Simultaneous removal of chlorobenzene and Cr(VI) from groundwater using microbial fuel cell with low-cost Si modified ferrihydrite electrodes.

Aromatic chlorinated compounds and Cr(VI) in groundwater pose significant challenges due to their resistance. This study explores microbial fuel cells using low-cost Si-modified ferrihydrite (SiFh) electrodes for simultaneous chlorobenzene and Cr(VI) removal. The voltage output of MFC assembled with SiFh modified electrode was approximately 1.63 times higher than the bare electrode, achieving 1.23 times higher in chlorobenzene degradation efficiency. CF-SiFh loaded MFC had the highest power generation and best EET efficiency, which was positive to greatest and fastest chlorobenzene removal. Microbial community analysis identified the dominance of Cupriavidus and Pandoraea in chlorobenzene oxidation, while Lentimicrobiaceae and Rhodobacteraceae were key genera that may facilitate direct and indirect electron transfer within the biofilms. Cr species analysis in solution and solids confirmed it was reduced to Cr(OH)3 or CrxFe1-x(OH)3 coprecipitates at cathode. MFCs with SiFh-modified electrodes thus offer a promising technology for simultaneous chlorinated compound and Cr(VI) removal, promising in contaminated groundwater remediation.

Online monitoring of methane transfer rates unveils nitrogen fixation dynamics in Methylococcus capsulatus.

This study explores methane utilization by the methanotrophic microorganism Methylococcus capsulatus (Bath) for biomass production, presenting a promising approach to mitigate methane emissions and foster the development sustainable biomaterials. Traditional screening methods for gas cultivations involve either serum flasks without online monitoring or costly, low-throughput fermenters. To address these limitations, the Respiration Activity MOnitoring System was augmented with methane sensors for real-time methane transfer rate (MTR) monitoring in shake flasks. Utilizing online monitoring of the MTR in shake flasks results in enhanced throughput and cost-effectiveness for cultivating M. capsulatus. Simultaneous monitoring of transfer rates for oxygen, methane, and carbon dioxide was conducted in up to eight shake flasks, ensuring the success of the cultivation process. Alterations in methane-to-oxygen transfer rate ratios and carbon fixation rates reveal the impact of transfer limitations on microbial growth. Detection of gas transfer limitations, exploration of process parameter influences, and investigations of medium components were enabled by the introduced method. Optimal nitrogen concentrations could be determined to ensure optimal growth. This streamlined approach accelerates the screening process, offering efficient investigations into metabolic effects, limitations, and parameter influences in gas fermentations without the need for elaborate offline sampling, significantly reducing costs and enhanced reproducibility.

Impact of hydromechanical stress on CHO cells' metabolism and productivity: Insights from shake flask cultivations with online monitoring of the respiration activity.

The hydromechanical stress is a relevant parameter for mammalian cell cultivations, especially regarding scale-up processes. It describes the mechanical forces exerted on cells in a bioreactor. The maximum local energy dissipation rate is a suitable parameter to characterize hydromechanical stress. In literature, different studies deal with the effects of hydromechanical stress on CHO cells in stirred tank reactors. However, they often focus on lethal effects. Furthermore, systematic examinations in smaller scales like shake flasks are missing. Thus, this study systematically considers the influence of hydromechanical stress on CHO DP12 cells in shake flask cultivations. By utilizing online monitoring of the oxygen transfer rate, the study simplifies and enhances the resolution of examinations. Results indicate that while lethal effects are absent, numerous sub-lethal effects emerge with increasing hydromechanical stress: The process time is prolonged. The time of glucose and glutamine depletion, and the lactate switch correlate positively linear with the logarithmic average energy dissipation rate while the maximum specific growth rate correlates negatively. Strikingly, the final antibody concentration only declines at the highest tested average energy dissipation rate of 3.84 W kg-1 (only tested condition with a turbulent flow regime and therefore a higher maximal local energy dissipation rate) from about 250 mg L-1 to about 180 mg L-1. This study presents a straightforward method to examine the impact of hydromechanical stress in shake flasks, easily applicable to any other suspension cell line. Additionally, it offers valuable insights for scale-up processes, for example into stirred tank reactors.

