Promoting the efficiency and selectivity of NO3--to-NH3 reduction on Cu-O-Ti active sites via preferential glycol oxidation with holes.

The combined reductive and oxidative reaction is the essence of a solar-driven photoredox system. Unfortunately, most of these efforts focus on the specific half-reactions, and the key roles of complete photoredox reactions have been overlooked. Taking the nitrate reduction reaction (NO3-RR) as a typical multiple-electrons involved process, the selective reduction of the NO3- into ammonia (NH3) synthesis with high efficiency is still a grand challenge. Herein, a rational oxidative half-reaction is tailored to achieve the selective conversion of NO3- to NH3 on Cu-O-Ti active sites. Through the coupled NO3-RR with glycol oxidation reaction system, a superior NH3 photosynthesis rate of 16.04 ± 0.40 mmol gcat-1 h-1 with NO3- conversion ratio of 100% and almost 100% of NH3 selectivity is reached on Cu-O-Ti bimetallic oxide cluster-anchored TiO2 nanosheets (CuOx@TNS) catalyst. A combination of comprehensive in situ characterizations and theoretical calculations reveals the molecular mechanism of the synergistic interaction between NO3-RR and glycol oxidation pair on CuOx@TNS. The introduction of glycol accelerates the h+ consumption for the formation of alkoxy (•R) radicals to avoid the production of •OH radicals. The construction of Cu-O-Ti sites facilitates the preferential oxidation of glycol with h+ and enhances the production of e- to participate in NO3-RR. The efficiency and selectivity of NO3--to-NH3 synthesis are thus highly promoted on Cu-O-Ti active sites with the accelerated glycol oxidative half-reaction. This work upgrades the conventional half photocatalysis into a complete photoredox system, demonstrating the tremendous potential for the precise regulation of reaction pathway and product selectivity.

Regulating the Selectivity of Nitrate Photoreduction for Purification or Ammonia Production by Cooperating Oxidative Half-Reactions.

The removal and conversion of nitrate (NO3-) from wastewater has become an important environmental and health topic. The NO3- can be reduced to nontoxic nitrogen (N2) for environmental remediation or ammonia (NH3) for recovery, in which the tailoring of the selectivity is greatly challenging. Here, by construction of the CuOx@TiO2 photocatalyst, the NO3- conversion efficiency is enhanced to ∼100%. Moreover, the precise regulation of selectivity to NH3 (∼100%) or N2 (92.67%) is accomplished by the synergy of cooperative redox reactions. It is identified that the selectivity of the NO3- photoreduction is determined by the combination of different oxidative reactions. The key roles of intermediates and reactive radicals are revealed by comprehensive in situ characterizations, providing direct evidence for the regulated selectivity of the NO3- photoreduction. Different active radicals are produced by the interaction of oxidative reactants and light-generated holes. Specifically, the introduction of CH3CHO as the oxidative reactant results in the generation of formate radicals, which drives selective NO3- reduction into N2 for its remediation. The alkyl radicals, contributed to by the (CH2OH)2 oxidation, facilitate the deep reduction of NO3- to NH3 for its upcycling. This work provides a technological basis for radical-directed NO3- reduction for its purification and resource recovery.

Dynamic in situ Formation of Cu2 O Sub-Nanoclusters through Photoinduced pseudo-Fehling's Reaction for Selective and Efficient Nitrate-to-Ammonia Photosynthesis.

Copper (Cu) is evidenced to be effective for constructing advanced catalysts. In particular, Cu2 O is identified to be active for general catalytic reactions. However, conflicting results regarding the true structure-activity correlations between Cu2 O-based active sites and efficiencies are usually reported. The structure of Cu2 O undergoes dynamic evolution rather than remaining stable under working conditions, in which the actual reaction cannot proceed over the prefabricated Cu2 O sites. Therefore, the dynamic construction of Cu2 O active sites can be developed to promote catalytic efficiency and reveal the true structure-activity correlations. Herein, by introducing the redox pairs of Cu2+ and reducing sugar into a photocatalysis system, it is clarified that the Cu2 O sub-nanoclusters (NCs), working as novel active sites, are on-site constructed on the substrate via a photoinduced pseudo-Fehling's route. The realistic interfacial charge separation and transformation capacities are remarkably promoted by the dynamic Cu2 O NCs under the actual catalysis condition, which achieves a milestone efficiency for nitrate-to-ammonia photosynthesis, including the targets of production rate (1.98±0.04 mol gCu -1 h-1 ), conversion ratio (94.2±0.91 %), and selectivity (98.6 %±0.55 %). The current work develops an effective strategy for integrating the active site construction into realistic reactions, providing new opportunities for Cu-based chemistry and catalysis sciences research.

