Three-dimensional observations of the electric field distribution of variable frequency microwaves, and scaling-up organic syntheses.

Variable Frequency Microwave (VFM) radiation provides a solution to the inhomogeneity of the electric field in the cavity, which has long led to a decline in the reliability of microwave chemical data and its industrial utilization. Herein, we report in-situ three-dimensional experimental measurements of the electric field's uniform distribution of VFMs within a multimode cavity under high power conditions, and their subsequent comparison to Fixed Frequency Microwaves (FFM) that could only be assessed earlier through theoretical analysis. We also examine the consequences of changes in VFM irradiation conditions and elucidate the threshold at which VFM irradiation might prove beneficial in syntheses. With an ultimate focus on the use of VFM microwave radiation toward industrial applications, we carried out an effective synthesis of 4-methylbyphenyl (4-MBP) in the presence of palladium (the catalyst) supported on activated carbon particulates (Pd/AC), and revisited two principal objectives: (a) the effective suppression of discharge phenomena (formation of hot spots), and (b) synthesis scale-up using a 5-fold increase in sample quantity and a 7.5-fold larger reactor size (diameter) than otherwise used in earlier studies.

Uptake of nanoparticles from sunscreen physical filters into cells arising from increased environmental microwave radiation: increased potential risk of the use of sunscreens to human health.

This study examines the microwave chemical risks posed by photocatalysts present in sunscreens (physical filters) against the increasing use of microwaves (radio waves) in the environment, sometimes referred to as electronic smog. Specifically, the study assesses the damage caused by silica-coated physical filters (photocatalysts, TiO2⋅ and/or ZnO) contained in commercially available sunscreens and fresh silica-coated ZnO for sunscreens to mouse skin fibroblasts cells (NIH/3T3) evaluated in vitro by the life/death of cells using two types of electromagnetic waves: UV light and microwave radiation, and under simultaneous irradiation with both UV light and microwaves. Conditions of the electromagnetic waves were such as to be of lower light irradiance than that of UVA/UVB radiation from incident sunlight, and with microwaves near the threshold power levels that affect human health. The photocatalytic activity of the physical filters was investigated by examining the degradation of the rhodamine B (RhB) dye in aqueous media and by the damage caused to DNA plasmids from E. coli. Compared to the photocatalytic activity of ZnO and TiO2 when irradiated with UV light alone, a clear enhanced photocatalytic activity was confirmed upon irradiating these physical filters concurrently with UV and microwaves. Moreover, the uptake of these metal oxides into the NIH/3T3 cells led to the death of these cells as a result of the enhanced photocatalytic activity of the metal oxides on exposure to microwave radiation.

Development of a microwave-discharge light-emitting diode (MDLED): a novel UV source for the UV-driven microwave-assisted TiO2 photocatalytic treatment of contaminated wastewaters.

This brief article reports on the fabrication of a prototype novel semiconductor digital device, a microwave-discharge light-emitting diode (MDLED), consisting of an LED and a Schottky barrier diode encapsulated in a quartz ampoule. Coating the surface of this ampoule with TiO2 yielded a new photocatalytic TiO2 unit (MDLED-TiO2) for use in treating contaminated wastewaters. To the extent that this MDLED-TiO2 is driven only by microwave energy, there is no need for electric wires or electrical AC power. As much of the activity of TiO2 photocatalyst is enhanced and ultraviolet light emission is generated only by irradiating with microwaves, the MDLED-TiO2 affords a simple water treatment device as demonstrated in the present study. The digital device consisted of 14 pieces of MDLED-TiO2  units immersed into a model contaminated wastewater toward the decomposition of organic pollutants and sterilization of natural bacteria-contaminated wastewaters performed in an energy-saving manner simply by irradiating the wastewaters with microwaves.

Verification of Microwave Effects on Molecular Clusters by Using Supersonic Molecular Jets.

