Black Titanium Oxide/Activated TaS2 Flakes Photoelectrode for Plasmon Assisted Hydrogen Evolution at Neutral pH at High Current Density.

A heterojunction photo-electrode(s) consisting of porous black titanium oxide (bTiO2) and electrochemically self-activated TaS2 flakes is proposed and utilized for hydrogen evolution reaction (HER). The self-activated TaS2 flakes provide abundant catalytic sites for HER and the porous bTiO2, prepared by electrochemical anodization and subsequent reduction serves as an efficient light absorber, providing electrons for HER. Additionally, Au nanostructures are introduced between bTiO2 and TaS2 to facilitate the charge transfer and plasmon-triggering ability of the structure created. After structure optimization, high HER catalytic activity at acidic pH and excellent HER activity at neutral pH are achieved at high current densities. In particular, with the utilization of bTiO2@TaS2 photoelectrode (neutral electrolyte, sunlight illumination) current densities of 250 and 500 mA cm-2 are achieved at overpotentials of 433, and 689 mV, respectively, both exceeding the "benchmark" Pt. The addition of gold nanostructures further reduces the overpotential to 360 and 543 mV at 250 and 500 mA cm-2, respectively. The stability of the prepared electrodes is investigated and found to be satisfying within 24 h of performance at high current densities. The proposed system offers an excellent potential alternative to Pt for the development of green hydrogen production on an industrial scale.

Rapid and Universal Synthesis of 2D Transition Metal (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) Sulfides through Oxide Sulfurization in CS2 Vapor.

Transition metal (TM) sulfides belong to the class of 2D materials with a wide application range. Various methods, including solvothermal, hydrothermal, chemical vapor deposition, and quartz ampoule-based approaches, have been employed for the synthesis of TM sulfides. Some of them face limitations due to the low stability of TM sulfides and their susceptibility to oxidation, and others require more sophisticated equipment or complex and rare precursors or are not scalable. In this work, we propose an alternative approach for the synthesis of 2D TM sulfides by sulfurization of corresponding metal oxides in the vapor of CS2 at elevated temperature. Subsequent treatment in liquid nitrogen allows exfoliation of created sulfides to a 2D structure. A proposed approach was successfully applied to nine transition metals: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W. The resulting materials were extensively characterized using various analytical techniques with a focus on their crystalline structure and 2D nature. Our approach offers several advantages including the use of simple precursors (CS2 and metal oxides), universality (in all cases, the sulfides were obtained), equipment simplicity (tube furnace and quartz reactor), short preparation time (3 h), and the ability of morphology and phase tuning (in particular cases) of the created materials by adjusting the temperature. In addition, gram-scale bulk materials can be obtained in the entry-level laboratories using the proposed approach.

Detection of trace amounts of insoluble pharmaceuticals in water by extraction and SERS measurements in a microfluidic flow regime.

Detection of trace amounts of poorly water-soluble pharmaceuticals or related (bio)solutions represents a key challenge in environment protection and clinical diagnostics. However, this task is complicated by low concentrations of pharmaceuticals, complex sample matrices, and sophisticated sample preparative routes. In this work, we present an alternative approach on the basis of an on-line flow extraction procedure and SERS measurements performed in a microfluidic regime. The advantages of our approach were demonstrated using ibuprofen (Ibu), which is considered as a common pharmaceutical contaminant in wastewater and should be monitored in various bioliquids. The extraction of Ibu from water to the dichloromethane phase was performed with an optimized microfluidic mixer architecture. As SERS tags, lipophilic functionalized gold multibranched nanoparticles (AuMs) were added to the organic phase. After microfluidic extraction, Ibu was captured by the functionalized AuM surface and recognized by on-line SERS measurements with up to 10-8 M detection limit. The main advantages of the proposed approach can be regarded as its simplicity, lack of need for preliminary sample preparation, high reliability, the absence of sample pretreatment, and low detection limits.

Optomechanical Processing of Silver Colloids: New Generation of Nanoparticle-Polymer Composites with Bactericidal Effect.