Photocatalytic Formamide Synthesis via Coupling of Electrophilic and Nucleophilic Radicals over Atomically Dispersed Bi Sites.

Formamide (HCONH2) plays a pivotal role in the manufacture of a diverse array of chemicals, fertilizers, and pharmaceuticals. Photocatalysis holds great promise for green fabrication of carbon-nitrogen (C-N) compounds owing to its environmental friendliness and mild redox capability. However, the selective formation of the C-N bond presents a significant challenge in the photocatalytic synthesis of C-N compounds. This work developed a photocatalytic radical coupling method for the formamide synthesis from co-oxidation of ammonia (NH3) and methanol (CH3OH). An exceptional formamide yield rate of 5.47 ± 0.03 mmol·gcat-1·h-1 (911.87 ± 0.05 mmol·gBi-1·h-1) was achieved over atomically dispersed Bi sites (BiSAs) on TiO2. An accumulation of 45.0 mmol·gcat-1 (0.2 g·gcat-1) of formamide was achieved after long-term illumination, representing the highest level of photocatalytic C-N compounds synthesis. The critical C-N coupling for formamide formation originated from the "σ-σ" interaction between electrophilic ●CH2OH with nucleophilic ●NH2 radical. The  BiSAs sites facilitated the electron transfer between reactants and photocatalysts and enhanced the nucleophilic attack of â—NH2 radical at the â—CH2OH radical, thereby advancing the selective C-N bond formation. This work deepens the understanding of the C-N coupling mechanism and offers an alternative and intriguing photocatalytic approach for the efficient and sustainable production of C-N compounds.

Continuous NO Upcycling into Ammonia Promoted by SO2 in Flue Gas: Poison Can Be a Gift.

Although ammonia (NH3) synthesis efficiency from the NO reduction reaction (NORR) is significantly promoted in recent years, one should note that NO is one of the major air pollutants in the flue gas. The limited NO conversion ratio is still the key challenge for the sustainable development of the NORR route, which potentially contributes more to contaminant emissions rather than its upcycling. Herein, we provide a simple but effective approach for continuous NO reduction into NH3, promoted by coexisting SO2 poison as a gift in the flue gas. It is significant to discover that SO2 plays a decisive role in elevating the capacity of NO absorption and reduction. A unique redox pair of SO2-NO is constructed, which contributes to the exceptionally high conversion ratio for both NO (97.59 ± 1.42%) and SO2 (99.24 ± 0.49%) in a continuous flow. The ultrahigh selectivity for both NO-to-NH3 upcycling (97.14 ± 0.55%) and SO2-to-SO42- purification (92.44 ± 0.71%) is achieved synchronously, demonstrating strong practicability for the value-added conversion of air contaminants. The molecular mechanism is revealed by comprehensive in situ technologies to identify the essential contribution of SO2 to NO upcycling. Besides, realistic practicality is realized by the efficient product recovery and resistance ability against various poisoning effects. The proposed strategy in this work not only achieves a milestone efficiency for NH3 synthesis from the NORR but also raises great concerns about contaminant resourcing in realistic conditions.

Beyond Purification: Highly Efficient and Selective Conversion of NO into Ammonia by Coupling Continuous Absorption and Photoreduction under Ambient Conditions.

Although the selective catalytic reduction technology has been confirmed to be effective for nitrogen oxide (NOx) removal, green and sustainable NOx re-utilization under ambient conditions is still a great challenge. Herein, we develop an on-site system by coupling the continuous chemical absorption and photocatalytic reduction of NO in simulated flue gas (CNO = 500 ppm, GHSV = 18,000 h-1), which accomplishes an exceptional NO conversion into value-added ammonia with competitive conversion efficiency (89.05 ± 0.71%), ammonia production selectivity (95.58 ± 0.95%), and ammonia recovery efficiency (>90%) under ambient conditions. The anti-poisoning capacities, including the resistance against factors of H2O, SO2, and alkali/alkaline/heavy metals, are also achieved, which presents strong environmental practicability for treating NOx in flue gas. In addition, the critical roles of corresponding chemical absorption and catalytic reduction components are also revealed by in situ characterizations. The emerging strategy herein not only achieves a milestone efficiency for sustainable NO purification but also opens a new route for contaminant resourcing in the near future of carbon neutrality.