Significance of zinc re-absorption in Zn dynamic regulation in marine fish revealed by pharmacokinetic model.

Zinc (Zn) is an essential but toxic trace element and is widely available in the natural environment. In the present study, we developed a re-absorption physiologically based pharmacokinetic (PBPK) model based on long-term dietary exposure to gain insights into the physiological mechanisms of uptake, tissue distribution, storage, and excretion of Zn in marine juvenile gilt-head breams Sparus aurata (with stomach). The PBPK model incorporated the kinetic processes of Zn transfer from fish liver to gastrointestinal system and used the Markov Monte Carlo algorithm to estimate the distribution of model parameters. The model fit indicated that the stomach and intestine of fish were key organs in regulating the concentration of Zn entering the internal environment, with excess exogenous Zn (120 mg/kg) being excreted in feces (rate constant of 5.23 d-1). Modeling results also indicated that liver (3.00 d-1), spleen (1.41 d-1) and kidney (0.51 d-1) were the main tissues responding to blood Zn flux by accumulation and detoxification. Fish kidneys exposed to 60 mg/kg and 120 mg/kg Zn had different regenerative capacities, resulting in different detoxification functions. A higher dietary Zn (120 mg/kg) disrupted the intestinal reabsorption process in marine fish. This study showed that exogenous Zn was directly accumulated in organs through the gastrointestinal-hepatic system, which is an important pathways for regulating metal homeostasis in marine fish. The results provided important understanding of the mechanisms of metal regulation and transport in marine fish.

Unraveling the impact of pH, sodium concentration, and medium osmolality on Vibrio natriegens in batch processes.

BACKGROUND: Vibrio natriegens, a halophilic marine γ-proteobacterium, holds immense biotechnological potential due to its remarkably short generation time of under ten minutes. However, the highest growth rates have been primarily observed on complex media, which often suffer from batch-to-batch variability affecting process stability and performance. Consistent bioprocesses necessitate the use of chemically defined media, which are usually optimized for fermenters with pH and dissolved oxygen tension (DOT) regulation, both of which are not applied during early-stage cultivations in shake flasks or microtiter plates. Existing studies on V. natriegens' growth on mineral media report partially conflicting results, and a comprehensive study examining the combined effects of pH buffering, sodium concentration, and medium osmolality is lacking. RESULTS: This study evaluates the influence of sodium concentration, pH buffering, and medium osmolality on the growth of V. natriegens under unregulated small-scale conditions. The maximum growth rate, time of glucose depletion, as well as the onset of stationary phase were observed through online-monitoring the oxygen transfer rate. The results revealed optimal growth conditions at an initial pH of 8.0 with a minimum of 300 mM MOPS buffer for media containing 20 g/L glucose or 180 mM MOPS for media with 10 g/L glucose. Optimal sodium chloride supplementation was found to be between 7.5 and 15 g/L, lower than previously reported ranges. This is advantageous for reducing industrial corrosion issues. Additionally, an osmolality range of 1 to 1.6 Osmol/kg was determined to be optimal for growth. Under these optimized conditions, V. natriegens achieved a growth rate of 1.97 ± 0.13 1/h over a period of 1 h at 37 °C, the highest reported rate for this organism on a mineral medium. CONCLUSION: This study provides guidelines for cultivating V. natriegens in early-stage laboratory settings without pH and DOT regulation. The findings suggest a lower optimal sodium chloride range than previously reported and establish an osmolality window for optimal growth, thereby advancing the understanding of V. natriegens' physiology. In addition, this study offers a foundation for future research into the effects of different ions and carbon sources on V. natriegens.