The properties of materials at the nanoscale open up new methodologies for engineering prospective materials usable in high-end applications. The preparation of composite materials with a high content of an active component on their surface is one of the current challenges of materials engineering. This concept significantly increases the efficiency of heterogeneous processes moderated by the active component, typically in biological applications, catalysis, or drug delivery. Here we introduce a general approach, based on laser-induced optomechanical processing of silver colloids, for the preparation of polymer surfaces highly enriched with silver nanoparticles (AgNPs). As a result, the AgNPs are firmly immobilized in a thin surface layer without the use of any other chemical mediators. We have shown that our approach is applicable to a broad spectrum of polymer foils, regardless of whether they absorb laser light or not. However, if the laser radiation is absorbed, it is possible to transform smooth surface morphology of the polymer into a roughened one with a higher specific surface area. Analyses of the release of silver from the polymer surface together with antibacterial tests suggested that these materials could be suitable candidates in the fight against nosocomial infections and could inhibit the formation of biofilms with a long-term effect.

Surface Plasmon-Polariton: A Novel Way To Initiate Azide-Alkyne Cycloaddition.

Plasmon catalysis has recently generated tremendous interest in the field of modern chemistry. Application of plasmon introduces the principally new stimulus for the activation of organic reactions, keeping the optical energy concentrated in the vicinity of plasmonic structure, creating an optical near-field enhancement as well as hot electron injection. In this work, for the first time, we presented a new way for the initiation of the azide-alkyne cycloaddition (AAC) using the surface plasmon-polariton wave, supported by the gold grating. With this concept in hand, the plasmon-active gold grating was functionalized with 4-ethynylbenzenediazonium compound. Then, surface-grafted 4-ethynylphenyl groups were plasmon activated and clicked with 4-azidobenzoic acid. Additional experiments allowed to exclude the potential effect of photon, heating, and metal impurities confirmed the key role of surface plasmon-polariton AAC activation. For the investigation of plasmon-induced AAC mechanism, 4-azidophenyl groups (instead of 4-ethynylphenyl groups) were also grafted to the grating surface. Further careful evaluation of reaction kinetics demonstrates that the AAC reaction rate is significantly higher in the case of acetylene activation than in the case of azide activation.

Rapid SERS-based recognition of cell secretome on the folic acid-functionalized gold gratings.

Nowadays, functionalization of the plasmon-supported nanostructured surface is considered as a powerful tool for tumour cell recognition. In this study, the SERS on a surface plasmon polariton-supported gold grating functionalized with folic acid was used to demonstrate an unpretentious recognition of melanoma-associated fibroblasts. Using cultivation media conditioned by different cells, we were able to detect reproducible differences in the secretome of melanoma-associated and normal control fibroblasts. The homogeneous distribution of plasmon energy along the grating surface was proved to provide excellent SERS signal reproducibility, while, to increase the affinity of (bio)molecules to SERS substrate, folic acid molecules were covalently grafted to the gold gratings. As proof of concept, fibroblasts were cultured in vitro, and culture media from the normal and tumour-associated lines were collected and analysed with our proposed SERS substrates. Identifying individual peaks of the Raman spectra as well as comparing their relative intensities, we showed that the proposed functional SERS platform can recognise the melanoma-associated cells without the need for further statistical spectral evaluation directly. We also demonstrated that the SERS chip created provided a stable SERS signal over a period of 90 days without loss of sensitivity. Graphical abstract.

Preparation of Selective and Reproducible SERS Sensors of Hg2+ Ions via a Sunlight-Induced Thiol⁻Yne Reaction on Gold Gratings.

In this contribution, we propose a novel functional surface-enhanced Raman spectroscopy (SERS) platform for the detection of one of the most hazardous heavy metal ions, Hg2+. The design of the proposed sensor is based on the combination of surface plasmon-polariton (SPP) supporting gold grating with the high homogeneity of the response and enhancement and mercaptosuccinic acid (MSA) based specific recognition layer. For the first time, diazonium grafted 4-ethynylphenyl groups have undergone the sunlight-induced thiol-yne reaction with MSA in the presence of Eosine Y. The developed SERS platform provides an extremely sensitive, selective, and convenient analytical procedure to detect mercury ions with limit of detection (LOD) as low as 10-10 M (0.027 µg/L) with excellent selectivity over other metals. The developed SERS sensor is compatible with a portable SERS spectrophotometer and does not require the expensive equipment for statistical methods of analysis.

