Sustainable bio-based solid phase extraction adsorbent for the determination of various types of organic compounds.

A sustainable, bio-based, mesoporous material, Starbon A800, was explored for use as an adsorbent in solid phase extraction (SPE). A solution containing seven nitrosamines was first used as a standard to optimise conditions for extraction efficiency with Starbon A800. After optimising conditions, 25 compounds of varying polarity (terpenes, phenolics, pesticides, PAHs, amines, and nitrosamines) were extracted with SPE using either Starbon® A800, C18 or Porous Graphitic Carbon (PGC) as the adsorbent, for comparison purposes. At the same time, 3 different elution solvents (heptane, dichloromethane, and ethanol) were used for each type of adsorbent. Hansen solubility parameters can be used to choose an appropriate elution solvent for the selected SPE adsorbent. The best average SPE recoveries found for the 25 various compounds were 83%, 79%, and 65% using Starbon A800, PGC, and C18 adsorbents respectively and these had dichloromethane as the elution solvent. The identification and quantification of components was carried out using UV-visible spectroscopy, two-dimensional gas chromatography (GCxGC) with time of flight/mass spectrometry (TOF/MS) or a nitrogen chemiluminescence detector (NCD). The optimized method was successfully applied to extract volatile organic compounds from red wine and tap water using Starbon A800. Starbon A800 was shown to be a promising, low-cost, green, scalable, alternative adsorbent for the extraction of various types of organic compounds of a wide range of polarities using SPE.

Fundamental properties and phosphorus transformation mechanism of soybean straw during microwave hydrothermal conversion process.

Microwave hydrothermal (MHT) conversion is emerging as a promising technology for the disposal and reutilization of biowastes. This study investigated the fundamental properties and phosphorus transformation mechanism of soybean straw during the MHT conversion process. The oxygen-containing functional groups in soybean straw were stripped, and a trend of dehydration was observed as the temperature increased during the MHT process. Cellulose was identified as the major component of the MHT solid products at high temperature. Glucose and glucuronic acid in the MHT liquid products were gradually converted to formic acid and acetic acid with increasing temperature and holding time. The characteristics of the MHT products directly affected the changes in P speciation and transformation. Most of the P was distributed in liquid products and the impact of holding time was not significant on P distribution at low MHT temperature. With the increase in temperature and holding time, P gradually transferred into the solid products. The proportion of organic phosphorus and soluble inorganic phosphorus in soybean straw was high, and it decreased noticeably after the MHT process. The increase in MHT temperature promoted the conversion of OP and AP into IP and NAIP respectively. P K-edge X-ray absorption near edge structure analysis reveals that Ca5(PO4)3(OH) was the major component of soybean straw and more Ca5(PO4)3(OH) was formed at lower MHT temperature. This study provides fundamental knowledge on the property changes of soybean straw and the transformation of phosphorus during MHT conversion process, which is essential for its disposal and further utilization.

Enhanced microwave assisted pyrolysis of waste rice straw through lipid extraction with supercritical carbon dioxide.

A combination of supercritical carbon dioxide (scCO2) extraction and microwave-assisted pyrolysis (MAP) have been investigated for the valorisation of waste rice straw. ScCO2 extraction of rice straw led to a 0.7% dry weight yield of lipophilic molecules, at elevated temperatures of 65 °C and pressures of 400 bar. Lipid compositions (fatty acids, fatty alcohol, fatty aldehydes, steroid ketones, phytosterols, n-alkanes and wax esters) of the waxes obtained by scCO2 were comparable to those obtained Soxhlet extraction using the potentially toxic solvent n-hexane. ScCO2 extraction positively influenced the pyrolysis heating rate, with a rate of 420 K min-1 for particles of 500-2000 µm, compared to 240 K min-1 for the same particle size of untreated straw. Particle size significantly affected cellulose decomposition and the distribution of pyrolysis products (gaseous, liquid and char), highlighting the importance of selecting an adequate physical pre-treatment. TG and DTG of the original rice straw and resulting biochar produced indicated that cellulose was completely decomposed during the MAP. While a rapid pressure change occurred at ∼120 °C (size > 2000 µm) and ∼130 °C (size 500-2000 µm) during MAP and was associated with the production of incondensable gas during cellulose decomposition, this takes place at significantly lower temperatures than those observed with conventional pyrolysis, 320 °C. Wax removal by scCO2 influences the dielectric properties of the straw, enhancing microwave absorption with rapid heating rates and elevated final pyrolysis temperatures, illustrating the benefits of combining these sustainable technologies within a holistic rice straw biorefinery.

