Search

Occupational exposure to trichloroethylene (TCE) causes a systemic skin disorder with hepatitis known as TCE hypersensitivity syndrome (TCE-HS). Human Leukocyte Antigen (HLA)-B*13:01 is its susceptibility factor; however, the immunological pathogenesis of TCE-HS remains unknown. We herein examined the hypothesis that autoantibodies to CYP2E1 are primarily involved in TCE-HS. A case–control study of 80 TCE-HS patients, 186 TCE-tolerant controls (TCE-TC), and 71 TCE-nonexposed controls (TCE-nonEC) was conducted to measure their serum anti-CYP2E1 antibody (IgG) levels. The effects of TCE exposure indices, such as 8-h time-weighted-average (TWA) airborne concentrations, urinary metabolite concentrations, and TCE usage duration; sex; smoking and drinking habits; and alanine aminotransferase (ALT) levels on the antibody levels were also analyzed in the two control groups. There were significant differences in anti-CYP2E1 antibody levels among the three groups: TCE-TC > TCE-HS patients > TCE-nonEC. Antibody levels were not different between HLA-B*13:01 carriers and noncarriers in TCE-HS patients and TCE-TC. The serum CYP2E1 measurement suggested increased immunocomplex levels only in patients with TCE-HS. Multiple regression analysis for the two control groups showed that the antibody levels were significantly higher by the TCE exposure. Women had higher antibody levels than men; however, smoking, drinking, and ALT levels did not affect the anti-CYP2E1 antibody levels. Anti-CYP2E1 antibodies were elevated at concentrations lower than the TWA concentration of 2.5 ppm for TCE exposure. Since HLA-B*13:01 polymorphism was not involved in the autoantibody levels, the possible mechanism underlying the pathogenesis of TCE-HS is that TCE exposure induces anti-CYP2E1 autoantibody production, and HLA-B*13:01 is involved in the development of TCE-HS.

Random road torsional excitation is a key excitation condition for transmission box vibration of tracked vehicles. In order to accurately analyze influences of random road torsional excitation on the vibration characteristics of the transmission box, a calculation method of this excitation for tracked vehicle is proposed based on the random expression of the roughness of standard road surface. Furthermore, random road torsional excitations under different road grades and vehicle speeds are simulated. With the finite element method and modal superposition method, the box body is discretized, and the elastic characteristics of the box body are characterized to explore the dynamics coupling mechanism of gear shafting and the box body. By considering bending-torsional coupling vibration of gear shafting under multi-source excitations, such as the fluctuated torque of engine and dynamic meshing stiffness of gears, dynamic coupling model of gear shafting and box body under random road torsional excitation is established. The dynamic response of the gearbox under random road torsion excitation is obtained by co-simulation with the variable step length Runge-Kutta method. Influences of different road grades, track preload and vehicle speeds on dynamic response characteristics of the gearbox are analyzed. Real vehicle road test scheme is designed to obtain surface acceleration response of the box body at different speeds on the cement road surface. Both test and simulation results are compared and analyzed to verify the accuracy of the simulation method, which provides a theoretical reference for dynamic optimization of the transmission box.

Monitoring biophysical signals such as body or organ movements and other physical phenomena is necessary for patient rehabilitation. However, stretchable flexible pressure sensors with high sensitivity and a broad range that can meet these requirements are still lacking. Herein, we successfully monitored various vital biophysical features and implemented in-sensor dynamic deep learning for knee rehabilitation using an ultrabroad linear range and high-sensitivity stretchable iontronic pressure sensor (SIPS). We optimized the topological structure and material composition of the electrode to build a fully stretching on-skin sensor. The high sensitivity (12.43 kPa−1), ultrabroad linear sensing range (1 MPa), high pressure resolution (6.4 Pa), long-term durability (no decay after 12000 cycles), and excellent stretchability (up to 20%) allow the sensor to maintain operating stability, even in emergency cases with a high sudden impact force (near 1 MPa) applied to the sensor. As a practical demonstration, the SIPS can positively track biophysical signals such as pulse waves, muscle movements, and plantar pressure. Importantly, with the help of a neuro-inspired fully convolutional network algorithm, the SIPS can accurately predict knee joint postures for better rehabilitation after orthopedic surgery. Our SIPS has potential as a promising candidate for wearable electronics and artificial intelligent medical engineering owing to its unique high signal-to-noise ratio and ultrabroad linear range. An ultrabroad-linear range (1 MPa) iontronic pressure sensor with superior sensitivity (12.43 kPa-1) and stretchability (up to 20%) was proposed for biophysical monitoring and deep learning-based knee-rehabilitation training.

