Inhibition mechanisms of perchlorate on the photosynthesis of cyanobacterium Synechocystis sp. PCC6803: Insights from physiology and transcriptome analysis.

Perchlorate (ClO4-) is a type of novel persistent inorganic pollutant that has gained increasing attention because of its high solubility, poor degradability, and widespread distribution. However, the impacts of perchlorate on aquatic autotrophs such cyanobacterium are still unclear. Herein, Synechocystis sp. PCC6803 (Synechocystis) was used to investigate the response mechanisms of perchlorate on cyanobacterium by integrating physiological and transcriptome analyses. Physiological results showed that perchlorate mainly damaged the photosystem of Synechocystis, and the inhibition degree of photosystem II (PSII) was severer than that of photosystem I (PSI). When the exposed cells were moved to a clean medium, the photosynthetic activities were slightly repaired but still lower than in the control group, indicating irreversible damage. Furthermore, perchlorate also destroyed the cellular ultrastructure and induced oxidative stress in Synechocystis. The antioxidant glutathione (GSH) content and the superoxide dismutase (SOD) enzyme activity were enhanced to scavenge harmful reactive oxygen (ROS) in Synechocystis. Transcriptome analysis revealed that the genes associated with "photosynthesis" and "electron transport" were significantly regulated. For instance, most genes related to PSI (e.g., psaf, psaJ) and the "electron transport chain" were upregulated, whereas most genes related to PSII (e.g., psbA3, psbD1, psbB, and psbC) were downregulated. Additionally, perchlorate also induced the expression of genes related to the antioxidant system (sod2, gpx, gst, katG, and gshB) to reduce oxidative damage. Overall, this study is the first to investigate the impacts and mechanisms of cyanobacterium under perchlorate stress, which is conducive to assessing the risk of perchlorate in aquatic environments.

Risk assessment of dietary perchlorate exposure in typical areas of fireworks manufacturing in China using a perchlorate intake model.

Perchlorate can disrupt the production of thyroid hormones, impact metabolism, and even affect the cognitive development of infants and toddlers. Typical areas of fireworks manufacturing might face severe perchlorate pollution due to perchlorate is an important raw material. But related study has not been reported. We assess the risk caused by perchlorate and identify the critical exposure pathways for different age/gender groups in typical area of fireworks manufacturing. Liuyang city, a major fireworks manufacturing center in China, was selected as study region. Perchlorate concentrations were measured in 230 local food samples from Liuyang using LC/MS/MS. Risks for different age/gender groups were estimated using a perchlorate intake model. The detection rate of perchlorate in samples from all eight food groups, including vegetables, fruits, meat, seafood, egg, cereal, beans, and drinking water was 100%, and the perchlorate concentrations were higher than those reported in the United States, Canada, South Korea, Kuwait, and other regions of China. Liuyang residents are currently facing an extremely high perchlorate dietary exposure risk, with the mean Estimated Daily Intakes (EDIs) approximately 6-49 times higher than US EPA's recommended reference dose (RfD, 0.7µg/kg bw/day), and 14-115 times higher than the tolerable daily intake (TDI, 0.3µg/kg bw/day) established by EFSA. Breast milk and drinking water are identified as the primary exposure pathways for infants and toddlers under the age of two, contributing 44-86% and 13-41% to their total exposure, respectively. For individuals > two years, vegetable consumption (constituting 54-66% of exposures) and ingestion of drinking water (constituting 23-32% of exposures) represent the chief exposure routes. The Hazard Quotient (HQ) values for Liuyang City residents all exceed 2, indicating an extremely high non-carcinogenic risk associated with perchlorate. Scientific and systematic perchlorate pollution control measures should be taken by local government.

Utility of ultra-portable ultrasound devices for the risk-stratification of thyroid dysfunctions in an emergency setting.

