Focusing light with a metal film coated patchy particle.

Microsphere-assisted super-resolution imaging is a promising technique that can significantly enhance the resolution of conventional optical microscopes. The focus of a classical microsphere is called photonic nanojet, which is a symmetric high-intensity electromagnetic field. Recently, patchy microspheres have been reported to have superior imaging performance than pristine microspheres, and coating microspheres with metal films leads to the formation of photonic hooks, which can enhance the imaging contrast of microspheres. Understanding the influence of metal patches on the near-field focusing of patchy particles is important for the rational design of a nanostructured microlens. In this work, we theoretically and experimentally showed that the light waves can be focused and engineered using patchy particles. When coating dielectric particles with Ag films, light beams with a hook-like structure or S-shaped structure can be generated. Simulation results show that the waveguide ability of metal films and the geometric asymmetry of patchy particles cause the formation of S-shaped light beams. Compared with classical photonic hooks, S-shaped photonic hooks have a longer effective length and a smaller beam waist at far-field region. Experiments were also carried out to demonstrate the generation of classical and S-shaped photonic hooks from patchy microspheres.

Boron Nitride-Doped Polyphenylenic Organogels.

Herein, we describe the synthesis of the first boron nitride-doped polyphenylenic material obtained through a [4 + 2] cycloaddition reaction between a triethynyl borazine unit and a biscyclopentadienone derivative, which undergoes organogel formation in chlorinated solvents (the critical jellification concentration is 4% w/w in CHCl3). The polymer has been characterized extensively by Fourier-transform infrared spectroscopy, solid-state 13C NMR, solid-state 11B NMR, and by comparison with the isolated monomeric unit. Furthermore, the polymer gels formed in chlorinated solvents have been thoroughly characterized and studied, showing rheological properties comparable to those of polyacrylamide gels with a low crosslinker percentage. Given the thermal and chemical stability, the material was studied as a potential support for solid-state electrolytes. showing properties comparable to those of polyethylene glycol-based electrolytes, thus presenting great potential for the application of this new class of material in lithium-ion batteries.

Heat-based transdermal delivery of a ramipril loaded cream for treating hypertension.

Angiotensin-converting enzyme (ACE) inhibitors play an important role in the development of anti-hypertension approaches, with ramipril being one of the most widely used ACE inhibitor prodrugs orally administered once or twice a day. Due to its low bioavailability, large amounts have to be administered to obtain a therapeutic effect. In this work, we propose a ramipril loaded pharmaceutical formulation in contact with an electrothermal actuator based on a gold nanohole array as an efficient approach to increase the transdermal ramipril flux. Using rats as an in vivo model, the effect on the systolic and diastolic blood pressure is evaluated, showing that under optimized conditions the blood pressure could be regulated. Heat activation resulted in total drug delivery out of a bandage loaded with 1 mg ramipril, revealing a flux of 50.9 ± 2.8 µg cm-2 h-1. Importantly, heat-based transdermal dispensing allowed efficient and rapid delivery of ramipril in spontaneously hypertensive rats, with its active form (ramiprilat) detected in blood as early as 5 minutes after delivery onset, accompanied by significant decrease in blood pressure.

High-resolution impedance mapping using electrically activated quantitative phase imaging.

Retrieving electrical impedance maps at the nanoscale rapidly via nondestructive inspection with a high signal-to-noise ratio is an unmet need, likely to impact various applications from biomedicine to energy conversion. In this study, we develop a multimodal functional imaging instrument that is characterized by the dual capability of impedance mapping and phase quantitation, high spatial resolution, and low temporal noise. To achieve this, we advance a quantitative phase imaging system, referred to as epi-magnified image spatial spectrum microscopy combined with electrical actuation, to provide complementary maps of the optical path and electrical impedance. We demonstrate our system with high-resolution maps of optical path differences and electrical impedance variations that can distinguish nanosized, semi-transparent, structured coatings involving two materials with relatively similar electrical properties. We map heterogeneous interfaces corresponding to an indium tin oxide layer exposed by holes with diameters as small as ~550 nm in a titanium (dioxide) over-layer deposited on a glass support. We show that electrical modulation during the phase imaging of a macro-electrode is decisive for retrieving electrical impedance distributions with submicron spatial resolution and beyond the limitations of electrode-based technologies (surface or scanning technologies). The findings, which are substantiated by a theoretical model that fits the experimental data very well enable achieving electro-optical maps with high spatial and temporal resolutions. The virtues and limitations of the novel optoelectrochemical method that provides grounds for a wider range of electrically modulated optical methods for measuring the electric field locally are critically discussed.

