pH-Dependent Chemical Transformations of Humic-Like Substances and Further Cognitions Revealed by Optical Methods.

Humic-like substances (HULIS) are macromolecular complex groups in water-soluble organic compounds (WSOC). pH is a crucial factor that influences the chemical transformations of HULIS in atmospheric particles, but this has been rarely investigated, especially under varying pH conditions. This study attempted to unveil the chemical transformation mechanisms of HULIS under a range of pH conditions using optical methods. The pH-dependent light absorption and fluorescence properties of HULIS were comprehensively analyzed; the acidity coefficient (pKa) of HULIS in relation to chemical structures was determined, and the hypothetical chemical transformation mechanisms of HULIS with increasing pH were analyzed by optical characterizations. The results suggested that pH greatly impacted the light absorption and fluorescence efficiencies of HULIS in both winter and summer seasons, and pKa was an important inflection point. The pKa of HULIS ranged from 3.5 to 8.0 in winter and 6.4 to 10.0 in summer. The acidic/basic groups were identified as -OH or -NH2 substituted quinolines, carboxylic aromatics, and pyridines. The pH-sensitive species accounted for about 6% and 21% of HULIS-C (carbon concentrations of HULIS) in winter and summer, respectively. The varying optical spectra with increasing pH might result from charge transfer or complex reactions with HULIS deprotonation.

Source apportionment of VOCs in a typical medium-sized city in North China Plain and implications on control policy.

Characteristics of atmospheric VOCs (volatile organic compounds) have been extensively studied in megacities in China, however, they are scarcely investigated in medium/small-sized cities in North China Plain (NCP). A comprehensive research on possible sources of VOCs was conducted in a medium-sized city of NCP, from May to September 2019. A total of 143 canister samples of 8 sites in Xuchang city were collected, and 57 VOC species were detected. The average VOC concentrations were 42.6 ± 31.6 µg/m3, with 53.7 ± 31.0 µg/m3 and 32.1 ± 27. 8 µg/m3, in the morning and afternoon, respectively. Alkenes and aromatics contributed 80% of the total ozone formation potential (OFP). Aromatics accounted for more than 95% of secondary organic aerosol potential (SOAP). VOCs were dominated by the local emission with significant transport from the southeast direction. PMF analysis extracted 6 sources, which were combustion (33.1%), LPG usage (19.3%), vehicular exhaust & fuel evaporation (15.8%), solvent usage (15.2%), industrial (9.11%) and biogenic (7.51%), respectively and they contributed 33.4%, 17.6%, 12.9%, 18.6%, 9.28% and 8.22% to the OFP, respectively. Combustion and LPG usage were the dominant VOC sources; and combustion, solvent usage and LPG usage were the main sources of OFP in Xuchang city, which were different to megacities in China with a high contribution from vehicular exhaust, solvent usage and industry, suggesting specific control strategies on VOCs need to be implemented in medium-sized city such as Xuchang city.

Unexpectedly high levels and health risks of atmospheric polychlorinated biphenyls in modern mechanical dismantling of obsolete electrical equipment: Investigations in a large integrated e-waste dismantling industrial estate.

Large industrial estates for electrical and electronic waste (e-waste) mechanical dismantling and recycling are gradually replacing outmoded small factories and intensive domestic workshops for e-waste manual and chemical dismantling. However, the air pollution and health risks of persistent organic pollutants during the modern mechanical processing of e-waste, especially obsolete electrical equipment, still remain unclear. Here, unexpectedly high levels (409.3 ng/m3) and health risks of airborne polychlorinated biphenyls (PCBs) were found during the mechanical processing of obsolete electric equipment or parts in a large integrated dismantling industrial estate, which is comparable to or a dozen times higher than those reported during chemical processing. In contrast, the levels (936.0 pg/m3) and health risks of particulate polybrominated diphenyl ethers (PBDEs) were all lower than those of previous studies. PCB emissions (44.9-3300.5 ng/m3) varied significantly across six mechanical dismantling places specifically treating waste motors, electrical appliances, hardware, transformers, and metals, respectively. The high PCB content and mass processing number of obsolete electrical equipment probably result in the highest PCB emissions from the mechanical dismantling of obsolete motors, followed by waste electrical appliances and metals. The PCB non-cancer and cancer risks associated with inhalation and dermal exposure in different mechanical dismantling places were all above the given potential risk limits. In particular, the health risks of dismantling obsolete motor exceeded the definite risk levels. Little difference in PCB emissions and health risks between working and non-working time suggested the importance of PCB volatilization from most e-waste. Such high PCB emissions and health risks of PCBs undoubtedly posed a severe threat to frontline workers, but fortunately, they decreased significantly with the increasing distance from the industrial estate. We highlight that PCB emissions and associated health risks from obsolete electrical equipment with high PCB content during mechanical dismantling activities should be of great concern.