The origin of the specific effect of microwaves on chemical reactions (the microwave effect) was investigated by examining the effect of microwaves on small groups of molecules such as clusters. The origin of the effect was verified by introducing 2.45 GHz microwaves into a system equipped with a supersonic molecular jet and a special microwave feedthrough to record the fluorescence excitation spectrum of molecules. The carrier gas was bubbled through water and introduced into a phenol-filled sample holder to generate phenol-water clusters. Subsequently, it was confirmed that exposure of the phenol-water clusters contained in the molecular jet ejected from the pulse valve to microwave radiation increased the fluorescence derived from the phenol monomer. This is considered to occur because the phenol-water clusters in the molecular jet absorb microwaves and collapse, thereby increasing the abundance of phenol monomers. This result suggests that microwaves affect not only bulk systems but also small groups of molecules, and that local selective heating, which is one of the causes of the microwave effect, may occur.

Synthesis of Recyclable Magnetic Cellulose Nanofibers from Ionic Liquids for Practical Applications in Separation Science.

The present study focused on coupling cellulose nanofibers (alternative materials for plastics and metals) with a magnetic ionic liquid (synthesized by a microwave-assisted method) through mixing to yield magnetic cellulose nanofibers (MCNFs) that can be recycled by attracting them to a magnet. Accordingly, two types of ionic liquids were synthesized: (a) 1-butyl-3-methylimidazolium tetrachloroferrate(III) {[bmim] FeCl4} and (b) 1-glycidyl-3-methylimidazolium tetrachloroferrate {[glmi]FeCl4}, which were characterized by the fast atom bombardment mass spectrometry (FAB-MS) technique. Impregnation of the cellulose nanofibers with the {[bmim]FeCl4} ionic liquid caused the latter to be physically adsorbed onto the nanofibers to produce {MCNF@{[bmim]FeCl4}, whereas the corresponding {[glmi]FeCl4} ionic liquid was chemically bonded to the cellulose nanofibers to yield magnetic {MCNF@[glmi]FeCl4} nanofibers. Under the experimental conditions used, the corresponding magnetic moments were 0.222 A m2 kg-1 for {MCNF@ {[bmim]FeCl4} and 0.095 A m2 kg-1 for {MCNF@[glmi]FeCl4}.

In Search of the Driving Factor for the Microwave Curing of Epoxy Adhesives and for the Protection of the Base Substrate against Thermal Damage.

This study used controlled microwaves to elucidate the response of adhesive components to microwaves and examined the advantages of microwave radiation in curing epoxy adhesives. Curing of adhesives with microwaves proceeded very rapidly, even though each component of the adhesive was not efficiently heated by the microwaves. The reason the adhesive cured rapidly is that microwave heating was enhanced by the electrically charged (ionic) intermediates produced by the curing reaction. In contrast, the cured adhesive displayed lower microwave absorption and lower heating efficiency, suggesting that the cured adhesive stopped heating even if it continued to be exposed to microwaves. This is a definite advantage in the curing of adhesives with microwaves, as, for example, adhesives dropped onto polystyrene could be cured using microwave heating without degrading the polystyrene base substrate.

Photoluminescent Carbon Quantum Dots: Synthetic Approaches and Photophysical Properties.

A number of synthetic methodologies and applications of carbon quantum dots (CQDs) have been reported since they were first discovered nearly two decades ago. Unlike metal-based or semiconductor-based (e. g., metal chalcogenides) quantum dots (MSQDs), CQDs have the unique feature of being prepared through a variety of synthetic protocols, which are typically understood from considerations of reaction models and photoluminescence mechanisms. Consequently, this brief review article describes quantum dots, in general, and CQDs, in particular, from various viewpoints: (i) their definition, (ii) their photophysical properties, and (iii) the superiority of CQDs over MSQDs. Where possible, comparisons are made between CQDs and MSQDs. First, however, the review begins with a general brief description of quantum dots (QDs) as nanomaterials (sizes≤10 nm), followed by a short description of MSQDs and CQDs. Described subsequently are the various top-down and bottom-up approaches to synthesize CQDs followed by their distinctive photophysical properties (emission spectra; quantum yields, Φs).

