Recent advances in catalytic and non-catalytic epoxidation of terpenes: a pathway to bio-based polymers from waste biomass.

Epoxides derived from waste biomass are a promising avenue for the production of bio-based polymers, including polyamides, polyesters, polyurethanes, and polycarbonates. This review article explores recent efforts to develop both catalytic and non-catalytic processes for the epoxidation of terpene, employing a variety of oxidizing agents and techniques for process intensification. Experimental investigations into the epoxidation of limonene have shown that these methods can be extended to other terpenes. To optimize the epoxidation of bio-based terpene, there is a need to develop continuous processes that address limitations in mass and heat transfer. This review discusses flow chemistry and innovative reactor designs as part of a multi-scale approach aimed at industrial transformation. These methods facilitate continuous processing, improve mixing, and either eliminate or reduce the need for solvents by enhancing heat transfer capabilities. Overall, the objective of this review is to contribute to the development of commercially viable processes for producing bio-based epoxides from waste biomass.

Synthesis of cyclic carbonates from CO2 cycloaddition to bio-based epoxides and glycerol: an overview of recent development.

Anthropogenic carbon dioxide (CO2) emissions contribute significantly to global warming and deplete fossil carbon resources, prompting a shift to bio-based raw materials. The two main technologies for reducing CO2 emissions are capturing and either storing or utilizing it. However, while capture and storage have high reduction potential, they lack economic feasibility. Conversely, by utilizing the CO2 captured from streams and air to produce valuable products, it can become an asset and curb greenhouse gas effects. CO2 is a challenging C1-building block due to its high kinetic inertness and thermodynamic stability, requiring high temperature and pressure conditions and a reactive catalytic system. Nonetheless, cyclic carbonate production by reacting epoxides and CO2 is a promising green and sustainable chemistry reaction, with enormous potential applications as an electrolyte in lithium-ion batteries, a green solvent, and a monomer in polycarbonate production. This review focuses on the most recent developments in the synthesis of cyclic carbonates from glycerol and bio-based epoxides, as well as efficient methods for chemically transforming CO2 using flow chemistry and novel reactor designs.

A comprehensive review of the current progresses and material advances in perovskite solar cells.

Recently, perovskite solar cells (PSCs) have attracted ample consideration from the photovoltaic community owing to their continually-increasing power conversion efficiency (PCE), viable solution-processed methods, and inexpensive materials ingredients. Over the past few years, the performance of perovskite-based devices has exceeded 25% due to superior perovskite films achieved using low-temperature synthesis procedures along with evolving appropriate interface and electrode-materials. The current review provides comprehensive knowledge to enhance the performance and materials advances for perovskite solar cells. The latest progress in terms of perovskite crystal structure, device construction, fabrication procedures, and challenges are thoroughly discussed. Also discussed are the different layers such as ETLs and buffer-layers employed in perovskite solar-cells, seeing their transmittance, carrier mobility, and band gap potentials in commercialization. Generally, this review delivers a critical assessment of the improvements, prospects, and trials of PSCs.

Synergistic effect of plasma power and temperature on the cracking of toluene in the N2 based product gas.

In this research, a dielectric barrier discharge (DBD) reactor is used to study the cracking of the toluene into C1-C6 hydrocarbons. The combined effect of parameters such as temperature (20-400 °C) and plasma power (10-40 W) was investigated to evaluate the DBD reactor performance. The main gaseous products from the decomposition of toluene include lower hydrocarbon (C1-C6). The cracking of toluene increases with power at all temperatures (20-400 °C). On the otherhand, it decreases from 92.8 to 73.1% at 10 W, 97.2 to 80.5% at 20, 97.5 to 86.5% at 30 W, and 98.4 to 93.7% at 40 W with raising the temperature from 20 to 400 °C. Nonetheless, as the temperature and plasma input power increase, the methane yield increases. At 40 W, the maximum methane yield was 5.1%. At 10 and 20 W, the selectivity to C2 increases as the temperature rises up to 400 °C. At 30 and 40 W, it began to drop after 300 °C due to the formation of methane and the yield of methane increases significantly beyond this temperature.

Prevalence of Personality Disorders in Adults With Attention Deficit Hyperactivity Disorder (ADHD).

