of fosfomycin was pH dependent with ~89% of fosfomycin being released in pH 5 after 24 h, which was 2-fold higher than that in pH 7. The magnetic properties of Fe3O4 NPs and the photothermal properties of PDA enabled the triggered release of fosfomycin upon the exposure to rotational magnetic field, or NIR laser irradiation. Additionally, the capability of using multifunctional Fe3O4@PDA HR to eliminate preformed bacterial biofilm was demonstrated. Upon exposure to the rotational magnetic field, the biomass of a preformed biofilm was significantly reduced by 65.3% after a 20 min treatment with Fe3O4@PDA HR. Again, due to the excellent photothermal properties of PDA, a dramatic biomass decline (72.5%) was achieved after 10 min of laser exposure. This study offers an alternative approach of using drug carrier platform as a physical mean to kill pathogenic bacteria along with its traditional use for drug delivery.

Copper-based catalysts for the electrochemical reduction of carbon dioxide: progress and future prospects.

There is an urgent need for the development of high performance electrocatalysts for the CO2 reduction reaction (CO2RR) to address environmental issues such as global warming and achieve carbon neutral energy systems. In recent years, Cu-based electrocatalysts have attracted significant attention in this regard. The present review introduces fundamental aspects of the electrocatalytic CO2RR process together with a systematic examination of recent developments in Cu-based electrocatalysts for the electroreduction of CO2 to various high-value multicarbon products. Current challenges and future trends in the development of advanced Cu-based CO2RR electrocatalysts providing high activity and selectivity are also discussed.

Switchable C2/C3 positional selectivity of thioisatins in a three-component domino reaction: combined computational and experimental studies.

The nucleophile-induced domino reaction is a featured reactivity mode of thioisatin, but the C2/C3 positional selectivity towards a nucleophile has not been understood in-depth. In this work, a domino reaction of thioisatin with bromoacetophenone and tryptamine hydrochloride to produce a benzothiophene-fused eight-membered N-heterocycle was described, showing that the Brønsted acid-base form of the amine partner was crucial for the selectivity, because using tryptamine instead of tryptamine hydrochloride gave a different product. Control experiments and density functional calculations revealed that the domino reaction using tryptamine or tryptamine hydrochloride was triggered by a condensation reaction at the C2 or C3 position of thioisatin, respectively. A delicate balance between local electrophilicity and polarization effect may be responsible for the observed selectivity.

Ultra-Sensitive Photo-Induced Hydrogen Gas Sensor Based on Two-Dimensional CeO2-Pd-PDA/rGO Heterojunction Nanocomposite.

A two-dimensional (2D) CeO2-Pd-PDA/rGO heterojunction nanocomposite has been synthesised via an environmentally friendly, energy efficient, and facile wet chemical procedure and examined for hydrogen (H2) gas sensing application for the first time. The H2 gas sensing performance of the developed conductometric sensor has been extensively investigated under different operational conditions, including working temperature up to 200 °C, UV illumination, H2 concentrations from 50-6000 ppm, and relative humidity up to 30% RH. The developed ceria-based nanocomposite sensor was functional at a relatively low working temperature (100 °C), and its sensing properties were improved under UV illumination (365 nm). The sensor's response towards 6000 ppm H2 was drastically enhanced in a humid environment (15% RH), from 172% to 416%. Under optimised conditions, this highly sensitive and selective H2 sensor enabled the detection of H2 molecules down to 50 ppm experimentally. The sensing enhancement mechanisms of the developed sensor were explained in detail. The available 4f electrons and oxygen vacancies on the ceria surface make it a promising material for H2 sensing applications. Moreover, based on the material characterisation results, highly reactive oxidant species on the sensor surface formed the electron-hole pairs, facilitated oxygen mobility, and enhanced the H2 sensing performance.

Graphene-based electrochemical sensors for antibiotic detection in water, food and soil: A scientometric analysis in CiteSpace (2011-2021).

The residues of antibiotics in the environment pose a potential health hazard, so highly sensitive detection of antibiotics has always appealed to analytical chemists. With the widespread use of new low-dimensional materials, graphene-modified electrochemical sensors have emerged as an excellent candidate for highly sensitive detection of antibiotics. Graphene, its derivatives and its composites have been used in this field of exploration in the last decade. In this review, we have not only described the field using traditional summaries, but also used bibliometrics to quantify the development of the field. The literature between 2011 and 2021 was included in the analysis. Also, the sensing performance and detection targets of different sensors were compared. We were able to trace not only the flow of research themes, but also the future areas of development. Graphene is a material that has a high potential to be used on a large scale in the preparation of electrochemical sensors. How to design a sensor with selectivity and low cost is the key to bring this material from the laboratory to practical applications.