Analysis on heat transfer performance of coaxial borehole heat exchanger in a layered subsurface with groundwater.

In the realm of ground source heat pump (GSHP) installations, the operational efficiency of borehole heat exchangers (BHEs) is heavily dependent on the complex configurations of geological formations, including soil stratification and the movement of underground water. Our research investigated the influences of ground structure characteristics on the heat transfer performance of coaxial BHEs. A coaxial borehole heat exchanger with a three-dimensional design was constructed, setting a typical geology from the Xiong'an New Region as the boundary condition. The homogenous model with equivalent physical properties overpredicted the water temperature exiting the coaxial BHE in the stratified ground with groundwater advection by 0.2 °C, while underpredicted the heat transfer rate by 10.8 % for the 24-h period; There exists an optimal inlet flow velocity to balance the heat injection and enhanced heat transfer for the optimal heat transfer rate, which was 0.4 m/s in this study; The increase of groundwater advection velocity decreased the outlet temperature by 0.5 %, enhanced the heat transfer per meter by 15.5 % and contributed to a smaller thermal influence radius during the 24-h period. This will contribute to the design of coaxial BHEs in complex geological structure.

Application of Silk Light Chain on a Graphene Composite Surface: A Molecular Dynamics and Electrochemical Experiment.

The surface functionalization of pristine graphene (PG) with beneficial biocomposites is important for biomedical and tissue engineering. This study introduces silk light chain as novel biocomposites to increase the biocompatibility of PG. We explored the supramolecular structures of the silk heavy and light chains. Through molecular dynamics, we compared and analyzed the structural effects and binding mechanisms of these domains in their interaction with PG. Our results highlighted a significant hydrophobic interaction between the silk light chain and PG, without structural collapse. The supramolecular structure of the silk light chain was identified by analyzing the amino acids bound to PG. Moreover, using the silk light chain, the hydrophobic surface of PG has changed to a hydrophilic surface, and the silk light-chain-PG electron transfer rate was evaluated for the graphene congeners: graphene oxide (GO) and reduced graphene oxide. Therefore, we are confident that the dispersibility and biocompatibility of PG can be increased using silk light chains, which will contribute to broadening the field of application of PG-based materials.

Effect of surfactant type and concentration on the gas-liquid mass transfer in biotrickling filters used for air pollution control.

Volatile organic compounds (VOCs) emitted into the atmosphere negatively affect the environment and human health. Biotrickling filtration, an effective technology for treating VOC-laden waste gases, faces challenges in removing hydrophobic VOCs due to their low water solubility and therefore limited bioavailability to microorganisms. Consequently, the addition of (bio)surfactants has proven to be a promising strategy to enhance the removal of hydrophobic VOCs in biotrickling filters (BTFs). Yet, up to now, no single study has ever performed a mass transfer characterization of a BTF under (bio)surfactants addition. In this study, the effect of (bio)surfactant addition on the gas-liquid mass transfer characteristics of two BTFs was measured by using oxygen (O2) as a model gas. Through an empirical correlation, the mass transfer coefficients (kLa) of two hydrophobic VOCs, toluene and hexane, which are of industrial and environmental significance, were estimated. One BTF was filled with expanded perlite, while the other with a mixture of compost and wood chips (C + WC). Both BTFs were operated under different liquid velocities (UL: 0.95 and 1.53 m h-1). Saponin, a biological surfactant, and Tween 80, a synthetic surfactant, were added to the recirculating liquid at different critical micelle concentrations (CMCs: 0-3 CMC). The higher interfacial and surface area of the perlite BTF compared to the C + WC BTF led to higher kLaO2 values regardless of the operational condition: 308 ± 18-612 ± 19 h-1 versus 42 ± 4-177 ± 24 h-1, respectively. Saponin addition at 0.5 and 1 CMC had positive effects on the perlite BTF, with kLaO2 values two times higher compared to those at 0 CMC. Tween 80 exhibited a neutral or slightly positive effect on the mass transfer of both BTFs under all conditions. Overall, the CMC, along with the physical characteristics of the packing materials and the operational conditions evaluated explained the results obtained. This study provides fundamental data essential to improve the performance and design of BTFs for hydrophobic VOCs abatement.

