Lead-207 NMR spectroscopy at 1.4 T: Application of benchtop instrumentation to a challenging I = ½ nucleus.

The practicality of obtaining liquid- and solid-state 207 Pb nuclear magnetic resonance (NMR) spectra with a low permanent-field magnet is investigated. Obtaining 207 Pb NMR spectra of salts in solution is shown to be viable for samples as dilute as 0.05 M. The concentration dependence of the 207 Pb chemical shifts for lead nitrate was investigated; the results are comparable with those obtained with high-field instruments. Likewise, the isotope effect of substituting D2 O for H2 O as the solvent was investigated and found to be comparable with those reported previously. Obtaining solid-state 207 Pb NMR spectra is challenging, but we demonstrate the ability to obtain such spectra for three unique solid samples. An axially symmetric 207 Pb powder pattern for lead nitrate and the powder pattern expected for lead chloride reveal linewidths dominated by shielding anisotropy, while 207 Pb-35/37 Cl J-coupling dominates in the methylammonium lead chloride perovskite material. Finally, recent innovations and the future potential of the instruments are considered.

Two-Step Structure Phase Transition, Dielectric Anomalies, and Thermochromic Luminescence Behavior in a Direct Band Gap 2D Corrugated Layer Lead Chloride Hybrid of [(CH3 )4 N]4 Pb3 Cl10.

A direct band gap 2D corrugated layer lead chloride hybrid, [(CH3 )4 N]4 Pb3 Cl10 (1), shows analogous topology to the {Mg3 F10 4- }∞ layer in Cs4 Mg3 F10 , and with the (CH3 )4 N+ cations locating in the inorganic layer voids and between the interlayers. Two reversible structural phase transitions occur in 1 at 225/210 K and 328/325 K upon heating/cooling, respectively. On going from the low- to intermediate-temperature phase, the space group changes from P21 /c to Cmca, and the crystallographic axis perpendicular to the layers is doubled with the order-disorder transformation of (CH3 )4 N+ cations between the interlayers. The intermediate- and high-temperature phases are isomorphic with similar cell parameters and packing structure; their main difference concerns the disorder degree of the (CH3 )4 N+ cations between the interlayers. The two-step structural phase transitions lead to dielectric anomalies around the corresponding Tc . Interestingly, 1 shows multiband emission, originating from the recombination of exciton and emission of defects. Moreover, 1 exhibits divergent thermochromic luminescent features around the Tc on the intermediate to low temperature transition.

Mechanisms of piperonyl butoxide cytotoxicity and its enhancement with imidacloprid and metals in Chinese hamster ovary cells.

The widespread use of chemicals and the presence of chemical and metal residues in various foods, beverages, and other consumables have raised concerns about the potential for enhanced toxicity. This study assessed the cytotoxic effects of Piperonyl butoxide (PBO) and its enhancement by combination with major contamination chemicals including Imidacloprid and metals, using different cytotoxic and genotoxic assays in Chinese hamster ovary (CHO) cells. PBO exhibited elevated cytotoxic effects in poly (ADP-ribose) polymerase (PARP) deficient CHO mutants but not in Glutathione S-transferase deficient CHO mutants. PBO cytotoxicity was enhanced by PARP inhibitor, Olaparib. PBO cytotoxicity was also enhanced with co-exposure to Imidacloprid, Lead Chloride, or Sodium Selenite. PBO induces γH2AX foci formation and apoptosis. The induction of DNA damage markers was elevated with PARP deficiency and co-exposure to Imidacloprid, Lead Chloride, or Sodium Selenite. Moreover, PBO triggers to form etch pits on plastic surfaces. These results revealed novel mechanisms of PBO cytotoxicity associated with PARP and synergistic effects with other environmental pollutants. The toxicological mechanisms underlying exposure to various combinations at different concentrations, including concentrations below the permitted limit of intake or the level of concern, require further study.

Precursor Engineering of Lead Acetate-Based Precursors for High-Open-Circuit Voltage Wide-Bandgap Perovskite Solar Cells.