Subcellular Localization of Epstein-Barr Virus BLLF2 and Its Underlying Mechanisms.

Epstein-Barr virus (EBV), the pathogen of several human malignancies, encodes many proteins required to be transported into the nucleus for viral DNA reproduction and nucleocapsids assembly in the lytic replication cycle. Here, fluorescence microscope, mutation analysis, interspecies heterokaryon assays, co-immunoprecipitation assay, RNA interference, and Western blot were performed to explore the nuclear import mechanism of EBV encoded BLLF2 protein. BLLF2 was shown to be a nucleocytoplasmic shuttling protein neither by a chromosomal region maintenance 1 (CRM1)- nor by a transporter associated with antigen processing (TAP)-dependent pathway. Yet, BLLF2's two functional nuclear localization signals (NLSs), NLS1 (16KRQALETVPHPQNRGR31) and NLS2 (44RRPRPPVAKRRRFPR58), were identified, whereas the predicted NES was nonfunctional. Finally, BLLF2 was proven to transport into the nucleus via a Ran-dependent and importin ß1-dependent pathway. This mechanism may contribute to a more extensive insight into the assembly and synthesis of EBV virions in the nucleus, thus affording a new direction for the treatment of viruses.

[Chemical Characteristics of Arsenic in PM2.5 in Beijing].

This study assesses the chemical characteristics of As in aerosol PM2.5 samples that were collected from July 2011 to May 2012 in Beijing, China. Total As, As(Ⅲ), and As(Ⅴ) were analyzed by inductively coupled plasma mass spectrometry (ICP-MS), high performance liquid chromatography (HPLC), and hydride generation atomic fluorescence (HG-AFS), respectively. The average concentrations of total As, As(Ⅲ) and As(Ⅴ) over the entire sampling period were (21.82±17.01), (3.15±1.94), and (10.78±5.39) ng·m-3, respectively. The average concentrations of total As, As(Ⅲ) and As(Ⅴ) were (16.62±5.80), (18.34±9.00), (21.49±10.22), and (29.52±27.97) ng·m-3 during the spring, (5.42±2.5), (1.61±0.51), (2.88±1.12), and (3.27±1.23) ng·m-3 during the summer, and (7.55±1.47), (13.57±13.34), (12.75±6.54), and (8.68±3.57) ng·m-3 during the winter, respectively. The average concentrations of As(Ⅲ) in different seasons were higher than As(Ⅴ) concentrations. Seasonal characteristics may be caused by seasonal differences in diffusion conditions, emission sources, and atmospheric oxidation. The ratios of average concentrations of As(Ⅲ)/As(Ⅴ) were 0.67 in spring, 0.13 in summer, 0.27 in autumn, and 0.44 in winter. Ratios of As(Ⅲ)/As(Ⅴ) were negatively correlated with relative humidity, which indicates that high humidity conditions may not have been favorable for the transformation of As(Ⅲ) into As(Ⅴ). As(Ⅲ)/As(Ⅴ) and As(Ⅲ) both showed positive correlations with Ca2+, thereby indicating that soil dust may have been an important source of As(Ⅲ).

The nuclear localization signal-mediated nuclear targeting of herpes simplex virus 1 early protein UL2 is important for efficient viral production.

Herpes simplex virus 1 (HSV-1) is a representative alphaherpesvirus that can provoke a series of severe diseases to human being, but its exact pathogenesis is not perfectly understood. UL2, a uracil-DNA glycosylase involved in the process of HSV-1 DNA replication, has been shown to be predominantly targeted to the nuclei in our previous study, yet little is established regarding the subcellular localization signal or its related function of UL2 during HSV-1 propagation. Here, by creating a number of UL2 variants merged with enhanced yellow fluorescent protein, an authentic nuclear localization signal (NLS) of UL2 was, for the first time, identified and profiled to amino acids (aa) 1 to 17 (MKRACSRSPSPRRRPSS), and 12RRR14 was indispensable for its nuclear accumulation. Besides, the predicted nuclear export signal (aa 225 to 240) of UL2 was determined to be nonfunctional. Based on the HSV-1 bacterial artificial chromosome and homologous recombination technique, three recombinant viruses with mutations of the identified NLS, deletion and revertant of UL2 were constructed to assess the effect of UL2 nuclear targeting on HSV-1 replication. Compared to the wild type HSV-1, UL2 deletion remarkably restrained viral production, and mutation of NLS targeting UL2 to cytoplasm (pan-cellular distribution) in recombinant virus-infected cells showed a certain degree of deficiency in HSV-1 proliferation. Moreover, recombinant virus with UL2 deletion exhibited serious damages of viral DNA synthesis and mRNA expression, and these processes were partially disrupted in the recombinant virus with UL2 NLS mutation. Collectively, we had established a functional NLS in UL2 and showed that the NLS-mediated nuclear translocation of UL2 was important for efficient production of HSV-1. These data were of significance for further clarifying the biological function of UL2 during HSV-1 infection.