Existing discriminative correlation filters suffer from the defects of potential spatial distractors and the degradation of appearance model caused by hard-temporal correlation. Aiming at this issue, a robust tracker which combines the adaptive spatial regularization and the temporal consistent constraint is proposed in this paper. First, we propose to take the extracted saliency map of the background as a reference weight to construct the spatial regularization term, with which the perceived performance of the filter against distractors is enhanced by learning the spatial sparse constraint adaptively. Second, we further implement the temporal consistent regularization formed by capturing dynamic appearance information from multiple historical frames with a high-confidence strategy to mitigate the model degradation. Third, we employ the alternating direction method of multipliers to solve the constrained optimization problem efficiently, thereby the computational complexity can be reduced. The concrete experimental results on OTB-2013, OTB-2015, Temple-Color-128 and VOT2016 benchmarks demonstrate that our tracker outperforms several state-of-the-art algorithms.

Recycling of spent lithium-ion batteries (LIBs) is of great importance for both critical metal supply and environmental protection. Although the physical chemistry is still focused on pyrometallurgy, hydrometallurgy and electrometallurgy, state-of-the-art recycling technologies are a trend that is turning towards being more material/energy efficient in line with the principles of green chemistry. For instance, selective recycling of specified metals and direct regeneration of battery materials are being trialled to develop short-cut processes that prevent secondary pollution generation and improve the atomic economy during the whole recycling process. In this review, a number of technologies for recycling spent LIBs are overviewed, especially at different recycling stages to stepwise recover battery materials. It is clearly understood that extraction of critical metals and subsequent regeneration of materials are only part of the recycling process, while pretreatment to obtain black mass powder from battery cells and pollution control, in view of the recycling process to minimise environmental impact, are also extremely important. Furthermore, green design of batteries, as well as process design in view of the whole life cycle of LIBs, are topping the list of the research which requires profound and elaborate efforts. It is expected that this review could provide a guideline for implementing green chemistry principles into spent LIB recycling and stimulate further discussions on improving the green degree of the process.

Pyrolysis is an effective method to remove organics (e.g. electrolytes and binders) from spent lithium-ion battery (LIB). In this study, the co-pyrolysis characteristics of fluorine-containing substances and active materials from LIB were investigated using thermogravimetric-differential scanning calorimetry (TG-DSC), infrared spectroscopy (IR), and mass spectrometry (MS) analysis. Associated with the pyrolysis, active materials adsorb the residues of electrolyte on the surface and into the pores (20-200 °C), while polyvinylidene fluoride (PVDF) forms a liquid film to cover the local surface of active materials (400-500 °C). These interactions prevent deep removal of organics, leaving fluorine-containing contaminants in active materials. The barrier effect of PVDF liquid mesophase on the removal of organics with secondary liquidous phase formation during pyrolysis was confirmed by in situ optical observation. The migration behavior of fluorine element during the pyrolysis of black mass (BM) from spent LIB was also investigated. With pyrolysis temperature increasing from 100 °C to 600 °C, the dissociable fluorine content in pyrolyzed BM increased from 1.4 wt% to 3.7 wt%. The fluorine-containing contaminants in BM cannot be removed completely by simply increasing pyrolysis temperature. This study provides a better understanding on the transformation of fluorine-containing pollutants during the pyrolysis of BM.