Wide-bandgap (WBG) perovskites have great potential for inclusion in efficient tandem solar cells, but large open-circuit voltage losses have limited device performance to date. Here, we show that a high-quality WBG perovskite, FA0.83Cs0.17Pb(I0.8Br0.2)3, with enlarged grain sizes and improved crystallinity can be achieved by incorporating lead chloride (PbCl2) into a lead acetate (PbAc2)-based precursor. The improved film quality resulted in the suppression of nonradiative recombination and a reduction in defect density. Efficient WBG perovskite solar cells (1.66 eV) with an efficiency of 19.3% and a high Voc of 1.22 V were fabricated using a facile one-step spin-coating method without the need for an antisolvent. Notably, the unencapsulated devices retained 90% of their initial power conversion efficiency after storage in a dry box (10% humidity) for 800 h.

Probing the effects of different lead compounds on the bioavailability of lead to plants.

Lead (Pb) is an important pollutant and is released into the environment in many forms. Different lead compounds have a variety of solubilities and so may impact on lead bioavailability and toxicity when added to soil. In this experimental study, we investigated the bioavailability of Pb in soil spiked with 300, 900 and 1500 mg/kg of Pb-acetate, PbCl2 and PbO using lettuce and wallaby grass. The concentration of Pb in the shoots of both species from control soils (2-3 mg/kg) was similar to previously reported concentrations in plants grown on uncontaminated soils. The Pb concentrations in the plant shoots increased with Pb concentrations in soil for lettuce (R2 = 0.526, P < 0.001) and wallaby grass (R2 = 0.776, P < 0.001). This study demonstrated that Pb bioavailability in soil was not affected by the type of Pb compound added to the soil for both plant species up to 1500 mg/kg Pb concentrations. Instead, the Pb concentration in the plant was best predicted by the total concentration of lead in the soil, irrespective of the original lead compound added to the soil. This research suggests that the original Pb compounds that contaminated the soil are unlikely to be an important factor in assessing Pb bioavailability, and hence risk, in soils.

Environmental benchmarks based on ecotoxicological assessment with planktonic species might not adequately protect benthic assemblages in lotic systems.

Freshwater ecosystems face widespread diffuse and point-source contamination. Species Sensitivity Distributions (SSDs) have been used as a tool to determine chemical concentration benchmarks that represent protective levels for most species in the environment. Here we used a SSD approach to assess on the adequacy of standard planktonic organisms to reflect the response of benthic communities, critically supporting the structure and function of lotic ecosystems. For the purpose, SSDs reflecting non-lethal responses of standard planktonic and selected benthic organisms were built based on EC50 values (collected in the literature or estimated following testing herein) regarding three model contaminants: potassium dichromate (PD), 3,5-dichlorophenol (DCP) and lead chloride (LC). The derived HC5 estimates were discriminatory between chemicals and the uncertainty associated with the estimate was remarkably low. The HC5 estimates with corresponding uncertainty were generally within the same order of magnitude for the three chemicals tested, with better discrimination between chemicals regarding their hazardous potential being achieved for benthic organisms: DCP was clearly less hazardous than PD, but LC tends to be as hazardous as PD and DCP (assuming the confidence interval ranges). Moreover, benthic communities were more sensitive to both DCP and PD, in this later case the HC5 being lower by more than one order of magnitude than that found for planktonic communities; for LC, confidence intervals overlapped, preventing a feasible assumption regarding differential sensitivity of the compared communities. Microphytobenthos was highlighted as the most sensitive group to the three tested chemicals in SSDs covering the benthic compartment, while SSDs with planktonic organisms did not consistently show trends in sensitivity ordering. Overall, our results suggest that protective benchmarks retrieved from SSDs built with the responses of standard planktonic organisms (which are the most commonly used for regulation purposes) do not adequately protect benthic communities.

Fast and Sensitive Solution-Processed Visible-Blind Perovskite UV Photodetectors.

The first visible-blind UV photodetector based on MAPbCl3 integrated on a substrate exhibits excellent performance, with responsivities reaching 18 A W(-1) below 400 nm and imaging-compatible response times of 1 ms. This is achieved by using substrate-integrated single crystals, thus overcoming the severe limitations affecting thin films and offering a new application of efficient, solution-processed, visible-transparent perovskite optoelectronics.

