Connection of spectral pattern of carbohydrate molecular structure to alteration of nutritional properties of by-products from coffee processing affected by microorganism fermentation.

Objective: The objective of this study was to determine internal structure spectral profile of by-products from coffee processing that were affected by added-microorganism fermentation duration in relation to truly absorbed feed nutrient supply in ruminant system. Methods: The by-products from coffee processing were fermented using commercial fermentation product, consisting of various microorganisms: for 0 (control), 7, 14, 21, and 28 days. In this study, the association and correlation of carbohydrate-related spectral profiles with chemical and nutritional properties (chemical composition, total digestible nutrient, bioenergy values, carbohydrate sub-fractions and predicted degradation and digestion parameters as well as milk value of feed. The vibrational spectra of coffee by-products samples after fermentation for 0 (control), 7, 14, 21, and 28 days were determined using a JASCO FT/IR-4200 spectroscopy coupled with accessory of Attenuated total reflectance (ATR). The molecular spectral analyses with univariate approach were conducted with the OMNIC 7.3 software. Results: Molecular spectral analysis parameters in fermented and non-fermented by-products from coffee processing included Structural carbohydrate, Cellulosic compounds, Non-structural carbohydrates, Lignin compound, CH-bending, structural carbohydrate peak1, Structural carbohydrate peak2, Structural carbohydrate peak3, Hemicellulosic compound, Non-structural carbohydrate peak1, non-structural carbohydrate peak2, non-structural carbohydrate peak3. The study results show that added-microorganism fermentation induced chemical and nutritional changes of coffee by-products including carbohydrate chemical composition profiles, bioenergy value, feed milk value, carbohydrate subfractions, estimated degradable and undegradable fractions in the rumen, and intestinal digested nutrient supply in ruminant system. Conclusion: In conclusion, carbohydrate nutrition value changes by added-microorganism fermentation duration were in an agreement with the change of their spectral profile in the coffee by-products. The studies show that the vibrational ATR-FT/IR spectroscopic technique could be applied as a rapid analytical tool to evaluate fermented by-products and connect with truly digestible carbohydrate supply in ruminant system.

Biomass-derived cellulose nanocrystals modified nZVI for enhanced tetrabromobisphenol A (TBBPA) removal.

Nano zero-valent iron (nZVI) is an advanced environmental functional material for the degradation of tetrabromobisphenol A (TBBPA). However, high surface energy, self-agglomeration and low electron selectivity limit degradation rate and complete debromination of bare nZVI. Herein, we presented biomass-derived cellulose nanocrystals (CNC) modified nZVI (CNC/nZVI) for enhanced TBBPA removal. The effects of raw material (straw, filter paper and cotton), process (time, type and concentration of acid hydrolysis) and synthesis methods (in-situ and ex-situ) on fabrication of CNC/nZVI were systematically evaluated based on TBBPA removal performance. The optimized CNC-S/nZVI(in) was prepared via in-situ liquid-phase reduction using straw as raw material of CNC and processing through 44 % H2SO4 for 165 min. Characterizations illustrated nZVI was anchored to the active sites at CNC interface through electrostatic interactions, hydrogen bonds and FeO coordinations. The batch experiments showed 0.5 g/L CNC-S/nZVI(in) achieved 96.5 % removal efficiency at pH = 7 for 10 mg/L initial TBBPA. The enhanced TBBPA dehalogenation by CNC-S/nZVI(in), involving in initial adsorption, reduction process and partial detachment of debrominated products, were possibly attributed to elevated pre-adsorption capacity and high-efficiency delivery of electrons synergistically. This study indicated that fine-tuned fabrication of CNC/nZVI could potentially be a promising alternative for remediation of TBBPA-contaminated aquatic environments.

Hydrogen Nanobubbles Generated In Situ from Nanoscale Zerovalent Iron with Water to Further Enhance Selenite Sequestration.

