[Clinical value of high frequency ultrasound in the diagnosis of hip joint involvement in patients with ankylosing spondylitis].

OBJECTIVE: To analyze the correlation between hip joint musculoskeletal ultrasound score and ankylosing spondylitis (AS) disease activity, as well as to investigate the value of high frequency ultrasound in the assessment of hip joint involvement in AS. METHODS: The clinical data of 244 patients with AS who were treated in the rheumatology department of from March 2019 to March 2022 were retrospectively analyzed. Among them, there 174 males and 70 females, aged from 19 to 58 years old with an average of (34.22±9.49) years old;the disease duration of AS patients ranged from 8 months to 26 years, with an average of (13.68±4.04) years.The 244 patients were divided into disease group (83 cases) and control group (161 cases) based in the presence of hip joint involuement. According to the the disease activity, patients in the disease group were further categorezed into active phase (45 cases) and stable phase (38 cases). The ultrasound scores of patients in the active and stable phases of the disease group and the control group were compared. Relevant factors of hip joint involvement in AS patients were analyzed, and analyze the correlation between ultrasound score and Bath ankylosing spondylitis disease activity score index(BASDAI), Bath ankylosing spondylitis functional index(BASFI), visual analogue score of pain (VAS), C-reactive protein (CRP), erythrocyte sedimentation rate (ESR), and the correlation between hip joint capsule score and tendon attachment end score and BASDAI, BASFI, VAS, CRP and ESR. RESULTS: The hip joint capsule score(3.06±1.12), femoral head score(1.45±0.43), tendon attachment end score(3.28±1.30) and total ultrasound score(6.65±2.31) of the disease group were higher than those of the control group(1.51±0.48)、(0.66±0.27)、(1.61±0.53)、(3.81±1.44)scores (P<0.05). Multifactor Logstic regression analysis showed that the course of disease, hip joint capsule score and total ultrasound score were independent risk factors for hip involvement in AS patients.The hip capsule score (3.65±1.22)and total ultrasound score(8.28±2.33) in the active phase of the disease group were higher than those in the stable phase (2.48±1.04)、( 6.82±1.96)scores(P<0.05). The hip joint capsule score and total ultrasonic score of AS patients were positively correlated with BASDAI, BASFI, VAS, CRP, and ESR (P<0.05, P<0.01).The score of tendon attachment end was positively correlated with CRP (P<0.05). The score of joint capsule effusion in AS patients was positively correlated with BASDAI, BASFI and VAS (P<0.05, P<0.01). The synovial blood flow score was positively correlated with BASDAI, VAS, CRP and ESR (P<0.05, P<0.01). The synovial thickening score was positively correlated with BASDAI, BASFI, VAS, CRP and ESR (P<0.05, P<0.01). There was no correlation between the score of tendon attachment end and BASDAI, BASFI, VAS, CRP and ESR. CONCLUSION: There is a correlation between hip joint ultrasonic score of hip joint and clinical indexes in AS patients.Hip joint capsule score and total ultrasonic score were independent risk factors for hip involvement in AS patients. High frequency ultrasound exhibits clinical value in the diagnosis of hip joint involvement in AS patients.

Semirational Design Strategy To Enhance the Thermostability and Catalytic Activity of Cytochrome P450 105D7 for the Degradation of the Pharmaceutically Active Compounds: Diclofenac.

Pharmaceutically active compounds are an important category of emerging pollutants, and their biological transformation processes in the environment are crucial for understanding and evaluating the migration, transformation, and environmental fate of emerging pollutants. The cytochrome P450 105 enzyme family has been proven to play an important role in the degradation of exogenous environmental pollutants. However, its thermostability and catalytic activity still need to be improved to better adapt to complex environmental conditions. This work elucidates the key mechanisms and important residues of the degradation reaction through multiple computational strategies, establishes a mutation library, and obtains 21 single-point mutation designs. Experimental verification showed that 16 single mutants had enhanced thermostability, with the R89F and L197Y mutants showing the highest increases in thermostability at 135 and 119% relative to the wild-type enzyme, respectively. Additionally, as a result of the higher specific activity of D390Q, it was selected for combination mutagenesis, ultimately resulting in three combination mutants (R89F/L197Y, R89F/D390Q, and R89F/L197Y/D390Q) with enhanced thermostability and catalytic activity. This study provides a modification approach for constructing efficient enzyme variants through semirational design and can contribute to the development of control technologies for emerging pollutants.

