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Nanosized zinc sulfides (nano-ZnS) have size-dependent and tunable physical and chemical properties that make them useful for a variety of technological applications. For example, structural changes, especially caused by strain, are pronounced in nano-ZnS < 5 nm in size, the size range typical of incidental nano-ZnS that form in the environment. Previous research has shown how natural organic matter impacts the physical properties of nano-ZnS but was mostly focused on their aggregation state. However, the specific organic molecules and the type of functional groups that are most important for controlling the nano-ZnS size and strain remain unclear. This study examined the size-dependent strain of nano-ZnS synthesized in the presence of serine, cysteine, glutathione, histidine, and acetate. Synchrotron total scattering pair distribution function analysis was used to determine the average crystallite size and strain. Among the different organic molecules tested, those containing a thiol group were shown to affect the particle size and size-induced strain most strongly when added during synthesis but significantly reduced the particle strain when added to as-formed nano-ZnS. The same effects are useful to understand the properties and behavior of natural nano-ZnS formed as products of microbial activity, for example, in reducing environments, or of incidental nano-ZnS formed in organic wastes.

This paper is focused on the in vivo release and biocompatibility evaluation in rats of some novel systems entrapping zinc chloride in lipid vesicles. The particles were prepared by zinc chloride immobilization inside lipid vesicles made using phosphatidylcholine, stabilized with 0.5% chitosan solution, and dialyzed for 10 h to achieve a neutral pH. The submicrometric systems were physico-chemically characterized. White Wistar rats, assigned into four groups of six animals each, were treated orally with a single dose, as follows: Group I (control): deionized water 0.3 mL/100 g body weight; Group II (Zn): 2 mg/kg body weight (kbw) zinc chloride; Group III (LV-Zn): 2 mg/kbw zinc chloride in vesicles; Group IV (LVC-Zn): 2 mg/kbw zinc chloride in vesicles stabilized with chitosan. Haematological, biochemical, and immune parameters were assessed after 24 h and 7 days, and then liver fragments were collected for histopathological examination. The use of zinc submicrometric particles-especially those stabilized with chitosan-showed a delayed zinc release in rats. No substantial changes to blood parameters, plasma biochemical tests, serum complement activity, or peripheral neutrophils phagocytic capacity were noted; moreover, the tested substances did not induce liver architectural disturbances. The obtained systems provided a delayed release of zinc, and showed good biocompatibility in rats.

Despite the versatility of quantum dots (QDs) in optoelectronics and biomedical field, their toxicity risks remain a considerable hindrance for clinical applications. Cytotoxicity of Cadmium containing QDs is well documented and reveals that they are toxic to cells. Reports suggest that the presence of toxic elements at the QD core (e.g., cadmium, selenium) is responsible for its toxicity in in vivo and in vitro levels. Hence, here the toxicity of heavy metal free ZnSe/ZnS QDs on two scenarios were assessed, (i) HEK cells as in vitro system and (ii) Swiss Albino mice as in vivo model. Before toxicity analysis, QDs subjected to various optical and physico-chemical characterization methods such as absorption and emission spectra analysis, observation under U.V light, TEM, DLS, Zeta potential, FTIR, Raman and XPS spectra, ICP-OES, TGA and DTG curve. It is very necessary to characterize the synthesized QDs because their toxicity greatly influenced by the physico-chemical properties. On checking the vulnerability of HEK cells on exposure to ZnSe/ZnS QDs, the obtained results disclose that ZnSe/ZnS QDs showed merest impact on cellular viability at a concentration less than 100 μg/ml. Acute toxicity of 10 mg/kg ZnSe/ZnS QDs was studied in mice and no clinical or behavioural changes were observed. It did not induce any changes in haematological parameters and any loss of body or organ weight. Moderate pathological changes were evident only in the liver, all others organs like kidney, spleen and brain did not show any manifestations of toxicity. Current work lays substantial bedrock for safe biomedical and environmental application of ZnSe/ZnS QDs in near future., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Rationale: Determination of phosphine exposure from zinc or aluminum phosphide fumigants continues to be a routine analytical requirement in veterinary forensic toxicology. There is a need for a more reliable and specific method than simple gas chromatography/mass spectrometry (GC/MS) analysis of sample solvent extracts, as GC/MS of extracts on capillary columns used for general screens involves significant interference from air peaks., Methods: GC/MS/MS headspace analysis of acid-generated phosphine gas enabled study of the feasibility of devising multiple reaction monitoring (MRM) approaches to the determination of phosphine with greater specificity., Results: Collision-induced dissociation in GC/MS/MS showed that phosphine generated m/z 34 → 31, 32 and 33 ion transitions by sequential proton release as well as minor transitions m/z 34 → 47, 34 → 63 and 63 → 31.5 by intermolecular collisions and double charging. Study of the formation of these product ions enabled development of MRM settings for a highly useful headspace method for phosphine detection., Conclusions: The method was validated over a working range of 5-100 ppm of phosphide generating phosphine gas which enabled retention of regular screen capillary columns without necessitating separation from air components. The method should have adequate sensitivity and reliability for veterinary toxicology laboratories confronting specimens from animals poisoned by crop fumigants., (© 2020 John Wiley & Sons, Ltd.)