Development of a Hg-free UV light source incorporating a Kr/Br2 gas, and its application for wastewater treatments.

Mercury lamps are typically the major light sources in water treatments. However, the use of mercury has raised some concerns with regard to the Minamata Convention on Mercury. As such, Hg-free microwave discharged electrodeless lamps (MDELs) that incorporate a rare gas and a halogen gas (R/H-MDEL) have been investigated with such Hg-free mixture filler gases as Kr/Cl2, Xe/Cl2, and Kr/Br2 (R/H). Of these, only the Kr/Br2-MDEL lamp is self-ignited at an inner pressure of 15 Torr when irradiated with microwave radiation. Accordingly, a novel Kr/Br2 three-layer MDEL (Kr/Br2-MDEL) photoreactor was fabricated to assess the optimal gas composition and gas pressure toward its performance vis-à-vis the treatment of model wastewaters contaminated with the tartrazine dye in aqueous media and with Escherichia coli (E. coli) bacteria. The extent of degradation of the tartrazine dye and sterilization of E. coli increased with irradiation time, with microwave radiation power (100, 200, and 300 W), and with increased sample flow rate 0.4 L min‒1 to 0.8 L min‒1. The tartrazine-contaminated wastewater was treated at a flow rate of 0.4 L min‒1 for 60 min of microwave irradiation by three different protocols that resulted in UV (62%) >> UV/ROS (24%) > ROS (0%); ROS denotes reactive oxygen species. After 5 min irradiation of the E.coli wastewater, also at 0.4 L min‒1, the order was UV (99.5%) ≈ UV/ROS (99.3%) >> ROS (14.5%). For comparison, the photosterilization of E. coli with an equivalent Hg/Ar-MDEL light source was also nearly complete (99.7%). Thus, the suitability of the environmentally friendlier Kr/Br2 gas fill to replace Hg/Ar filler gas in MDELs for the photoelimination of organic pollutants and microbial disinfection in aqueous media has been demonstrated.

Microwave-driven hydrogen production (MDHP) from water and activated carbons (ACs). Application to wastewaters and seawater.

This article reports on low-temperature steam reforming and water-gas shift processes to generate hydrogen efficiently when water is passed through microwave-heated activated carbon (AC) particulates, in contrast to conventional steam reforming that is not particularly efficient at temperatures around 600 °C. The microwave-driven method performed efficiently at this temperature producing hydrogen with yields of 70% or more, as a result of the microscopic local microwave heating of the AC particulates. To the extent that the activated carbon is produced from plant biomass-related raw materials, the carbon dioxide produced is carbon neutral. Conditions for hydrogen generation were optimized with regard to the size of the AC particles, the water flow rate, and the size of the reactor. For practical applications of this microwave-based method, hydrogen was also generated efficiently with yields of 75-80% when using spent activated carbons (large size distribution) and model contaminated wastewaters and artificial seawater; significant energy was saved under the conditions used. The re-use of spent ACs eliminates the need for their disposal after being used in water and sewage treatments. In addition, the presence of any organic matter in wastewaters is also a likely effective source of hydrogen (yields, 75-85%). And not least, although generation of hydrogen from seawater is a difficult electrolytic process, the microwave method proved to be an attractive and efficient technology toward hydrogen generation from seawater with yields of 85 to 90%. Addition of Pt deposits on the activated carbon support, however, provided no advantages over pristine AC particulates.

A novel green chemistry gelation method for polyvinyl pyrrolidone (PVP) and dimethylpolysiloxane (silicone): microwave-induced in-liquid-plasma.