Composition engineering of halide perovskite allows the tunability of the band gap over a wide range so that photons can be effectively harvested, an aspect that is of critical importance for increasing the efficiency of photocatalysis under sunlight. However, the poor stability and the low photocatalytic activity of halide perovskites prevent use of these defect-tolerant materials in wide applications involving photocatalysis. Here, an alcohol-based photocatalytic system for dye degradation demonstrated high stability through the use of double perovskite of Cs2 AgBiBr6 . The reaction rate on Cs2 AgBiBr6 is comparable to that on CdS, a model inorganic semiconductor photocatalyst. The fact of fast reaction between free radicals and dye molecules indicates the unique catalytic properties of the Cs2 AgBiBr6 surface. Deposition of metal clusters onto Cs2 AgBiBr6 effectively enhances the photocatalytic activity. Although the stability (five consecutive photocatalytic cycles without obvious decrease of efficiency) requires further improvements, the results indicate the significant potential of Cs2 AgBiBr6 -based photocatalysis.

The preparation of 3D functional isolated mesoscopic assemblies remains a challenge in the self-assembly of polymers. Here, well-defined 3D hexagonal and hexagram prisms with uniform dimensions are acquired by the crystallization of the inclusion complex composed of a crystalline molecule tris-o-phenylenedioxycyclotriphosphazene (TPP) and a block copolymer. The crystalline TPP plays an important role in the self-assembling process. The faceted morphologies of the hexagonal and hexagram prisms are infrequent in the self-assembly field of soft materials. The formation of the prisms experiences a 3D growth mechanism. The epitaxial growth, accompanied by the heterogeneous nucleation in the edges, yields the growth of inclusion crystals. This study provides a path to construct well-defined polymeric soft materials with broad utility based on numerous supramolecular complexes.

Objectives Occupational exposure to trichloroethylene (TCE) induces trichloroethylene hypersensitivity syndrome (TCEHS), which causes hypersensitivity dermatitis and hepatitis. However, whether TCE itself or its two metabolites, trichloroethanol (TCEOH) and trichloroacetic acid (TCA), are involved in TCEHS remains unclear. Therefore, in this study we explored the allergens causing TCEHS and characterized TCEHS‐related liver injury in guinea pigs. Method The guinea pig maximization test was performed using TCE, TCEOH, and TCA as candidate allergens. Skin inflammation was scored, and liver function and histopathological changes were evaluated by biochemical tests and hematoxylin and eosin staining, respectively. Results The sensitization rates for TCE, TCEOH, and TCA were 90.0%, 50.0%, and 0.0%, respectively. In the TCE and TCEOH experimental groups, the skin showed varying degrees of erythema with eosinophil granulocyte infiltration in the dermis. Additionally, serum alanine aminotransferase and γ‐glutamyl transpeptidase levels increased significantly, and histological analysis revealed focal hepatocellular necrosis with inflammatory cell infiltration in the liver. Conclusions TCE is the main cause of allergy and TCEOH is a secondary factor for allergy in guinea pigs. TCE and TCEOH can cause immune‐mediated skin sensitization complicated by focal hepatic necrosis.

Occupational trichloroethylene (TCE) exposure can cause hypersensitivity syndrome (TCE-HS). The human leukocyte antigen (HLA)-B*13:01 is reportedly an important allele involved in TCE-HS onset. However, the threshold exposure level causing TCE-HS in relation to HLA-B*13:01 remains unknown. We conducted a case-control study comprising 37 TCE-HS patients and 97 age- and sex-matched TCE-tolerant controls from the Han Chinese population. Urine and blood of patients were collected on the first day of hospitalization, and those of controls were collected at the end of their shifts. Urinary trichloroacetic acid (TCA) was measured as an exposure marker, and end-of-shift levels in the patients were estimated using the biological half-life of 83.7 h. HLA-B genotype was identified using DNA from blood. Crude odds ratios (ORs) for TCE-HS in the groups with urinary TCA concentration >15 mg/L to ≤50 mg/L and of >50 mg/L were 21.9 [95% confidence interval (CI) 4.2–114.1] and 27.6 (6.1–125.8), respectively, when the group with urinary TCA ≤15 mg/L was used as a reference. The frequency of HLA-B*13:01, the most common allele in the patients, was 62.2% (23/37), which was significantly higher than 17.5% (17/97) in the TCE-tolerant controls, with a crude OR of 8.4 (3.1–22.6). The mutually-adjusted ORs for urinary TCA >15 to ≤50 mg/L, >50 mg/L, and for HLA-B*13:01 were 33.4 (4.1–270.8), 34.0 (5.3–217.1), and 11.0 (2.4–50.7), respectively. In conclusion, reduction of TCE exposure to ≤15 mg/L is required for TCE-HS prevention because urinary TCA concentration >15 mg/L showed increased risk of TCE-HS, regardless of whether the patients had the HLA-B*13:01 allele.