PURPOSE: We previously showed that the rapid TSH (rTSH) screening is able to detect a high prevalence of thyroid diseases in patients presenting to the Emergency department (ED), with a 7% prevalence of undiagnosed thyroid dysfunctions. The purpose of the present study is to implement our diagnostic flow-chart for thyroid dysfunctions in the ED with a rapid point-of-care thyroid ultrasound (rPOCUS). METHODS: rPOCUS was performed by an app-based mobile ultrasound device (Lumify® by Philips Healthcare) in patients with suppressed rTSH undergoing urgent procedures requiring iodinate contrast media. RESULTS: Our results suggest that rPOCUS is cost- and time-effective for the management of patients with a newly diagnosed hyperthyroidism requiring urgent iodinated contrast media or amiodarone administration. Moreover, this handled US scanner avoided rTSH measurement in patients found to have a normal thyroid gland, and detected some incidental findings (nodules, heterogeneous echotexture), which would lead to further diagnostic investigations. CONCLUSION: We demonstrate, for the first time, that rPOCUS greatly improves the management of patients attending the ED, including the prompt characterization and correct treatment of hyperthyroidism, and the prevention of iodine-induced thyrotoxicosis.

Approaching the Thermostability Limit of Nitrogen-Rich Heterocyclic Perchlorate-Based Energetic Materials.

In recent years, driven by ever-increasing application of energetic materials in deep-seated mineral resource exploitation and aerospace engineering, the mining of advanced safe energetic materials with significant thermal stability has drawn widespread publicity. Here, a tricyclic bridged energetic compound 2-amino-4,6-bis(3,5-diamino-4-nitropyrazol-1-yl)-1,3,5-triazine (NPX-03) was prepared using simple synthetic route. Furthermore, an interesting highly thermostable nitrogen-rich perchlorate, NPX-03·2HClO4, was prepared by the self-assembly reaction of NPX-03 and HClO4, displaying a thermal decomposition peak temperature of 375.9 °C. Moreover, NPX-03·2HClO4 exhibits good detonation velocity (D = 8187 m s-1) and insensitivity (IS = 50 J, FS > 360 N), thereby being promising candidates for advanced insensitive high-energy materials.

Serum levels of perchlorate and chlorate in pregnant women from south China and the related health risk with thyroid function.

Perchlorate and chlorate are recognized as ubiquitously inorganic pollutants inenvrionment owing to their high solubility in water and resistance to degradation. Previous studies have confirmed the potential adverse effects of perchlorate and chlorate on human thyroid function, along with implications for fetal growth and development. The fetus grows and develops pregnant women's womb and absorbs nutrients from her body. However, there is still limited information on prenatal exposure to perchlorate and chlorate and the related health risks, especially in China. In this study, a total of 430 serum specimens obtained from pregnant females residing in Southern China were analyzed to ascertain the levels of perchlorate and chlorate, and explore the relationship between perchlorate and chlorate and thyroid function by linear regression, WQS, and QGC. The measured serum levels of perchlorate and chlorate were comparatively elevated, demonstrating median values of 0.693 µg/L and 1.36 µg/L, respectively. The estimated exposure dose of perchlorate in 19.7% of pregnant women exceeded the USEPA reference dose, indicating potential health risks. Although no significant association was found between serum perchlorate and thyroid hormone levels, the exposure to perchlorate for pregnant women in Southern China is cause for concern given their sensitivity to chemicals during pregnancy and the relatively high internal exposure levels.

Combination of electro-oxidation and biological processes for lindane landfill leachate treatment: simultaneous degradation of contaminants and biological reduction of electro-generated chloride-derived by-products.