Gas nanobubbles used for water treatment and recovery give rise to great concern for their unique advantages of less byproducts, higher efficiency, and environmental friendliness. Nanoscale zerovalent iron (nZVI), which has also been widely explored in the field of environmental remediation, can generate gas hydrogen by direct reaction with water. Whether nanoscale hydrogen bubbles can be produced to enhance the pollution removal of the nZVI system is one significant concern involved. Herein, we report direct observations of in situ generation of hydrogen nanobubbles (HNBs) from nZVI in water. More importantly, the formed HNBs can enhance indeed the reduction of Se(IV) beyond the chemical reduction ascribed to Fe(0), especially in the anaerobic environment. The possible mechanism is that HNBs enhance the reducibility of the system and promote electron transport in the solution. This study demonstrates a unique function of HNBs combined with nZVI for the pollutant removal and a new approach for in situ HNB generation for potential applications in the fields of in situ remediation agriculture, biotechnology, medical treatment, health, etc.

Research updates and progress on nutritional significance of the amides I and II, alpha-helix and beta-sheet ratios, microbial protein synthesis, and steam pressure toasting condition with globar and synchrotron molecular microspectroscopic techniques with chemometrics.

This article aims to review research updates and progress on the nutritional significance of the amides I and II, the alpha-helix and beta-sheet ratios, the microbial protein synthesis, and the steam pressure toasting condition in food and feed with globar and synchrotron molecular microspectroscopic techniques plus chemometrics (both univariate and multivariate techniques). The review focused on (I) impact of the amides I and II, and the alpha-helix and beta-sheet-structure ratios in food and feeds; (II) Current research progress and update in synchrotron technique and application in feed and food molecular structure studies that are associated with nutrition delivery; (III) Impact of thermal processing- steam pressure toasting condition on feed and food; (IV). Impact of the microbial protein synthesis and methodology on feed and food; and (V). Impact on performance and production of ruminants with Faba beans.

TEMPO oxidized cellulose nanocrystal (TOCNC) scaffolded nanoscale zero-valent iron (nZVI) for enhanced chromium removal.

The conventional carboxymethyl cellulose (CMC) stabilization hampered available active sites of adsorption and reduction, due to irregular shape of nanoscale zero-valent iron (nZVI) particles with augmented average size and passivated surface, leading to insufficient removal and poor resistance against complex environmental conditions. Herein, we presented (2,2,6,6-Tetramethylpiperidine-1-oxyl)-mediated (TEMPO-mediated) oxidation of cellulose nanocrystal (TOCNC) scaffolded nZVI (nZVI@TOCNC) with enhanced efficiency for chromium removal in comparison with CMC stabilized nZVI (nZVI@CMC). The anchoring of nZVI at the functional sites of TOCNC was initiated by liquid-phase chemical reduction method. The nZVI@TOCNC showed improved nZVI distribution with uniform particle size and thinner shell (∼1 nm). Characterizations using FT-IR, XPS and XRD demonstrated that bindings between TOCNC and nZVI were through hydrogen bonds, electrostatic attractions, coordination-covalent bonds and bidentate chelation. TOCNC with shorter branch-chain (-COC-) surrounding the nZVI could potentially form a porous and compact "mesh" to rigidly encapsulate nZVI, while CMC wrapped around nZVI in the way of traditional polymeric stabilizers. Thus, 0.5 g/L nZVI@TOCNC achieved 99.96% Cr (Ⅵ) removal efficiency (20 mg/L) at pH = 7 and the removal capacity were up to 55.86 mg/g. The nZVI@TOCNC consistently presented higher removal efficiency than nZVI@CMC under wide pH range (3-7). Cr (Ⅵ) was reduced to Cr (Ⅲ) by nZVI@TOCNC with deposition of CrxFe1-x (OH)3 and Cr2O3. The predominant mechanisms of removal probably consisted of electrostatic attractions, reduction, co-precipitation and surface complexation. The pseudo-second-order kinetic model well-fitted the sorption kinetic, indicating TOCNC scaffold stabilized nZVI for efficient reduction of Cr (Ⅵ) through multi-layer adsorption. As a template and delivery carrier, TOCNC shows promising potential to further improve the capability and practice of nZVI for in situ treatment of industrial waste water with heavy metal pollution.