The focus of this article rests on our discovery that a water-soluble polymer could be cross-linked to form a gel using a novel Green Chemistry gelation method: the microwave-induced in-liquid-plasma (MILP) method that requires neither a cross-linking agent nor an initiator as are required in the conventional chemical method. For instance, the water-soluble polyvinyl pyrrolidone (PVP) polymer was gelled by MILP plasma irradiation within a few minutes without using toxic cross-linking agents and initiators. As well, the hydrophobic dimethylpolysiloxane macromolecule was dispersed in aqueous media to a colloidal sol, which could then also be easily gelled under MILP irradiation conditions within a few minutes, in comparison to the conventional method that often requires several hours to days for gelation to occur in the presence of cross-linking agents and initiators. The viscosity of the MILP silicone gel was greater than a similar gel formed by the conventional method. In contrast, the viscosity of the MILP-formed PVP gel was lower than the viscosity of the PVP gel obtained from the conventional method. Gels were characterized by 13C-NMR spectrometry, FT-IR spectroscopy, SEM microscopy, viscosity measurements, and dynamic light scattering for particle size distributions. Plausible mechanistic stages for the two gelation occurrences have been inferred as involving the synergistic effects from microwaves, together with the sound waves (cavitation microbubbles), heat, UV and ˙OH radicals resulting from the microwave-generated in-liquid-plasma.

Enhanced Degradation of Organic Pollutants with Microwave-induced Plasma-in-liquid (MPL): Case of Flame Retardant Tetrabromobisphenol-A in Alkaline Aqueous Media.

We report the enhanced degradation of a widely used brominated flame retardant, tetrabromobisphenol-A (TBBPA), which is soluble only in organic solvents and strongly alkaline solutions, where most advanced oxidation processes (AOPs) for such substrates tend to be rather inefficient. We further report an environmentally friendly method (microwave-induced plasma-in-liquid; MPL) that operates efficiently in alkaline aqueous media without the need for organic solvents to enhance the solubility of TBBPA in water. The enhanced debromination and almost complete mineralization of TBBPA under alkaline conditions occurs within 20 min of MPL irradiation. This method, which is a new member of the AOP family, provides a simple and green approach to detoxify aqueous media contaminated with TBBPA, which requires only electric power and neither catalysts nor oxidizing agents. Several intermediate species have been identified by liquid chromatography/mass spectrometry (LC-MS), following events that involved reactive oxygen species (ROSs) such as·OH, whose first task was to approach the substrate at carbon atoms bearing the highest electron densities.

Role of alkan-1-ol solvents in the synthesis of yellow luminescent carbon quantum dots (CQDs): van der Waals force-caused aggregation and agglomeration.

Carbon quantum dots (CQDs; luminescent carbon nanoparticles, size < 10 nm) have attracted much attention with respect to their eco-friendliness and multi-functionality. The solvent-dependent photoluminescence of CQDs has been well investigated to optimize the synthesis process and homogeneous dispersion. Although some alkan-1-ol solvents, such as ethanol, have been well utilized empirically as good solvents when synthesizing highly photoluminescent CQDs, the role of alkan-1-ol solvents, particularly long-chain alkan-1-ols (e.g., 1-nonanol, 1-decanol), has not yet been clarified. Herein, we demonstrate a method for the synthesis of strongly yellow emitting CQDs using solvothermal treatment and elucidate the role of alkan-1-ol solvents in the photoluminescence of CQDs. These CQDs have been characterized using theoretical calculations, ex situ morphological observations using transmission electron microscopy (TEM) and dynamic light scattering (DLS), and 500 MHz 1H nuclear magnetic resonance (NMR) and 13C NMR spectroscopy. A comparative study of alkan-1-ol solvents suggests a mechanism for the agglomeration and aggregation of carbon precursors, intermediates, and CQDs, which is expected to lead to further synthesis studies on highly luminescent CQDs.

Microwave-/UV-assisted Enhancement of the Wettability of Photoactive TiO2 Substrates Coated on an Inactive Ti/i-TiO2 Base.