Optimization of enzymatic synthesis of theaflavins from potato polyphenol oxidase.

Theaflavin (TF), a chemical component important in measuring the quality of fermented tea, has a strong natural antioxidant effect and many pharmacological functions. Enzymatic oxidation has become a widely used method for preparing TFs at the current research stage. Using plant exogenous polyphenol oxidase (PPO) to enzymatically synthesize TFs can significantly increase yield and purity. In this study, tea polyphenols were used as the reaction substrate to discuss the optimal synthesis conditions of potato PPO enzymatic synthesis of theaflavins and the main products of enzymatic synthesis of TFs. The optimal enzymatic synthesis conditions were as follows: pH of the reaction system was 5.5, reaction time was 150 min, substrate concentration was 6.0 mg/mL, reaction temperature was 20 °C, and the maximum amount of TFs produced was 651.75 µg/mL. At the same time, high-performance liquid chromatography was used to determine the content of theaflavins and catechins in the sample to be tested, and the dynamic changes and correlations of the main catechins and theaflavins in the optimal enzymatic system were analyzed. The results showed that epicatechin (EC), epigallocatechin (EGC), epicatechin gallate (ECG), and epigallocatechin gallate (EGCG) are all the main substrates synthesis of TFs. The main substrate of TFs and its strongest enzymatic catalytic effect on EGCG make theaflavin-3,3'-digallate (TFDG) the most important synthetic monomer. In this study, theaflavins were synthesized by polyphenol oxidase catalysis, which laid a foundation for industrialization of theaflavins.

Smoking Paradox in Stroke Survivors?: Uncovering the Truth by Interpreting 2 Sets of Data.

Background and Purpose- The observation that smokers with stroke could have better outcome than nonsmokers led to the term "smoking paradox." The controversy of such a complex claim has not been fully settled, even though different case mix was noted. Analyses were conducted on 2 independent data sets to evaluate and determine whether such a paradox truly exists. Methods- Taiwan Stroke Registry with 88 925 stroke cases, and MJ cohort with 541 047 adults participating in a medical screening program with 1630 stroke deaths developed during 15 years of follow-up (1994-2008). Primary outcome for stroke registry was functional independence at 3 months by modified Rankin Scale score ≤2, for individuals classified by National Institutes of Health Stroke Scale score at admission. For MJ cohort, mortality risk by smoking status or by stroke history was assessed by hazard ratio. Results- A >11-year age difference in stroke incidence was found between smokers and nonsmokers, with a median age of 60.2 years for current smokers and 71.6 years for nonsmokers. For smokers, favorable outcome in mortality and in functional assessment in 3 months with modified Rankin Scale score ≤2 stratified by the National Institutes of Health Stroke Scale score was present but disappeared when age and sex were matched. Smokers without stroke history had a ≈2-fold increase in stroke deaths (2.05 for ischemic stroke and 1.53 for hemorrhagic stroke) but smokers with stroke history, 7.83-fold increase, overshadowing smoking risk. Quitting smoking at earlier age reversed or improved outcome. Conclusions- "The more you smoke, the earlier you stroke, and the longer sufferings you have to cope." Smokers had 2-fold mortality from stroke but endured stroke disability 11 years longer. Quitting early reduced or reversed the harms.

Electrolyte disorders are ERAS-associated in patients undergoing hepato-pancreato-biliary surgery.