Ultrasensitive and reproducible SERS platform of coupled Ag grating with multibranched Au nanoparticles.

Surface-enhanced Raman scattering (SERS) spectroscopy is an extremely sensitive analytical technique that is capable of identifying the vibration signatures of target molecules up to single-molecule sensitivity. In this work, the ultrahigh sensitivity of SERS has been achieved through the immobilization of sharp-edges specific nanoparticles - so-called gold multibranched NPs (AuMs) on the silver grating surface through the biphenyl dithiol. This approach allows combining the extremely high SERS enhancement factor (better than that in the case of AuMs immobilized on the flat Ag film) with perfect reproducibility of Raman signals. The grating was created on the polymer substrate using the excimer laser modification and further metal deposition and has an "active" area 5 × 10 mm2, enabling the macroscale SERS substrate preparation. The wet-chemistry synthesized AuMs were then immobilized on the grating surface and the produced structure allows SERS measurements with a portable Raman spectrophotometer. The prepared structures were checked using the AFM, UV-Vis, and Raman spectroscopy techniques.

Label-free SERS-ML detection of cocaine trace in human blood plasma.

The widespread consumption of cocaine poses a significant threat to modern society. The most effective way to combat this problem is to control the distribution of cocaine, based on its accurate and sensitive detection. Here, we proposed the detection of cocaine in human blood plasma using a combination of surface enhanced Raman spectroscopy and machine learning (SERS-ML). To demonstrate the efficacy of our proposed approach, cocaine was added into blood plasma at various concentrations and drop-deposited onto a specially prepared disposable SERS substrate. SERS substrates were created by deposition of metal nanoclusters on electrospun polymer nanofibers. Subsequently, SERS spectra were measured and as could be expected, the manual distinguishing of cocaine from the spectra proved unfeasible, as its signal was masked by the background signal from blood plasma molecules. To overcome this issue, a database of SERS spectra of cocaine in blood plasma was collected and used for ML training and validation. After training, the reliability of proposed approach was tested on independently prepared samples, with unknown for SERS-ML cocaine presence or absence. As a result, the possibility of rapid determination of cocaine in blood plasma with a probability above 99.5% for cocaine concentrations up to 10-14 M was confirmed. Therefore, it is evident that the proposed approach has the ability to detect trace amounts of cocaine in bioliquids in an express and simple manner.

Polymer-Metal Bilayer with Alkoxy Groups for Antibacterial Improvement.

Many bio-applicable materials, medical devices, and prosthetics combine both polymer and metal components to benefit from their complementary properties. This goal is normally achieved by their mechanical bonding or casting only. Here, we report an alternative easy method for the chemical grafting of a polymer on the surfaces of a metal or metal alloys using alkoxy amine salt as a coupling agent. The surface morphology of the created composites was studied by various microscopy methods, and their surface area and porosity were determined by adsorption/desorption nitrogen isotherms. The surface chemical composition was also examined by various spectroscopy techniques and electrokinetic analysis. The distribution of elements on the surface was determined, and the successful bonding of the metal/alloys on one side with the polymer on the other by alkoxy amine was confirmed. The composites show significantly increased hydrophilicity, reliable chemical stability of the bonding, even interaction with solvent for thirty cycles, and up to 95% less bacterial adhesion for the modified samples in comparison with pristine samples, i.e., characteristics that are promising for their application in the biomedical field, such as for implants, prosthetics, etc. All this uses universal, two-step procedures with minimal use of energy and the possibility of production on a mass scale.

Plasmon-Mediated Organic Photoelectrochemistry Applied to Amination Reactions.

Organic electrochemistry is currently experiencing an era of renaissance, which is closely related to the possibility of carrying out organic transformations under mild conditions, with high selectivity, high yields, and without the use of toxic solvents. Combination of organic electrochemistry with alternative approaches, such as photo-chemistry was found to have great potential due to induced synergy effects. In this work, we propose for the first time utilization of plasmon triggering of enhanced and regio-controlled organic chemical transformation performed in photoelectrochemical regime. The advantages of the proposed route is demonstrated in the model amination reaction with formation of C-N bond between pyrazole and substituted benzene derivatives. Amination was performed in photo-electrochemical mode on the surface of plasmon active Au@Pt electrode with attention focused on the impact of plasmon triggering on the reaction efficiency and regio-selectivity. The ability to enhance the reaction rate significantly and to tune products regio-selectivity is demonstrated. We also performed density functional theory calculations to inquire about the reaction mechanism and potentially explain the plasmon contribution to electrochemical reaction rate and regioselectivity.

