Elucidating the Bioinspired Synthesis Process of Magnetosomes-Like Fe3O4 Nanoparticles.

Iron oxide nanoparticles are a kind of important biomedical nanomaterials. Although their industrial-scale production can be realized by the conventional coprecipitation method, the controllability of their size and morphology remains a huge challenge. In this study, a kind of synthetic polypeptide Mms6-28 which mimics the magnetosome protein Mms6 is used for the bioinspired synthesis of Fe3O4 nanoparticles (NPs). Magnetosomes-like Fe3O4 NPs with uniform size, cubooctahedral shape, and smooth crystal surfaces are synthesized via a partial oxidation process. The Mms6-28 polypeptides play an important role by binding with iron ions and forming nucleation templates and are also preferably attached to the [100] and [111] crystal planes to induce the formation of uniform cubooctahedral Fe3O4 NPs. The continuous release and oxidation of Fe2+ from pre-formed Fe2+-rich precursors within the Mms6-28-based template make the reaction much controllable. The study affords new insights into the bioinspired- and bio-synthesis mechanism of magnetosomes.

Magnetic vagus nerve stimulation alleviates myocardial ischemia-reperfusion injury by the inhibition of pyroptosis through the M2AChR/OGDHL/ROS axis in rats.

BACKGROUND: Myocardial ischemia-reperfusion (I/R) injury is accompanied by an imbalance in the cardiac autonomic nervous system, characterized by over-activated sympathetic tone and reduced vagal nerve activity. In our preceding study, we pioneered the development of the magnetic vagus nerve stimulation (mVNS) system. This system showcased precise vagus nerve stimulation, demonstrating remarkable effectiveness and safety in treating myocardial infarction. However, it remains uncertain whether mVNS can mitigate myocardial I/R injury and its specific underlying mechanisms. In this study, we utilized a rat model of myocardial I/R injury to delve into the therapeutic potential of mVNS against this type of injury. RESULTS: Our findings revealed that mVNS treatment led to a reduction in myocardial infarct size, a decrease in ventricular fibrillation (VF) incidence and a curbing of inflammatory cytokine release. Mechanistically, mVNS demonstrated beneficial effects on myocardial I/R injury by inhibiting NLRP3-mediated pyroptosis through the M2AChR/OGDHL/ROS axis. CONCLUSIONS: Collectively, these outcomes highlight the promising potential of mVNS as a treatment strategy for myocardial I/R injury.

Nonmetal doped carbon nitride nanosheet as photocatalyst for degradation of 4, 5-dichloroguaiacol.

Metal-free photocatalysts for high efficient photocatalytic degradation of pollutants have attracted growing concern in recent years. Herein, relying on density functional theory (DFT) calculations, boron and phosphorus doped C2N layers were explored for the potential of utilization as photocatalysts for 4, 5-dichloroguaiacol (4, 5-DCG) removal. Our computations revealed that the adsorption energy of 4, 5-DCG on B@N-doped C2N layers were 26.56 kcal mol-1, and the ΔG≠ of initial reactions of 4, 5-DCG with OH were also reduced onto the B@N-doped C2N substrates. The band gap of B@N-doped C2N was 2.27 eV. The obtained results showed that the doping of boron atom into C2N layer narrows bandgap, and retains well catalytic performance and adsorption properties. Hence, B@N-doped C2N layer is a promising photocatalyst for organic pollutants removal. Possible degradation pathways of 4, 5-DCG and aquatic toxicity assessment during degradation were also carried out. Products with higher toxicity would be formed and the transformation products were still toxic to three nutrient levels of aquatic organisms (green algae, fish, and daphnia).

CRPC Membrane-Camouflaged, Biomimetic Nanosystem for Overcoming Castration-Resistant Prostate Cancer by Cellular Vehicle-Aided Tumor Targeting.