PURPOSE: Emerging evidences have raised concerns about electrolyte disorders caused by restrictive fluid management in the enhanced recovery after surgery (ERAS) protocol. This study aims to investigate the morbidity and treatment of electrolyte disorders associated with ERAS in patients undergoing hepato-pancreato-biliary (HPB) surgery. METHODS: Clinical data from 157 patients under the ERAS program and 166 patients under the traditional (Non-ERAS) program after HPB surgery were retrospectively analyzed. Risk factors and predictive factors of postoperative electrolyte disorders were analyzed by logistic regression analysis and receiver operator characteristic (ROC) curve analysis, respectively. RESULTS: The average of intravenous fluid, sodium, chloride, and potassium supplementation after surgery were significantly lower in the ERAS group. Hypokalemia was the most common type of electrolyte disorders in the ERAS group, whose incidence was substantially increased compared to that in the Non-ERAS group [28.77% vs. 8.97%, p < 0.001, on postoperative (POD) 5]. Logistic regression analysis identified the ERAS program and age as independent risk factors of hypokalemia. ROC curve analysis identified serum potassium levels below 3.76 mmol/L on POD 3 (area under curve 0.731, sensitivity 58.54%, specificity 82.69%) as a predictive factor for postoperative hypokalemia in ERAS patients. Oral supplementation at an average of 35.41 mmol potassium per day was effective in restoring the ERAS-associated hypokalemia. CONCLUSIONS: ERAS procedures were particularly associated with a lower supplementation of potassium and a higher incidence of hypokalemia in patients after HPB surgery. Oral potassium supplementation could be an adopted ERAS program for the elderly undergoing HPB surgery.

Early white matter injuries associated with dopamine transporter dysfunction in patients with acute CO intoxication: A diffusion kurtosis imaging and Tc-99m TRODAT-1 SPECT study.

PURPOSE: Patients with CO intoxication were demonstrated to exhibit white matter (WM) injuries, changes in substantia nigra, dopamine transporter dysfunctions of striatum and Parkinsonism symptoms. We aimed to investigate the relationship between WM injuries of dopaminergic pathways and dopamine transporter dysfunctions of the striatum in patients with acute CO intoxication using both diffusion kurtosis imaging (DKI) and single photon-emission computed tomography (SPECT). MATERIALS AND METHODS: Seventeen patients with acute CO intoxication and 19 age- and gender-matched healthy subjects were enrolled. DKI data were acquired from all participants and Tc-99m-TRODAT-1 SPECT scan was performed on each patient. DKI datasets were fitted to obtain axial, radial and mean diffusivity, fractional anisotropy, axial, radial and mean kurtosis for voxel-based comparison. In addition, the TRODAT-1 binding ratio of the striatum was calculated using the occipital cortices as a reference. In significant regions, correlational analysis was performed to understand the relationship between DKI indices and TRODAT-1 binding ratio. RESULTS: The results showed that DKI indices were significantly altered in multiple WM regions broadly involving the basal ganglia-thalamocortical circuit and nigrostriatal pathway. The correlation analysis further revealed significant correlations between DKI indices and the TRODAT-1 binding ratio in the nigrostriatal pathway (absolute correlation coefficients ranged from 0.5992 to 0.6950, p<0.05), suggesting that CO-induced early WM injuries were associated with dopamine transporter dysfunctions of striatum. CONCLUSION: We concluded that DKI and Tc-99m-TRODAT-1 SPECT scans were helpful in early detection of global WM injuries associated with dysfunctions of dopamine transporter in patients with acute CO intoxication. KEY POINTS: • Voxel-based diffusion kurtosis imaging analysis was helpful in globally detecting early white matter injuries in patients with acute CO intoxication. • CO-induced early white matter injuries were broadly located in basal ganglia-thalamocortical circuit and nigrostriatal pathway. • Early white matter injuries in dopaminergic pathways were significantly correlated with dopamine transporter dysfunctions of the striatum.

One-Year Risk of Recurrent Stroke and Death Associated with Vertebrobasilar Artery Stenosis and Occlusion in a Cohort of 10,515 Patients.