Background The etiologies of autism spectrum disorder (ASD) are yet unclear. Previous studies suggested that ASD is associated with environmental heavy metals. Thus, the present study analyzed the levels of 41 heavy metals and the associated environmental factors in children with ASD. Methods The 25 children diagnosed with ASD were included in the case group (ASD group), while the 18 age- and gender-matched healthy children who came for routine care were included in the typical development group (TD group). The levels of heavy metal in the blood were measured in both groups. The questionnaire survey collected the demographic information, socioeconomic information, and risk factors of potential heavy metal sources for the analysis of risk factors. Results A total of 25 children were included in the ASD group and 18 in the TD group. The blood manganese (Mn) level was significantly higher in the ASD group than the TD group . The father’s educational level was significantly higher in the ASD group than the TD group. The living status was mainly scattered for the ASD children and daycare for the TD group. The frequency of book-reading, washing hand with sanitizer/soap, and the folic acid intake by the mother before pregnancy was significantly lower in the ASD group than the TD group, while the percentage of birth disorder history was significantly higher in the ASD group than the TD group. Binary logistic regression analysis showed that the folic acid intake by the mother before pregnancy and father’s education level beyond junior college were protective factors for ASD. Also, the frequencies of washing hands with sanitizer every time, sometimes, and hardly acted as protective factors for ASD. Conclusion Blood Mn level was significantly higher in ASD than TD, suggesting that environmental Mn exposure could be a risk factor of ASD in children. Folic acid intake by the mother before pregnancy and father’s education levels are protective factors for ASD. Concentrated heavy metal in the blood in prenatal or early life exposures which suggested ASD is needed in the future study.

Occupational trichloroethylene (TCE) exposure can induce life-threatening generalized dermatitis accompanied by hepatitis: TCE hypersensitivity syndrome (HS). Since the patients’ exposure levels have not been fully clarified, this study estimated end-of-shift urinary concentrations of trichloroacetic acid (TCA) and their lower limit below which the disease occurrence was rare. TCA concentration was measured in 78 TCE HS patients whose urine was collected at admission between 2nd and 14th d after their last shift. Then a linear regression model was used to calculate the mean TCA concentration with 95% confidence interval (95% CI) and 95% prediction interval (95% PI) in the end-of-shift urine. The estimated mean concentration was 83 (95% CI, 49–140) mg/l with 95% PI 9.6–720 mg/l. TCA concentrations were also measured in the end-of-shift urine of 38 healthy workers involved in the same job as were the patients. The geometric mean and its 95% CI were 127 mg/l and 16–984 mg/l, respectively. The exposure levels in HS patients might have thus overlapped with those in workers without HS. Accordingly, it was suggested that HS occurred in the environment where the workers were exposed to the TCE concentration corresponding to the urinary TCA concentration as low as 10 mg/l.