The impact of chemical engineering and technological advances on managing diabetes: present and future concepts.

Monitoring blood glucose levels for diabetic patients is critical to achieve tight glycaemic control. As none of the current antidiabetic treatments restore lost functional ß-cell mass in diabetic patients, insulin injections and the use of insulin pumps are most widely used in the management of glycaemia. The use of advanced and intelligent chemical engineering, together with the incorporation of micro- and nanotechnological-based processes have lately revolutionized diabetic management. The start of this concept goes back to 1974 with the description of an electrode that repeatedly measures the level of blood glucose and triggers insulin release from an infusion pump to enter the blood stream from a small reservoir upon need. Next to the insulin pumps, other drug delivery routes, including nasal, transdermal and buccal, are currently investigated. These processes necessitate competences from chemists, engineers-alike and innovative views of pharmacologists and diabetologists. Engineered micro and nanostructures hold a unique potential when it comes to drug delivery applications required for the treatment of diabetic patients. As the technical aspects of chemistry, biology and informatics on medicine are expanding fast, time has come to step back and to evaluate the impact of technology-driven chemistry on diabetics and how the bridges from research laboratories to market products are established. In this review, the large variety of therapeutic approaches proposed in the last five years for diabetic patients are discussed in an applied context. A survey of the state of the art of closed-loop insulin delivery strategies in response to blood glucose level fluctuation is provided together with insights into the emerging key technologies for diagnosis and drug development. Chemical engineering strategies centered on preserving and regenerating functional pancreatic ß-cell mass are evoked in addition as they represent a permanent solution for diabetic patients.

Plasmon-Driven Electrochemical Methanol Oxidation on Gold Nanohole Electrodes.

Direct methanol oxidation is expected to play a central role in low-polluting future power sources. However, the sluggish and complex electro-oxidation of methanol is one of the limiting factors for any practical application. To solve this issue, the use of plasmonic is considered as a promising way to accelerate the methanol oxidation reaction. In this study, we report on a novel approach for achieving enhanced methanol oxidation currents. Perforated gold thin film anodes were decorated with Pt/Ru via electrochemical deposition and investigated for their ability for plasmon-enhanced electrocatalytic methanol oxidation in alkaline media. The novel methanol oxidation anode (AuNHs/PtRu), combining the strong light absorption properties of a gold nanoholes array-based electrode (AuNHs) with surface-anchored bimetallic Pt/Ru nanostructures, known for their high activity toward methanol oxidation, proved to be highly efficient in converting methanol via the hot holes generated in the plasmonic electrode. Without light illumination, AuNHs/PtRu displayed a maximal current density of 13.7 mA/cm2 at -0.11 V vs Ag/AgCl. Enhancement to 17.2 mA/cm2 was achieved under 980 nm laser light illumination at a power density of 2 W/cm2. The thermal effect was negligible in this system, underlining a dominant plasmon process. Fast generation and injection of charge carriers were also evidenced by the abrupt change in the current density upon laser irradiation. The good stability of the interface over several cycles makes this system interesting for methanol electro-oxidation.

Direct Visualization of Current-Stimulated Oxygen Migration in YBa2Cu3O7-δ Thin Films.

The past years have witnessed major advancements in all-electrical doping control on cuprates. In the vast majority of cases, the tuning of charge carrier density has been achieved via electric field effect by means of either a ferroelectric polarization or using a dielectric or electrolyte gating. Unfortunately, these approaches are constrained to rather thin superconducting layers and require large electric fields in order to ensure sizable carrier modulations. In this work, we focus on the investigation of oxygen doping in an extended region through current-stimulated oxygen migration in YBa2Cu3O7-δ superconducting bridges. The underlying methodology is rather simple and avoids sophisticated nanofabrication process steps and complex electronics. A patterned multiterminal transport bridge configuration allows us to electrically assess the directional counterflow of oxygen atoms and vacancies. Importantly, the emerging propagating front of current-dependent doping δ is probed in situ by optical microscopy and scanning electron microscopy. The resulting imaging techniques, together with photoinduced conductivity and Raman scattering investigations, reveal an inhomogeneous oxygen vacancy distribution with a controllable propagation speed permitting us to estimate the oxygen diffusivity. These findings provide direct evidence that the microscopic mechanism at play in electrical doping of cuprates involves diffusion of oxygen atoms with the applied current. The resulting fine control of the oxygen content would permit a systematic study of complex phase diagrams and the design of electrically addressable devices.