Real lindane landfill leachate (HCH-LL) is characterised by high chlorinated organic compounds concentrations (primarily hexachlorocyclohexane (HCH) isomers and degradation products generated during more than 40 years of ageing), posing environmental and human health risks. In this work, the co-treatment of real HCH-LL (pre-treated via electro-oxidation (EO)) and urban wastewater using an activated sludge process operated in an anoxic/oxic sequencing batch (A/O-SBR) mode was investigated. EO tests were conducted employing either a boron-doped diamond (BDD) anode or a dimensionally stable anode (DSA), resulting in effective HCH isomers removal (>93 % after 20 Ah/L). Chloride-derived by-products (CDBPs) such as free chlorine (up to 828 mg Cl2/L), chlorate (up to 972 mg/L) (formed with EO (DSA)) and perchlorate (up to 1830 mg/L) (with EO (BDD)) persisted after the treatment. EO (DSA) resulted in inhibitory effects (up to 100 % respiration inhibition) on the biological process. Conversely, EO (BDD) negligibly affected biological respiration (up to 20 % less than without pre-treatment), while perchlorate bio-reduction by A/O-SBR was poor (28 %). Acetate addition in pre-treated HCH-LL for perchlorate bio-reduction allowed to achieve simultaneous contaminants removal (> 99 %) and CDBPs reduction (up to 100 %). Biodegradation and bio-adsorption tests without pre-treatment showed partial HCH isomers removal (about 40 %) and poor bio-adsorption.

Suppression of Hippocampal Neurogenesis and Oligodendrocyte Maturation Similar to Developmental Hypothyroidism by Maternal Exposure of Rats to Ammonium Perchlorate, a Gunpowder Raw Material and Known Environmental Contaminant.

The environmental contaminant perchlorate raises concern for hypothyroidism-related brain disorders in children. This study investigated the effects of developmental perchlorate exposure on hippocampal neurogenesis and oligodendrocyte (OL) development. Pregnant Sprague-Dawley rats were administered with ammonium perchlorate (AP) in drinking water at concentrations of 0 (control), 300, and 1000 ppm from gestation day 6 until weaning [postnatal day (PND) 21]. On PND 21, offspring displayed decreased serum triiodothyronine and thyroxine concentrations at 1000 ppm and thyroid follicular epithelial cell hyperplasia at ≥300 ppm (accompanying increased proliferation activity at 1000 ppm). Hippocampal neurogenesis indicated suppressed proliferation of neurogenic cells at ≥300 ppm, causing decreases in type-1 neural stem cells (NSCs) and type-2a neural progenitor cells. In addition, an increase of SST+ GABAergic interneurons and decreasing trend for ARC+ granule cells were observed at 1000 ppm. CNPase+ mature OLs were decreased in number in the dentate gyrus hilus at ≥300 ppm. At PND 77, thyroid changes had disappeared; however, the decrease of type-1 NSCs and increase of SST+ interneurons persisted, CCK+ interneurons were increased, and white matter tissue area was decreased at 1000 ppm. Obtained results suggest an induction of hypothyroidism causing suppressed hippocampal neurogenesis (targeting early neurogenic processes and decreased synaptic plasticity of granule cells involving ameliorative interneuron responses) and suppressed OL maturation during the weaning period. In adulthood, suppression of neurogenesis continued, and white matter hypoplasia was evident. Observed brain changes were similar to those caused by developmental hypothyroidism, suggesting that AP-induced developmental neurotoxicity was due to hypothyroidism.

Analysis and detection of homemade explosive TACP.

This paper focuses on tetraamminecopper(II) perchlorate (TACP), a relatively newly used and popular homemade explosive that is insufficiently described in the literature. The compound was analyzed using commonly used forensic laboratory techniques such as FTIR, Raman, XRPD, and DTA. The TACP molecule was labeled with four 15N atoms on ammonia ligands to assign vibrational modes to the resulting bands. The paper also describes the thermal decomposition of TACP using thermoanalytical methods TGA/MS. The TACP decomposes to the final product CuO in six distinct ranges, releasing N2O, NO, HCl, O2, H2O, and NH3. It has been found that TACP is not a stable compound and will decompose spontaneously to ammonia, ammonium perchlorate, and basic copper perchlorate within a few months if exposed to air at room temperature. Residues of precursors have been detected in TACP prepared by four improvised preparation methods published on the Internet. These residues can be used to identify the precursor used in the preparation. The post-blast residues of TACP are of ordinary shape, but the use of TACP as an explosive can be indicated by the presence of a high content of copper and chlorine atoms in post-blast residues. The results of canine detection of TACP indicate that the dog is able to detect TACP, but the dog is likely to focus on the smell of ammonia in the TACP odor.