Objectives The aims of present study were to determine the prevalence of work-related musculoskeletal disorders (WRMSDs) among sonographers in China and to provide evidence for appropriate intervention measures to be taken. Methods A self-reported questionnaire was used to screen WRMSDs experienced by sonographers during the past 12 months. This questionnaire survey was created and hosted on the WeChat official account platform for sonographers. Results In the present study, 567 sonographers from 521 medical institutions completed the questionnaire. The vast majority (99.3%) of respondents reported experiencing symptoms of WRMSDs for at least one body region during the past 12 months. Work-related musculoskeletal pain or discomfort was most frequently reported for the neck (95.1%), right shoulder (84.1%), lower back (82.4%), right wrist/hand (81.0%), upper back (78.1%), right forearm/elbow (72.0%), and left shoulder (66.1%). Scanning hours per day, number of patients per day, and years of experience were positively associated with the occurrence and frequency of experiencing WRMSDs of some common and specific anatomical regions. Taking a regular rest break during the scanning working day was associated with a reduction of WRMSDs of the right shoulder and right wrist/hand. Adopting a sitting posture while performing scanning was associated with a reduction of WRMSDs, particularly for the lower back and the neck. Performing regular physical activity during leisure time was associated with a reduction of WRMSDs of the neck. Conclusions The prevalence of WRMSDs among sonographers in China was extremely high. It is necessary and essential to reduce the number of scanning hours and patients per day, adopt a sitting posture while performing scanning, schedule regular rest breaks during the scanning working day, and encourage performance of regular physical activity during leisure time to alleviate this WRMSD issue experienced by sonographers.

This paper presents a new fringe projection method for surface-shape measurement that uses novel fringe-width encoded fringe patterns. Specifically, the projection patterns are adjusted with the width of the fringe as the codeword. The wrapped phase with coding information is obtained by using the conventional wrapped phase calculation method, and the fringe order can be identified from the wrapped phase. After the fringe order is corrected based on the region growing algorithm, the fringe order and the wrapped phase can be directly used to reconstruct the surface. Static and dynamic measurements demonstrated the ability of the method to perform 3D shape measurement with only three projected patterns, single camera and projector in the least case.

In recent years, high value utilization of waste biomass has been a hot topic in scientific research. Herein, waste eggshell (ES) rich in sulfonic groups was utilized as a natural modified support to load Pd and Ag nanoparticles (NPs), leading to efficient Pd-Ag/ES catalysts for the catalytic hydrogenation of 1,3-butadiene. Through series of characterizations such as SEM, TEM, BET, XPS, and FTIR, it was found that the porous ES not only has hierarchical structures to facilitate the metal dispersion, but also interacts strongly with Pd and Ag NPs via the inherent surface sulfonic groups, which are responsible for the enhanced catalytic performance. The optimized Pd-Ag/ES catalyst exhibited butenes selectivity of 95.8% and 1,3-butadiene conversion of 95% at 45 °C with excellent stability for at least 30 h on-stream. Furthermore, the first-principles density functional theory (DFT) calculation and in situ DRIFTS were performed to explore the plausible mechanism underlying the enhanced catalytic performance due to sulfonic groups. It is suggested that the sulfonic groups can effectively reduce the adsorption energy of butenes and 1,3-butadiene on the surface of Pd NPs which are beneficial to the selectivity of butenes. This work exemplifies that the waste ES with inherent sulfonic groups can be used as excellent support materials for loading active metal nanoparticles for selective hydrogenation reactions. Collectively, we verified that biological waste like eggshell has a great potential in serving as catalyst carrier due to its unique advantages.

This work has selected high density polyethylene (HDPE), activated carbon (AC) and molecular sieves to form microwave pyrolysis system and studied the effects of reaction conditions and material mixing mode on the products. The mass ratio of HDPE and AC is between 100:60 and 100:330, and different heating power combinations (20–40% of the maximum power of 900 W) are used to meet the heat transfer requirements in different stages. The heating properties of the AC and the interaction between materials are also discussed. The results show that the temperature distribution of reaction system tends to be higher in the center, which makes the products discharge quickly. Therefore, adopting continuous heating, reducing the residence time and the amount of AC can promote wax formation and the maximum yield was 87.75 wt%. While adopting intermittent heating and complete mixing mode, increasing the residence time and the AC amount are beneficial to the liquid formation (mainly between C7 and C20) with the maximum yield of 82.36 wt%. The catalyst can enhance the break of long chain hydrocarbons and shorten the whole reaction time. However, the catalytic effect on the further pyrolysis of the product is limited due to the high heating speed of microwave field.