A Double-Deck Structure of Reduced Graphene Oxide Modified Porous Ti3C2Tx Electrode towards Ultrasensitive and Simultaneous Detection of Dopamine and Uric Acid.

Considering the vital physiological functions of dopamine (DA) and uric acid (UA) and their coexistence in the biological matrix, the development of biosensing techniques for their simultaneous and sensitive detection is highly desirable for diagnostic and analytical applications. Therefore, Ti3C2Tx/rGO heterostructure with a double-deck layer was fabricated through electrochemical reduction. The rGO was modified on a porous Ti3C2Tx electrode as the biosensor for the detection of DA and UA simultaneously. Debye length was regulated by the alteration of rGO mass on the surface of the Ti3C2Tx electrode. Debye length decreased with respect to the rGO electrode modified with further rGO mass, indicating that fewer DA molecules were capable of surpassing the equilibrium double layer and reaching the surface of rGO to achieve the voltammetric response of DA. Thus, the proposed Ti3C2Tx/rGO sensor presented an excellent performance in detecting DA and UA with a wide linear range of 0.1-100 µM and 1-1000 µM and a low detection limit of 9.5 nM and 0.3 µM, respectively. Additionally, the proposed Ti3C2Tx/rGO electrode displayed good repeatability, selectivity, and proved to be available for real sample analysis.

Stereoselective [4 + 3] annulation of azadienes and ethyl 4-bromo-3-oxobutanoate: construction of benzindeno-fused azepine derivatives.

The benzindenoazepine ring system is an attractive scaffold for biologically active compounds. This work reported a NaH-promoted cycloaddition between azadienes and ethyl 4-bromo-3-oxobutanoate, which delivered a series of benzindenoazepines with good yields and stereoselectivities. Such benzindenoazepine derivatives were not easily obtained by using a traditional approach. The application of this cycloaddition strategy has been extended to azadienes bearing a benzofuran or benzothiophene moiety. The utility of this method was showcased by gram-scale experiments and synthetic transformations of the product.

Catalyst-controlled switchable [4 + 1], [4 + 3] and [3 + 2] domino reactions of azadienes and MBH carbonates: diverse synthesis of benzothiophene fused derivatives.

Catalyst-controlled switchable domino reactions between azadienes bearing a benzothiophene moiety and isatin-derived MBH carbonates were developed. The [4 + 1] annulation was triggered in the presence of DABCO, giving a variety of benzothiophene fused pyrrole derivatives, while the [4 + 3] annulation occurred when changing the catalyst to DMAP. Furthermore, the [3 + 2] annulation mode was observed with the use of catalytic Ph2PMe. Additionally, the synthetic utility of these domino reactions was demonstrated by gram-scale experiments and simple transformations of the products. To the best of our knowledge, catalyst-controlled synthesis of benzothiophene fused or spiro derivatives has rarely been reported.

Early sex determination of Ginkgo biloba based on the differences in the electrocatalytic performance of extracted peroxidase.

Ginkgo biloba is a dioecious plant. Male ginkgoes are mainly used in landscaping, while females are mainly used for fruit production. However, sex identification of ginkgo is a difficult task, especially at the seedling stage. In this work, we present for the first time the use of electrochemical techniques for the identification of ginkgo sex based on the differences in peroxides within male and female ginkgos. Graphene was used to concentrate peroxides in ginkgo extract, thereby improving electrochemical signal sensitivity. The electrochemical reduction of hydrogen peroxide catalyzed by peroxidase was used as a prob for sex determination in ginkgo. This electrochemical identification technique can be used not only for the analysis of adult ginkgo, but also successfully for the analysis of tissue culture seedlings and live seedlings. This electrochemical sensor has excellent discrimination ability due to the difference in peroxidase content in the leaves and petiole of ginkgo of different sexes. This electrochemical sensor allows for a rapid identification of the sex of ginkgo and has a very strong potential for field analysis.

Divergent Construction of Benzothiophene-Fused N-Heterocycles via Stereotunable Three-Component Domino Reactions.

A stereotunable three-component domino strategy among thioisatin, 2-bromo-1-phenylethan-1-one, and cyclohexane-1,2-diamine under catalyst-free conditions was disclosed. A wide range of benzothiophene-fused polycycles and eight-membered N-heterocycles were synthesized by regulating the stereoconfiguration of cyclohexane-1,2-diamines. The detailed mechanism and the origin of the chemoselectivity were explored by density functional calculations. Analysis of the geometrical structures of key transition states revealed that the existence of favorable intramolecular attractions, and the steric effect governed the chemoselectivity observed.

Intertwined Carbon Nanotubes and Ag Nanowires Constructed by Simple Solution Blending as Sensitive and Stable Chloramphenicol Sensors.