Osteosarcoma-targeted Cu and Ce based oxide nanoplatform for NIR II fluorescence/magnetic resonance dual-mode imaging and ros cascade amplification along with immunotherapy.

BACKGROUND: As the lethal bone tumor, osteosarcoma often frequently occurs in children and adolescents with locally destructive and high metastasis. Distinctive kinds of nanoplatform with high therapeutical effect and precise diagnosis for osteosarcoma are urgently required. Multimodal optical imaging and programmed treatment, including synergistic photothermal-chemodynamic therapy (PTT-CDT) elicits immunogenetic cell death (ICD) is a promising strategy that possesses high bio-imaging sensitivity for accurate osteosarcoma delineating as well as appreciable therapeutic efficacy with ignorable side-effects. METHODS AND RESULTS: In this study, mesoporous Cu and Ce based oxide nanoplatform with Arg-Gly-Asp (RGD) anchoring is designed and successfully constructed. After loading with indocyanine green, this nanoplatform can be utilized for precisely targeting and efficaciously ablating against osteosarcoma via PTT boosted CDT and the closely following ICD stimulation both in vitro and in vivo. Besides, it provides off-peak fluorescence bio-imaging in the second window of near-infrared region (NIR II, 1000-1700 nm) and Magnetic resonance signal, serves as the dual-mode contrast agents for osteosarcoma tissue discrimination. CONCLUSION: Tumor targeted Cu&Ce based mesoporous nanoplatform permits efficient osteosarcoma suppression and dual-mode bio-imaging that opens new possibility for effectively diagnosing and inhibiting the clinical malignant osteosarcoma.

Characterization of VOC emissions and health risk assessment in the plastic manufacturing industry.

Volatile organic compounds (VOCs) significantly contribute to ozone pollution formation, and many VOCs are known to be harmful to human health. Plastic has become an indispensable material in various industries and daily use scenarios, yet the VOC emissions and associated health risks in the plastic manufacturing industry have received limited attention. In this study, we conducted sampling in three typical plastic manufacturing factories to analyze the emission characteristics of VOCs, ozone formation potential (OFP), and health risks for workers. Isopropanol was detected at relatively high concentrations in all three factories, with concentrations in organized emissions reaching 322.3 µg/m3, 344.8 µg/m3, and 22.6 µg/m3, respectively. Alkanes are the most emitted category of VOCs in plastic factories. However, alkenes and oxygenated volatile organic compounds (OVOCs) exhibit higher OFP. In organized emissions of different types of VOCs in the three factories, alkenes and OVOCs contributed 22.8%, 67%, and 37.8% to the OFP, respectively, highlighting the necessity of controlling them. The hazard index (HI) for all three factories was less than 1, indicating a low non-carcinogenic toxic risk; however, there is still a possibility of non-cancerous health risks in two of the factories, and a potential lifetime cancer risk in all of the three factories. For workers with job tenures exceeding 5 years, there may be potential health risks, hence wearing masks with protective capabilities is necessary. This study provides evidence for reducing VOC emissions and improving management measures to ensure the health protection of workers in the plastic manufacturing industry.

Periodic DFT calculations for the heterogeneous formation of 2-chlorothiophenoxy radical from 2-chlorothiophenol on Cu(111) surface in fly ash.