Associations of Perchlorate, Nitrate, and Thiocyanate with Bone Mineral Density in the US General Population: A Multi-Cycle Study of NHANES 2011-2018.

BACKGROUND: Perchlorate, nitrate, and thiocyanate are widely recognized as endocrine disrupting chemicals, which are closely related to thyroid function. Animal and human studies show a correlation between thyroid hormone and bone mineral density (BMD). However, it remains unknown whether perchlorate, nitrate, and thiocyanate were associated with BMD. This study aimed to explore the association between perchlorate, nitrate, and thiocyanate exposure with BMD. METHOD: A cross-sectional analysis among 5607 participants from the 2011-2018 National Health and Nutrition Examination Survey (NHANES) was conducted in the present study. Perchlorate, nitrate, and thiocyanate were detected in urine by ion chromatography. Survey-weighted generalized linear regression, restricted cubic splines, and qgcomp models were used to assess the association of BMDs with single and mixed perchlorate, nitrate, and thiocyanate exposures. In addition, age, gender, and BMI stratified these associations. RESULTS: Negative associations were found between perchlorate and nitrate with BMDs. Furthermore, based on the qgcomp model results, the combined association of perchlorate, nitrate, and thiocyanate exposure was negatively associated with BMDs (ß = -0.017, 95% CI: -0.041, -0.024 for total BMD; ß = -0.017, 95% CI: -0.029, -0.005 for lumbar BMD). Additionally, there was a significant effect after gender, age, and BMI stratification between perchlorate, nitrate, and thiocyanate with BMDs in the normal weight group (ß = -0.015, 95% CI: -0.020, -0.011 for total BMD; ß = -0.022, 95% CI: -0.028, -0.016 for lumbar BMD) and children and adolescents group (ß = -0.025, 95% CI: -0.031, -0.019 for total BMD; ß -0.017, 95% CI: -0.029, -0.005 for lumbar BMD). CONCLUSIONS: The present study indicated a negative correlation between BMDs and urinary perchlorate, nitrate, and thiocyanate levels, with nitrate being the main contributor to the mixture effect. People with normal weight and children and adolescents were more likely to be affected.

Recent advance in Artificial Anion Channels and Their Selectivity.

Nature performs critical physiological functions using a series of structurally and functionally diverse membrane proteins embedded in cell membranes, in which native ion protein channels modify the electrical potential inside and outside the cell membrane through charged ion movements. Consequently, the cell responds to external stimuli, playing an essential role in various life activities, such as nerve excitation conduction, neurotransmitter release, muscle movement, and control of cell differentiation. Supramolecular artificial channels, which mimic native protein channels in structure and function, adopt unimolecular or self-assembled structures, such as crown ethers, cyclodextrins, cucurbiturils, column arenes, cyclic peptide nanotubes, and metal-organic artificial channels, in channel construction strategies. Owing to the various driving forces involved, artificial synthetic ion channels can be divided into artificial cation and anion channels in terms of ion selectivity. Cation selectivity usually originates from ion coordination, whereas anion selectivity is related to hydrogen bonding, ion pairing, and anion-dipole interactions. Several studies have been conducted on artificial cation channels, and several reviews have summarized them in detail; however, the research on anions is still in the initial stages, and related reviews have rarely been reported. Hence, this article primarily focuses on the recent research on anion channels.

[Rapid determination of chlorate and perchlorate in tea by ion exchange chromatography-tandem mass spectrometry].