Prognostic impact of muscle invasion in buccal mucosa squamous cell carcinoma.

OBJECTIVE: The objective of the study was to assess the prognostic value of muscle invasion (MI), a key histopathological feature of tumor aggressiveness, and construct a superior prognostic prediction model combining the current TNM staging system. MATERIALS AND METHODS: MI was analyzed in the whole-slide images from a total of 301 patients with primary buccal mucosa squamous cell carcinoma (BMSCC). Survival times of patients with/without MI were evaluated by Kaplan-Meier analysis. MI was further combined with the TNM staging system to explore its predictive value for prognosis. Moreover, 204 cases of head and neck carcinoma from the TCGA database were included. RESULTS: MI positive rate reached to 76% (229/301) in patients with BMSCC. MI was associated with poor overall survival (p = 0.012) and disease-free survival (p = 0.022). The novel system (TNM staging combined with MI) revealed strong predictive performance, with the largest area under the curve (OS: p < 0.001, DFS: p < 0.004). MI and the established classification system were also had good predictive ability in the TCGA cohort. CONCLUSIONS: MI is an independent predictor of poor prognosis of BMSCC. The inclusion of MI in prediction system can augment the risk stratification of patients with oral squamous cell carcinoma and may assist in the clinical decision-making process.

Electrochemical reduction of wastewater by non-noble metal cathodes: From terminal purification to upcycling recovery.

A shift beyond conventional environmental remediation to a sustainable pollutant upgrading conversion is extremely desirable due to the rising demand for resources and widespread chemical contamination. Electrochemical reduction processes (ERPs) have drawn considerable attention in recent years in the fields of oxyanion reduction, metal recovery, detoxification and high-value conversion of halogenated organics and benzenes. ERPs also have the potential to address the inherent limitations of conventional chemical reduction technologies in terms of hydrogen and noble metal requirements. Fundamentally, mechanisms of ERPs can be categorized into three main pathways: direct electron transfer, atomic hydrogen mediation, and electrode redox pairs. Furthermore, this review consolidates state-of-the-art non-noble metal cathodes and their performance comparable to noble metals (e.g., Pd, Pt) in electrochemical reduction of inorganic/organic pollutants. To overview the research trends of ERPs, we innovatively sort out the relationship between the electrochemical reduction rate, the charge of the pollutant, and the number of electron transfers based on the statistical analysis. And we propose potential countermeasures of pulsed electrocatalysis and flow mode enhancement for the bottlenecks in electron injection and mass transfer for electronegative pollutant reduction. We conclude by discussing the gaps in the scientific and engineering level of ERPs, and envisage that ERPs can be a low-carbon pathway for industrial wastewater detoxification and valorization.

Multiperspective quantitative tumor-stroma ratio reveals histological areas associated with poor outcomes in oral squamous cell carcinoma.

AIMS: Different regions of oral squamous cell carcinoma (OSCC) have particular histopathological characteristics, and the individual histological characteristics of the tumors are poorly understood. Therefore, calculating the proportion of tumor cells in different regions that allow assessment of the prognostic outcomes for OSCC patients would be of great clinical significance. METHODS AND RESULTS: We established an open-source software-based analytic pipeline that defines the inner tumor and invasive tumor front (ITF) in pancytokeratin-stained whole slide images (WSIs) and quantifies the tumor-stroma ratio (TSR) within the two regions. We applied this method to 114 patients with OSCC and predicted patient prognosis by the TSR. The proportion of tumor area in the inner tumor was generally higher than that in the ITF (p < 0.0001). TSR was an independent prognostic factor for overall survival (OS) (p = 0.016), disease-free survival (DFS) (p = 0.026), and relapse-free survival (RFS) (p = 0.037) in inner tumor, and TSR was an independent prognostic factor for OS (p = 0.00052), DFS (p = 0.035), and metastasis-free survival (MFS) (p = 0.038) in the ITF. Tumor-low status was associated with poorer prognosis. There was a significant correlation between the TSR and perineural invasion (PNI) in the inner tumor (p = 0.009). CONCLUSIONS: The histopathological characteristics of different regions of OSCC may be used to develop the potential prognostic markers. The TSR of the inner tumor is more targeted in predicting prognosis and accurately assesses the risk of PNI+.