Survival and its relationship with the type of peritoneal solute transfer rate, in patients with chronic kidney disease incident on peritoneal dialysis therapy in RTS Colombia between the years 2007-2017.

INTRODUCTION: In some studies, the peritoneal solute transfer rate (PSTR) through the peritoneal membrane has been related to an increased risk of mortality. It has been observed in the literature that those patients with rapid diffusion of solutes through the peritoneal membrane (high/fast transfer) and probably those with high average transfer characterized by the Peritoneal Equilibrium Test (PET) are associated with higher mortality compared to those patients who have a slow transfer rate. However, some authors have not documented this fact. In the present study, we want to evaluate the (etiological) relationship between the characteristics of peritoneal membrane transfer and mortality and survival of the technique in an incident population on peritoneal dialysis in RTS Colombia during the years 2007-2017 using a competing risk model. MATERIALS AND METHODS: A retrospective cohort study was carried out at RTS Colombia in the period between 2007 and 2017. In total, there were 8170 incident patients older than 18 years, who had a Peritoneal Equilibration Test (PET) between 28 and 180 days from the start of therapy. Demographic, clinical, and laboratory variables were evaluated. The (etiological) relationship between the type of peritoneal solute transfer rate at the start of therapy and overall mortality and technique survival were analyzed using a competing risk model (cause-specific proportional hazard model described by Royston-Lambert). RESULTS: Patients were classified into four categories based on the PET result: Slow/Low transfer (16.0%), low average (35.4%), high average (32.9%), and High/Fast transfer (15.7%). During follow-up, with a median of 730 days, 3025 (37.02%) patients died, 1079 (13.2%) were transferred to hemodialysis and 661 (8.1%) were transplanted. In the analysis of competing risks, adjusted for age, sex, presence of DM, HTA, body mass index, residual function, albumin, hemoglobin, phosphorus, and modality of PD at the start of therapy, we found cause-specific HR (HRce) for high/fast transfer was 1.13 (95% CI 0.98-1.30) p = 0.078, high average 1.08 (95% CI 0.96-1.22) p = 0.195, low average 1.09 (95% CI 0.96-1.22) p = 0.156 compared to the low/slow transfer rate. For technique survival, cause-specific HR for high/rapid transfer of 1.22 (95% CI 0.98-1.52) p = 0.66, high average HR was 1.10 (95% CI 0.91-1.33) p = 0.296, low average HR of 1.03 (95% CI 0.85-1.24) p = 0.733 compared with the low/slow transfer rate, adjusted for age, sex, DM, HTA, BMI, residual renal function, albumin, phosphorus, hemoglobin, and PD modality at start of therapy. Non-significant differences. CONCLUSIONS: When evaluating the etiological relationship between the type of peritoneal solute transfer rate and overall mortality and survival of the technique using a competing risk model, we found no etiological relationship between the characteristics of peritoneal membrane transfer according to the classification given by Twardowski assessed at the start of peritoneal dialysis therapy and overall mortality or technique survival in adjusted models. The analysis will then be made from the prognostic model with the purpose of predicting the risk of mortality and survival of the technique using the risk subdistribution model (Fine & Gray).

Optimization of guar gum-based anti-browning coating for prolonging the shelf life of cut potatoes.