Copper plays a crucial role in the heterogenous dissociation of chlorothiophenols (CTPs) to form chlorothiophenoxy radicals (CTPRs), which is the initial and critical step in the formation of polychlorinated thianthrenes/dibenzothiophenes (PCTA/DTs). Here, first-principles calculations were performed to investigate the activity of Cu(111) surface towards the formation of adsorbed 2-CTPR from 2-CTP. The interaction between 2-CTP and Cu(111) surface was explored to find stable adsorption configurations. Besides, the decomposition routes of 2-CTP on the Cu(111) surface were further explored. Moreover, the effects of water on the formation of absorbed 2-CTPR on the Cu(111) surface were examined. Our results demonstrate that the flat adsorption of 2-CTP on the surface with adsorption energy in the range of -33.21 kcal/mol to -28.37 kcal/mol is more stable than the vertical adsorption with adsorption energy ranging from -23.53 kcal/mol to -13.38 kcal/mol. The Cu(111) surface catalyzes the conversion of 2-CTP into the adsorbed 2-CTPR with a modest energy barrier of 9.46 kcal/mol. Furthermore, water molecules exhibit stronger catalytic activity in this process with a decreased energy barrier of 5.87 kcal/mol through "water bridge" and hydrogen bonding. Specifically, the water accepts the hydrogen atom from 2-CTP and donates another hydrogen to the surface via "water bridge". This research provides a molecular-level understanding of the heterogeneous formation of PCTA/DTs by fly ash, suggesting novel approaches for control strategy and legislation of dioxin analogues.

Influence of oil extraction on concentration distributions, migration, secondary formation and carcinogenic risk of NPAHs and OPAHs in air and soil in an oilfield development area in China.

Oil extraction leads to environmental pollution from the oilfields and dweller activities, however, knowledge of the concentration distributions, migration, secondary formation and toxicity of nitrated/oxygenated polycyclic aromatic hydrocarbons (N/OPAHs) in oilfield regions is limited. In this research, atmospheric and soil samples in 7 different location types in an important oil industrial base in China were gathered. The ΣNPAHs and ΣOPAHs in the air ranged from 0.05 to 2.47 ng/m3 and 0.14-22.72 ng/m3, respectively, and in soil ranged from 0.22 to 17.81 ng/g and 9.69-66.86 ng/g, respectively. Both NPAHs and OPAHs in the atmosphere exhibited higher concentrations during winter. The atmospheric NPAH concentrations decreased exponentially with distance from urban area especially in the summer, revealing the impact of vehicles on the air in the Yellow River Delta area. High NPAH and OPAH concentrations were found only in soil near oil extraction facilities, indicating that the impact of oil extraction is limited to the soil near the extraction facilities. The air-soil exchanges of N/OPAHs were assessed through fugacity fraction analysis, and NPAHs were in the equilibrium-deposition state and OPAHs were in the net-deposition state in the winter. Higher incremental lifetime cancer risk (ILCR) occurred at the urban, industrial, and oilfield sites in the atmospheric samples, and the soil samples had the largest ILCR values in the oilfield sites. However, ILCR values for both air and soil did not exceed the threshold of 10-6.

Unveiling the overlooked direct emissions of particulate organic nitrates from ship.

Particulate organic nitrates (pONs) have drawn growing interests due to their effects on nitrogen cycling, air pollution, and regional climate. While secondary formation is typically considered as the major source of pONs, direct emissions from various sources remain poorly explored. Ship exhausts have been known as an important source of reactive nitrogen species, yet pONs emissions from ship have been rarely characterized. In this study, we conducted atmospheric measurement of pONs during a ship-based cruise measurement campaign in the East China Sea and also emission measurement of pONs from ship exhausts. During the ship-based cruise, total five typical kinds of pONs were determined and the average total concentrations of five pONs were 479 ± 193 and 250 ± 139 ng m-3 when sampling was influenced by ship emissions or not, respectively, indicating the notable impact of ship exhaust plumes on ambient pONs. Further, five typical pONs were successfully identified and quantified from ship exhausts, with the average total concentration of 1123 ± 406 µg m-3. The much higher pONs levels in ship exhausts than in ambient particulate matters demonstrated ship emission as an important source for pONs. Additionally, their emission factors from ship exhausts were determined as at a range of 0.1-12.6 mg kWh-1. The chemical transport model simulations indicate that direct pONs emissions from ship exert a significant contribution to atmospheric pONs, especially in the clean marine atmosphere. These findings provide compelling evidence for direct emission of pONs from ship and its considerable effects. We call for further studies to better characterize the direct pONs emissions from ship and other potential sources, which should be incorporated into global and regional models.