Generation mechanism of singlet oxygen from the interaction of peroxymonosulfate and chloride in aqueous systems.

Peroxymonosulfate (PMS, HSO5-) is a widely-used disinfectant and oxidant in environmental remediation. It was deemed that PMS reacted with chloride (Cl-) to form free chlorine during water purification. Here, we demonstrated that singlet oxygen (1O2) was efficiently generated from PMS and Cl- interaction. Mechanism of 1O2 formation was uniquely verified by the reaction of HSO5- and chlorine molecule (Cl2) and the oxygen atoms in 1O2 deriving from the peroxide group of HSO5- were revealed. Density functional theory calculations determined that the reaction of HSO5- and Cl2 was thermodynamically favorable and exergonic at 37.8 kcal/mol. Quite intriguingly, 1O2 was generated at a higher yield (1.5 × 105 M - 1 s - 1) than in the well-known reaction of H2O2 with Cl2 (35 M - 1 s - 1). Besides chlorine, 1O2 formed in PMS-Cl- interaction dominated the degradation of micropollutants, also it substantially enhanced the damage of deoxynucleoside in DNA, which were beneficial to micropollutant oxidation and pathogen disinfection. The contribution of 1O2 for carbamazepine degradation was enhanced at higher Cl- level and lower pH, and reached 96.3% at pH 4.1 and 5 min. Natural organic matter (NOM) was a sink for chlorine, thereby impeding 1O2 formation to retard carbamazepine degradation. 1O2 also played important roles (48.3 - 63.5%) on the abatement of deoxyguanosine and deoxythymidine at pH 4.1 and 10 min in PMS/Cl-. On the other hand, this discovery also alerted the harm of 1O2 for human health as it can be formed during the interaction of residual PMS in drinking water/swimming pools and the high-level Cl- in human bodies.

Insights into the Selective Transformation of Ceria Sulfation and Iron/Manganese Mineralization for Enhancing the Selective Recovery of Rare Earth Elements.

To cope with the urgent and unprecedented demands for rare earth elements (REEs) in sophisticated industries, increased attention has been paid to REE recovery from recycled streams. However, the similar geochemical behaviors of REEs and transition metals often result in poor separation performance due to nonselectivity. Here, a unique approach based on the selective transformation between ceria sulfation and iron/manganese mineralization was proposed, leading to the enhancement of the selective separation of REEs. The mechanism of the selective transformation of minerals could be ascribed to the distinct geochemical and metallurgical properties of ions, resulting in different combinations of cations and anions. According to hard-soft acid-base (HSAB) theory, the strong Lewis acid of Ce(III) was inclined to combine with the hard base of sulfates (SO42-), while the borderline acid of Fe(II)/Mn(II) prefers to interact with oxygen ions (O2-). Both in situ characterization and density functional theory (DFT) calculation further revealed that such selective transformation might trigger by the generation of an oxygen vacancy on the surface of CeO2, leading to the formation of Ce2(SO4)3 and Fe/Mn spinel. Although the electron density difference of the configurations (CeO2-x-SO4, Fe2O3-x-SO4, and MnO2-x-SO4) shared a similar direction of the electron transfer from the metals to the sulfate-based oxygen, the higher electron depletion of Ce (QCe = -1.91 e) than Fe (QFe = -1.66 e) and Mn (QMn = -1.64 e) indicated the higher stability in the Ce-O-S complex, resulting in the larger adsorption energy of CeO2-x-SO4 (-6.88 eV) compared with Fe2O3-x-SO4 (-3.10 eV) and MnO2-x-SO4 (-2.49 eV). This research provided new insights into the selective transformation of REEs and transition metals in pyrometallurgy and thus offered a new approach for the selective recovery of REEs from secondary resources.

Kaempferol prevents acetaminophen-induced liver injury by suppressing hepatocyte ferroptosis via Nrf2 pathway activation.