Castration-resistant prostate cancer (CRPC) is the most common malignant tumor of the male urinary system. Nanodrug delivery systems (NDDS) have been widely applied in drug delivery for tumor therapy; however, nanotherapeutics encounter various biological barriers that prevent successful accumulation of drugs, specifically at diseased sites. Therefore, there is an urgent need to develop a CRPC-targeting nanocomposite with fine biocompatibility for penetrating various biological barriers, delivering sufficient drugs to the targeting site and improving therapeutic efficiency. In this work, CRPC cell membranes were firstly adapted as biomimetic vectors for the encapsulating PEG-PLGA polymer containing the chemotherapy drug docetaxel (DTX). The CRPC membrane-camouflaged nanoparticles can easily escape early recognition by the immune system, penetrate the extracellular barrier, and evade clearance by the circulatory system. In addition to the characteristics of traditional nanoparticles, the CRPC cell membrane contains an arsenal of highly specific homotypic moieties that can be used to recognize the same cancer cell types and increase the targeted drug delivery of DTX. In vivo fluorescence and radionuclide dual-model imaging were fulfilled by decorating the biomimetic nanosystem with near-infrared dye and isotope, which validated the homotypic targeting property offered by the CRPC cell membrane coating. Importantly, remarkably improved therapeutic efficacy was achieved in a mice model bearing CRPC tumors. This homologous cell membrane enabled an efficient drug delivery strategy and enlightened a new pathway for the clinical application of tumor chemotherapy drugs in the future.

Unravelling the effects of complexation of transition metal ions on the hydroxylation of catechol over the whole pH region.

Catechol pollutants (CATPs) serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes. Little information is available on the effects of complexation of metal ions on CATPs degradation. This work presents a systematical study of •OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes (AOPs). Results show that the pH-dependent complexation of metal ions (Zn2+, Cu2+, Ti4+ and Fe3+) promotes the deprotonation of catechol under neutral and even acidic conditions. The radical adduct formation (RAF) reactions are both thermodynamically and kinetically favorable for all dissociation and complexation species, and OH/O- group-containing C positions are more vulnerable to •OH attack. The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation. At pH 7, the apparent rate constant (kapp) values for different systems follow the order of catechol+Ti4+ ≈ catechol+Zn2+ > catechol+Cu2+ > catechol+Fe3+ > catechol. The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs. The toxicity assessment indicates that the •OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.

Climate change may interact with nitrogen fertilizer management leading to different ammonia loss in China's croplands.

Despite research into the response of ammonia (NH3 ) volatilization in farmland to various meteorological factors, the potential impact of future climate change on NH3 volatilization is not fully understood. Based on a database consisting of 1063 observations across China, nonlinear NH3  models considering crop type, meteorological, soil and management variables were established via four machine learning methods, including support vector machine, multi-layer perceptron, gradient boosting machine and random forest (RF). The RF model had the highest R2 of 0.76 and the lowest RMSE of 0.82 kg NH3 -N ha-1 , showing the best simulation capability. Results of model importance indicated that NH3 volatilization was mainly controlled by total input of N fertilizer, followed by meteorological factors, human managements and soil characteristics. The NH3 emissions of China's cereal production (paddy rice, wheat and maize) in 2018 was estimated to be 3.3 Mt NH3 -N. By 2050, NH3 volatilization will increase by 23.1-32.0% under different climate change scenarios (Representative Concentration Pathways, RCPs), and climate change will have the greatest impact on NH3 volatilization in the Yangtze river agro-region of China due to high warming effects. However, the potential increase in NH3 volatilization under future climate change can be mitigated by 26.1-47.5% through various N fertilizer management optimization options.

A SYBR Green I-based real-time polymerase chain reaction assay for detection and quantification of canine bufavirus.

Canine bufavirus (CBuV) was first discovered in puppies in Italy in 2016, and subsequent studies have reported its possible relationship with acute enteritis. Currently, there is no specific and quantitative detection method for CBuV. This study examined the conserved NS1 gene and used a pair of specific primers to establish a direct SYBR Green I-based real-time quantitative polymerase chain reaction (qPCR) method for the detection and quantification of CBuV. In the sensitivity experiment, the detection limit of SYBR Green I-based real-time qPCR was 4.676 × 101 copies/µL and that of conventional PCR (cPCR) was 4.676 × 103 copies/µL. Furthermore, the qPCR method did not detect other viruses in dogs, indicating good specificity. The intra-assay coefficient of variation was 0.07-0.55% and the inter-assay coefficient of variation was 0.03-0.11%, indicating good repeatability. In clinical sample testing, the detection rate of qPCR was 5.0% (6/120), higher than that of cPCR (2.5%, 3/120). In addition, the samples that tested CBuV-positive in this experiment were all from dogs with acute enteritis. In summary, the SYBR Green I-based qPCR method established in this study has good sensitivity, specificity, and reproducibility for clinical sample detection and can also assist in future research on CBuV.