Electrothermal patches driving the transdermal delivery of insulin.

Transdermal patches have become a widely used approach for painless delivery of drugs. One major current limitation of these systems remains the restricted skin permeation of proteins and peptides as exemplified by insulin, necessitating different considerations for their successful transdermal delivery. We present a novel patch design based on the integration of nano-engineered heating elements on polyimide substrates for electrothermal transdermal therapy. The results reveal that tuning of the electrical resistivity of an array of gold nanoholes, patterned on polyimide, facilitates a fast-responding electrothermal skin patch, while post-coating with reduced graphene oxide offers capabilities for drug encapsulation, like insulin. Application of insulin-loaded patches to the skin of mice resulted in blood glucose regulation within minutes. While demonstrated for insulin, the skin patches might be well adapted to other low and high molecular weight therapeutic drugs, enabling on-demand electrothermal transdermal delivery.

Kinked Silicon Nanowires: Superstructures by Metal-Assisted Chemical Etching.

We report on metal-assisted chemical etching of Si for the synthesis of mechanically stable, hybrid crystallographic orientation Si superstructures with high aspect ratio, above 200. This method sustains high etching rates and facilitates reproducible results. The protocol enables the control of the number, angle, and location of the kinks via successive etch-quench sequences. We analyzed relevant Au mask catalyst features to systematically assess their impact on a wide spectrum of etched morphologies that can be easily attained and customized by fine-tuning of the critical etching parameters. For instance, the designed kinked Si nanowires can be incorporated in biological cells without affecting their viability. An accessible numerical model is provided to explain the etch profiles and the physicochemical events at the Si/Au-electrolyte interface and offers guidelines for the development of finite-element modeling of metal-assisted Si chemical etching.

High spatial resolution electrochemical biosensing using reflected light microscopy.

If the analyte does not only change the electrochemical but also the optical properties of the electrode/solution interface, the spatial resolution of an electrochemical sensor can be substantially enhanced by combining the electrochemical sensor with optical microscopy. In order to demonstrate this, electrochemical biosensors for the detection of hydrogen peroxide and glucose were developed by drop casting enzyme and redox polymer mixtures onto planar, optically transparent electrodes. These biosensors generate current signals proportional to the analyte concentration via a reaction sequence which ultimately changes the oxidation state of the redox polymer. Images of the interface of these biosensors were acquired using bright field reflected light microscopy (BFRLM). Analysis showed that the intensity of these images is higher when the redox polymer is oxidized than when it is reduced. It also revealed that the time needed for the redox polymer to change oxidation state can be assayed optically and is dependent on the concentration of the analyte. By combining the biosensor for hydrogen peroxide detection with BFRLM, it was possible to determine hydrogen peroxide in concentrations as low as 12.5 µM with a spatial resolution of 12 µm × 12 µm, without the need for the fabrication of microelectrodes of these dimensions.

Dopamine-functionalized cyclodextrins: modification of reduced graphene oxide based electrodes and sensing of folic acid in human serum.

A mandatory step in any sensor fabrication is the introduction of analyte-specific recognition elements to the transducer surface. In this study, the possibility to anchor ß-cyclodextrin-modified dopamine to a reduced graphene oxide based electrochemical transducer for the sensitive and selective sensing of folic acid is demonstrated. The sensor displays good electrocatalytic activity toward the oxidation of folic acid. The strong affinity of the surface-confined ß-cyclodextrin for folic acid, together with favorable electron transfer characteristics, resulted in a sensor with a detection limit of 1 nM for folic acid and a linear response up to 10 µM. Testing of the sensor on serum samples from healthy individuals and patients diagnosed with folic acid deficiency validated the sensing capability. Graphical abstract.

Graphene-modified electrodes for sensing doxorubicin hydrochloride in human plasma.

Doxorubicin (DOX), an anthracycline molecule, is currently one of the most widely used anticancer drugs in clinics. Systematic treatment of patients with DOX is known to be accompanied by several unpleasant side effects due to the toxicity of the drug. Thus, monitoring of DOX concentration in serum samples has become increasingly important to avoid side effects and ensure therapeutic efficiency. In this study, we discuss the construction of a disposable electrochemical sensor for the direct monitoring of DOX in clinical blood samples. The sensor is based on coating a gold electrode in a flexible integrated electrode construct formed on polyimide sheets using photolithography, with nitrogen-doped reduced graphene oxide (N-rGO) suspended in chitosan. Under optimized conditions, a linear relationship between the oxidative peak current and the concentration of DOX in the range of 0.010-15 µM with a detection limit of 10 nM could be achieved. The sensor was adapted to monitor DOX in serum samples of patients under anticancer treatment. Graphical abstract.