Acetaminophen (APAP)-induced liver injury (AILI) has become a growing public health problem. Ferroptosis, an iron-dependent form of cell death associated with lipid peroxide accumulation, has been recently implicated in AILI. The activation of the Nrf2 signaling pathway is a potential therapy for AILI. Kaempferol (KA), a flavonoid widely existing in edible plants, has been reported to exert profound anti-inflammatory and antioxidant activities. This study aimed to investigate whether KA exerts anti-AILI effects via the Nrf2 signaling pathway. Mice were fasted for 22 h and injected intraperitoneally with APAP (250 mg kg-1) to induce AILI. Mice were pre-injected intragastrically with KA for 2 h followed by APAP injection. The hepatic injury was observed by H&E staining. Biochemical parameters of the serum and liver were measured using kits. KA alleviated hepatic injury and inflammatory response in AILI mice and ameliorated APAP-induced hepatic iron overload and oxidative stress in mice. In addition, the protective effects of KA against APAP-induced hepatotoxicity were examined in L02 cells in vitro. Cell viability was assayed by the CCK8 assay. Mitochondrial reactive oxygen species (ROS) in L02 cells were detected by MitoSox fluorescence. KA reversed the APAP-induced decrease in cell viability and GSH levels and inhibited the accumulation of intracellular ROS. Furthermore, KA activated the Nrf2 pathway and upregulated Gpx4 in mouse livers and L02 cells to inhibit ferroptosis induced by APAP. Finally, molecular docking indicated the potential interaction of KA with Keap1. Taken together, KA ameliorated oxidative stress and ferroptosis-mediated AILI by activating Nrf2 signaling.

Vibrational Molecular Spectroscopy as a Tool to Study Molecular Structure Features of Cool-Season Chickpeas Impacted by Varieties and Thermal Processing in Relation to Nutrient Availability in Ruminants.

To our knowledge, there is no study on the relationship between molecular spectral features and nutrient availability in chickpeas. The purpose of this study was to reveal molecular structure spectral profiles among cool-season adapted CDC chickpea varieties and detect the molecular structure changes induced by thermal processing methods using vibrational Fourier-transform infrared (FTIR) spectroscopy. Three varieties of chickpea samples (CDC Alma, Cory, Frontier) were finely ground using a 0.12 mm screen. Spectral analyses were conducted using a JASCO FTIR-4200 spectroscope with Spectra Manager II software in the mid-infrared region from ca. 4000−800 cm−1 with a 4 cm−1 resolution. Data were analyzed using the "Mixed" procedure of SAS 9.4. Multiple regression was performed with PROC REG analysis for variable selection. Results showed that amide I area was higher (p = 0.038) in CDC Frontier than CDC Cory (30.85 vs. 24.64 AU). Amide I peak height (p = 0.028) was also higher in CDC Frontier and CDC Alma (0.45 AU in both) than CDC Cory (0.36 AU). Cellulosic compound (CEC) to total CHO (TCHO) area ratio was higher in CDC Frontier (0.05 AU) than the other two varieties (0.14 AU in both). As to thermal treatment impact, the results showed that total amide area was higher (p = 0.013) with autoclave and microwave heating (47.38 and 45.19 AU, respectively) than dry heating (33.06 AU). The CEC area was also higher (p < 0.001) for autoclave and microwave heating (3.74 and 3.61 AU, respectively) than dry heating (2.20 AU). Moreover, the ratio of amide I to II height was higher (p = 0.022) with microwave heating than dry heating (1.44 vs. 1.16 AU, respectively). Relationship analysis showed that the effective degraded crude protein (EDCP) and bypass dry matter (% BDM) were associated with STCHO peaks and CEC height (p < 0.05, R2 = 0.68). Also, feed milk value (FMVDVE) was associated with STC1, STC_A, and CEC_A (p < 0.05, R2 = 0.85). In conclusion, vibrational molecular spectroscopy mid-infrared FTIR was able to reveal different molecular spectral characteristics among the cool-season adapted CDC chickpea varieties and detect molecular structure changes induced by thermal processing (dry heating, autoclaving, and microwave heating).