OBJECTIVE: To estimate the prevalence of PDs according to Millon's evolution-based model among adult ADHD outpatients. METHOD: Cross-sectional study of consecutive patients referred to an adult ADHD clinic. PDs were evaluated with Millon Clinical Multiaxial Inventory-III (MCMI-III). RESULTS: One-hundred-eighty-one participants had valid MCMI-III, of whom147 were diagnosed with ADHD. Mean age: 32.97, SD:11.56, females: 74 (50.3%). Among the 147 participants with ADHD, 29 (19.7%) did not meet criteria for any PD, 43 (29.3%) met the criteria for one PD, 34 (23.1%) for two PDs and the rest three or more. Most common PD was Dependent (n = 58) followed by Depressive (n = 45). Inattentive sub-type was associated with dependent PD, while combined type with antisocial, negativistic (passive/aggressive) and sadistic PD. CONCLUSION: Particular personality profiles were more common with different ADHD subtypes. Given the developmental origins of PD, further research may help identify possible links with childhood difficulties.

Holistic assessment of patients with chronic mental disorders who attend a metabolic clinic in Sligo Town catchment area.

BACKGROUND: People with serious mental illness exhibit higher morbidity and mortality rates of chronic diseases than the general population. AIMS: The aim of this study was to establish a dedicated clinic for patients with chronic mental illness to monitor physical health and quality of life in accordance with best practice guidelines. METHODS: Patients were invited to attend the clinic. The following areas were examined: personal and family history of cardiovascular disease, diet, exercise, and smoking. Mental state examination, waist circumference, BP, pulse, ECG and BMI. Laboratory tests including U + E, LFTs, HbA1c, Lipid profile and other tests as appropriate such as serum lithium. AIMS scale, HoNOS and WHOQOL-BREF scales as additional indicators of global health. RESULTS: A total of 80 patients attended during 3.5 years of clinic. Mean age was 54.9 years (SD: 13.81) at first contact and 45% were females. Mean years in the service was 19.66 (SD: 11.54) and mean number of previous hospital admissions was 4.4 (SD: 5.63). Metabolic syndrome was present in 42% at first assessment. A statistically significant improvement was found for the psychological domain of the WHOQOL-BREF and the HoNOs, particularly at third assessment. (ß = 4.64, Wald x2 = 7.38, df:1, p = 0.007, CI:1.3-8.1, ß = - .889, Wald x2 = 4.08, df:1, p = 0.043, CI: - 1.752 to - .026) respectively. CONCLUSION: The results show a high prevalence of physical health conditions in this cohort, some of which represent a new diagnosis. This implicates better allocation of existing resources for screening and early detection, and potential to run joint clinics with primary care.

Prevalence of attention deficit hyperactivity disorder in an adult mental health service in the Republic of Ireland.

OBJECTIVE: Attention Deficit Hyperactivity Disorder (ADHD) is well recognised in childhood. However, recognition that it commonly persists into adulthood is relatively recent. This study is the 2nd phase of a two-phase epidemiological investigation of the prevalence of adult ADHD in outpatients in Ireland. METHOD: In phase-1, 634 participants were screened with Adult ADHD Self-Report Scale (ASRS) and Wender Utah Rating Scale (WURS). Those scoring positive in both scales have been invited to participate in the 2nd phase where the scales Conners' Adult ADHD Diagnostic Interview (CAADID), Mini International Neuropsychiatric Interview (MINI), and Global Assessment of Functioning (GAF) were administered, plus clinical evaluation based in DSM-5. RESULTS: 131 were eligible, 110 participated (84.0%). Using the CAADID (DSM-IV criteria) 71 were diagnosed with ADHD. Projecting to the total sample (N = 634) the prevalence was 13.25%, CI:95%:10.71-16.14. Converting the DSM-IV criteria to DSM-5, 89 had ADHD (prevalence:16.72%, CI: 13.9-19.86). Using clinical evaluation, 86 were diagnosed with ADHD (prevalence:16.09%, CI:13.31-19.18). Only 3 cases were diagnosed before with ADHD. Comorbidity was higher in those with ADHD, with the median number of additional diagnoses 2 (min 0 max 8, IQR 3) Also, they had significantly higher rates of depression and recurred depression. Agreement between DSM-IV and DSM-5 was high (rho = 0.90, p < .0001). CONCLUSIONS: High rates of undiagnosed ADHD were found to be present among AMHS attendees. Clinicians in AMHS need to be knowledgeable and alert to possible ADHD among their caseloads, and offer appropriate intervention. Interventions are urgently required to increase the detection and treatment of adult ADHD.

A Comprehensive Review on Zeolite Chemistry for Catalytic Conversion of Biomass/Waste into Green Fuels.