Nitrogen-Doped Starbons®: Methodology Development and Carbon Dioxide Capture Capability.

Five nitrogen sources (glycine, ß-alanine, urea, melamine and nicotinamide) and three heating methods (thermal, monomodal microwave and multimodal microwave) are used to prepare nitrogen-doped Starbons® derived from starch. The materials are initially produced at 250-300 °C (SNx 300y ), then heated in vacuo to 800 °C to produce nitrogen-doped SNx 800y 's. Melamine gives the highest nitrogen incorporation without destroying the Starbon® pore structure and the microwave heating methods give higher nitrogen incorporations than thermal heating. The carbon dioxide adsorption capacities of the nitrogen-doped Starbons® determined gravimetrically, in many cases exceed those of S300 and S800. The carbon dioxide, nitrogen and methane adsorption isotherms of the most promising materials are measured volumetrically. Most of the nitrogen-doped materials show higher carbon dioxide adsorption capacities than S800, but lower methane and nitrogen adsorption capacities. As a result, the nitrogen-doped Starbons® exhibit significantly enhanced carbon dioxide versus nitrogen and methane versus nitrogen selectivities compared to S800.

Revealing roles of CO2 and N2 in pressurized hydrothermal carbonization process for enhancing energy recovery and carbon sequestration.

In this study, CO2- and N2-pressurized hydrothermal carbonization processes were investigated to understand the catalytic effects of CO2 on hydrochar production and its quality (e.g., surface properties, energy recovery, and combustion behaviour). Both CO2- and N2-pressurized HTC processes could enhance the energy recovery (from 61.5% to 63.0-67.8%) in hydrochar by enhancing the dehydration reactions. Nonetheless, the two systems exhibited contrasting trends in volatile release, oxygen removal, and combustion performance as a function of increasing pressure. High N2 pressure enhanced deoxygenation reaction, facilitating the release of volatiles and increasing the hydrochar aromaticity and combustion activation energy (172.7 kJ/mol for HC/5N). Without the contribution of CO2, excessively high pressure may cause an adverse impact on the fuel performance owing to higher oxidation resistance. This study presents an important and feasible strategy to utilise CO2-rich flue gas in the HTC process to produce high-quality hydrochar for renewable energy and carbon recovery.

Quantifying Faculty Perception of Diversity, Equity, and Inclusion Within Academic Otolaryngology-Head and Neck Surgery Departments.

OBJECTIVE: Investigating faculty perceptions of diversity, equity, and inclusion (DEI) among academic otolaryngology programs. STUDY DESIGN: Quantitative survey. SETTING: Academic otolaryngology departments. METHODS: The DEI Inventory was developed by a multi-institutional health equity consortium and disseminated within 16 academic otolaryngology programs. The inventory consisted of 25 items graded on a 5-point Likert scale (strongly disagree to strongly agree), 2 yes/no questions, and 5 items reflecting overall DEI, stress, and burnout among academic otolaryngologists. Validated imposter phenomenon and personality trait measures were also included. RESULTS: The inventory received 158 (31.0%) partial and 111 (21.8%) full responses. No significant differences were identified in DEI scores by race. Compared to males, females reported lower scores on the overall DEI Inventory (3.6 vs 4.3, p < .001). Female respondents also reported greater levels of imposter phenomenon than their male counterparts (53.2 vs 47.5, p = .049). CONCLUSION: Preliminary responses to our DEI Inventory suggest that faculty perception of DEI is not impacted by race. Female faculty report considerably lower perceptions of DEI than their male counterparts and experience greater levels of imposter phenomenon. The results of the DEI Inventory can help departments design meaningful interventions to improve levels of DEI among faculty.

Optimization of green and environmentally-benign synthesis of isoamyl acetate in the presence of ball-milled seashells by response surface methodology.

Ball-milled seashells, as a nano-biocomposite catalyst and natural source of CaCO3 in its aragonite microcrystalline form with fixed CO2, was optimized for the synthesis of isoamyl acetate (3-methylbutyl ethanoate) by response surface methodology with a five-level three-factor rotatable circumscribed central composite design. The seashells nano-biocomposite has proved to be an excellent heterogeneous multifunctional catalyst for the green and environmentally-benign synthesis of isoamyl acetate from acetic acid and isoamyl alcohol under solvent-free conditions. A high yield of 91% was obtained under the following optimal conditions: molar ratio of alcohol: acetic acid (1:3.7), catalyst loading (15.7 mg), the reaction temperature (98 °C), and the reaction time (219 min). The outstanding advantages of this protocol are the use of an inexpensive, naturally occurring and easily prepared nano-biocomposite material having appropriate thermal stability and without any modifications using hazardous reagents, lower catalyst loading and reaction temperature, no use of corrosive Bronsted acids as well as toxic azeotropic solvents or water adsorbents, and simplicity of the procedure.