Carbonyl-Based π-Conjugated Materials: From Synthesis to Applications in Lithium-Ion Batteries.

The constant growth in the global energy demand together with the increasing awareness of clean and sustainable development has strongly pushed scientists to search for metal-free, low-cost, environmentally friendly functional energy-storage systems (ESSs). Among the reported organic electrode materials, carbonyl-based π-conjugated compounds show excellent rate capabilities and cycling stabilities and are powerful candidates for the next generation of rechargeable lithium-ion batteries (LIBs). Benefiting from the molecular structure versatility and design feasibility, the electrochemical properties of organic and polymeric materials can be easily tuned. This Review summarizes recent efforts in the search for carbonyl-based π-conjugated electrode materials in LIBs with a focus on the synthetic strategies developed to improve their electrochemical performance. The use of these materials in flexible, all-organic LIBs is highlighted as a unique direction towards widespread applications of LIBs.

Efficient capture and photothermal ablation of planktonic bacteria and biofilms using reduced graphene oxide-polyethyleneimine flexible nanoheaters.

Bacterial infections are one of the leading causes of disease worldwide. Conventional antibiotics are becoming less efficient, due to antibiotic-resistant bacterial strains. Therefore, the development of novel antibacterial materials and advanced treatment strategies are becoming increasingly important. In the present work, we developed a simple and efficient strategy for effective bacterial capture and their subsequent eradication through photothermal killing. The developed device consists of a flexible nanoheater, comprising a Kapton/Au nanoholes substrate, coated with reduced graphene oxide-polyethyleneimine (K/Au NH/rGO-PEI) thin films. The Au NH plasmonic structure was tailored to feature strong absorption in the near-infrared (NIR) region, where most biological matter has limited absorption, while PEI was investigated for its strong binding with bacteria through electrostatic interactions. The K/Au NH/rGO-PEI device was demonstrated to capture and eliminate effectively both planktonic Gram-positive Staphilococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) bacteria after 10 min of NIR (980 nm) irradiation and, to destroy and eradicate Staphilococcus epidermidis (S. epidermidis) biofilms after 30 min irradiation. The technique developed herein is simple and universal with potential applications for eradication of different micro-organisms.

Kinked silicon nanowires-enabled interweaving electrode configuration for lithium-ion batteries.

A tri-dimensional interweaving kinked silicon nanowires (k-SiNWs) assembly, with a Ni current collector co-integrated, is evaluated as electrode configuration for lithium ion batteries. The large-scale fabrication of k-SiNWs is based on a procedure for continuous metal assisted chemical etching of Si, supported by a chemical peeling step that enables the reuse of the Si substrate. The kinks are triggered by a simple, repetitive etch-quench sequence in a HF and H2O2-based etchant. We find that the inter-locking frameworks of k-SiNWs and multi-walled carbon nanotubes exhibit beneficial mechanical properties with a foam-like behavior amplified by the kinks and a suitable porosity for a minimal electrode deformation upon Li insertion. In addition, ionic liquid electrolyte systems associated with the integrated Ni current collector repress the detrimental effects related to the Si-Li alloying reaction, enabling high cycling stability with 80% capacity retention (1695 mAh/gSi) after 100 cycles. Areal capacities of 2.42 mAh/cm2 (1276 mAh/gelectrode) can be achieved at the maximum evaluated thickness (corresponding to 1.3 mgSi/cm2). This work emphasizes the versatility of the metal assisted chemical etching for the synthesis of advanced Si nanostructures for high performance lithium ion battery electrodes.

Flexible Nanoholey Patches for Antibiotic-Free Treatments of Skin Infections.

Despite the availability of different antibiotics, bacterial infections are still one of the leading causes of hospitalization and mortality. The clinical failure of antibiotic treatment is due to a general poor antibiotic penetration to bacterial infection sites as well as the development of antibiotic-resistant pathogens. In the case of skin infection, the wound is covered by exudate, making it impermeable to topical antibiotics. The development of a flexible patch allowing a rapid and highly efficient treatment of subcutaneous wound infections via photothermal irradiation is presented here. The skin patch combines the near-infrared photothermal properties of a gold nanohole array formed by self-assembly of colloidal structures on flexible polyimide films with that of reduced graphene oxide nanosheets for laser-gated pathogen inactivation. In vivo tests performed on mice with subcutaneous skin infection and treated with the photothermal skin patch show wound healing of the infected site, while nontreated areas result in necrotic muscular fibers and bacterial infiltrate. No loss in efficiency is observed upon multiple use of these patches during in vivo experiments because of their robustness.