Chloramphenicol (CAP) is a harmful compound associated with human hematopathy and neuritis, which was widely used as a broad-spectrum antibacterial agent in agriculture and aquaculture. Therefore, it is significant to detect CAP in aquatic environments. In this work, carbon nanotubes/silver nanowires (CNTs/AgNWs) composite electrodes were fabricated as the CAP sensor. Distinguished from in situ growing or chemical bonding noble metal nanomaterials on carbon, this CNTs/AgNWs composite was formed by simple solution blending. It was demonstrated that CNTs and AgNWs both contributed to the redox reaction of CAP in dynamics, and AgNWs was beneficial in thermodynamics as well. The proposed electrochemical sensor displayed a low detection limit of up to 0.08 µM and broad linear range of 0.1-100 µM for CAP. In addition, the CNTs/AgNWs electrodes exhibited good performance characteristics of repeatability and reproducibility, and proved suitable for CAP analysis in real water samples.

Fe3O4@polydopamine and Exo III-assisted homogeneous biorecognition reaction for convenient and ultrasensitive detection of kanamycin antibiotic.

Herein, we report a Fe3O4@polydopamine (PDA) nanocomposite and exonuclease III (Exo III)-assisted homogeneous fluorescence biosensing method for ultrasensitive detection of kanamycin (Kana) antibiotic. A hairpin DNA containing the Kana-aptamer sequence (HP) was first designed for the highly specific biorecognition of the target analyte. Because of the aptamer biorecognition-induced structural change of HP and the highly effective catalyzed reaction of Exo III, a large amount of fluorophore labels were released from the designed fluorescence DNA probe. During the homogeneous reaction process, the Exo III-assisted dual recycling significantly amplified the fluorescence signal output. Moreover, the excessive probes were easily adsorbed and separated by the Fe3O4@PDA nanocomposite, which decreased the background signal and increased the signal-to-noise ratio. These strategies result in the excellent analytical performance of the method, including a very low detection limit of 0.023 pg mL-1 and a very wide linear range of six orders of magnitude. In addition, this method has convenient operation, excellent selectivity, repeatability and satisfactory reliability, and does not involve the design and utilization of complicated DNA sequences. Thus, it exhibits a promising prospect for practical applications.

Correction: Determination of sulfonamides in blood using acetonitrile-salt aqueous two-phase extraction coupled with high-performance liquid chromatography and liquid chromatography-tandem mass spectrometry.

Correction for 'Determination of sulfonamides in blood using acetonitrile-salt aqueous two-phase extraction coupled with high-performance liquid chromatography and liquid chromatography-tandem mass spectrometry' by Wei Yu et al., Anal. Methods, 2013, 5, 5983-5989, DOI: 10.1039/C3AY40902C.

Construction of Benzothiophene or Benzothiopheno[2,3-e]azepinedione Derivatives via Three-Component Domino or One-Pot Sequences.

An efficient three-component domino or one-pot strategy has been developed for the synthesis of medicinally important benzothiophene and benzothiopheno[2,3-e]azepinedione derivatives for the first time. Amine-promoted selective cleavage of C-S bond of thioisatin is the key step in this process. The reported methodology benefits from environmentally friendly solvent (H2O), wide substrate scope, good functional group tolerance, and high reaction yields.

Polydopamine Nanosphere with In-Situ Loaded Gentamicin and Its Antimicrobial Activity.

The mussel inspired polydopamine has acquired great relevance in the field of nanomedicines, owing to its incredible physicochemical properties. Polydopamine nanoparticles (PDA NPs) due to their low cytotoxicity, high biocompatibility and ready biodegradation have already been widely investigated in various drug delivery, chemotherapeutic, and diagnostic applications. In addition, owing to its highly reactive nature, it possesses a very high capability for loading drugs and chemotherapeutics. Therefore, the loading efficiency of PDA NPs for an antibiotic i.e., gentamicin (G) has been investigated in this work. For this purpose, an in-situ polymerization method was studied to load the drug into PDA NPs using variable drug: monomer ratios. Scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) confirmed the successful loading of drug within PDA NPs, mainly via hydrogen bonding between the amine groups of gentamicin and the hydroxyl groups of PDA. The loading amount was quantified by liquid chromatography-mass spectrometry (LC-MS) and the highest percentage loading capacity was achieved for G-PDA prepared with drug to monomer ratio of 1:1. Moreover, the gentamicin loaded PDA NPs were tested in a preliminary antibacterial evaluation using the broth microdilution method against both Gram-(+) Staphylococcus aureus and Gram-(-) Pseudomonas aeruginosa microorganisms. The highest loaded G-PDA sample exhibited the lowest minimum inhibitory concentration and minimum bactericidal concentration values. The developed gentamicin loaded PDA is very promising for long term drug release and treating various microbial infections.