Numerous attempts have been made to produce new materials and technology for renewable energy and environmental improvements in response to global sustainable solutions stemming from fast industrial expansion and population growth. Zeolites are a group of crystalline materials having molecularly ordered micropore arrangements. Over the past few years, progress in zeolites has been observed in transforming biomass and waste into fuels. To ensure effective transition of fossil energy carriers into chemicals and fuels, zeolite catalysts play a key role; however, their function in biomass usage is more obscure. Herein, the effectiveness of zeolites has been discussed in the context of biomass transformation into valuable products. Established zeolites emphasise conversion of lignocellulosic materials into green fuels. Lewis acidic zeolites employ transition of carbohydrates into significant chemical production. Zeolites utilise several procedures, such as catalytic pyrolysis, hydrothermal liquefaction, and hydro-pyrolysis, to convert biomass and lignocelluloses. Zeolites exhibit distinctive features and encounter significant obstacles, such as mesoporosity, pore interconnectivity, and stability of zeolites in the liquid phase. In order to complete these transformations successfully, it is necessary to have a thorough understanding of the chemistry of zeolites. Hence, further examination of the technical difficulties associated with catalytic transformation in zeolites will be required. This review article highlights the reaction pathways for biomass conversion using zeolites, their challenges, and their potential utilisation. Future recommendations for zeolite-based biomass conversion are also presented.

Recent Progress in Surface and Interface Engineering for Electrocatalytic CO2 Reduction.

The conversion of CO2 through CO2 reduction reaction (CO2 RR) into valuable products has potential to lessen the greenhouse effect caused by uncontrolled CO2 emissions. Challenges of CO2 RR reaction lie in the stabilization of the reaction intermediate and the activation of the inert chemical bond of CO2 , but the application of CO2 RR at large scale is limited by the high cost and structural instability of traditional catalysts. By applying CO2 RR catalyst with delicate structure of stable CO2 intermediate to industrial production, the problems such as high cost of CO2 conversion, low catalytic selectivity and poor catalytic efficiency can be effectively solved, showing better application value and significance than traditional catalysts. This review focuses on the defects, and metal-support interaction (MSI) effect to modify the catalyst and other strategies to enhance the effectiveness of CO2 reduction. The challenges and prospects from the three perspectives are also discussed to provide suggestions for the designing of efficient CO2 RR catalysts in the future. This review offers new insights and research perspectives of reducing CO2 emission through recycling CO2 , and neutralizing the carbon cycle.

Plasma-assisted removal of methanol in N2, dry and humidified air using a dielectric barrier discharge (DBD) reactor.

In this work, a non-thermal plasma dielectric barrier discharge (DBD) was used to remove methanol from ambient air. The effects of carrier gases (N2, dry and humidified air), power (2-10 W), inlet concentration (260-350 ppm), and residence time (1.2-3.3 s) were investigated to evaluate the performance of the plasma DBD reactor in terms of removal efficiency, product selectivity and reduction of unwanted by-products at ambient temperature and atmospheric pressure. It was found that the conversion of methanol increased with power and residence time regardless of the carrier gas used. However, the removal efficiency decreased with the increasing concentration of CH3OH. Almost complete removal of methanol (96.7%) was achieved at 10 W and a residence time of 3.3 s in dry air. The removal efficiency of methanol followed a sequence of dry air > humidified air > N2 carrier gas. This was due to the action of the O radical in dry air, which dominates the decomposition process of the plasma system. The introduction of water vapour into the DBD system decreased the removal efficiency but had a number of significant advantages: increased CO2 selectivity and yield of H2, it significantly reduced the formation of O3, CO and higher hydrocarbons. These influences are probably due to the presence of potent OH radicals, and the conversion pathways for the various effects are proposed. It is important to note that no solid residue was formed in the DBD reactor in any carrier gas. Overall, this research indicates that methanol can be almost completely removed with the correct operating parameters (96.7% removal; 10 W; 3.3 s) and shows that humidification of the gas stream is beneficial.

Association of Wender Utah Rating Scale (WURS)-61 items with clinical psychiatric diagnosis in adulthood.

BACKGROUND: The Wender Utah Rating Scale (WURS) is a widely used retrospective scale in adults presenting for ADHD evaluations which features items relating to childhood symptoms. AIMS: The aim of this study is to establish if certain childhood symptoms (including ADHD) as identified by the WURS-61 are associated with specific mental health disorders in adulthood. METHODS: Case-control study of N=630 attending Adult Mental Health Services (AMHS) and a control group without mental disorders (N=96). RESULTS: The mean age of the participants was 39.81 (SD 12.94) of which 387 (53.3%) were females. There were no significant differences between cases and controls in terms of age (t= 1.829, df 724, p=.068) and gender (x2=1.123, df 1, p=.289). Exploratory factor analysis of WURS-61 reveals 5 factors. Using factor scores and after cross-tabulation, we found that: The presence of childhood impulsivity, emotional lability and distress in addition to inattention/disorganisation were significantly associated with adult ADHD diagnosis (F90). WURS items which suggests childhood conduct problems were associated with a number of adult diagnoses, when present either on its own (psychoactive substance use, or when present in combination with childhood impulsivity, emotional lability and distress (personality disorders). CONCLUSION: There is an association between certain childhood behaviours and risk for later development of personality disorders, and psychoactive substance use. There is overlap of childhood symptoms to those who later diagnosed in adulthood with ADHD, personality disorders, and substance abuse.