BACKGROUND: The natural history of vertebrobasilar artery (VBA) stenosis or occlusion remains understudied. METHODS: Patients with diagnosis of ischemic stroke or transient ischemic attack (TIA) who were noted to have VBA stenosis based on computed tomography or magnetic resonance imaging or catheter-based angiogram were selected from Taiwan Stroke Registry. Cox proportional hazards model was used to determine the hazards ratio (HR) of recurrent stroke and death within 1 year of index event in various groups based on severity of VBA stenosis (none to mild: 0-49%; moderate to severe: 50-99%: occlusion: 100%) after adjusting for differences in demographic and clinical characteristics between groups at baseline evaluation. RESULTS: None to mild or moderate to severe VBA stenosis was diagnosed in 6972 (66%) and 3,137 (29.8%) among 10,515 patients, respectively, and occlusion was identified in 406 (3.8%) patients. Comparing with patients who showed none to mild stenosis of VBA, there was a significantly higher risk of recurrent stroke (HR 1.21, 95% CI 1.01-1.45) among patients with moderate to severe VBA stenosis. There was a nonsignificantly higher risk of recurrent stroke (HR 1.49, 95% CI 0.99-2.22) and significantly higher risk of death (HR 2.21, 95% CI 1.72-2.83), among patients with VBA occlusion after adjustment of potential confounders. CONCLUSIONS: VBA stenosis or occlusion was relatively prevalent among patients with TIA or ischemic stroke and associated with higher risk of recurrent stroke and death in patients with ischemic stroke or TIA who had large artery atherosclerosis.

Three-in-One Oxygen Vacancies: Whole Visible-Spectrum Absorption, Efficient Charge Separation, and Surface Site Activation for Robust CO2 Photoreduction.

A facile and controllable in situ reduction strategy is used to create surface oxygen vacancies (OVs) on Aurivillius-phase Sr2 Bi2 Nb2 TiO12 nanosheets, which were prepared by a mineralizer-assisted soft-chemical method. Introduction of OVs on the surface of Sr2 Bi2 Nb2 TiO12 extends photoresponse to cover the whole visible region and also tremendously promotes separation of photoinduced charge carriers. Adsorption and activation of CO2 molecules on the surface of the catalyst are greatly enhanced. In the gas-solid reaction system without co-catalysts or sacrificial agents, OVs-abundant Sr2 Bi2 Nb2 TiO12 nanosheets show outstanding CO2 photoreduction activity, producing CO with a rate of 17.11 µmol g-1 h-1 , about 58 times higher than that of the bulk counterpart, surpassing most previously reported state-of-the-art photocatalysts. Our study provides a three-in-one integrated solution to advance the performance of photocatalysts for solar-energy conversion and generation of renewable energy.

Highly Efficient Performance and Conversion Pathway of Photocatalytic NO Oxidation on SrO-Clusters@Amorphous Carbon Nitride.

This work demonstrates the first molecular-level conversion pathway of NO oxidation over a novel SrO-clusters@amorphous carbon nitride (SCO-ACN) photocatalyst, which is synthesized via copyrolysis of urea and SrCO3. The inclusion of SrCO3 is crucial in the formation of the amorphous carbon nitride (ACN) and SrO clusters by attacking the intralayer hydrogen bonds at the edge sites of graphitic carbon nitride (CN). The amorphous nature of ACN can promote the transportation, migration, and transformation of charge carriers on SCO-ACN. And the SrO clusters are identified as the newly formed active centers to facilitate the activation of NO via the formation of Sr-NOδ(+), which essentially promotes the conversion of NO to the final products. The combined effects of the amorphous structure and SrO clusters impart outstanding photocatalytic NO removal efficiency to the SCO-ACN under visible-light irradiation. To reveal the photocatalytic mechanism, the adsorption and photocatalytic oxidation of NO over CN and SCO-ACN are analyzed by in situ DRIFTS, and the intermediates and conversion pathways are elucidated and compared. This work presents a novel in situ DRIFTS-based strategy to explore the photocatalytic reaction pathway of NO oxidation, which is quite beneficial to understand the mechanism underlying the photocatalytic reaction and advance the development of photocatalytic technology for environmental remediation.

Treatment and prognosis of subdural hematoma in patients with spontaneous intracranial hypotension.