Genetic characterization and phylogenetic analysis of duck-derived waterfowl parvovirus in Anhui province, eastern China.

Recently, a novel duck-origin goose parvovirus (N-GPV) was reported to cause short beak and dwarfism syndrome in ducks. In this study, we performed complete genome sequencing and analyzed three different duck-derived parvoviruses that infected different breeds of ducks. Phylogenetic trees based on gene sequences indicated that they were classical goose parvovirus (C-GPV), Muscovy duck parvovirus (MDPV), and N-GPV. Furthermore, potential recombination events were found. These results improve our understanding of the diversity of duck-derived parvoviruses in Anhui province, eastern China, and provide a reference for the prevention of associated diseases.

Ozonolysis of Permethrin in the Atmosphere: Mechanism, Kinetics, and Evaluation of Toxicity.

Pyrethroid, a pesticide widely used worldwide, could mimic, block, or synergize the effects of endogenous hormones in humans or mammals after entering into the atmosphere and after being sprayed and applied in large quantities. This research aims to study the mechanism, kinetics, and eco-toxicity evaluation of the ozonolysis of permethrin (PER)-one of the typical pyrethroid (type I) pesticides. Existing experimental studies only predicted that ozonolysis of PER could generate a cycloperoxy analogue of PER (IM13-1-11), and the reaction mechanism has not yet been completed. To make up for the lack of experimental results, the 13 primary reaction pathways of PER and ozone, as well as the subsequent reactions of Criegee intermediates with small molecules such as NOx, COx, SO2, and O2, have been studied to propose new reaction paths by quantum chemical calculations in this work. We calculated the total reaction rate constant of PER and ozone at 298 K and 1 atm based on the calculated thermodynamic data and the transition state theory (TST), which was compared with the experimental values to prove the reliability of our results. Based on the quantitative structure and activity relationship, we predicted the acute and chronic toxicity of PER and its products of ozonolysis to three representative organisms-fish, daphnia, and green algae to avoid animal experiments. The results show that ozonolysis products of PER are still extremely harmful to the environment and should be taken seriously, although the products have less toxicity than PER.

TaqMan-based real-time polymerase chain reaction assay for specific detection of bocavirus-1 in domestic cats.

Feline bocavirus-1 (FBoV-1) was first discovered in Hong Kong in 2012, and studies have indicated that the virus may cause feline hemorrhagic enteritis. Currently, there is a lack of an effective and quantitative method for FBoV-1 detection. In this study, a TaqMan-based quantitative real-time PCR (qPCR) for FBoV-1 detection was established. Primers and probes were designed to target the conserved region of the FBoV-1 NS1 gene. The sensitivity analysis indicated that the minimum detection limit was 4.57 × 101 copies/µL. The specificity test revealed no cross-reaction with seven other common feline viruses, including the same species-FBoV-2 and FBoV-3. The sensitivity of this method was 100 times higher than that of conventional PCR (cPCR). The established method showed good repeatability, with the intra-assay and inter-assay coefficients of variation of 0.18%-1.00% and 0.27%-0.45%, respectively. Furthermore, the analysis of feline feces revealed that the detection rate by qPCR was 7.0% (9/128), whereas that by cPCR was 4.7% (6/128). In conclusion, the established qPCR assay can quantitatively detect FBoV-1 with a high sensitivity, high specificity, and good reproducibility, making it a promising technique for the clinical detection of and basic and epidemiological research on FBoV-1.

Theoretical Study of Ozonation of Methylparaben and Ethylparaben in Aqueous Solution.