Efficient adsorption of bulky reactive dyes from water using sustainably-derived mesoporous carbons.

Hazardous reactive dyes can cause serious environmental problems, as they are difficult to remove from water using conventional adsorbents due to their large molecular sizes and bulky structures. Sustainable mesoporous carbons derived from alginic acid demonstrated promising adsorbent capacity for several representative industrial bulky reactive dye molecules that account for almost 30% of the global textile dye market: Procion Yellow H-XEL (PY), Remazol Black (RB), Procion Crimson H-XEL (PC) and Procion Navy H-XEL (PN). These new adsorbents showed high mesoporosity (>90%) and large pore diameters (>20 nm) facilitating more straightforward and efficient adsorption and desorption processes when compared with predominately microporous activated carbon (AC), Norit, of similar surface chemistry, or with Silica gel (Sgel) that shows good mesoporosity but is hydrophilic. Their adsorption capacity was also significantly higher than that of both AC and Sgel, verifying suitability for bulky dye elimination from wastewater. Adsorption kinetic studies showed a best fit with the Elovich model, indicating a heterogeneous surface adsorption process. The adsorption isotherm data was best represented via the Toth model for almost all adsorbent/dye systems (R2 ≥ 0.98), validating the results of the Elovich model whereby the adsorbent is structurally heterogenous with multilayer dye coverage. From thermodynamic analysis, the derived parameters of ΔG (-11.6 âˆ¼ -6.2 kJ/mol), ΔH and ΔS demonstrate a spontaneous, enthalpy controlled adsorption process that was exothermic for RB (-10.0 kJ/mol) and PC (-23.9 kJ/mol) and endothermic for PY (3.9 kJ/mol) and PN (13.2 kJ/mol). Overall these alginic acid based mesoporous carbons are cost-effective, sustainable and efficient alternatives to current predominantly microporous adsorbent systems.

Reaction Optimization for Greener Chemistry with a Comprehensive Spreadsheet Tool.

Green chemistry places an emphasis on safer chemicals, waste reduction, and efficiency. Processes should be optimized with green chemistry at the forefront of decision making, embedded into research at the earliest stage. To assist in this endeavor, we present a spreadsheet that can be used to interpret reaction kinetics via Variable Time Normalization Analysis (VTNA), understand solvent effects with linear solvation energy relationships (LSER), and calculate solvent greenness. With this information, new reaction conditions can be explored in silico, calculating product conversions and green chemistry metrics prior to experiments. The application of this tool was validated with literature case studies. Reaction performance was predicted and then confirmed experimentally for examples of aza-Michael addition, Michael addition, and an amidation. The combined analytical package presented herein permits a thorough examination of chemical reactions, so that the variables that control reaction chemistry can be understood, optimized, and made greener for research and education purposes.

Delayed use of bioenergy crops might threaten climate and food security.

The potential of mitigation actions to limit global warming within 2 °C (ref. 1) might rely on the abundant supply of biomass for large-scale bioenergy with carbon capture and storage (BECCS) that is assumed to scale up markedly in the future2-5. However, the detrimental effects of climate change on crop yields may reduce the capacity of BECCS and threaten food security6-8, thus creating an unrecognized positive feedback loop on global warming. We quantified the strength of this feedback by implementing the responses of crop yields to increases in growing-season temperature, atmospheric CO2 concentration and intensity of nitrogen (N) fertilization in a compact Earth system model9. Exceeding a threshold of climate change would cause transformative changes in social-ecological systems by jeopardizing climate stability and threatening food security. If global mitigation alongside large-scale BECCS is delayed to 2060 when global warming exceeds about 2.5 °C, then the yields of agricultural residues for BECCS would be too low to meet the Paris goal of 2 °C by 2200. This risk of failure is amplified by the sustained demand for food, leading to an expansion of cropland or intensification of N fertilization to compensate for climate-induced yield losses. Our findings thereby reinforce the urgency of early mitigation, preferably by 2040, to avoid irreversible climate change and serious food crises unless other negative-emission technologies become available in the near future to compensate for the reduced capacity of BECCS.