OBJECTIVE: The objective of this article is to elucidate the outcome, prognostic predictors and timing of surgical intervention for subdural hematoma (SDH) in patients with spontaneous intracranial hypotension (SIH). METHODS: Patients with SDH were identified retrospectively from 227 consecutive SIH patients. Data were collected on demographics, clinical courses, neuroimaging findings, and treatment of SDH, which was later divided into conservative treatment, epidural blood patches (EBP), and surgical intervention. Poor outcome was defined as severe neurological sequelae or death. RESULTS: Forty-five patients (20%) with SDH (mean maximal thickness 11.9 ± 6.2 mm) were recruited. All 15 patients with SDH <10 mm achieved good outcomes by either conservative treatment or EBP. Of 30 patients with SDH ≥10 mm, patients with uncal herniation (n = 3) had poor outcomes, even after emergent surgical evacuation (n = 2), compared to those without (n = 27) (100% vs. 0%, p < 0.001). Fourteen patients underwent surgical evacuation, resulting in good outcomes in all 12 who received early intervention and poor outcomes in the remaining two who received delayed intervention after Glasgow Coma Scale (GCS) score ≤8 (100% vs. 0%, p = 0.01). CONCLUSIONS: Uncal herniation results in poor outcomes in patients with SIH complicated with SDH. In individuals with SDH ≥10 mm and decreased GCS scores, early surgical evacuation might prevent uncal herniation.

Increased intracortical inhibition in hyperglycemic hemichorea-hemiballism.

Hemichorea-hemiballism (HC-HB) in uncontrolled diabetes mellitus is an uncommon manifestation of hyperglycemia. The pathophysiology of hyperglycemic HC-HB is not well understood. A previous report showed increased intracortical inhibition in the motor cortex in a patient with diabetes with HC-HB. The objective of this study is to investigate motor cortex excitability in patients with hyperglycemic HC-HB. We hypothesized that intracortical inhibition measured with transcranial magnetic stimulation, which likely reflects the excitability of cortical γ-aminobutyric acid (GABA)ergic circuits, would be impaired in patients with hyperglycemic HC-HB. We studied 15 patients with mean age 71.5 years (range, 48-94 y) and 12 age-matched healthy subjects. The motor cortex contralateral to the hemichorea was tested. Transcranial magnetic stimulation measures included motor evoked potential, recruitment curve, GABAA mediated short interval intracortical inhibition, intracortical facilitation, and GABAB mediated silent period duration and long interval intracortical inhibition. No significant difference was found in motor threshold, recruitment curve response, short interval intracortical inhibition, or intracortical facilitation in both rest and active conditions between patients with hyperglycemic HC-HB and normal subjects. However, long interval intracortical inhibition was significantly increased during muscle activation but not at rest in patients with hyperglycemic HC-HB. The silent period duration is also increased in patients with hyperglycemic HC-HB. We concluded that long interval intracortical inhibition and silent period are increased in the motor cortex contralateral to the hemichorea in hyperglycemic HC-HB, but only during muscle activation. Hemichorea-hemiballism may be associated with increased GABAB receptor-mediated inhibitory activity in the motor cortex.

Comparison of activities of daily living impairments in Parkinson's disease patients as defined by the Pill Questionnaire and assessments by neurologists.

OBJECTIVES: To compare the clinical judgment of experienced neurologists after interviewing Parkinson's disease (PD) patients and their caregivers with the use of the Pill Questionnaire to determine the presence of impairments on activities of daily living (ADL). BACKGROUND: ADL impairment is a criterion for the diagnosis of dementia associated with PD. The Pill Questionnaire has been recommended as a screening tool to assess ADL impairment in PD patients, but its usefulness and validity have not been fully investigated. METHODS: We recruited idiopathic PD patients from 12 hospitals in Taiwan, and the patients underwent clinical assessments, a neuropsychological test battery and the Unified Parkinson Disease Rating Scale evaluation. The Pill Questionnaire was administered by study assistants. Patient and caregiver interviews were performed by experienced neurologists who were blinded to the Pill Questionnaire results. RESULTS: In total, 284 PD patients (mean age 71.8±9 years, mean education 8.7±5.3 years, mean disease duration 5.4±5.3 years) were recruited. 63 patients showed ADL impairment by the Pill Questionnaire, and 108 patients showed ADL impairment by neurologists' clinical interviews. κ Statistics showed moderate agreement between the two methods (κ=0.521, p<0.001). Of the 108 patients who were diagnosed with ADL impairment by neurologists, only 56 patients (51.9%) showed impairment according to the Pill Questionnaire. Most of the missed patients had milder cognitive impairment and lower motor disability. CONCLUSIONS: A comprehensive interview is essential to determine the presence of ADL impairment in PD patients, especially in patients with early PD.

Mechanically treated Mn2O3 triggers peracetic acid activation for superior non-radical oxidation of micropollutants: Identification of reactive complexes.