Unscented Kalman filter for airship model uncertainties and wind disturbance estimation.

An airship is lighter than an air vehicle with enormous potential in applications such as communication, aerial inspection, border surveillance, and precision agriculture. An airship model is made up of dynamic, aerodynamic, aerostatic, and propulsive forces. However, the computation of aerodynamic forces remained a challenge. In addition to aerodynamic model deficiencies, airship mass matrix suffers from parameter variations. Moreover, due to the lighter-than-air nature, it is also susceptible to wind disturbances. These modeling issues are the key challenges in developing an efficient autonomous flight controller for an airship. This article proposes a unified estimation method for airship states, model uncertainties, and wind disturbance estimation using Unscented Kalman Filter (UKF). The proposed method is based on a lumped model uncertainty vector that unifies model uncertainties and wind disturbances in a single vector. The airship model is extended by incorporating six auxiliary state variables into the lumped model uncertainty vector. The performance of the proposed methodology is evaluated using a nonlinear simulation model of a custom-developed UETT airship and is validated by conducting a kind of error analysis. For comparative studies, EKF estimator is also developed. The results show the performance superiority of the proposed estimator over EKF; however, the proposed estimator is a bit expensive on computational grounds. However, as per the requirements of the current application, the proposed estimator can be a preferred choice.

Ultrathin Two-Dimensional Plasmonic PtAg Nanosheets for Broadband Phototheranostics in Both NIR-I and NIR-II Biowindows.

Broadband near-infrared (NIR) photothermal and photoacoustic agents covering from the first NIR (NIR-I) to the second NIR (NIR-II) biowindow are of great significance for imaging and therapy of cancers. In this work, ultrathin two-dimensional plasmonic PtAg nanosheets are discovered with strong broadband light absorption from NIR-I to NIR-II biowindow, which exhibit outstanding photothermal and photoacoustic effects under both 785 and 1064 nm lasers. Photothermal conversion efficiencies (PCEs) of PtAg nanosheets reach 19.2% under 785 nm laser and 45.7% under 1064 nm laser. The PCE under 1064 nm laser is higher than those of most reported inorganic NIR-II photothermal nanoagents. After functionalization with folic acid modified thiol-poly(ethylene glycol) (SH-PEG-FA), PtAg nanosheets endowed with good biocompatibility and 4T1 tumor-targeted function give high performances for photoacoustic imaging (PAI) and photothermal therapy (PTT) in vivo under both 785 and 1064 nm lasers. The effective ablation of tumors in mice can be realized without side effects and tumor metastasis by PAI-guided PTT of PtAg nanosheets under 785 or 1064 nm laser. The results demonstrate that the prepared PtAg nanosheets with ultrathin thickness and small size can serve as a promising phototheranostic nanoplatform for PAI-guided PTT of tumors in both NIR-I and NIR-II biowindows.

Evoking ordered vacancies in metallic nanostructures toward a vacated Barlow packing for high-performance hydrogen evolution.

Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H2O in the HER.

Removal of toluene as a toxic VOC from methane gas using a non-thermal plasma dielectric barrier discharge reactor.

Methane is the main component of biogas, which could be used as a renewable energy source for electricity, source of heat, and biofuel production after upgrading from biogas. It also contains toxic compounds which cause environmental and human health problems. Therefore, in this work, the removal of a toxic compound (toluene) from methane gas was studied using a dielectric barrier discharge (DBD) reactor. It was observed that the removal of the toxic compound could be achieved from methane carrier gas using a dielectric barrier discharge reactor, and it depends on plasma input power. The maximum removal of the toxic compound was 85.9% at 40 W and 2.86 s. The major gaseous products were H2 and lower hydrocarbons (LHC) and the yield of these products also increases with input power. In the current study, the yield of gaseous products depends on the decomposition of toxic compounds and methane, because the decomposition of methane also produces H2 and lower hydrocarbons. The percentage yield of H2 increases from 0.43-4.74%. Similarly, the yield of LHC increases from 0.56-7.54% under the same reaction conditions. Hence, input power promoted the decomposition of the toxic compound and enhanced the yield of gaseous products.