Tailoring wood waste biochar as a reusable microwave absorbent for pollutant removal: Structure-property-performance relationship and iron-carbon interaction.

This study innovated the concept in designing an efficient and reusable microwave (MW) absorbent through concurrent exploitation of carbon graphitization, oxygen functionalization, and carbothermal iron reduction underpinned by an endothermic co-pyrolysis of wood waste and low-dosage iron. A powerful MW assimilation was accomplished from nanoscale amorphous magnetic particles as well as graphitized microporous carbon-iron skeleton in the biochar composites. Relative to a weak magnetic loss derived from the iron phase, the graphitic carbon architecture with abundant surface functionalities (i.e., CO and CO) exhibited a strong dielectric loss, which was thus prioritized as major active sites during MW reuse. The MW-absorbing biochar demonstrated a fast, robust, and durable removal of a refractory herbicide (2,4-dichlorophenoxy acetic acid) under mild MW irradiation with zero chemical input, low electricity consumption, and negligible Fe dissolution. Overall, this study will foster carbon-neutral industrial wastewater treatment and wood waste valorization.

Rapid and efficient adsorption of methylene blue dye from aqueous solution by hierarchically porous, activated starbons®: Mechanism and porosity dependence.

Hierarchically porous activated Starbons® derived from starch are found to make excellent adsorbents for methylene blue, even in the presence of other dyes and inorganic salts, highlighting their potential to be used in water purification. The optimal material (S950C90) has a methylene blue adsorption capacity (891 mg g-1) almost nine times higher than that of unactivated S800 and four times higher than that of commercial activated carbon at 298 K. The adsorption of methylene blue onto optimal materials (S950C90 and S800K4) reaches equilibrium within 5 min. Adsorption data for all the adsorbents show a good fit to the Freundlich isotherm which allows the Gibbs free energies of adsorption to be calculated. The adsorption capacities increase as the pH of the methylene blue solution increases, allowing the dye to be desorbed by treatment with acidic ethanol and the Starbon® materials reused. Porosimetry and SEM-EDX imaging indicate that methylene blue adsorbs throughout the surface and completely fills all the micropores in the Starbon® adsorbent. The methylene blue adsorption capacities show excellent correlations with both the BET surface areas and the micropore volumes of the materials.

A modest proposal for a new way forward for clinical research: Involve insurance companies.

Is it time for medical insurance companies to organize and fund clinical research that evaluates the role of new treatments (drugs or device-based therapies) in the context of existing clinical paradigms for common diseases?

Speciation evolution and transformation mechanism of P during microwave hydrothermal process of sewage sludge.

Due to the global shortage of phosphate ore, sewage sludge is an important resource for P recovery. This study aims to investigate how P was migrated and transformed during the microwave hydrothermal (MHT) process of sewage sludge. The effects of MHT and hydrothermal (HT) conversion were compared. The results reveals that there were no significant differences on the P distribution and speciation changes between the HT and MHT products, especially under high hydrothermal temperature. Ortho-P/Pyro-P was the dominant P form in the hydrothermal solid products, and high temperature promoted the transformation of C-O-P to Ortho-P/Pyro-P. The analysis of X-ray absorption near edge structure (XANES) shows that Ca5(PO4)3OH was formed after the hydrothermal processes. The relative abundance of Ca-P decreased first and then increased with increasing hydrothermal temperature. Moderate MHT temperature (170 °C) and holding time (30-60 min) promoted the transformation of P to the liquid products. Generally, the effect of MHT temperature was more significant than that of heating type and holding time on the variations of P distribution and speciations.

Artificial intelligence to diagnose ear disease using otoscopic image analysis: a review.

AI relates broadly to the science of developing computer systems to imitate human intelligence, thus allowing for the automation of tasks that would otherwise necessitate human cognition. Such technology has increasingly demonstrated capacity to outperform humans for functions relating to image recognition. Given the current lack of cost-effective confirmatory testing, accurate diagnosis and subsequent management depend on visual detection of characteristic findings during otoscope examination. The aim of this manuscript is to perform a comprehensive literature review and evaluate the potential application of artificial intelligence for the diagnosis of ear disease from otoscopic image analysis.

The Alaska Native Tumour Registry: fifty years of cancer surveillance data for Alaska Native people.