Room-temperature highly sensitive triethylamine detection by few-layer Nb2CTxMXene nanosheets.

MXene, a class of two-dimensional materials that are emerging as rising stars in the field of materials, are receiving much attention in sensing. Ti3C2TxMXene, the most maturely researched MXene, is widely used in energy, biomedical, laser, and microwave shielding applications and has also been expanded to gas sensing and wearable electronics applications. Compared with Ti3C2Tx, Nb2CTxMXene is more difficult to etch and has higher resistances at room temperature; so, few studies have been reported on their use in the sensing field. Based on the preparation of few-layer Nb2CTxMXene by intercalation, this study thoroughly examined their gas-sensing properties. The successfully prepared few-layer Nb2CTxshowed good selectivity and high sensitivity to triethylamine at room temperature, with response values up to 47.2% for 50 ppm triethylamine and short response/recovery time (22/20 s). This study opens an important path for the design of novel Nb-based MXene sensors for triethylamine gas detection.

PM2.5 pollution modulates the response of ozone formation to VOC emitted from various sources: Insights from machine learning.

Numerous studies have linked ozone (O3) production to its precursors and fine particulate matter (PM2.5), while the complex interaction effects of PM2.5 and volatile organic compounds (VOCs) on O3 remain poorly understood. A systematic approach based on an interpretable machine learning (ML) model was utilized to evaluate the primary driving factors that impact O3 and to elucidate how changes in PM2.5, VOCs from different sources, NOx, and meteorological conditions either promote or inhibit O3 formation through their individual and synergistic effects in a tropical coastal city, Haikou, from 2019 to 2020. The results suggest that under low PM2.5 levels, alongside the linear O3-PM2.5 relationship observed, O3 formation is suppressed by PM2.5 with higher proportions of traffic-derived aerosol. Vehicle VOC emissions contributed maximally to O3 formation at midday, despite the lowest concentration. VOCs from fossil fuel combustion and industry emissions, which have opposing effects on O3, act as inhibitors and promoters by inducing diverse photochemical regimes. As PM2.5 pollution escalates, the impact of these VOCs reverses, becoming more pronounced in shaping O3 variation. Sensitivity analysis reveals that the O3 formation regime is VOC-limited, and effective regional O3 mitigation requires prioritizing substantial VOC reductions to offset enhanced VOC sensitivity induced by the co-reduction in PM2.5, with a focus on industrial and vehicular emissions, and subsequently, fossil fuel combustion once PM2.5 is effectively controlled. This study underscores the potential of the SHAP-based ML approach to decode the intricate O3-NOx-VOCs-PM2.5 interplay, considering both meteorological and atmospheric compositional variations.

Surface curvature-induced oriented assembly of sushi-like Janus therapeutic nanoplatform for combined chemodynamic therapy.