Surface-Enhanced Raman Spectroscopy and Artificial Neural Networks for Detection of MXene Flakes' Surface Terminations.

The properties of MXene flakes, a new class of two-dimensional materials, are strictly determined by their surface termination. The most common termination groups are oxygen-containing (=O or -OH) and fluorine (-F), and their relative ratio is closely related to flake stability and catalytic activity. The surface termination can vary significantly among MXene flakes depending on the preparation route and is commonly determined after flake preparation by using X-ray photoelectron spectroscopy (XPS). In this paper, as an alternative approach, we propose the combination of surface-enhanced Raman spectroscopy (SERS) and artificial neural networks (ANN) for the precise and reliable determination of MXene flakes' (Ti3C2Tx) surface chemistry. Ti3C2Tx flakes were independently prepared by three scientific groups and subsequently measured using three different Raman spectrometers, employing resonant excitation wavelengths. Manual analysis of the SERS spectra did not enable accurate determination of the flake surface termination. However, the combined SERS-ANN approach allowed us to determine the surface termination with a high accuracy. The reliability of the method was verified by using a series of independently prepared samples. We also paid special attention to how the results of the SERS-ANN method are affected by the flake stability and differences in the conditions of flake preparation and Raman measurements. This way, we have developed a universal technique that is independent of the above-mentioned parameters, providing the results with accuracy similar to XPS, but enhanced in terms of analysis time and simplicity.

Smart multi stimuli-responsive electrospun nanofibers for on-demand drug release.

Here, we report poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAm-co-AAc) microgel-loaded polycaprolactone (PCL) nanofibers as temperature-, pH- and electro-responsive materials. First, the PNIPAm-co-AAc microgels were prepared by precipitation polymerization and then electrospun with PCL. The morphology of the prepared materials, analysed by scanning electron microscopy, showed a narrow nanofiber distribution in the range of 500-800 nm, depending on microgel content. Refractometry measurements, performed at pH4 and 6.5, as well as in distilled water, indicated the thermo- and pH-responsive behaviour of the nanofibers between 31 and 34 °C. After being thoroughly characterized, the prepared nanofibers were loaded with crystal violet (CV) or gentamicin as model drugs. The application of a pulsed voltage led to a pronounced increase in drug release kinetics, which was also dependent on microgel content. In addition, long-term temperature- and pH-responsive release was demonstrated. Next, the prepared materials displayed switchable antibacterial activity against S. aureus and E. coli. Finally, cell compatibility tests showed that NIH 3T3 fibroblasts spread evenly over the nanofiber surface, confirming that the nanofibers serve as a favourable support for cell growth. Overall, the prepared nanofibers offer switchable drug release and appear to have considerable biomedical potential, particularly in wound healing.

Beyond the Platinum Era─Scalable Preparation and Electrochemical Activation of TaS2 Flakes.

Among 2D materials, transition-metal dichalcogenides (TMDCs) of group 5 metals recently have attracted substantial interest due to their superior electrocatalytic activity toward hydrogen evolution reaction (HER). However, a straightforward and efficient synthesis of the TMDCs which can be easily scaled up is missing. Herein, we report an innovative, simple, and scalable method for tantalum disulfide (TaS2) synthesis, involving CS2 as a sulfurizing agent and Ta2O5 as a metal precursor. The structure of the created TaS2 flakes was analyzed by Raman, XRD, XPS, SEM, and HRTEM techniques. It was demonstrated that a tuning between 1T (metallic) and 3R (semiconductor) TaS2 phases can be accomplished by varying the reaction conditions. The created materials were tested for HER, and the electrocatalytic activity of both phases was significantly enhanced by electrochemical self-activation, up to that comparable with the Pt one. The final values of the Tafel slopes of activated TaS2 were found to be 35 and 43 mV/dec for 3R-TaS2 and 1T-TaS2, respectively, with the corresponding overpotentials of 63 and 109 mV required to reach a current density of 10 mA/cm2. We also investigated the mechanism of flake activation, which can be attributed to the changes in the flake morphology and surface chemistry. Our work provides a scalable and simple synthesis method to produce transition-metal sulfides which could replace the platinum catalyst in water splitting technology.