Like other Indigenous Circumpolar populations, Alaska Native (AN) people experience different patterns of cancer than their non-Indigenous counterparts. Every 5 years, the Alaska Native Tumour Registry releases a comprehensive report on cancer among AN people; this study provides 50 years of cancer surveillance data. Five-year annual-average age-adjusted incidence rates were calculated for time-periods ranging 1969-2018. AN data were compared with data for US whites (SEER 9). Mortality rates were calculated for 1994-2018 using data from the National Center for Health Statistics. During 2014-2018, there were 2,401 cases of invasive cancer among AN people. Among these, the most commonly diagnosed cancers were colorectal (405 cases, 17% of all cancers), lung and bronchus (373 cases, 16% of all cancers), and female breast (340 cases, 14% of all cancers). Lung cancer was the leading cause of cancer death, followed by colorectal and female breast cancers. These leading cancers are screenable, and preventable through lifestyle modifications including tobacco cessation, healthy eating and engaging in physical activity. These data provide important information to support cancer prevention and control among AN people. Cancer surveillance has been a valuable tool throughout the Circumpolar North to support reducing the burden of cancer among Indigenous populations.Abbreviations: ANAI: Alaska Native/American Indian; AN: Alaska Native; USW: U.S. White(s); ANMC: Alaska Native Medical Center; ANTR: Alaska Native Tumour Registry; IR: Incidence Rate; CI: Confidence Interval; RR: Rate Ratio; ICD-O-3: International Classification of Diseases for Oncology - Third Edition; SEER: Surveillance, Epidemiology and End Results.

Complications of nasal SARS-CoV-2 testing: a review.

Transnasal swab testing for the detection of SARS-CoV-2 is well established. The Centers for Disease Control and Prevention advocates swabbing either of the anterior nares, middle turbinate, or nasopharynx for specimen collection depending on available local resources. The purpose of this review is to investigate complications related to transnasal SARS-CoV-2 testing with specific attention to specimen collection site and swab approach. The literature demonstrates that while nasopharyngeal swabbing is associated with an increased risk of complications, it should remain the gold-standard test due to greater diagnostic accuracy relative to anterior nasal and middle turbinate swabs.

Electrical conductivity of beech sawdust using graphite catalytic coating: unlocking the microwave-assisted thermolysis efficiency of lignocellulosic biomass.

The coating of the beech sawdust using a catalytic amount of graphite (as low as 0.25 wt%) allowed a step improvement in the microwave-assisted thermolysis. Results demonstrated that the pyrolysis performance was linked to an electrical conductivity threshold of the coated samples rather than a gradual increase. With as low as 0.13 mS m-1 of electrical conductivity, the 0.75 wt% graphite coated sawdust (250-500 µm) was efficiently gasified with up to 43 wt% of gas (30 wt% of carbon monoxide, 25 vol% of hydrogen). Initial particle size impacted the thermolysis performance where optimal size (250-500 µm) provided high heat homogeneity due to efficient graphite coating and low temperature gradient between the outer and inner part of the sawdust. The small initial particle size (75-250 µm) was unsuitable for microwave pyrolysis, exhibiting a too large surface area for efficient coating with 0.75 wt% of graphite which was confirmed by the absence of electrical conductivity (<0.003 mS m-1). The electrical conductivity can be used as a marker to evaluate the suitability of the sample for microwave-assisted pyrolysis. Unlike simple graphite mixing, the mechanical coating allowed more than 20-fold decrease of susceptor quantity, providing more homogeneous samples with higher reproducibility.

Polymer Chemistry Applications of Cyrene and its Derivative Cygnet 0.0 as Safer Replacements for Polar Aprotic Solvents.

This study explores a binary solvent system composed of biobased Cyrene and its derivative Cygnet 0.0 for application in membrane technology and in biocatalytic synthesis of polyesters. Cygnet-Cyrene blends could represent viable replacements for toxic polar aprotic solvents. The use of a 50 wt % Cygnet-Cyrene mixture makes a practical difference in the production of flat sheet membranes by nonsolvent-induced phase separation. New polymeric membranes from cellulose acetate, polysulfone, and polyimide are manufactured by using Cyrene, Cygnet 0.0, and their blend. The resultant membranes have different morphology when the solvent/mixture and temperature of the casting solution change. Moreover, Cyrene, Cygnet 0.0, and Cygnet-Cyrene are also explored for substituting diphenyl ether for the biocatalytic synthesis of polyesters. The results indicate that Cygnet 0.0 is a very promising candidate for the enzymatic synthesis of high molecular weight polyesters.