The impact of guar gum (GG), crude algae ethanolic extract (CAEE), and turmeric essential oil (TEO) incorporated edible coating formulations on the quality of cut potatoes was investigated at room temperature (27 ±â€¯3 °C, 70-85 % RH) storage using a rotatable central composite design. Besides, 30 % glycerol, 5 % calcium chloride, and 3 % ascorbic acid (w/w) were added to the coating solution as additives. The surface color, respiration rate, water vapor transmission rate, visible mold growth, and sensory analysis were assessed after seven days of storage. The inclusion of ascorbic acid and TEO in edible coating demonstrated a more effective delay in browning. The coated potatoes had lower OTR, CTR, and WVTR values for GG concentrations of 0.5 to 1 g/100 mL than the control. Compared to additives, higher concentrations of GG improved response parameters. The WVTR value of coated potatoes was significantly impacted by the interaction between CAEE and TEO with GG. Incorporating CAEE and TEO into the formulations of guar gum led to a reduction in the permeability of the coating to oxygen and water vapor. The seven days of extended shelf life compared to two days of control were observed with the optimized coating formulation. Furthermore, the application of the coating treatment proved effective in preventing enzymatic browning and creating a barrier against moisture and gases, contributing to prolonged freshness during extended storage periods.

Fate of multi-residue insecticides and their metabolites in the process of vinification: Analytical method validation, dissipation kinetics, processing factor, and risk assessment.

In viticulture, the use of synthetic chemical formulations introduces insecticide residues into harvested grapes and further into processed grape products, posing a safety concern to consumers. This study investigated the fate of ten insecticide residues and their metabolites from vine to wine. A rapid validated multi-residue approach using QuEChERS extraction and LC-MS/MS configuration was employed for targeted analysis in grape, pomace, and wine. The targeted insecticides showed satisfactory mean recoveries (76.03-111.95%) and precision (RSD = 0.75-7.90%) across the three matrices, with a matrix effect ranging from -16.88 to 35.18%, particularly higher in pomace. Preliminary grape washing effectively removed 15.52-61.31% of insecticide residues based on water solubility and systemic nature. Residue dissipation during fermentation ranged from 73.19% to 87.15% with a half-life spanning from 1 to 5.5 days. The mitigation rate was observed at 12.85-26.81% for wine and 17.76-51.55% for pomace, with the highest transfer rate for buprofezin (51.55%) to pomace and fipronil (25.72%) to wine. Calculated processing factors (PF) for final wine ranged from 0.16 to 0.44, correlating strongly with the octanol-water partition ratio of targeted insecticides. The reported PF, calculated hazard quotient (HQ) (0.003-5.800%), and chronic hazard index (cHI) (2.041-10.387%) indicate reduced residue concentrations in wine and no potential chronic risk to consumers, ensuring a lower dietary risk to wine consumers.

Diffusion-driven fed-batch fermentation in perforated ring flasks.

PURPOSE: Simultaneous membrane-based feeding and monitoring of the oxygen transfer rate shall be introduced to the newly established perforated ring flask, which consists of a cylindrical glass flask with an additional perforated inner glass ring, for rapid bioprocess development. METHODS: A 3D-printed adapter was constructed to enable monitoring of the oxygen transfer rate in the perforated ring flasks. Escherichia coli experiments in batch were performed to validate the adapter. Fed-batch experiments with different diffusion rates and feed solutions were performed. RESULTS: The adapter and the performed experiments allowed a direct comparison of the perforated ring flasks with Erlenmeyer flasks. In batch cultivations, maximum oxygen transfer capacities of 80 mmol L-1 h-1 were reached with perforated ring flasks, corresponding to a 3.5 times higher capacity than in Erlenmeyer flasks. Fed-batch experiments with a feed reservoir concentration of 500 g glucose L-1 were successfully conducted. Based on the oxygen transfer rate, an ammonium limitation could be observed. By adding 40 g ammonium sulfate L-1 to the feed reservoir, the limitation could be prevented. CONCLUSION: The membrane-based feeding, an online monitoring technique, and the perforated ring flask were successfully combined and offer a new and promising tool for screening and process development in biotechnology.

Effects of the timing of maternal SARS-CoV-2 infection and vaccination status on placental transfer of antibodies to neonates: A cross-sectional study.