Titanium dioxide (TiO2) has been proven to be an excellent system for wettability patterning purposes because of its super hydrophilic ability and its oxidative/reductive degradation of substances when exposed to UV radiation. TiO2 substrates upon which was deposited a self-assembled monolayer (SAM) of n-octadecyltrimethoxysilane (ODS) shifts the surface to become super hydrophobic, which when subjected to UV irradiation causes the ODS compound to be degraded with the substrate turning back to be super hydrophilic. Such events allow wettability patterns to be easily created. The objective of this study was to reduce the time required to construct a wettability pattern. For this purpose, highly photoactive TiO2 nanoparticles were coated onto a titanium plate whose surface had been previously oxidized at high temperatures in an electric furnace. The subsequent TiO2/Ti system was microwaved and simultaneously irradiated with ultraviolet light (UV) to further accelerate its photocatalytic activity. Using a set of photomasks and both UV and microwave irradiation, the generation of a pattern was achieved 15 times faster (2 min versus 30 min) compared to an earlier result that used only UV radiation.

Probing the effect(s) of the microwaves' electromagnetic fields in enzymatic reactions.

This paper examines the effects that electromagnetic fields from microwave radiation have in enzymatic reactions. Hydrolysis of proteins in beef (in vivo case) and casein (in vitro case) by the papain enzyme, a major industrial enzyme, is used herein as a model reaction to assess, under highly controlled conditions, the various parameters of microwave radiation (electric field, magnetic field, pulsed microwave irradiation, continuous microwave irradiation) as they might influence these in vivo and in vitro enzymatic reactions. The effect(s) of the microwaves' electromagnetic fields was clearly evidenced in the in vivo case, contrary to the in vitro case where no such effect was observed, likely due to the nature of the hydrolysis reaction and to the autolysis (self-digestion) of the papain enzyme. Additionally, the effect of pulsed versus continuous microwave irradiation was further assessed by examining the catalase-assisted decomposition of hydrogen peroxide.

Development of a Hg-free UV light source and its performance in photolytic and photocatalytic applications.

Constraints on light sources that use mercury (arc lamps) are evolving with the establishment of the Minamata Convention, which has led to the proliferation of LEDs. However, no LED light source emits intense ultraviolet radiation at wavelengths below 300 nm for photolytic applications. Thus, it is necessary to develop suitable UV light sources for the decontamination of wastewater and water sterilization processing. Herein, we explore various substitute gases (e.g., N2, Ar, He and SF6) to replace mercury, which is commonly employed in arc lamps, using an EL (electroluminescence) quartz assembly platform similar to microwave-discharge electrodeless lamps. Although nitrogen is an inexpensive and safe gas, it cannot generate significant UV radiation in the UVC region of 200-300 nm. This problem in the Hg-free light source was resolved by mixing a very small quantity of sulfur hexafluoride (SF6) as an additive filler gas in a nitrogen-, argon- or helium-filled assembly. The low-pressure mercury lamp consisting of Hg/Ar filler gases is ca. 25% more efficient than the novel N2/SF6 lamp toward the photolytic decomposition of Rhodamine-B (RhB) dye-contaminated wastewater (1.66 × 10-4 mM min-1versus 1.22 × 10-4 mM min-1). Nonetheless, the latter has proven far more efficient than an LED source emitting 365 nm radiation (0.057 × 10-4 mM min-1). The addition of TiO2 to RhB-contaminated wastewater demonstrated that this Hg-free N2/SF6 light source is as efficient as the corresponding Hg/Ar electroluminescent lamp toward the photocatalytic decomposition of the RhB dye pollutant.

Microwave Flow Chemistry as a Methodology in Organic Syntheses, Enzymatic Reactions, and Nanoparticle Syntheses.

Several studies have used microwaves as a heat source for carrying out various types of reactions employing circulation reaction vessels. The microwave flow chemical synthesis methodology is most appropriate in the use of microwaves in chemical syntheses. It can attenuate the problem of microwave heating (non-uniform heating and penetration depth) and maximize the benefits (rapid heating and first temperature adjustments). In this brief review, we examine and explain some of the relevant features of microwave heating with applicative examples of the usage of microwave flow chemistry equipment in carrying out organic syntheses, enzymatic reactions, and (not least) nanoparticle syntheses.

A grading system that predicts the risk of dialysis induction in IgA nephropathy patients based on the combination of the clinical and histological severity.