Ion exchange chromatography-tandem mass spectrometry (IEC-MS/MS) has recently become the preferred method for detecting ionic substances in tea. In this study, an IEC-MS/MS method was developed for the rapid determination of chlorate and perchlorate residues in tea samples. The optimal sample extraction process, pretreatment column, and chromatographic and mass spectrometric conditions were systematically investigated. In the optimal process, the tea samples were ultrasonically extracted with methanol-water (13∶7, v/v), and a PRiME HLB SPE column was used to purify the sample extract. An AceChrom Hybri-A IEC column (150 mm×2.1 mm, 5.0 µm) was used for separation, and 100 mmol/L ammonium acetate-acetonitrile (40∶60, v/v) was used as the mobile phase for isocratic elution. The flow rate was 0.3 mL/min, the column temperature was 40 ℃, and the injection volume was 5.0 µL. The mass spectrometric data were collected in negative electrospray ionization mode combined with multiple reaction monitoring (MRM) mode to achieve the rapid and accurate separation and qualitative analysis of the desired chemical components. Quantification was performed using the internal standard (IS) method. The measurement results showed a good linear relationship when the mass concentrations of chlorate and perchlorate were between 2.00-200 and 1.00-100 µg/L, respectively, with correlation coefficients (r2) greater than 0.9990. The average recoveries of chlorate and perchlorate at three spiked levels of low, medium, and high ranged from 88.54% to 97.25% with relative standard deviations (RSDs, n=7) of 3.2%-5.2%. The limits of detection for chlorate and perchlorate were 12.0 and 8.0 µg/kg, respectively, while the limits of quantification were 40.0 and 26.6 µg/kg, respectively. The results of tests conducted to assess the linearity, specificity, accuracy, precision, and applicability of the method to the analysis of chlorate and perchlorate in 15 tea samples collected from a local market demonstrated its validity for the routine analysis of tea samples. The proposed method is simple, rapid, sensitive, and accurate, and can meet requirements for the rapid screening and quantitative analysis of residual trace chlorate and perchlorate in large quantities of tea samples.

Modeling adsorption reactions of ammonium perchlorate on rutile and anatase surfaces.

In this work, the effects of two TiO2 polymorphs on the decomposition of ammonium perchlorate (NH4ClO4) were studied experimentally and theoretically. The interactions between AP and various surfaces of TiO2 were modeled using density functional theory (DFT) calculations. Specifically, the adsorption of AP on three rutile surfaces (1 1 0), (1 0 0), and (0 0 1), as well as two anatase surfaces (1 0 1), and (0 0 1) were modeled using cluster models, along with the decomposition of adsorbed AP into small molecules. The optimized complexes of the AP molecule on TiO2 surfaces were very stable, indicating strong covalent and hydrogen bonding interactions, leading to highly energetic adsorption reactions. The calculated energy of adsorption (ΔEads) ranged from -120.23 to -301.98 kJ/mol, with highly exergonic calculated Gibbs free energy (ΔGads) of reaction, and highly exothermic enthalpy of reaction (ΔHads). The decomposition of adsorbed AP was also found to have very negative ΔEdec values between -199.08 and -380.73 kJ/mol. The values of ΔGdec and ΔHdec reveal exergonic and exothermic reactions. The adsorption of AP on TiO2 surfaces anticipates the heat release of decomposition, in agreement with experimental results. The most common anatase surface, (1 0 1), was predicted to be more reactive for AP decomposition than the most stable rutile surface, (1 1 0), which was confirmed by experiments. DFT calculations show the mechanism for activation of the two TiO2 polymorphs is entropy driven.

Comparative effects of ammonium nitrogen on perchlorate degradation performance under heterotrophic condition with different carbon sources.