Toxicity and transport of metal-based nanoparticles (M-NPs) in environmental waters strongly depend on their speciation. A detailed understanding of the composition and speciation of M-NPs is necessary in order to move this field forward. Unfortunately, there is a shortage of analytical methods for metal-sulfide nanoparticles (MS-NPs) in the environment. In this work, a cloud point extraction (CPE) method combined with liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (LC-ICPMS) is developed for sensitive determination of Ag 2 S- and ZnS-NPs. Under the condition of 0.15% (w/v) of Triton X-114 (TX-114), pH 5, 20 mM NaNO 3 , incubation temperature of 45 °C, and time of 15 min, MS-NPs and non-MS-NPs were extracted into the surfactant-rich phase. With the sequent addition of 10 mM bis(p-sulfonatophenyl)phenylphosphane dehydrate dipotassium (BSPP) aqueous solution (100 μL) into the CPE-obtained extract, the non-MS-NPs were selectively dissociated into their ionic counterparts while maintaining the original size and shape of Ag 2 S- and ZnS-NPs. Interestingly, the micelle-mediated behavior suddenly disappeared with the addition of BSPP. Thus, the extract can be injected to LC-ICPMS for speciation analysis of trace Ag 2 S- and ZnS-NPs. This method exhibited excellent reproducibility (relative standard deviations < 4.9%), high sensitivity with the respective detection limits of 8 ng/L for Ag 2 S-NPs and 15 ng/L for ZnS-NPs, enabling recoveries of 81.3-96.6% for Ag 2 S-NPs and 83.9-93.5% for ZnS-NPs when they were spiked into three environmental water samples. Due to its potential applicability to low concentrations of Ag 2 S- and ZnS-NPs, this method is particularly convenient for monitoring the transformations of AgNPs and ZnO-NPs in the environment.

The asymmetric flow field-flow fractionation (AF4) coupled on-line with elemental (inductively coupled plasma-mass spectrometry, ICP-MS) and molecular (fluorescence and UV) detection has been investigated as a powerful tool for the characterization of bioinorganic nano-conjugates. In this study, we described methods for the characterization of biotin-antibody complexes bioconjugated with streptavidin quantum dots (QDs-SA-b-Ab). Operating parameters of AF4 separation technique were optimized and two procedures are proposed using a channel thickness of 350 μm and 500 μm. The use of a 500 μm spacer allowed to achieve an efficient AF4 separation of the QDs-SA-b-Ab complexes from the excess of individual species used in the bioconjugation that was required for a proper characterization of the bioconjugates. Optimization of the AF4 allowed a separation resolution good enough to isolate the QDs-SA-b-Ab bioconjugates from the free excess of b-Ab and QD-SA. The efficiency of the bioconjugation process could be then calculated, obtaining a value of 86% for a 1 QDs-SA: 5 b-Ab bioconjugation ratio. In addition, sample recovery around 90% was achieved., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Colloidal CdSe/ZnS quantum dots were water solubilized by overcoating with an amphiphilic polymer. Human serum albumin (HSA) as a model protein was either adsorbed or chemically linked to the surface of the polymer-coated quantum dots. As the quantum dots are intrinsically fluorescent, and as the polymer coating and the HSA were fluorescent labeled, the final nanoparticle had three differently fluorescent components: the quantum dot core, the polymer shell, and the human serum albumin corona. Cells were incubated with these hybrid nanoparticles, and after removal of non-internalized nanoparticles, exocytosis of the three components of the nanoparticles was observed individually by flow cytometry and confocal microscopy. The data indicate that HSA is partly transported with the underlying polymer-coated quantum dots into cells. Upon desorption of proteins, those initially adsorbed to the quantum dots remain longer inside cells compared to free proteins. Part of the polymer shell is released from the quantum dots by enzymatic degradation, which is on a slower time scale than protein desorption. Data are quantitatively analyzed, and experimental pitfalls, such as the impact of cell proliferation and fluorescence quenching, are discussed.