Dry heating, moist heating, and microwave irradiation of cold-climate-adapted barley grain-Effects on ruminant-relevant carbohydrate and molecular structural spectral profiles.

Different feed processing techniques affect barley digestibility and nutrient utilization in ruminants. To our knowledge, there are few studies on the interactive relationship between carbohydrate molecular structure profiles of cool-season-adapted barley grain and nutritional characteristics for ruminants. The objectives of this study were: (1) to investigate the effect of different technological processing methods on carbohydrate chemical profiles, Cornell Net Carbohydrate and Protein System-carbohydrate subfractions, ruminal and intestinal carbohydrate digestion of barley grain in dairy cows; (2) to study the effect of heat processing on carbohydrate molecular structure of barley grain using advanced molecular spectroscopy; and (3) to associate processing-induced changes in carbohydrate molecular structure with changes in carbohydrate metabolic profiles in dairy cows. Barley grain samples collected from Crop Research Field in Western Canada underwent four different processing treatments: control, dry heating (120°C for 60 min in an air-ventilated oven), moist heating (120°C for 60 min in an autoclave), and microwave irradiation (900 W and 2450 MHz for 5 min in a microwave). The heating conditions used in the current study induced some changes in rumen-degradable and -undegradable digestible fibre (CB3) fraction. Intestinally digestible CB3 was decreased after moist heating. Moist heating decreased starch digestibility compared to the other three treatments. The processing-induced carbohydrate molecular structure changes, which was revealed by advanced vibrational molecular spectroscopic technique (attenuated total reflectance-Fourier transform infrared), could be used to predict carbohydrate nutritional value.

Identification of Biological Functions and Prognostic Value of NNMT in Oral Squamous Cell Carcinoma.

BACKGROUND: Nicotinamide N-methyltransferase (NNMT) is a metabolic enzyme that catalyzes the methylation of nicotinamide (NAM) to generate 1-methyl nicotinamide (MNAM). Although previous studies have shown that NNMT is frequently dysregulated to promote the onset and progression of many malignancies, its expression profile, prognostic value and function in oral squamous cell carcinoma (OSCC) are still unknown. METHODS: We used untargeted metabolomics based on mass spectrometry to analyze potential metabolite differences between tumors and matched adjacent normal tissues in 40 OSCC patients. Immunohistochemistry (IHC) was used to analyze the NNMT expression profile in OSCC, and the diagnostic and prognostic values of NNMT were evaluated. Next, qPCR and Western blot were used to compare the expression of NNMT in five OSCC cell lines. Stable transfected cell lines were constructed, and functional experiments were carried out to elucidate the effects of NNMT on the proliferation and migration of OSCC cells. Finally, gene set enrichment analysis (GSEA) was performed using The Cancer Genome Atlas (TCGA) data to investigate the potential functional mechanisms of NNMT in OSCC. RESULTS: We found that the nicotinamide metabolic pathway was abnormally activated in OSCC tumor tissues compared with normal tissues. NNMT was expressed ubiquitously in tumor cells (TCs) and fibroblast-like cells (FLCs) but was absent in tumor-infiltrating lymphocytes (TILs). OSCC patients with highly expressed NNMT in TCs had higher risk of lymph node metastasis and showed a worse pattern of invasion (POI). Moreover, patients with highly expressed NNMT were also susceptible to postoperative recurrence. Highly expressed NNMT can independently predict shorter disease-free survival and recurrence-free survival. Functionally, we demonstrated that the ectopic expression of NNMT promoted OSCC tumor cell proliferation and migration in vitro. Conversely, silencing exerted significantly opposite effects in vitro. In addition, GSEA showed that highly expressed NNMT was mainly enriched in the epithelial-mesenchymal transformation (EMT) pathway, which displayed a significant positive correlation with the six classic EMT markers. CONCLUSIONS: Our study uncovered that NNMT may be a critical regulator of EMT in OSCC and may serve as a prognostic biomarker for OSCC patients. These findings might provide novel insights for future research in NNMT-targeted OSCC metastasis and recurrence therapy.