BACKGROUND: Chemodynamic therapy (CDT) based on Fenton/Fenton-like reaction has emerged as a promising cancer treatment strategy. Yet, the strong anti-oxidation property of tumor microenvironment (TME) caused by endogenous glutathione (GSH) still severely impedes the effectiveness of CDT. Traditional CDT nanoplatforms based on core@shell structure possess inherent interference of different subunits, thus hindering the overall therapeutic efficiency. Consequently, it is urgent to construct a novel structure with isolated functional units and GSH depletion capability to achieve desirable combined CDT therapeutic efficiency. RESULTS: Herein, a surface curvature-induced oriented assembly strategy is proposed to synthesize a sushi-like novel Janus therapeutic nanoplatform which is composed of two functional units, a FeOOH nanospindle serving as CDT subunit and a mSiO2 nanorod serving as drug-loading subunit. The FeOOH CDT subunit is half covered by mSiO2 nanorod along its long axis, forming sushi-like structure. The FeOOH nanospindle is about 400 nm in length and 50 nm in diameter, and the mSiO2 nanorod is about 550 nm in length and 100 nm in diameter. The length and diameter of mSiO2 subunit can be tuned in a wide range while maintaining the sushi-like Janus structure, which is attributed to a Gibbs-free-energy-dominating surface curvature-induced oriented assembly process. In this Janus therapeutic nanoplatform, Fe3+ of FeOOH is firstly reduced to Fe2+ by endogenous GSH, the as-generated Fe2+ then effectively catalyzes overexpressed H2O2 in TME into highly lethal ·OH to achieve efficient CDT. The doxorubicin (DOX) loaded in the mSiO2 subunit can be released to achieve combined chemotherapy. Taking advantage of Fe3+-related GSH depletion, Fe2+-related enhanced ·OH generation, and DOX-induced chemotherapy, the as-synthesized nanoplatform possesses excellent therapeutic efficiency, in vitro eliminating efficiency of tumor cells is as high as ~ 87%. In vivo experiments also show the efficient inhibition of tumor, verifying the synthesized sushi-like Janus nanoparticles as a promising therapeutic nanoplatform. CONCLUSIONS: In general, our work provides a successful paradigm of constructing novel therapeutic nanoplatform to achieve efficient tumor inhibition.

[Ozone Pollution Characteristics and Formation Mechanism in a Typical Tropical Seaside City].

To investigate the pollution characteristics and formation mechanism of ambient air ozone(O3) in a typical tropical seaside city, we conducted an observational experiment on O3 and its precursors at an urban site in Haikou, Hainan Province, from June to October 2019. The O3 pollution characteristics were analyzed comprehensively; the O3-NOx-VOCs sensitivities and key precursors were determined, and the control strategies for O3 pollution were carried out. The results were as follows:1 O3 pollution in Haikou mainly occurred in September and October, with daily maximum 8-h O3 concentrations in the range of 39-190 µg·m-3, and the daily variation in O3 was unimodal, peaking at approximately 14:00. 2 The concentrations of NO2 and VOCs were higher during O3 pollution episodes than their respective mean values in Haikou City. The increased O3 precursor concentrations were an important factor leading to O3 pollution, whereas O3 pollution was also influenced by regional transport, with pollutants mainly transported from the northeastern part of Haikou City. 3 O3-NOx-VOCs sensitivity in Haikou City was in the VOCs and NOx transitional regime, and the most sensitive precursors in various months were different. O3 formation in September was sensitive to anthropogenic VOCs the most; however, in October it was sensitive to NOx. 4 In the future, the reduction ratio of VOCs to NOx should be 1:1-4:1 to control O3 pollution effectively in Haikou.

New insight into biodegradation mechanism of phenylurea herbicides by cytochrome P450 enzymes: Successive N-demethylation mechanism.

Phenylurea herbicides (PUHs) present one of the most important herbicides, which have cause serious effects on ecological environment and humans. Nowadays enzyme strategy shows great advantages in degradation of PUHs. Here density functional theory (DFT), quantitative structure - activity relationship (QSAR) and quantum mechanics/molecular mechanics (QM/MM) approaches are used to investigate the degradation mechanism of PUHs catalyzed by P450 enzymes. Two successive N-demethylation pathways are identified and two hydrogen abstraction (H-abstraction) reaction pathways are identified as the rate-determining step through high-throughput DFT calculations. The Boltzmann-weighted average energy barrier of the second H-abstraction pathway (19.95 kcal/mol) is higher than that of the first H-abstraction pathway (16.80 kcal/mol). Two QSAR models are established to predict the energy barriers of the two H-abstraction pathways based on the quantum chemical descriptors and mordred molecular descriptors. The determination coefficient (R2) values of QSAR models are > 0.9, which reveal that the established QSAR models have great predictive capability. QM/MM calculations indicate that human P450 enzymes are more efficient in degradation of PUHs than crop and weed P450 enzymes. Correlations between energy barriers and key structural/charge parameters are revealed and key parameters that have influence on degradation efficiency of PUHs are identified. This study provides lateral insights into the biodegradation strategy and removal method of PUHs and valuable information for designing or engineering of highly efficient degradation enzymes and genetically modified crops.