OBJECTIVE To explore whether polymorphic variants of the HTR1B gene are associated with the susceptibility of Raynauds' Phenomenon (RP) coursed by vibration. METHODS 148 subjects exposed to vibration for more than 2 years were classified into either induced white finger (VWF) group (n = 72), or non-VWF group (n = 76). Vibration exposure levels were measured and assessed following ISO 5349-1:2001 protocol. All workers were genotyped by sequencing for the single nucleotide polymorphisms (SNPs) in the 5'-flanking and coding region of HTR1B. Genetic characteristics and linkage disequilibrium (LD) were analyzed with Haploview. Serum serotonin levels of each subject were detected using ELISA. The association between the susceptibility of vascular damage and genotype was analyzed via logistic regression. RESULTS 7 known SNPs were obtained and their allele frequencies were inserted into the Hardy-Weinberg equilibrium. rs6297 variant genotype had an increased risk of VWF compared with wild genotype (OR = 2.14, 95% CI = 1.04- 4.58, P

Patients with asthma have a higher incidence of obstructive sleep apnea (OSA). However, the association between OSA and the exacerbation of severe asthma remains unclear. In this study, we aimed to investigate the prevalence of OSA in a cross-sectional study of asthma patients and to prospectively examine the significance of the effect of OSA on severe asthma exacerbations.One hundred and forty-six patients with asthma and 157 matched-controlled individuals were enrolled in this study. The patients with asthma were prospectively studied for one year, and exacerbation episodes were identified based on the patients' medical histories. Lung function and the percentages of eosinophils in induced sputum samples were determined, and the frequencies of severe asthma exacerbations during the previous year were evaluated in the group of patients with asthma.The rates of OSA were 19.2% (28/146) among the patients with asthma and 9.6% (15/157) among the control individuals (p = 0.016). The frequency of severe asthma exacerbations was significantly higher among the asthma patients with OSA compared with those who did not have OSA (p 0.001). The apnea-hypopnea index (AHI) correlated significantly with the number of severe asthma exacerbations (r = 0.507, 95% confidence interval [CI] 0.357-0.637, p 0.001). Logistic regression analyses determined that the AHI was significantly associated with the occurrence of severe asthma exacerbations (odds ratio 1.322, 95% CI 1.148-1.523, p 0.001).Patients with asthma had a high prevalence of OSA, which was an important factor associated with severe asthma exacerbations.

In recent years, metal-organic frameworks (MOFs) have received extensive interest because of the diversity of their composition, structure, and function. To promote the MOFs' function and performance, the construction of hollow structural metal-organic frameworks and nanoparticle-MOF composites is significantly effective but remains a considerable challenge. In this article, a transformation strategy is developed to synthesize hollow structural Co-MOF-74 by solvothermal transformation of ZIF-67. These Co-MOF-74 particles exhibit a double-layer hollow shell structure without remarkable shape change compared to original ZIF-67 particles. The formation of hollow structure stemmed from the density difference of Co between ZIF-67 and Co-MOF-74. By this strategy, hollow structural Co-MOF-74 with different sizes and shapes are obtained from corresponding ZIF-67, and metal nanoparticles@Co-MOF-74 is synthesized by corresponding nanoparticles@Co-ZIF-67. To verify the structural advantages of hollow structural Co-MOF-74 and Ag nanoparticles@Co-MOF-74, photocatalytic CO2 reduction is used as a model reaction. Conventionally synthesized Co-MOF-74 (MOF-74-C), hollow structural Co-MOF-74 synthesized by transformation method (MOF-74-T) and Ag nanoparticles@Co-MOF-74 (AgNPs@MOF-74) are used as cocatalysts in this reaction. As a result, the cocatalytic activity of MOF-74-T and AgNPs@MOF-74 is 1.8 times and 3.8 times that of MOF-74-C, respectively.