Iron-Based Nanocatalysts for Electrochemical Nitrate Reduction.

Nitrate has a high level of stability and persistence in water, endangering human health and aquatic ecosystems. Due to its high reliability and efficiency, the electrochemical nitrate reduction reaction (NO3 RR) is regarded as the best available option for mitigating excess nitrate in water and wastewater, especially for the removal of trace levels of nitrate. One of the most critical factors in the electrochemical reduction are the catalysts, which directly affect the reaction efficiency of nitrate removal. Iron-based nanocatalysts, which have the advantages of nontoxicity, wide availability, and low cost, have emerged as a promising electrochemical NO3 RR material in recent years. This review covers major aspects of iron-based nanocatalysts for electrochemical NO3 RR, including synthetic methods, structural design, performance enhancement, electrocatalytic nitrate reduction test, and reduction mechanism. The recent progress of iron-based nanocatalysts for electrochemical NO3 RR and the mechanism of functional advantages for modified structures are reviewed from the perspectives of loading, doping, and assembly strategies, in order to realize the conversion from pollutant nitrate to harmless nitrogen or ammonia and other sustainable products. Finally, challenges and future directions for the development of low-cost and highly-efficient iron-based nanocatalysts are explored.

Electrocatalytic Hydrogenation Boosts Reduction of Nitrate to Ammonia over Single-Atom Cu with Cu(I)-N3C1 Sites.

The conversion of nitrate to ammonia can serve two important functions: mitigating nitrate pollution and offering a low energy intensity pathway for ammonia synthesis. Conventional ammonia synthesis from electrocatalytic nitrate reduction reactions (NO3RR) is often impeded by incomplete nitrate conversion, sluggish kinetics, and the competition of hydrogen evolution reactions. Herein, atomic Cu sites anchored on micro-/mesoporous nitrogen-doped carbon (Cu MNC) with fine-tuned hydrophilicity, micro-/mesoporous channels, and abundant Cu(I) sites were synthesized for selective nitrate reduction to ammonia, achieving ambient temperature and pressure hydrogenation of nitrate. Laboratory experiments demonstrated that the catalyst has an ammonia yield rate per active site of 5466 mmol gCu-1 h-1 and transformed 94.8% nitrate in wastewater containing 100 mg-N L-1 to near drinking water standard (MCL of 5 mg-N L-1) at -0.64 V vs RHE. Extended X-ray absorption fine structure (EXAFS) and theoretical calculations showed that the coordination environment of Cu(I) sites (Cu(I)-N3C1) localizes the charge around the central Cu atoms and adsorbs *NO3 and *H onto neighboring Cu and C sites with balanced adsorption energy. The Cu(I)-N3C1 moieties reduce the activation energy of rate-limiting steps (*HNO3 → *NO2, *NH2 → *NH3) compared with conventional Cu(II)-N4 and lead to a thermodynamically favorable process to NH3. The as-prepared electrocatalytic cell can run continuously for 84 h (14 cycles) and produce 21.7 mgNH3 with only 5.64 × 10-3 kWh energy consumption, suitable for decentralized nitrate removal and ammonia synthesis from nitrate-containing wastewater.

Visualizing hazardous solids with cryogenic electron microscopy (Cryo-EM).

Recent developments point to exciting potential of cryogenic electron microscopy (cryo-EM) for fundamental environmental research, especially for characterizing environmental samples with a high-water content. As a matter of fact, most environmental materials including soils, sediments, biomass, solid wastes and sludge are hydrated. This perspective provides a brief synopsis of cryo-EM and highlights emerging applications in environmental research. With cryogenic techniques, specimens are preserved by rapid freezing and observed with electron microscopes operating at high-vacuum and low temperature to keep the ice in amorphous state and reduce the effect of radiation damage. So far, cryo-EM has been successfully applied to advance fundamental understanding of physical, chemical and biological mechanisms due to its desirable properties to maintain the native state of hydrated samples and visualize structures at high resolution in three dimensions. The cryo-EM technique also has significant applications to the technology development of pathogen detection, sludge dewatering, waste treatment, and green chemical production from cellular biomass as cellular water content can be clearly observed and manipulated at the single cell level.