Perchlorate (ClO4-) mainly exists in the form of ammonium perchlorate in industrial production. However, the degradation mechanisms of different concentrations of ammonium nitrogen (NH4+-N) and ClO4- mixed pollutants in the environment are not well understood. This study aims to explore the potential of different types of carbon sources for ClO4- and NH4+-N biodegradation. Experimental results showed that the concentration and type of carbon sources are decisive to simultaneous removal of NH4+-N and ClO4-. Under condition of C(COD)/C(ClO4-) ratio of 21.15 ± 4.40, the simultaneously removal efficiency of ClO4- and NH4+-N in acetate (Ace) was relatively higher than that in methanol (Met). C(NH4+-N)/C(ClO4-) ratio of 9.66 ± 0.51 and C(COD)/C(ClO4-) ratio of 2.51 ± 0.87 promoted ClO4- reduction in glucose-C (Glu-C). However, high concentration of Glu could cause pH decrease (from 7.57 to 4.59), thereby inhibiting ClO4- reduction. High-throughput sequencing results indicated that Proteobacteria and Bacteroidetes have made a major contribution to the simultaneous removal of NH4+-N and ClO4-. They are two representative bacterial phyla for participating in both ClO4- reduction and denitrification. Notably, the abundance of main ClO4- degrading bacteria (such as Proteobacteria, Chloroflexi, and Firmicutes) significantly increased by 528.57 % in Glu-C. It can be inferred that the concentration of carbon source and NH4+-N were the most important factors determining the removal efficiency of ClO4- by influencing changes in the core microbial community. This study will provide new techniques and mechanistic insights for the simultaneous removal of mixed ClO4- and nitrogen pollutants, which can also provide theoretical support for innovation in future biological treatment processes.

Occurrence and removal technologies of perchlorate in water: A systematic review and bibliometric analysis.

The pollution resulting from the emergence of the contaminant perchlorate is anticipated to have a substantial effect on the water environment in the foreseeable future. Considerable research efforts have been devoted to investigating treatment technologies for addressing perchlorate contamination, garnering widespread international interest in recent decades. A systematic review was conducted utilizing the Web of Science, Scopus, and Science Direct databases to identify pertinent articles published from 2000 to 2024. A total of 551 articles were chosen for in-depth examination utilizing VOS viewer. Bibliometric analysis indicated that countries such as China, the United States, Chile, India, Japan, and Korea have been prominent contributors to the research on this topic. The order of ClO4- occurrence was as follows: surface water > groundwater > drinking water. Various remediation methods for perchlorate contamination, such as adsorption, ion-exchange, membrane filtration, chemical reduction, and biological reduction, have been suggested. Furthermore, the research critically evaluated the strengths and weaknesses of each approach and offered recommendations for addressing their limitations. Advanced technologies have shown the potential to achieve notably enhanced removal of perchlorate and co-contaminants from water sources. However, the low concentration of perchlorate in natural water sources and the high energy consumption related to these technologies need to be solved in order to effectively remove perchlorate from water.

Methane-Driven Perchlorate Reduction by a Microbial Consortium.

The phenomenon of methane oxidation linked to perchlorate reduction has been reported in multiple studies; yet, the underlying microbial mechanisms remain unclear. Here, we enriched suspended cultures by performing methane-driven perchlorate reduction under oxygen-limiting conditions in a membrane bioreactor (MBR). Batch test results proved that perchlorate reduction was coupled to methane oxidation, in which acetate was predicted as the potential intermediate and oxygen played an essential role in activating methane. By combining DNA-based stable isotope probing incubation and high-throughput sequencing analyses of 16S rRNA gene and functional genes (pmoA, pcrA, and narG), we found that synergistic interactions between aerobic methanotrophs (Methylococcus and Methylocystis) and perchlorate-reducing bacteria (PRB; Denitratisoma and Dechloromonas) played active roles in mediating methane-driven perchlorate reduction. This partnership was further demonstrated by coculture experiments in which the aerobic methanotroph could produce acetate to support PRB to complete perchlorate reduction. Our findings advance the understanding of the methane-driven perchlorate reduction process and have implications for similar microbial consortia linking methane and chlorine biogeochemical cycles in natural environments.