Parabens are widely employed in toothpaste, cosmetics, textiles, beverages, and preservatives, causing a serious environmental concern because they are endocrine-disrupting compounds (EDCs). As one of the highly reactive oxidants, ozone has a great effect on EDC removal. To understand the degradation and transformation of parabens in the aquatic environment and their toxicity to aquatic organisms, the degradation reaction of parabens initiated by O3 was studied meticulously using quantum chemical calculations. The degradation process includes multiple initial reaction channels and consequent degradation pathways of the Criegee intermediates. Through thermodynamic data, the rate constants were computed using the transition state theory (TST). At a temperature of 298 K and a pressure of 1 atm, the calculated rate constants were 3.92 and 3.94 M-1 s-1 for methylparaben (MPB) and ethylparaben (EPB), respectively. The rate constants increased as the temperature increased or as the length of the alkyl chain on the benzene ring increased. Through the ecotoxicity assessment procedure, the ecotoxicity of parabens and the products in the degradation process can be assessed. Most degradation byproducts are either less toxic or nontoxic. Some byproducts are still harmful, such as oxalaldehyde (P2) and ethyl 2,3-dioxopropanoate (P10). Furthermore, the ecological toxicity of parabens increased with augmentation of the alkyl chain on the benzene ring. The effect of the alkyl chain length on the benzene ring in the compound cannot be ignored.

Ozonation of diclofenac in the aqueous solution: Mechanism, kinetics and ecotoxicity assessment.

The pharmaceutical and personal care products (PPCPs) in aquatic environment have aroused more interest recently. Many of them are hard to degrade by the typical biological treatments. Diclofenac (DCF), as a significant anti-inflammatory drug, is a typical PPCP and widely existed in water environment. It is reported that DCF has adverse effects on aquatic organisms. This work aims to investigate the mechanism, kinetics and ecotoxicity assessment of DCF transformation initiated by O3 in aqueous solution, and provide a solution to the degradation of DCF. The O3-initiated oxidative degradations of DCF were performed by quantum chemical calculations, including thirteen primary reaction pathways and subsequent reactions of the Criegee intermediates with H2O, NO and O3. Based on the thermodynamic data, the kinetic parameters were calculated by the transition state theory (TST). The total reaction rate constant of DCF initiated by O3 is 2.57 × 103 M-1 s-1 at 298 K and 1 atm. The results show that the reaction rate constants have a good correlation with temperature. The acute and chronic toxicities of DCF and its degradation products were evaluated at three different trophic levels by the ECOSAR program. Most products are converted into less toxic or harmless products. Oxalaldehyde (P3) and N-(2,6-dichlorophenyl)-2-oxoacetamide (P6) are still harmful to the three aquatic organisms, which should be paid more attention in the future.

Degradation of prosulfocarb by hydroxyl radicals in gas and aqueous phase: Mechanisms, kinetics and toxicity.

Prosulfocarb (PSC) is a thiocarbamate herbicide mainly used in winter cereals and a relevant aerosol precursor under OH radicals (OH) photooxidation conditions. We investigated the environmental risks, mechanisms, kinetics and products for the PSC withOH by employing theoretical chemical calculations. Two reaction types of H-abstraction andOH-addition reactions were taken into account. Whether in the atmosphere or aqueous particles, the most favorable pathway was the H-abstraction in the N-alkyl groups close to nitrogen atom. Subsequent reactions of primary intermediates were considered at different conditions. The total rate constants were determined as 2.62 × 10-10 cm3 molecule-1 s-1 and 4.96 × 10-11 cm3 molecule-1 s-1 at 298 K in atmosphere and aqueous particles, respectively. In natural water with theOH concentration of 10-15-10-18 mol l-1, the half-lives (t1/2) of PSC in theOH-initiated reactions were calculated as t1/2 = 2.40 × 104-2.40 × 107 s. With regard to the influence on human health and the ecosystem, oxidized products of PSC were estimated to be mutagenicity negative and had no obvious bioaccumulation potential. The aquatic toxicity of PSC and its degradation products was evaluated and the assessment results showed that the degradation of PSC was a toxicity-reduced process but they were still at toxic and harmful levels.

Theoretical investigation on the contribution of HO, SO4- and CO3- radicals to the degradation of phenacetin in water: Mechanisms, kinetics, and toxicity evaluation.