Coupling of plasmonic hot spots with shurikens for superchiral SERS-based enantiomer recognition.

Detection of enantiomers is a challenging problem in drug development as well as environmental and food quality monitoring where traditional optical detection methods suffer from low signals and sensitivity. Application of surface enhanced Raman scattering (SERS) for enantiomeric discrimination is a powerful approach for the analysis of optically active small organic or large biomolecules. In this work, we proposed the coupling of disposable chiral plasmonic shurikens supporting the chiral near-field distribution with SERS active silver nanoclusters for enantio-selective sensing. As a result of the plasmonic coupling, significant difference in SERS response of optically active analytes is observed. The observations are studied by numerical simulations and it is hypothesized that the silver particles are being excited by superchiral fields generated at the surface inducing additional polarizations in the probe molecules. The plasmon coupling phenomena was found to be extremely sensitive to slight variations in shuriken geometry, silver nanostructured layer parameters, and SERS excitation wavelength(s). Designed structures were able to discriminate cysteine enantiomers at concentrations in the nanomolar range and probe biomolecular chirality, using a common Raman spectrometer within several minutes. The combination of disposable plasmonic substrates with specific near-field polarization can make the SERS enantiomer discrimination a commonly available technique using standard Raman spectrometers.

Nitrogen Photoelectrochemical Reduction on TiB2 Surface Plasmon Coupling Allows Us to Reach Enhanced Efficiency of Ammonia Production.

Ammonia is one of the most widely produced chemicals worldwide, which is consumed in the fertilizer industry and is also considered an interesting alternative in energy storage. However, common ammonia production is energy-demanding and leads to high CO2 emissions. Thus, the development of alternative ammonia production methods based on available raw materials (air, for example) and renewable energy sources is highly demanding. In this work, we demonstrated the utilization of TiB2 nanostructures sandwiched between coupled plasmonic nanostructures (gold nanoparticles and gold grating) for photoelectrochemical (PEC) nitrogen reduction and selective ammonia production. The utilization of the coupled plasmon structure allows us to reach efficient sunlight capture with a subdiffraction concentration of light energy in the space, where the catalytically active TiB2 flakes were placed. As a result, PEC experiments performed at -0.2 V (vs. RHE) and simulated sunlight illumination give the 535.2 and 491.3 µg h-1 mgcat-1 ammonia yields, respectively, with the utilization of pure nitrogen and air as a nitrogen source. In addition, a number of control experiments confirm the key role of plasmon coupling in increasing the ammonia yield, the selectivity of ammonia production, and the durability of the proposed system. Finally, we have performed a series of numerical and quantum mechanical calculations to evaluate the plasmonic contribution to the activation of nitrogen on the TiB2 surface, indicating an increase in the catalytic activity under the plasmon-generated electric field.

Creation and Plasmon-Assisted Photosensitization of Annealed Z-Schemes for Sunlight-Only Water Splitting.

Solely light-induced water splitting represents a promising avenue for a carbon-free energy future, based on reliable energy sources. Such processes can be performed using coupled semiconductor materials (the so-called direct Z-scheme design) that facilitate spatial separation of (photo)excited electrons and holes, prevent their recombination, and allow water-splitting half-reactions proceeding at each corresponding semiconductor side. In this work, we proposed and prepared a specific structure, based on WO3g-x/CdWO4/CdS coupled semiconductors, created by annealing of a common WO3/CdS direct Z-scheme. WO3-x/CdWO4/CdS flakes were further combined with a plasmon-active grating for the creation of the so-called artificial leaf design, making possible complete utilization of the sunlight spectrum. The proposed structure enables water splitting with high production of stoichiometric amounts of oxygen and hydrogen without undesirable catalyst photodegradation. Several control experiments confirm the creation of electrons and holes participating in the water splitting half-reaction in a spatially selective manner.