Impacts of QM region sizes and conformation numbers on modelling enzyme reactions: a case study of polyethylene terephthalate hydrolase.

A quantum mechanics/molecular mechanics (QM/MM) approach is a broadly used tool in computational enzymology. Treating the QM region with a high-level DFT method is one of the important branches. Here, taking leaf-branch compost cutinase-catalyzed polyethylene terephthalate depolymerization as an example, the convergence behavior of energy barriers as well as key structural and charge features with respect to the size of the QM region (up to 1000 atoms) is systematically investigated. BP86/6-31G(d)//CHARMM and M06-2X/6-311G(d,p)//CHARMM level of theories were applied for geometry optimizations and single-point energy calculations, respectively. Six independent enzyme conformations for all the four catalytic steps (steps (i)-(iv)) were considered. Most of the twenty-four cases show that at least 500 QM atoms are needed while only two rare cases show that ∼100 QM atoms are sufficient for convergence when only a single conformation was considered. This explains why most previous studies showed that 500 or more QM atoms are required while a few others showed that ∼100 QM atoms are sufficient for DFT/MM calculations. More importantly, average energy barriers and key structural/charge features from six conformations show an accelerated convergence than that in a single conformation. For instance, to reach energy barrier convergence (within 2.0 kcal mol-1) for step (ii), only ∼100 QM atoms are required if six conformations are considered while 500 or more QM atoms are needed with a single conformation. The convergence is accelerated to be more rapid if hundreds and thousands of conformations were considered, which aligns with previous findings that only several dozens of QM atoms are required for convergence with semi-empirical QM/MM MD simulations.

Double-Edged Role of VOCs Reduction in Nitrate Formation: Insights from Observations during the China International Import Expo 2018.

Aerosol nitrate (NO3-) constitutes a significant component of fine particles in China. Prioritizing the control of volatile organic compounds (VOCs) is a crucial step toward achieving clean air, yet its impact on NO3- pollution remains inadequately understood. Here, we examined the role of VOCs in NO3- formation by combining comprehensive field measurements conducted during the China International Import Expo (CIIE) in Shanghai (from 10 October to 22 November 2018) and multiphase chemical modeling. Despite a decline in primary pollutants during the CIIE, NO3- levels increased compared to pre-CIIE and post-CIIE─NO3- concentrations decreased in the daytime (by -10 and -26%) while increasing in the nighttime (by 8 and 30%). Analysis of the observations and backward trajectory indicates that the diurnal variation in NO3- was mainly attributed to local chemistry rather than meteorological conditions. Decreasing VOCs lowered the daytime NO3- production by reducing the hydroxyl radical level, whereas the greater VOCs reduction at night than that in the daytime increased the nitrate radical level, thereby promoting the nocturnal NO3- production. These results reveal the double-edged role of VOCs in NO3- formation, underscoring the need for transferring large VOC-emitting enterprises from the daytime to the nighttime, which should be considered in formulating corresponding policies.

Distributions of PAHs, NPAHs, OPAHs, BrPAHs, and ClPAHs in air, bulk deposition, soil, and water in the Shandong Peninsula, China: Urban-rural gradient, interface exchange, and long-range transport.

A systematic study of the movement of PAHs (Polycyclic aromatic hydrocarbons) and their derivatives through air, soil, and water is key to understanding the exchange and transport mechanisms of these pollutants in the environment and for ultimately improving environmental quality. PAHs and their derivatives, such as nitrated PAHs (NPAHs), oxygenated PAHs (OPAHs), brominated PAHs (BrPAHs) and chlorinated PAHs (ClPAHs), were analyzed in air, bulk deposition, soil, and water samples collected from urban, rural, field, and background sites on the eastern coast of China. The goal was to investigate and discuss their spatiotemporal variations, exchange fluxes, and transport potential. The concentrations of PAHs and their derivatives in the air and bulk deposition displayed distinct seasonal patterns, with higher concentrations observed during the winter and spring and lower concentrations during the summer and autumn. NPAHs exhibited the opposite trend. Significant urban-rural gradients were observed for most of the PAHs and their derivatives. According to the air-soil fugacity calculations, 2-3 ring PAHs, BrPAHs, and ClPAHs were found to volatilize from the soil into the air, while 4-7 ring PAHs, OPAHs, and NPAHs deposited from the air into the soil. The air-water fugacity of the PAHs and their derivatives indicated that surface water was an important source for the ambient atmosphere in Qingdao. The characteristic travel distances (CTDs) and persistence (Pov) for atmospheric transport were much lower than that for the water samples, which may be due to the longer half-lives of PAHs and their derivatives in water. NPAHs and ClPAHs with long transport distances and strong persistence in water could lead to a significant impact on marine pollution.