Elimination of basic blue 9 by electrocoagulation coupled with pelletized natural dead leaves (Sapindus mukorossi) biosorption.

Elimination of basic blue 9 (BB-9), a cationic textile dye, by electrocoagulation coupled with biosorption exploiting pelletized natural dead leaves (PNDL) of Sapindus mukorossi, an economic alternative biosorbent, was investigated. The experimental runs were conducted in a laboratory-scale hybrid reactor loaded with Al electrodes, aeration spargers and PNDL packed twin suspended buckets. The pelletized adsorbents offer key advantages of good mechanical stability, lesser clogging risk, and easy disengagement as compared to powdered adsorbents. The parameters of current density, pH, PNDL dose, and initial dye concentration were studied for the decolorization and COD removal efficiency. The experimental results revealed that up to 99.9% decolorization and 90.01% COD removal efficiency achieved after 8 min at optimum condition of current density (j)=20.27 mA/cm2, pH = 9, PNDL dose = 6 g/L, and initial dye concentration = 50 mg/L. The BB-9 elimination followed the first-order kinetics with K1=0.318 min-1 and R2=0.997. The results revealed the potential of PNDL as a feasible biosorbent with the effective performance of the coupled process.

Size-Dependent Phase Transformation of Noble Metal Nanomaterials.

As an important aspect of crystal phase engineering, controlled crystal phase transformation of noble metal nanomaterials has emerged as an effective strategy to explore novel crystal phases of nanomaterials. In particular, it is of significant importance to observe the transformation pathway and reveal the transformation mechanism in situ. Here, the phase transformation behavior of face-centered cubic (fcc) Au nanoparticles (fcc-AuNPs), adhering to the surface of 4H nanodomains in 4H/fcc Au nanorods, referred to as 4H-AuNDs, during in situ transmission electron microscopy imaging is systematically studied. It is found that the phase transformation is dependent on the ratio of the size of the monocrystalline nanoparticle (NP) to the diameter of 4H-AuND. Furthermore, molecular dynamics simulation and theoretical modeling are used to explain the experimental results, giving a size-dependent phase transformation diagram which provides a general guidance to predict the phase transformation pathway between fcc and 4H Au nanomaterials. Impressively, this method is general, which is used to study the phase transformation of other metal NPs, such as Pd, Ag, and PtPdAg, adhering to 4H-AuNDs. The work opens an avenue for selective phase engineering of nanomaterials which may possess unique physicochemical properties and promising applications.

Elemental Segregation in Multimetallic Core-Shell Nanoplates.

In this work, we report an element segregation phenomenon in two-dimensional (2D) core-shell nanoplates, subsequently resulting in the formation of yolk-cage nanostructures after selective electrochemical etching. By using PtCu nanoplates as templates, PtCu@Pd core-shell nanoplates are formed. Interestingly, during the growth of Ru on the PtCu@Pd core-shell nanoplates, due to the selective element diffusion, PtCuPd@PdCu@Ru nanoplates are obtained. After selectively etching of PdCu in PtCuPd@PdCu@Ru using electrochemical method, the PtCuPd@Ru yolk-cage nanostructures are obtained. As a proof-of-concept application, this unique nanostructure shows superior electrocatalytic activity and stability toward the methanol oxidation reaction as compared to the PtCu nanoplates and commercial Pt/C catalyst.

Synthesis of self-assembled PtPdAg nanostructures with a high catalytic activity for oxygen reduction reactions.

Designing a self-assembling structure for a Pt-based catalyst offers a great opportunity to enhance the electrocatalytic performance and maximize the use of precious metals. Herein, we report an etching method based on thermal treatment for the removal of less active metals from Pt-based alloys for the enhancement of the oxygen reduction reaction. PtPdAg nanostructures' self-assembly can be easily controlled to the dimer stage or nanowires by stirring the nanoparticles in formamide with or without potassium iodide under heat for specific times. Thus oxygen reduction reaction-favoring PtPdAg hollow nanoparticle, nanodimer and nanowire catalysts are synthesized, all of which have been demonstrated to be promoting factors for the ORR. In a Pt-based catalyst, the arrangement and configuration of the surface or topmost few layer atoms influence the adsorption of oxygen and activation for ORR. The PtPdAg dimer catalyst shows excellent ORR activity compared to other PtPdAg nanostructures and commercial Pt/C i.e. 7.2 times higher specific activity and 4.1 times higher mass activity. We further carried out DFT calculations and from the results, we conclude that the most chemically inequivalent structure such as PtPdAg/C nanodimer alloys possesses the weakest oxygen binding energy.