Dietary exposure assessment of perchlorate and chlorate in infant formulas marketed in Shanghai, China.

Perchlorate and chlorate are ubiquitous pollutants that can adversely affect the thyroid function in humans. This study assessed the potential health risks associated with the dietary exposure of infants and young children to perchlorate and chlorate present in infant formulas available in Shanghai. The assessment was based on risk monitoring data from 150 samples of infant formulas in Shanghai between 2020 and 2022, along with the dietary consumption data of infants and young children. The detection rates of perchlorate and chlorate in infant formulas were 46.0% and 98.7%, with mean contents of 9.98 µg/kg and 112.01 µg/kg, and the maximum values of 151.00 µg/kg and 1475.00 µg/kg, respectively. The mean and 95th percentile (P 95) values of daily perchlorate exposure of 0-36-month-old infant and young children via infant formulas were 0.07 and 0.17 µg/kg body weight (bw) per day, respectively, which were lower than the tolerable daily intake (TDI) of perchlorate (0.3 µg/kg bw per day). The mean and P 95 values of chlorate exposure via infant formulas in 0-36-month-old infants and young children were 0.83 and 1.89 µg/kg bw per day, which were lower than the TDI of chlorate (3 µg/kg bw per day). The P 95 exposure of different age groups (0-6 months, 7-12 months and 13-36 months) of infants and young children to perchlorate and chlorate in infant formulas was below the TDI. Therefore, the risk associated with the exposure of 0-36-month-old infants and young children to perchlorate and chlorate from infant formulas in Shanghai is considered acceptable. Prioritizing environmental pollution control efforts to reduce the levels of perchlorate and chlorate in food products is important to safeguard the health of the infants and children under the One Health concept.

Molecular dynamics simulation on crystal morphology of NH4ClO4.

CONTEXT: Ammonium perchlorate (NH4ClO4, abbreviated as AP) has the advantages of high oxygen content, high density, and good compatibility, and has significant application prospects in the field of energetic materials. The crystal morphology has a great influence on the properties and sensibility of energetic materials, and a single experimental means is difficult in exploring the crystals; therefore, the crystal morphology of AP is investigated using molecular dynamics simulation complemented with experiments, to theoretically analyze the differences in AP crystal habit and the interactions between solvent molecules and the main growing crystal surfaces of AP. The results show that AP crystal is mainly composed of five independent crystal surfaces (0 0 1), (0 1 0), (1 0 0), (1 0 1), and (1 0 -1) in vacuum using the BFDH laws, with (0 0 1) surface being the main growth crystal surface. In contrast, in H2O solvent, the (1 0 1) and (1 0 -1) surfaces disappear, and the AP mainly consists of (0 0 1), (0 1 0), and (1 0 0) surfaces with a rectangular shape. The crystal morphology obtained from theoretical prediction is in good agreement with that obtained from experimental culture. This paper can provide a new idea for the cultivation and preparation of AP large crystals, and promote the application of AP crystals in energetic materials. METHODS: The crystal morphologies of AP in vacuum and H2O solvent under Dreiding force field were predicted based on attachment energy model by using molecular dynamics method in Materials Studio 2019 software. The entire molecular dynamics simulation was carried out under the NTV system, the temperature control method was selected as Anderson, and the system temperature was set to 298 K. The simulation time was set to 40 ps, the step size was set to 1 fs, and the data were outputted every 5000 steps.

Perchlorate in foodstuffs from South China and its implication for human dietary exposure.