Unexpected enhancement of sulfuric acid-driven new particle formation by alcoholic amines: The role of ion-induced nucleation.

New particle formation (NPF) contributes more than half of the global aerosol. Diethanolamine (DEA) and methyldiethanolamine (MDEA) are the most common amines used to remove CO2 and H2S, which are lost to the atmosphere from CO2 chemical absorbers, livestock and consumer products and are involved in sulfuric acid (SA)-driven NPF. Ion-induced nucleation (IIN) is an important nucleation pathway for NPF. We investigated the role of IIN on DEA and MDEA enhancing SA-driven NPF using density functional method (DFT), molecular dynamics (MD) simulation and atmospheric cluster dynamics code (ACDC). The effects of SO42-, H3O+, NH4+, HSO4-, NO3-, ammonia, methylamine, dimethylamine, trimethylamine and water (W) on the nucleation of SA-DEA were further investigated. The enhancement ability of DEA is greater than that of dimethylamine (DMA) and MDEA. Participation in SA-based NPF is a removal pathway for DEA and MDEA. DEA-SA clusters are generated that not only aggregate DEA and SA molecules, but also increase further growth of atmospheric ions. The very low Gibbs formation free energy highlights the importance of ion-induced nucleation for SA-based NPF. The order of the ability of common atmospheric ions to increase the (SA)(DEA) cluster nucleation is SO42- > H3O+ > NH4+ > HSO4- > NO3-. The addition of 20 water molecules increases the (SA)(DEA)9 cluster from 1.882 nm to 2.053 nm, promoting SA-based NPF. The atmospheric ions accelerate the aggregation rate of the (SA)5(DEA)5 cluster within 15 ns?

The effects of the gas-liquid interface and gas phase on Cl/ClO radical interaction with water molecules.

In the marine boundary layer (MBL), chlorine (Cl) and chlorine monoxide (ClO) are powerful oxidants with high concentrations. The gas-liquid interface is also ubiquitous in the MBL as a favorable site for atmospheric reactions. Understanding the role of water in Cl/ClO radical chemistry is essential for predicting their behavior in the atmosphere and developing effective strategies for mitigating their harmful effects. However, the research studies on the system of Cl/ClO radicals on the surface of water droplets are still insufficient. In previous studies, we have found unique results related to the hydroxyl radical at the interface using ab initio molecular dynamics (AIMD). In this work, we have used AIMD to investigate interactions between Cl/ClO radicals and water molecules at the gas-liquid interface. Radical mobility, radial distribution functions, coordination, and population analyses were conducted to investigate the surface preference, bonding pattern, and track Cl/ClO radicals in the water droplets. In addition, density functional theory (DFT) analysis was conducted to compare the results at the gas-liquid interface with those in the gas phase. We found that Cl/ClO radicals tend to remain near the gas-liquid interface in water droplet systems and outside of water clusters in gas phase systems. The ClO radical can form O*-H and Cl-O bonds with water molecules; however, neither the O*-O hemibond nor the Cl-H bond was detected in all systems. Different dominant structures were obtained for ClO in the interface and gas phase. The ClO radical can be bonded to one water molecule from its oxygen side, (H2O)0-Cl-O*-(H2O)1 at the interface, or to two water molecules from the chlorine and oxygen sides, (H2O)1-Cl-O*-(H2O)1 in the gas phase. Meanwhile, the Cl radical can only form a dominant structure like Cl*-(H2O)1 at the gas-liquid interface by making a Cl*-O hemibond. Providing a thorough explanation of the Cl/ClO radical behavior at the gas-liquid interface, this study will improve our understanding of the MBL's oxidizing capacity and pollution causes.