Plasmon assisted Ti3C2Tx grafting and surface termination tuning for enhancement of flake stability and humidity sensing performance.

Humidity sensors play a critical role in monitoring human activities, environmental health, food processing and storage, and many other fields. Recently, some 2D materials, particularly MXenes, have been considered as promising candidates for creating humidity sensors because of their high surface area, surface-to-bulk ratio, and excellent conductivity, arising from the high concentration and mobility of free electrons. In this work, we propose the plasmon-assisted surface modification and termination tuning of common MXene (Ti3C2Tx) to enhance their response to humidity and increase their stability against oxidation. Hydrophobic (-C6H4-CF3) and hydrophilic (-C6H4-COOH) chemical moieties were covalently grafted to the Ti3C2Tx surface using plasmon-mediated diazonium chemistry. In situ Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS) measurements, performed at different humidity levels indicate that surface modification significantly affects penetration of water molecules in Ti3C2Tx films. As a result, the sensitivity of the flakes to the presence of water molecules was significantly altered. Additionally, proposed surface grafting commonly proceeds on the less stable MXene surface sites, where flake oxidation commonly initiates. As a result of the modification, such "weak" and more chemically active sites were blocked and Ti3C2Tx stability was significantly enhanced.

Ciprofloxacin-Loaded Poly(N-isopropylacrylamide-co-acrylamide)/Polycaprolactone Nanofibers as Dual Thermo- and pH-Responsive Antibacterial Materials.

Nanofibers are an attractive option in drug release, especially as antibacterial materials. However, there is no universal antibacterial material and little attention has been devoted to bacteria-nanofiber attachment. Poly(N-isopropylacrylamide-co-acrylamide) is particularly interesting due to its dual thermo- and pH-responsive nature. Here, we prepared stimuli-responsive antibacterial nanofibers by the blend electrospinning of polycaprolactone (PCL), various concentrations of PNIPAm-co-AAm and ciprofloxacin (CIP). The lower critical solution temperature (LCST) of PNIPAm-co-AAm was determined by refractometry in distilled water and buffer solutions at pH 4 and 7.4. Based on the results obtained, we performed release tests, which indicated that the amount of released CIP and its release kinetics were dependent on nanofiber composition. Moreover, the nanofibers showed enhanced release at temperatures below LCST and, in turn, this led to enhanced antibacterial activity, as demonstrated by disk diffusion tests on Staphylococcus epidermidis and Escherichia coli. In addition, both bacterial strains demonstrated much lower attachment to CIP-loaded PCL/PNIPAm-co-AAm compared with CIP-loaded PCL nanofibers. Furthermore, cytocompatibility tests, performed using primary human dermal fibroblasts, produced similar good cell spreading regardless of PNIPAm-co-AAm concentration. Collectively, our results show that the proposed nanofibers have considerable potential as materials, which promote wound healing and significantly decrease the probability of bacterial infection.

Decoration of Ultramicrotome-Cut Polymers with Silver Nanoparticles: Effect of Post-Deposition Laser Treatment.

Today, ultramicrotome cutting is a practical tool, which is frequently applied in the preparation of thin polymeric films. One of the advantages of such a technique is the decrease in surface roughness, which enables an effective recording of further morphological changes of polymeric surfaces during their processing. In view of this, we report on ultramicrotome-cut polymers (PET, PEEK) modified by a KrF excimer laser with simultaneous decoration by AgNPs. The samples were immersed into AgNP colloid, in which they were exposed to polarized laser light. As a result, both polymers changed their surface morphology while simultaneously being decorated with AgNPs. KrF laser irradiation of the samples resulted in the formation of ripple-like structures on the surface of PET and worm-like ones in the case of PEEK. Both polymers were homogeneously covered by AgNPs. The selected area of the samples was then irradiated by a violet semiconductor laser from the confocal laser scanning microscope with direct control of the irradiated area. Various techniques, such as AFM, FEGSEM, and CLSM were used to visualize the irradiated area. After irradiation, the reverse pyramid was formed for both types of polymers. PET samples exhibited thicker transparent reverse pyramids, whereas PEEK samples showed thinner brownish ones. We believe that his technique can be effectively used for direct polymer writing or the preparation of stimuli-responsive nanoporous membranes.