Perchlorate, an aqueous-soluble compound resistant to degradation, is mainly used in the synthesis of pyrotechnics, herbicides, and other products. It serves as a pivotal component in the production of fireworks, rocket fuel, and explosives. Perchlorate was recognized as a pollutant owing to the potential toxic risk to thyroid function, which could pose a potential threat to the nervous system of infants and pregnant women. Some study had found that perchlorate existed in food, water and air. This study aimed to investigate the levels of perchlorate in six types of foods (n = 570) from South China, and evaluate potential exposure risks for residents. Vegetables were found to have the highest median levels of foods, attributed to elevated water content in leafy vegetables and facile solubility of perchlorate in water. The relatively low levels of perchlorate in food compared to other studies could attribute to the fact that the period of food we purchased in this study was during the wet season while the contaminants, such as perchlorate, were diluted. The maximum hazard quotient (HQ) values for all residents consuming different foods and water were all higher than 1 This suggested that there is a potential health risk of perchlorate to residents in South China. Those may be attributed to the high levels of perchlorate in some individual samples of meat and eggs. However, the 95th percentile of HQ values in all residents was less than 1, indicating that there is no potential health risk of perchlorate to most residents in South China.

Clinical course of congenital hypothyroidism with gland in situ and necessity of L-thyroxine therapy after re-evaluation.

CONTEXT: Clinical course and need for long-term L-thyroxine (LT4) therapy of congenital hypothyroidism (CH) with gland in situ (GIS) remain unclear. OBJECTIVE: To describe the clinical history of CH with GIS and evaluate the proportion of patients who can suspend therapy during follow-up. DESIGN AND SETTING: Retrospective evaluation of patients followed at referral regional center for CH of Pisa. PATIENTS: 77 patients with confirmed primary CH and GIS after positive neonatal screening were included. All children started LT4 at CH confirm. INTERVENTIONS: At 3 years of age, 55 children underwent a clinical re-evaluation after withdrawal of therapy with hormonal examinations, imaging of the thyroid gland with ultrasonography and 123-iodine with perchlorate discharge test. Subsequent periodic controls of thyroid function were executed and, when possible, a new attempt to stop LT4 was performed. Adequate follow-up data (at least 6 months after treatment suspension trial) were available for 49 patients. RESULTS: Among the 55 patients who were reassessed, 18 (32.7%) were euthyroid. Considering subsequent follow-up, 49% of patients were no longer treated and 51% were taking therapy. No differences in neonatal parameters were observed between the two groups; LT4 dose before the last trial off medication was higher in permanent CH (p 0.016). CONCLUSION: Monitoring of thyroid function in children with CH and GIS is necessary to evaluate the need for substitution and avoid overtreatment. Even if therapy can be suspended, patients need to be monitored because apparently normal thyroid function may decline several months after withdrawal of LT4.

A Crystalline-Water Electrolyte Enabled High Depth-of-Discharge Anodes in Aqueous Zinc Metal Batteries.

Aqueous zinc metal batteries are regarded as a promising energy storage solution for a green and sustainable society in the future. However, the practical application of metallic zinc anode is plagued by the thermodynamic instability issue of water molecules in conventional electrolytes, which leads to severe dendrite growth and side reactions. In this work, an ultra-thin and high areal capacity metallic zinc anode is achieved by utilizing crystalline water with a stable stoichiometric ratio. Unlike conventional electrolytes, the designed electrolyte can effectively suppress the reactivity of water molecules and diminish the detrimental corrosion on the metallic zinc anode, while preserving the inherent advantages of water molecules, including great kinetic performance in electrolytes and H+ capacity contribution in cathodes. Based on the comprehensive performance of the designed electrolyte, the 10 µm Zn||10 µm Zn symmetric cell stably ran for 1000 h at the current density of 1 mA cm-2, and the areal capacity of 1 mAh cm-2, whose depth-of-discharge is over 17.1%. The electrochemical performance of the 10 µm Zn||9.3 mg cm-2 polyaniline (PANI) full-cell demonstrates the feasibility of the designed electrolyte. This work provides a crucial understanding of balancing activity of water molecules in aqueous zinc metal batteries.