OBJECTIVES: To assess the effects of timing of maternal severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection and vaccination status on placental transfer of antibodies to neonates. METHODS: In this cross-sectional study, chemiluminescence was employed to measure SARS-CoV-2 IgG antibody titers in paired maternal-infant samples from women infected during pregnancy who were vaccinated or unvaccinated. Generalized linear regression assessed factors affecting antibody transfer in infected pregnant women and neonatal titers. RESULTS: The group with ≥90 days between infection and delivery showed a higher antibody transfer rate than the <90 days group (ß= 0.33, 95%CI: 0.01-0.65). Neonatal IgG titers correlated significantly with maternal titers and with maternal infections more than 90 days before delivery. Among infected pregnant women, those who had received 2 or 3 doses of vaccine before pregnancy had higher neonatal antibody titers than those who were not vaccinated (ß = 57.70, 95%CI: 31.33-84.07). CONCLUSION: Neonates born to pregnant women who were vaccinated before infection showed higher antibody titers than neonates of pregnant women who were not vaccinated before infection. The transfer rate is higher in pregnant women with ≥90 days from infection to delivery than in those with <90 days. These findings highlight the importance of timely maternal vaccination to optimize maternal and infant immunity.

Online monitoring of the respiration activity in 96-deep-well microtiter plate Chinese hamster ovary cultures streamlines kill curve experiments.

Cell line generation of mammalian cells is a time-consuming and labor-intensive process, especially because of challenges in clone selection after transfection. Antibiotics are common selection agents for mammalian cells due to their simplicity of use. However, the optimal antibiotic concentration must be determined with a kill curve experiment before clone selection starts. The traditional kill curve experiments are resource-intensive and time-consuming due to necessary sampling and offline analysis effort. This study, thus, explores the potential of online monitoring the oxygen transfer rate (OTR), as a non-invasive and efficient alternative for kill curve experiments. The OTR is monitored using the Transfer-rate Online Measurement (TOM) system and the micro(µ)-scale Transfer-rate Online Measurement (µTOM) device, which was used for mammalian cells first. It could be shown that the OTR curves for both devices align perfectly, affirming consistent cultivation conditions. The µTOM device proves effective in performing kill curve experiments in 96-deep-well plates without the need for sampling and offline analysis. The streamlined approach reduces medium consumption by 95%, offering a cost-effective and time-efficient solution for kill curve experiments. The study validates the generalizability of the method by applying it to two different CHO cell lines (CHO-K1 and sciCHO) with two antibiotics (puromycin and hygromycin B) each. In conclusion, the broad application of OTR online monitoring for CHO cell cultures in 96-deep-well plates is highlighted. The µTOM device proves as a valuable tool for high-throughput experiments, paving the way for diverse applications, such as media and clone screening, cytotoxicity tests, and scale-up experiments.

Investigating the performance of a perforated pooled circular stepped cascade aeration system for intensive aquaculture.

Aeration plays a crucial role in aquaculture to maintain adequate dissolved oxygen (DO) levels in water, which is essential for supporting aquatic life. However, traditional aeration systems such as paddlewheel aerators or diffused air aerators often come with high energy consumption, frequent maintenance, and greater operational costs. To address these challenges, this research paper presents the development and evaluation of a more sustainable and cost-effective aerator, named the perforated pooled circular stepped cascade aerator (PPCSC), for intensive aquaculture. Laboratory experiments were conducted in a masonry tank to assess the performance of the PPCSC aerator with different bottom radii (Rb) and discharges (Q). The results showed that the highest standard aeration efficiency (SAE) of 4.564 ± 0.6662 kg O2/kWh was achieved with a bottom radii (Rb) of 0.75 m and a discharge (Q) of 0.016 m3/s. A developed regression model was found to effectively evaluate the standard oxygen transfer rate (SOTR) and SAE for different Rb and Q values used in the PPCSC system. Both Rb and Q were found to significantly impact the SOTR and SAE of the PPCSC aerator. Overall, the PPCSC aerator is a promising option for small-scale tank-based intensive aquaculture due to its high performance and lower operational costs.