Indirect oxidation induced by reactive free radicals, such as hydroxyl radical (HO), sulfate radical (SO4-) and carbonate radical (CO3-), plays an important or even crucial role in the degradation of micropollutants. Thus, the coadjutant degradation of phenacetin (PNT) by HO, SO4- and CO3-, as well as the synergistic effect of O2 on HO and HO2 were studied through mechanism, kinetics and toxicity evaluation. The results showed that the degradation of PNT was mainly caused by radical adduct formation (RAF) reaction (69% for Г, the same as below) and H atom transfer (HAT) reaction (31%) of HO. For the two inorganic anionic radicals, SO4- initiated PNT degradation by sequential radical addition-elimination (SRAE; 55%), HAT (28%) and single electron transfer (SET; 17%) reactions, while only by HAT reaction for CO3-. The total initial reaction rate constants of PNT by three radicals were in the order: SO4- > HO > CO3-. The kinetics of PNT degradation simulated by Kintecus program showed that UV/persulfate could degrade target compound more effectively than UV/H2O2 in ultrapure water. In the subsequent reaction of PNT with O2, HO and HO2, the formation of mono/di/tri-hydroxyl substitutions and unsaturated aldehydes/ketones/alcohols were confirmed. The results of toxicity assessment showed that the acute and chronic toxicity of most products to fish increased and to daphnia decreased, and acute toxicity to green algae decreased while chronic toxicity increased.

Deriving Emission Factors and Estimating Direct Nitrous Oxide Emissions for Crop Cultivation in China.

Updating and refining the N2O emission factors (N2O-EFs) are vital to reduce the uncertainty in estimates of direct N2O emissions. Based on a database with 1151 field measurements across China, the N2O-EFs were established via three approaches including the maximum likelihood method, a linear regression with an intercept and a linear regression with the intercept set to 0 using 70% of the observations. The remaining 30% of the observations were then used to evaluate the predicted N2O-EFs. The third method had the highest R2 of 0.39 and the best model efficiency of 0.38 with no significant bias, showing the best calculation efficiency. The results showed that the N2O-EFs varied with agroregions, crops, and management patterns. The agroregions of Huang-Huai-Hai and Yangtze River had the higher N2O-EFs in maize and wheat seasons than other regions, and the highest N2O-EFs of 0.66-0.92% in the rice season was found in the South and Southwest agroregions. Both fertilizer types and water regimes had the remarkable effects on N2O-EFs. Based on the best estimation by the selected method, direct N2O emissions from China's crop cultivation were estimated to be 194 Gg N2O-N with a 95% confidence interval of 180-208 Gg N2O-N in the year 2016.

Mechanisms and Kinetic Parameters for the Gas-Phase Reactions of 3-Methyl-3-buten-2-one and 3-Methyl-3-penten-2-one with Ozone.

Ozonolysis of unsaturated ketones is a common atmospheric chemical process that plays a significant role in controlling the atmospheric budget of OH and O3, organic acids, and secondary organic aerosols (SOA). In this work, the detailed reaction mechanism and rate coefficients for the reactions of O3 with two unsaturated ketones, 3-methyl-3-buten-2-one (MBO332) and 3-methyl-3-penten-2-one (MPO332), were investigated by using density functional theory (DFT) and Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results indicate that the major products are butanedione and formaldehyde for MBO332, and butanedione and acetaldehyde for MPO332. Possible reaction mechanism and thermodynamic parameters of some complex stable Criegee intermediates (SCIs) RR'COO were also be investigated in this study. Some organic peroxides can be regarded as the main products for the further reactions of SCIs. The rate constants calculated with O3 are 2.59 × 10-16 cm3 molecule-1 s-1 and 2.28 × 10-16 cm3 molecule-1 s-1 for MBO332 and MPO332 at 298 K and 1 atm. The total rate constant is negatively correlated with temperature (200-400 K) and positively correlated with pressure. The atmospheric half-lives of MBO332 and MPO332 based on O3 are estimated.

Magnetoferritin: Process, Prospects, and Their Biomedical Applications.