Solar-energy-driven CO2 conversion into value-added chemical fuels holds great potential renewable energy generation. However, most of the photocatalysts facilitate a two-electron reduction process producing CO, hard for the eight-electron CH4 production pathways which can stockpile more solar energy for further utilization. Herein, we developed an in situ assembly strategy to fabricate the lead-free perovskite Cs2AgBiBr6@g-C3N4 Z-scheme system in toluene and the Cs2AgBiBr6@g-C3N4 type-II heterojunction structure in CH2Cl2. By combining the reducing ability of the conduction band of g-C3N4 and the oxidizing ability of the valence band of Cs2AgBiBr6 perovskite, this Z-scheme system exhibits superior CH4 production in photocatalytic CO2 reduction, in contrast to the high CO selectivity for the heterojunction photocatalysts, which is 10-fold and 16-fold higher than that of pure g-C3N4 and pure CABB, respectively. The stability (four consecutive photocatalytic cycles in solvent methanol as sacrificial reagent without obvious decrease of efficiency) and the mechanism (the prominent activity and the high CH4 production selectivity boosted by Z-scheme system) were demonstrated. In this work, the first report for constructing lead-free halide perovskite Z-scheme and type-II photocatalytic systems for the regulation products selectivity of CO2 reduction reaction provides a promising strategy for the fabrication other types of inorganic/organic heterojunction systems.

Carriers generated inside semiconductors during photocatalytic processes are highly energetic and can locally drive reactions that are otherwise difficult or impossible through thermally driven catalysis. However, a model photocatalytic system with high activity and long-term stability is still lacking. Based on surface charge-induced activation, we designed a photocatalytic system of dehydrogenation of methanol and a high activity (95% photon-to-hydrogen efficiency at 405 nm) and long-term durability (still being active after operation for a week) was achieved. The presence of NiCl2 inside the system dramatically changes the adsorption behaviors of reactants and products on catalytic centers and leads to great enhancements in both the catalytic activity and long-term durability of the photocatalyst. This work highlights the importance of electronic property of the surface of catalytic centers for designing efficient and stable photocatalytic systems for solving energy and environment problems.

Calcium carbonate nanomaterials (nano-CaCO3) are widely used in both manufacturing and consumer products, but their potential health hazards remain unclear. The objective of this study was to survey workplace exposure levels and health effects of workers exposed to nano-CaCO3. Personal and area sampling, as well as real-time and dust monitoring, were performed to characterize mass exposure, particle size distribution, and particle number exposure. A total of 56 workers (28 exposed workers and 28 unexposed controls) were studied in a cross-sectional study. They completed physical examinations, spirometry, and digital radiography. The results showed that the gravimetric nano-CaCO3 concentration was 5.264 ± 6.987 mg/m3 (0.037–22.192 mg/m3) at the workplace, and 3.577 ± 2.065 mg/m3 (2.042–8.161 mg/m3) in the breathing zone of the exposed workers. The particle number concentrations ranged from 8193 to 39 621 particles/cm3 with a size range of 30–150 nm. The process of packing had the highest gravimetric and particle number concentrations. The particle number concentration positively correlated with gravimetric concentrations of nano-CaCO3. The levels of hemoglobin, creatine phosphokinase (CK), lactate dehydrogenase, and high-density lipoprotein cholesterol (HDL-C) in the nano-CaCO3 exposure group increased significantly, but the white blood cell count (WBC), Complement 3 (C3), total protein (TP), uric acid, and creatinine (CREA) all decreased significantly. The prevalence rate of pulmonary hypofunction was significantly higher (p = 0.037), and the levels of vital capacity (VC), forced vital capacity (FVC), forced expiratory volume in one second (FEV1), FEV1/FVC, peak expiratory flow and forced expiratory flow 25% (FEF 25%), FEF 25–75% were negatively correlated with gravimetric concentrations of nano-CaCO3 (p 3 exposure level was associated with pulmonary hypofunction (p = 0.005). Meanwhile, a dose-effect relationship was found between the accumulated gravimetric concentrations of nano-CaCO3 and the prevalence rate of pulmonary hypofunction (p = 0.048). In conclusion, long-term and high-level nano-CaCO3 exposure can induce pulmonary hypofunction in workers. Thus, lung function examination is suggested for occupational populations with nano-CaCO3 exposure. Furthermore, future health protection efforts should focus on senior workers with accumulation effects of nano-CaCO3 exposure.