Predicting solute transfer rate in patients initiating peritoneal dialysis.

BACKGROUND: While assessment of membrane characteristics is fundamental to peritoneal dialysis (PD) prescription in patients initiating therapy, peritoneal equilibration test has theoretical and practical drawbacks. We wished to determine whether an equation using simple clinical variables could predict fast (above population mean) peritoneal solute transfer rate without dialysate sampling. METHODS: We measured peritoneal solute transfer rate, as determined by peritoneal equilibration test using the 4-h dialysate to plasma creatinine ratio, in consecutive PD outpatients attending a single tertiary hospital for their first clinical follow-up within 3 months of dialysis initiation. An equation estimating peritoneal solute transfer rate based on readily available clinical variables was generated in a randomly selected modeling group and tested in a distinct validation group. RESULTS: We included 712 patients, with 562 in the modeling group and 150 in the validation group. Mean age was 58.4 ± 15.9 with 431 (60.5%) men. Mean peritoneal solute transfer rate value was 0.73 ± 0.13. An equation based on gender, race, serum sodium and albumin yielded a receiving operator characteristics (ROC) area under the curve (AUC) to detect fast peritoneal solute transfer rate (> 0.73) of 0.74 (0.67-0.82). Estimated peritoneal solute transfer rate values based on percentiles 15th (> 0.66), 20th (> 0.68), 25th (> 0.69) and 30th (> 0.70) could rule out fast peritoneal solute transfer rate with negative predictive values of 100%, 93.5%, 84.2% and 80.0%, respectively. CONCLUSIONS: An equation based on simple clinical variables allows ruling out fast transport in a significant proportion of patients initiating PD with a high degree of confidence without requiring dialysate sampling. This could prove useful in guiding dialysis prescription of PD patients in daily clinical practice, particularly in low-resource settings.

The effect of gold nanostructure morphology on label-free electrochemical immunosensor design.

In this research, various electrodeposition techniques were used to form gold nanostructures (AuNSs) on the surface of graphite rod electrode (GE). Three distinct AuNS morphologies on GE have been achieved based on the composition of electrodeposition solution. The use of H2SO4 as a supporting electrolyte resulted in the formation of smaller but more numerous AuNSI with a modified electrode's electroactive surface area (EASA) of 0.213 cm2. Exchanging the supporting electrolyte to KNO3 and increasing HAuCl4 concentration facilitated the formation of bigger AuNSII particles with electrode EASA of 0.116 cm2. Finally, a partial coverage of GE by branched gold nanostructures (AuNSIII) was achieved with an estimated EASA of 0.110 cm2, when the HAuCl4 and KNO3 concentrations were increased further. Estimated values of heterogeneous electron transfer rate constant did not depend on AuNS morphology. Electrode modified with AuNSI exhibited the highest bovine serum albumin (BSA) immobilization efficiency and the highest relative response for the detection of specific polyclonal antibodies against BSA (p-anti-BSA) compared to other modified electrodes. The limit of p-anti-BSA detection in PBS buffer was calculated as 0.63 nM, while in blood serum it was 0.71 nM. Linear ranges were from 1 to 7 nM and from 1 to 5 nM, respectively.

Electrooxidation of chlorophene and dichlorophen by reactive electrochemical membrane: Key determining factors of removal efficiency.