Nanocellulose fine-tuned poly(acrylic acid) hydrogel for enhanced diclofenac removal.

Hydrogel was recognized as one of the most promising materials for adsorption of pharmaceuticals and personal care products (PPCPs). The highly efficient bio-based nanocelluloses fine-tuned poly(acrylic acid) hydrogel (PAA/NC) adsorbent was constructed by adjusting aspect ratio, surface charge and crystallinity of NC. The cross-linked networks were fabricated through a single-step free-radical polymerization via steric effect and hydrogen bonds. The uniform three-dimensional structures with abundant macropores and mesopores were in-situ visualized by the cryogenic-scanning electron microscopy (Cryo-SEM). The diclofenac adsorption capacity of TEMPO oxidized cellulose nanofibers (TCNF) incorporated PAA hydrogel (PAA/TCNF, 559.8 mg·g-1) was circa 2.1 times higher than pristine PAA (293.5 mg·g-1) due to the elevated specific surface area, favorable spatial structure with unimpeded channels and abundant surface-charged carboxylic groups. Moreover, PAA/NC hydrogel exhibited a wide-pH applicability and high salinity tolerance. The adsorption was predominantly determined by hydrogen bonds, validated by XPS and FT-IR analysis. It was demonstrated developed PAA/NC hydrogel with unique porous structure significantly enhanced adsorption capacity for potential application in the purification of refractory organic pollutants-containing wastewater.

Engineering PD-L1 Cellular Nanovesicles Encapsulating Epidermal Growth Factor for Deep Second-Degree Scald Treatment.

Scars are common and intractable consequences after scalded wound healing, while monotherapy of epidermal growth factors does not solve this problem. Maintaining the stability of epidermal growth factors and promoting scarless healing of wounds is paramount. In this study, engineering cellular nanovesicles overexpressing PD-L1 proteins, biomimetic nanocarriers with immunosuppressive efficacy, were successfully prepared to encapsulate epidermal growth factors for maintaining its bioactivity. Remarkably, PD-L1 cellular nanovesicles encapsulating epidermal growth factors (EGF@PDL1 NVs) exerted desired therapeutic effect by attenuating the overactivation of T cell immune response and promoting skin cells migration and proliferation. Hence, EGF@PD-L1 NVs promoted wound healing and prevented scarring in deep second-degree scald treatment, demonstrating a better effect than using individual PD-L1 NVs or EGF. This research proved that EGF@PD-L1 NVs is considered an innovative and thorough therapy of deep second-degree scald.

Small Extracellular Vesicles Derived From MSCs Have Immunomodulatory Effects to Enhance Delivery of ASO-210 for Psoriasis Treatment.

Mesenchymal stem cells (MSCs) have been increasingly used for treating autoimmune diseases due to their immune modulation functions, but inefficient homing to the target tissue and safety issues limits their wide application. Recently, increasing studies demonstrate small extracellular vesicles (sEVs) as key mediators of MSCs to exert their immunomodulatory effects. In this study, we found that sEVs derived from human umbilical cord MSCs stimulated by IFN-γ (IFNγ-sEVs) inhibited proliferation and activation of peripheral blood mononuclear cells and T cells in vitro. Furthermore, we confirmed that IFNγ-sEVs reduced psoriasis symptoms including thickness, erythema, and scales of skin lesions; exhausted Th17 cells, increased Th2 cells; and reduced enrichment of inflammatory cytokines such as IL-17A, IFN-γ, IL-6, and TNF-α in both spleen and skin lesions in vivo. Importantly, IFNγ-sEVs significantly improved the delivery efficiency and stability of ASO-210, the antisense oligonucleotides of miR-210 block the immune imbalance and subsequent psoriasis development. Our results reveal MSC-sEVs as promising cell-free therapeutic agents and ideal delivery vehicles of antisense oligonucleotides for psoriasis treatment.