Ferritin is a spherical iron storage protein composed of 24 subunits and an iron core. Using biomimetic mineralization, magnetic iron oxide can be synthesized in the cavity of ferritin to form magnetoferritin (MFt). MFt, also known as a superparamagnetic protein, is a novel magnetic nanomaterial with good biocompatibility and flexibility for biomedical applications. Recently, it has been demonstrated that MFt had tumor targetability and a peroxidase-like catalytic activity. Thus, MFt, with its many unique properties, provides a powerful platform for tumor diagnosis and therapy. In this review, we discuss the biomimetic synthesis and biomedical applications of MFt.

Different fates of deposited NH4+ and NO3- in a temperate forest in northeast China: a 15 N tracer study.

Increasing atmospheric reactive nitrogen (N) deposition due to human activities could change N cycling in terrestrial ecosystems. However, the differences between the fates of deposited NH4+ and NO3- are still not fully understood. Here, we investigated the fates of deposited NH4+ and NO3-, respectively, via the application of 15 NH4 NO3 and NH415 NO3 in a temperate forest ecosystem. Results showed that at 410 days after tracer application, most 15NH4+ was immobilized in litter layer (50 ± 2%), while a considerable amount of 15NO3- penetrated into 0-5 cm mineral soil (42 ± 2%), indicating that litter layer and 0-5 cm mineral soil were the major N sinks of NH4+ and NO3-, respectively. Broad-leaved trees assimilated more 15 N under NH415 NO3 treatment compared to under 15 NH4 NO3 treatment, indicating their preference for NO3--N. At 410 days after tracer application, 16 ± 4% added 15 N was found in aboveground biomass under 15NO3- treatment, which was twice more than that under 15NH4+ treatment (6 ± 1%). At the same time, approximately 80% added 15 N was recovered in soil and plants under both treatments, which suggested that this forest had high potential for retention of deposited N. These results provided evidence that there were great differences between the fates of deposited NH4+ and NO3-, which could help us better understand the mechanisms and capability of forest ecosystems as a sink of reactive nitrogen.

Nitrogen addition affects chemical compositions of plant tissues, litter and soil organic matter.

Increasing nitrogen (N) deposition or fertilization has been found to significantly affect carbon (C) cycling. However, a comprehensive understanding of how different C chemical components of plant, litter, and soil would respond to external N addition is still lacking. We compiled data of 1,160 observations from 52 individual studies and conducted a meta-analysis of N addition effects on 18 variables related to C chemical compositions in terrestrial ecosystems. Results showed that plant lignin (+7.13%), plant protein (+25.94%), and soil lignin (+7.30%) were significantly increased by N addition, and plant hemicellulose (-4.39%) was significantly decreased, whereas plant fiber, plant cellulose, plant non-structural carbohydrate (NSC), litter lignin, and litter cellulose were not significantly changed. The effects of N addition on C chemical composition varied among different ecosystems/plant types and different forms of N addition. Increasing treatment duration did not significantly change the effects of N addition on the chemical composition of plant, litter, and soil C. With increasing N addition rate, the effect of N addition on plant lignin, plant fiber, plant cellulose, and plant protein increased, while the effect of N addition on plant hemicellulose, plant NSC, and litter cellulose became more negative. Our meta-analysis provided a systematic evaluation of the responses of different C chemical components to N addition in the plant-litter-soil continuum. Results suggest that the change of plant and soil C chemical composition under N addition may be beneficial for ecosystem C sequestration and could affect ecosystem structure and function in the future.

Orientation-Dependent Thermogenesis of Assembled Magnetic Nanoparticles in the Presence of an Alternating Magnetic Field.

Thanks to thermogenesis in the presence of an alternating magnetic field, magnetic nanoparticles could play a promising role in local heating in vivo. However, the flexible control of thermogenesis for the given nanomaterials remains challenging. Here, we propose that the thermogenesis of assembled magnetic nanoparticles can be controlled by orientation of the film relative to an external field. This idea arises from the principle of energy conservation that is formulated by Poynting's theorem in electromagnetics. We firstly prove that the thermogenesis of magnetic nanoparticles under an alternating magnetic field is directly related to the energy flux of the field rather than to the field's intensity. Then, alteration of the orientation can lead to different incident electromagnetic energies for the nanoparticle film, where the cross-section of the energy absorption plays a crucial role. We developed a method to directly measure the complex susceptibility of an assembled film to confirm this point. This work could be of great importance for applications based on the electromagnetic energy conversion of nanomaterials.