Synergistic effect of the composite films formed by zeolitic imidazolate framework 8 (ZIF-8) and porous nickel films for enhanced amperometric sensing of hydrazine.

A novel ZIF-Ni composite film has been successfully prepared by a facile method involving the in situ deposition of ZIF-8 on a nickel porous film which is fabricated by selectively etching copper from a dense Ni/Cu alloy film. The nanostructures of the resulting ZIF-Ni composite films are carefully examined by a combination of scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, Fourier transform infrared (FT-IR) spectroscopy, energy dispersive X-ray (EDX), and nitrogen adsorption-desorption. Cyclic voltammetric and amperometric studies show the enhanced electrocatalytic properties of the ZIF-Ni composite film electrodes toward hydrazine oxidation relative to the synergistic effect of ZIF-8 and porous Ni films. The application potential of the composite films as amperometric detectors is explored for the determination of hydrazine. A high sensitivity of 805.5 µA mM-1 for hydrazine detection with a low detection limit of 0.021 µM (S/N = 3) and a wide linear range from 2.5 µM to 28 mM are revealed for this new type of composite film as the detecting electrode. Moreover, the composite films exhibit excellent selectivity and remarkable stability for the oxidation of hydrazine. This can offer new opportunities for the fast and selective detection of hydrazine and provide a promising platform for sensor designs for hydrazine detection.

Clinician Effectiveness in Assessing Fitness to Drive of Medically At-Risk Older Adults.

OBJECTIVES: To model the relative contributions of driver data and clinical judgments to clinical ratings of driver capability for a state licensing authority and to compare ratings with on-road test results. DESIGN: Retrospective, logistic regression. SETTING: Missouri Driver License Bureau. PARTICIPANTS: Adults aged 60 and older (N = 652; 52% male) evaluated by a physician of their choosing and a portion subsequently road tested (n = 286). MEASUREMENTS: Clinical data from an evidence-based physician statement (Form 1528). A three-level rating (likely capable, unclear, not capable) was collapsed into two outcomes (0 likely capable; 1 unclear, not capable) as the dependent variable. Independent variables (predictors) were age, sex, driving exposure, recent crash or police action, number of medical conditions, medication side effects, driver insight, and disease functional severity rating for driving. RESULTS: Three variables in the model (Nagelkerke coefficient of determination = 0.64; P < .001) were significant in the expected direction: disease functional severity for driving (odds ratio (OR = 6.65), insight (OR = 2.35), and age (OR = 1.06). Proportionately more drivers rated likely capable (73%) passed the road test than those rated unclear or not capable (62%). CONCLUSION: Judgments of disease severity, decrements in driver insight, and older age influenced clinician ratings of driving capability. Correspondence of physician ratings to on-road test outcomes was imperfect, highlighting the complexities in translation of clinical judgments to on-road performance. Both means of assessment have important and additive roles in driver licensing.

Electrochemical fabrication of copper-containing metal-organic framework films as amperometric detectors for bromate determination.

A facile electrochemical plating strategy has been employed to prepare the electroactive metal-organic framework film (NENU-3) onto a copper electrode in the acid electrolyte containing 1,3,5-benzenetricarboxylic acid (H3BTC) and phosphotungstic acid (PTA). The as-made NENU-3 films have been characterized using powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analyses (TGA). These analyses indicate that NENU-3 films have high phase purity and high stability. Further, different electrochemical techniques are utilized for measuring the electrochemical behaviors of the NENU-3 film electrodes. Accordingly, the kinetic parameters of a NENU-3 film electrode towards the electrocatalytic reduction of bromate are obtained, including the electron transfer coefficient (α), the catalytic rate constant (ks), and the diffusion coefficient (D). The film electrodes present excellent electrocatalytic ability for the bromate reduction, and can be used successfully for the amperometric detection of bromate. Under the optimized conditions, the proposed sensor exhibits a wide linear range (0.05-72.74 mM) and a lower detection limit (12 µM) measured by chronoamperometry (CA). Moreover, the films possess high electrochemical stability and strong anti-interference capability in the bromate detection process. It has been demonstrated that the electrochemical plating method reported here offers a reliable and efficient way to fabricate MOF films on conductive substrates for bromate detection.