Mechanochemical Synthesis of PEDOT:PSS Hydrogels for Aqueous Formulation of Li-Ion Battery Electrodes.

Water-soluble binders can enable greener and cost-effective Li-ion battery manufacturing by eliminating the standard fluorine-based formulations and associated organic solvents. The issue with water-based dispersions, however, remains the difficulty in stabilizing them, requiring additional processing complexity. Herein, we show that mechanochemical conversion of a regular poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) water-based dispersion produces a hydrogel that meets all the requirements as binder for lithium-ion battery electrode manufacture. We particularly highlight the suitable slurry rheology, improved adhesion, intrinsic electrical conductivity, large potential stability window and limited corrosion of metal current collectors and active electrode materials, compared to standard binder or regular PEDOT:PSS solution-based processing. When incorporating the active materials, conductive carbon and additives with PEDOT:PSS, the mechanochemical processing induces simultaneous binder gelation and fine mixing of the components. The formed slurries are stable, show no phase segregation when stored for months, and produce highly uniform thin (25 µm) to very thick (500 µm) films in a single coating step, with no material segregation even upon slow drying. In conjunction with PEDOT:PSS hydrogels, technologically relevant materials including silicon, tin, and graphite negative electrodes as well as LiCoO2, LiMn2O4, LiFePO4, and carbon-sulfur positive electrodes show superior cycling stability and power-rate performances compared to standard binder formulation, while significantly simplifying the aqueous-based electrode assembly.

A new design of organic radical batteries (ORBs): carbon nanotube buckypaper electrode functionalized by electrografting.

A novel hybrid material displaying a fast and reversible charge storage capability is prepared by electrografting of an alkoxyamine-bearing acrylate onto a carbon nanotube buckypaper, followed by the quantitative generation of an electroactive polynitroxide.

Unconventional molecule-resolved current rectification in diamondoid-fullerene hybrids.

The unimolecular rectifier is a fundamental building block of molecular electronics. Rectification in single molecules can arise from electron transfer between molecular orbitals displaying asymmetric spatial charge distributions, akin to p-n junction diodes in semiconductors. Here we report a novel all-hydrocarbon molecular rectifier consisting of a diamantane-C60 conjugate. By linking both sp(3) (diamondoid) and sp(2) (fullerene) carbon allotropes, this hybrid molecule opposingly pairs negative and positive electron affinities. The single-molecule conductances of self-assembled domains on Au(111), probed by low-temperature scanning tunnelling microscopy and spectroscopy, reveal a large rectifying response of the molecular constructs. This specific electronic behaviour is postulated to originate from the electrostatic repulsion of diamantane-C60 molecules due to positively charged terminal hydrogen atoms on the diamondoid interacting with the top electrode (scanning tip) at various bias voltages. Density functional theory computations scrutinize the electronic and vibrational spectroscopic fingerprints of this unique molecular structure and corroborate the unconventional rectification mechanism.

Surface coating mediated swelling and fracture of silicon nanowires during lithiation.

Surface passivation of silicon anodes is an appealing design strategy for the development of reliable, high-capacity lithium-ion batteries. However, the structural stability of the coating layer and its influence on the lithiation process remain largely unclear. Herein, we show that surface coating mediates the swelling dynamics and the fracture pattern during initial lithiation of crystalline silicon nanopillars. We choose conformally nickel coated silicon architectures as a model system. Experimental findings are interpreted based on a chemomechanical model. Markedly different swelling and fracture regimes have been identified, depending on the coating thickness and silicon nanopillar diameter. Nanopillars with relatively thin coating display anisotropic swelling similar to pristine nanopillars, but with different preferred fracture sites. As the coating thickness increases, the mechanisms become isotropic, with one randomly oriented longitudinal crack that unzips the core-shell structure. The morphology of cracked pillars resembles that of a thin-film electrode on a substrate, which is more amenable to cyclic lithiation without fracture. The knowledge provided here helps clarify the cycling results of coated nanosilicon electrodes and further suggests design rules for better performance electrodes through proper control of the lithiation and fracture.