Histological classification is essential in the clinical management of immunoglobulin A nephropathy (IgAN). However, there are limitations in predicting the prognosis of IgAN based on histological information alone, which suggests the need for better prognostic models. Therefore, we defined a prognostic model by combining the grade of clinical severity with the histological grading system by the following processes. We included 270 patients and explored the clinical variables associated with progression to end-stage renal disease (ESRD). Then, we created a predictive clinical grading system and defined the risk grades for dialysis induction by a combination of the clinical grade (CG) and the histological grade (HG). A logistic regression analysis revealed that the 24-h urinary protein excretion (UPE) and the estimated glomerular filtration rate (eGFR) were significant independent variables. We selected UPE of 0.5 g/day and eGFR of 60 ml/min/1.73 m2 as the threshold values for the classification of CG. The risk of progression to ESRD of patients with CG II and III was significantly higher than that of patients with CG I. The patients were then re-classified into nine compartments based on the combination of CG and HG. Furthermore, the nine compartments were grouped into four risk groups. The risk of ESRD in the moderate, high, and super-high-risk groups was significantly higher than that in the low-risk group. Herein, we are giving a detailed description of our grading system for IgA nephropathy that predicted the risk of dialysis based on the combination of CG and HG.

Chronic intermittent hypoxia-mediated renal sympathetic nerve activation in hypertension and cardiovascular disease.

In sleep apnea syndrome (SAS), chronic intermittent hypoxia (CIH) is believed to activate the sympathetic nerve system, and is thus involved in cardiovascular diseases (CVD). However, since patients with SAS are often already obese, and have diabetes and/or hypertension (HT), the effects of CIH alone on sympathetic nerve activation and its impacts on CVD are largely unknown. We, therefore, examined the effects of CIH on sympathetic nerve activation in non-obese mice to determine whether renal sympathetic nerve denervation (RD) could ameliorate CIH-mediated cardiovascular effects. Male C57BL/6 (WT) mice were exposed to normal (FiO2 21%) or CIH (10% O2, 12 times/h, 8 h/day) conditions for 4 weeks with or without RD treatment. Increased urinary norepinephrine (NE), 8-OHdG, and angiotensinogen levels and elevated serum asymmetric dimethyl arginine levels were observed in the CIH model. Concomitant with these changes, blood pressure levels were significantly elevated by CIH treatment. However, these deleterious effects by CIH were completely blocked by RD treatment. The present study demonstrated that CIH-mediated renal sympathetic nerve activation is involved in increased systemic oxidative stress, endothelial dysfunction, and renin-angiotensin system activation, thereby contributing to the development of HT and CVD, thus could be an important therapeutic target in patients with SAS.

Effect of Zinc Acetate Dihydrate (NobelzinR) Treatment on Anemia and Taste Disorders in Patients with Chronic Kidney Disease with Hypozincemia.

Some patients with chronic kidney disease (CKD) receiving hemodialysis develop erythropoietin-resistant anemia, possibly due to zinc deficiency. The frequency of zinc deficiency in CKD (stages 1-5 and 5D) and CKD improvement via zinc supplementation are not completely verified. Here 500 CKD patients (Stage 1/2, n=100; Stage 3, n=100; Stage 4, n=100, Stage n=5, 100; Stage 5D, n=100) will be recruited to determine the frequency of serum zinc deficiency at each CKD stage. Patients with serum zinc concentrations <80 µg/dL will be treated with zinc acetate dihydrate (NobelzinR) to evaluate its effects on hypozincemia, taste disturbances, and anemia.

Improvement of Wettability of Photocatalytic TiO2-Coated Wafers by Microwave/UV Pre-treatment.

The wettability efficiency of TiO2-coated Ti substrate wafers was improved using a microwave/UV pre-treatment method. With the assistance of microwave heating, TiO2 substrates coating with P25 completely achieved super hydrophilic state within 5 min, which is twice as fast compared with only UV irradiation condition. Moreover, when the microwave power was increased, improvement in the wettability activity was observed. Apart from P25, coating with brookite also resulted in a good performance. The contact angle was 0° with only 10 min of irradiation.