Multifunctional effect of Al2O3, SiO2 and CaO on the volatilization of PbO and PbCl2 during waste thermal treatment.

Minerals including Al2O3, SiO2 and CaO are predominant matrixes in waste, and are thought to facilitate lead (Pb) emission control. This study distinguished the inhibition of each mineral on common stable Pb-containing compounds, including highly volatile PbCl2 and less volatile PbO. Al2O3 can lower the volatilization temperature of Pb by 29 °C due to the generation of a eutectic compound and play a minor but non-negligible role in reducing Pb volatilization. The most conspicuous inhibition effect was exerted by SiO2 and a mixture of Al2O3 and SiO2, which completely integrated PbO into the glass phase at 690 °C and prohibited its migration. In contrast, SiO2 had no significant inhibition on volatile PbCl2. CaO inhibited PbO volatilization in the absence of oxygen by controlling its diffusion, while it converted PbO to Ca2PbO4 in the presence of oxygen, thus controlling Pb diffusion and decreasing the Pb volatilization ratio and rate. The influence of CaO on PbCl2 was complex because CaO can convert PbCl2 to PbO with formation of CaCl2, and CaCl2 can also be a Cl-donor for PbO. The roles of mineral matrixes in Pb conversion were shown to be important for Pb emission control.

Autophagy plays a protective role in cell death of osteoblasts exposure to lead chloride.

Lead (Pb) is a toxic heavy metal widespreadly used in industrial field. Prior studies showed that Pb exposure had detrimental effects on osteoblasts. The mechanisms underlying Pb-induced damage are complex. Autophagy can protect cells from various cytotoxic stimuli. In the present study, the aim of our research was to investigate whether Pb could activate autophagy to play a protective role against osteoblasts apoptosis. Our results indicated that PbCl2 induced autophagy and autophagic flux in MC3T3-E1 murine osteoblastic cell by RT-PCR, western blot, as well as fluorescence microscopy analysis of GFP-LC3, AO and MDC staining. Pb increased the apoptosis of osteoblasts, evidenced by western blot and Hoechst 33258 staining assessment. In addition, inhibiting autophagy by 3-MA further increased the osteoblasts apoptosis after Pb exposure, showed by flow cytometry and Hoechst 33258 staining. Furthermore, phosphorylation of mTOR and p70S6K was inhibited by Pb exposure, indicating that Pb might induce autophagy in osteoblasts via inhibiting mTOR pathway. Altogether, these evidence suggested that Pb exporsure promoted autophagy flux in osteoblasts. The activation of autophagy by Pb played a protective role in osteoblasts apoptosis, which might be mediated through the mTOR pathway.

Probit analysis of comparative assays on toxicities of lead chloride and lead acetate to in vitro cultured human umbilical cord blood lymphocytes.

This work describes that cytotoxicity of lead chloride and lead acetate to in vitro cultured lymphocytes from human umbilical cord blood, using four monitoring methods namely, trypan blue staining, acridine orange/ethidium bromide staining, 3-[4,5-dimethylthiazol-2-yl] 2,5-diphenyl tetrazolium bromide (MTT) and neutral red uptake assays; lead genotoxicity to lymphocytes was monitored by comet assay. The MIC value in each method was invariably 300 mg/L for PbCl2. Lethal concentration25 (LC25) values were almost in an agreeable range: 691.83 to 831.76 mg/L; LC50 values in each method were almost in the range: 1174.9 to 1348.9 mg/L; LC100 values were in the range: 3000 to 3300 mg/L, for lead chloride. Similarly, The MIC value in each method were invariably 150 mg/L; LC25 values were almost in the range: 295.12 to 371.53 mg/L; LC50 values were in the range: 501.18 to 588.84 mg/L; LC100 value was 1500 mg/L in all assays, for lead acetate. The comet assay also indicated that the LC100 values were 3300 mg/L lead chloride and 1500 mg/L lead acetate. Thus, both cytotoxicity and genotoxicity were recorded at 3300 mg/L lead chloride and 1500 mg/L lead acetate with lymphocytes.