A TM polarization absorber based on a graphene-silver asymmetrical grating structure for near-infrared frequencies.

In this paper, a TM polarization multi-band absorber is achieved in a graphene-Ag asymmetrical grating structure. The proposed absorber can achieve perfect absorption at 1108 nm, 1254 nm, and 1712 nm (the absorption exceeds 98.4% at the three peaks). Results show that the perfect absorption effect originates from the excitation of magnetic polaritons (MPs) in the silver ridge grating; a LC equivalent circuit model is utilized to confirm the finite-difference-time-domain (FDTD) simulation. The influences of the incident angle, polarization angle, and geometrical size on the absorption spectrum are investigated. Moreover, a quadruple band absorber and a quintuple band absorber are also designed by introducing more silver grating ridges in one period. The proposed graphene-Ag asymmetrical structure has some advantages compared with other absorbers such as the ability to be independently tuned and a simple structure. Thus, the proposed structure can be applied in the areas of multiple absorption switches, near-infrared modulators, and sensors.

New insight into the removal process of benzotriazole UV stabilizers by UV/H2O2: Integrating quantum chemical calculation with CFD simulation.

Benzotriazole UV stabilizers (BT-UVs) are important UV absorbers. As high-production chemicals and potential hazards, their ubiquitous presence in aquatic environments is of greatly pressing concern. Herein, the removal of six typical BT-UVs by UV/H2O2 was comprehensively investigated by quantum chemistry calculation integrated with CFD simulation. Utilizing such a micro and macro incorporated model in treating contaminants is the first report. From the micro-view, degradation mechanisms of BT-UVs by •OH oxidation were determined, and corresponding rate constants were obtained with values of 109∼1010 M-1s-1. In a macroscopic aspect, combining the established kinetic model and CFD simulation, the effects of UV lamp power (P), volumetric flow rate (Qv), and H2O2 dosage ([H2O2]0) on removal yields of BT-UVs were expounded, increasing P or [H2O2]0 or decreasing Qv are effective in improving removal yields of BT-UVs, but the enhancement was abated when P or [H2O2]0 increased to a certain level. When [H2O2]0 is 5 mg/L and Qv is decreased from 0.1 to 0.05 m3/h, the removal yields of BT-UVs could achieve more than 95% (P = 150 W) and 99% (P = 250 W), respectively. This work provides a new interdisciplinary insight for investigating organic contaminant removal in potential industrial applications of UV/H2O2 systems.

Versatile synthesis of metal-compound based mesoporous Janus nanoparticles.

The construction of mesoporous Janus nanoparticles (mJNPs) with controllable components is of great significance for the development of sophisticated nanomaterials with synergistically enhanced functionalities and applications. However, the compositions of reported mJNPs are mainly the functionally inert SiO2 and polymers. The universal synthesis of metal-compound based mJNPs with abundant functionalities is urgently desired, but remains a substantial challenge. Herein, we present a hydrophilicity mediated interfacial selective assembly strategy for the versatile synthesis of metal-compound based mJNPs. Starting from the developed silica-based mJNPs with anisotropic dual-surface of hydrophilic SiO2 and hydrophobic organosilica, metal precursor can selectively deposit onto the hydrophilic SiO2 subunit to form the metal-compound based mJNPs. This method shows good universality and can be used for the synthesis of more than 20 kinds of metal-compound based mJNPs, including alkali-earth metal compounds, transition metal compounds, rare-earth metal compounds etc. Besides, the composition of the metal-compound subunit can be well tuned from single to multiple metal elements, even high-entropy complexes. We believe that the synthesis method and obtained new members of mJNPs provide a very broad platform for the construction and application of mJNPs with rational designed functions and structures.