This study systematically investigated the variable main electrooxidation mechanism of chlorophene (CP) and dichlorophen (DCP) with the change of reaction conditions at Ti4O7 anode operated in batch and reactive electrochemical membrane (REM) modes. Significant degradation of CP and DCP was observed, that is, CP exhibited greater removal efficiency in batch mode at 0.5-3.5 mA cm-2 and REM operation (0.5 mA cm-2) with a permeate flow rate of 0.85 cm min-1 under the same reaction conditions, while DCP exhibited a faster degradation rate with the increase of current density in REM operation. Density functional theory (DFT) simulation and electrochemical performance tests indicated that the electrooxidation efficiency of CP and DCP in batch mode was primarily affected by the mass transfer rates. And the removal efficiency when anodic potentials were less than 1.7 V vs SHE in REM operation was determined by the activation energy for direct electron transfer (DET) reaction, however, the adsorption function of CP and DCP on the Ti4O7 anode became a dominant factor in determining the degradation efficiency with the further increase of anodic potential due to the disappeared activation barrier. In addition, the degradation pathways of CP and DCP were proposed according to intermediate products identification and frontier electron densities (FEDs) calculation, the acute toxicity of CP and DCP were also effectively decreased during both batch and REM operations.

Inverted region in the reaction of the quinone reduction in the A1-site of photosystem I from cyanobacteria.

Photosystem I from the menB strain of Synechocystis sp. PCC 6803 containing foreign quinones in the A1 sites was used for studying the primary steps of electron transfer by pump-probe femtosecond laser spectroscopy. The free energy gap (- ΔG) of electron transfer between the reduced primary acceptor A0 and the quinones bound in the A1 site varied from 0.12 eV for the low-potential 1,2-diamino-anthraquinone to 0.88 eV for the high-potential 2,3-dichloro-1,4-naphthoquinone, compared to 0.5 eV for the native phylloquinone. It was shown that the kinetics of charge separation between the special pair chlorophyll P700 and the primary acceptor A0 was not affected by quinone substitutions, whereas the rate of A0 → A1 electron transfer was sensitive to the redox-potential of quinones: the decrease of - ΔG by 400 meV compared to the native phylloquinone resulted in a ~ fivefold slowing of the reaction The presence of the asymmetric inverted region in the ΔG dependence of the reaction rate indicates that the electron transfer in photosystem I is controlled by nuclear tunneling and should be treated in terms of quantum electron-phonon interactions. A three-mode implementation of the multiphonon model, which includes modes around 240 cm-1 (large-scale protein vibrations), 930 cm-1 (out-of-plane bending of macrocycles and protein backbone vibrations), and 1600 cm-1 (double bonds vibrations) was applied to rationalize the observed dependence. The modes with a frequency of at least 1600 cm-1 make the predominant contribution to the reorganization energy, while the contribution of the "classical" low-frequency modes is only 4%.

Comprehensive and cumulative risk evaluation of dietary exposure to aflatoxins and ochratoxin A on fermented teas worldwide by a new assessment model.

Recently, mycotoxin risks in fermented tea have received high attention, but mycotoxin transfer rates from tealeaf to infusion during brewing were rarely considered. In addition, the assessment data (i.e., mycotoxin occurrences and tea consumption) in previous assessments were usually limited. Here, a comprehensive and cumulative risk assessment of aflatoxins and ochratoxin A was performed using a tea assessment model, by which mycotoxin transfer rates were included and the assessment data were collected worldwide. By 10 times of brewing, the aflatoxin transfer rate was only 2.94% and OTA was 63.65%. Besides the extreme case, hazard quotients (HQs) from all consumers were lower than the threshold of 1.0, indicating no noncarcinogenic risk; the P95 cumulative margin of exposure (1/MoET) values were 2.52E-04 (30-39 years of age) and 2.42E-04 (≥50 years of age) for two high exposure groups under the upper bound scenario, which a little higher than the carcinogenic risk threshold of 1.00E-04. Notably, the P95 cumulative 1/MoET values (3.24E-03 -7.95E-03) by food assessment model were ten times higher than those of by tea assessment model. The comparative results showed that mycotoxin dietary risks on tea consumption by food assessment model were much overestimated. The result of this study indicated that the contaminants transfer rates should be considered for risk assessment on tea consumption in future work.