This study used a simple mechanical ball milling strategy to significantly improve the ability of Mn2O3 to activate peracetic acid (PAA) for sustainable and efficient degradation of organic micropollutant (like bisphenol A, BPA). BPA was successfully removed and detoxified via PAA activation by the bm-Mn2O3 within 30 min under neutral environment, with the BPA degradation kinetic rate improved by 3.4 times. Satisfactory BPA removal efficiency can still be achieved over a wide pH range, in actual water and after reuse of bm-Mn2O3 for four cycles. The change in hydrophilicity of Mn2O3 after ball milling evidently elevated the affinity of Mn2O3 for binding to PAA, while the reduction in particle size exposed more active sites contributing partially to catalytic oxidation. Further analysis revealed that BPA oxidation in the ball mill-treated Mn2O3 (bm-Mn2O3)/PAA process mainly depends on the bm-Mn2O3-PAA complex (i.e., Mn(III)-OO(O)CCH3) mediated non-radical pathway rather than R-O• and Mn(IV). Especially, the existence of the Mn(III)-PAA complex was definitely verified by in situ Raman spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Simultaneously, density functional theory calculations determined that PAA adsorbs readily on manganese sites thereby favoring the formation of Mn(III)-OO(O)CCH3 complexes. This study advances an in-depth understanding of the underlying mechanisms involved in the manganese oxide-catalyzed activation of PAA for superior non-radical oxidation of micropollutants.

Transcallosal inhibition in patients with callosal infarction.

Recent studies in normal subjects suggested that callosal motor fibers pass through the posterior body of the corpus callosum (CC), but this has not been tested in patients with callosal infarction. The objective of this study is to define the pathways involved in transcallosal inhibition by examining patients with infarctions in different subregions of the CC. We hypothesized that patients with lesions in the posterior one-half of the CC would have greater reduction in transcallosal inhibition between the motor cortices. Twenty-six patients with callosal infarction and 14 healthy subjects were studied. The callosal lesions were localized on sagittal MRI and were attributed to one of five segments of the CC. Transcranial magnetic stimulation was used to assess ipsilateral silent period (iSP) and short- and long-latency interhemispheric inhibition (SIHI and LIHI, respectively) originating from both motor cortices. The results showed that the iSP areas and durations were markedly reduced bilaterally in patients with callosal infarction compared with normal subjects. Patients with callosal infarctions also had less IHI bidirectionally compared with normal subjects. iSP areas and durations were lower in patients with lesions than in patients without lesions in segment 3 (posterior midbody) of the CC. Lesion burden in the posterior one-half of the CC negatively correlated transcallosal inhibition measured with iSP and SIHI. Our study suggests that callosal infarction led to reduced transcallosal inhibition, as measured by iSP, SIHI, and LIHI. Fibers mediating transcallosal inhibition cross the CC mainly in the posterior one-half.

Efficient purification of a nitrate and chlorate mixture in water via photoredox activated intermediate coupling-decoupling pathway.

Nitrate (NO3-) is a widespread contaminant that threatens human health and ecological safety. Meanwhile, the disinfection byproducts chlorate (ClO3-) is generated inevitably in conventional wastewater treatment. Therefore, the contaminants mixture of NO3- and ClO3- are universal in common emission units. Photocatalysis technology is a feasible approach for the synergistic abatement of contaminant mixture, where matching suitable oxidation reactions is a potential strategy to improve the photocatalytic reduction reactions. Herein, formate (HCOOH) oxidation is introduced to facilitate the photocatalytic reduction of the NO3- and ClO3- mixture. As a result, high purification efficiency of NO3- and ClO3- mixture are achieved, evidenced by 84.6% e--dependent removal of the mixture at a reaction time of 30 min, with 94.5% N2 selectivity and 100% Cl- selectivity, respectively. Specifically, by the close combination of in-situ characterizations and theoretical calculations, the detailed reaction mechanism is revealed, in which the intermediate coupling-decoupling route from NO3- reduction and HCOOH oxidation is established by the chlorate-induced photoredox activation, leading to the significantly enhanced efficiency for the wastewater mixture purification. The practical application of this pathway is established for simulated wastewater to show its wide applicability. This work provides new insights into photoredox catalysis technology for its environmental application.