Background: Cadmium (Cd) exposure has adverse health effects in children. Diet contributes to Cd exposure, but dietary components could affect body Cd levels., Objective: To examine associations between diet and urinary Cd (U-Cd) in children., Methods: In this cross-sectional study conducted in Montevideo, Uruguay, Cd exposure of 5-8 year old children (n = 279 with complete data) was assessed in first morning urine (U-Cd), a marker of long-term exposure, measured by ICP-MS and adjusted for specific gravity. Distribution of U-Cd was (median [5%, 95%]: 0.06 [0.02, 0.17] μg/L); data were natural-log-transformed (ln) for statistical analyses. Serum ferritin (SF), an indicator of iron stores, was measured in fasting samples. Trained nutritionists completed two non-consecutive 24-h dietary recalls with both child and caregiver present. Measures of iron, zinc, calcium and fiber intake, and the consumption of grains, root vegetables, milk, and foods rich in heme iron (white and read meats) and non-heme iron (legumes, spinach, broccoli, tomatoes, dried fruit) were derived. Multivariable ordinary least squares (OLS) and ordinal regressions were used to examine associations among tertiles of water Cd, SF, diet, and U-Cd. OLS models were further stratified by sex., Results: In covariate-adjusted models, SF was not related to ln-U-Cd. Children in highest tertile of iron and zinc intake had lower ln-U-Cd: (-0.23 [-0.42, -0.03]) and (-0.25 [-0.44, -0.05]), respectively, compared to the reference group. Children consuming higher amounts of foods rich in heme iron had slightly lower ln-U-Cd (-0.17 [-0.36, 0.03]). High grain consumption was related to higher ln-U-Cd (0.25 [0.06, 0.45])., Conclusions: Diets rich in grains were related to higher urinary Cd levels among children living in the context of low Cd pollution. Higher intake of iron and zinc was related to lower Cd levels. Given that urinary Cd is mainly a marker of long-term exposure, these findings should be further corroborated., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A current remaining challenge in nanotechnology is the fast and reliable determination of the ratios between engineered nanoparticles and the species attached to their surface after chemical functionalization. The approach proposed herein based on the online coupling of asymmetric flow field-flow fractionation (AF4) with inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS) allows for the first time the direct determination of such ratios in CdSe/ZnS core-shell quantum dot:rat monoclonal IgG2a antibody (QD:Ab) conjugate mixtures in a single run without any previous sample preparation (i.e., derivatization). AF4 provides full recovery and adequate resolution of the resulting bioconjugate from the excess of nanoparticles and proteins used in the different bioconjugation mixtures (1:1, 2:1, and 3:1 QD:Ab molar ratios were assessed). The point-by-point determination by ICP-MS/MS of the metal to sulfur ratios along the bioconjugate fractographic peak allowed disclosing the mixture of the different species in the bioconjugated sample, providing not only the limits of the range of QD:Ab ratios in the different bioconjugate species resulting after functionalization but also a good estimation of their individual relative abundance in the mixture. Interestingly, a wide variety of compositions were observed for the different bioconjugate mixtures studied (QD:Ab molar ratios ranging from 0.27 to 4.6). The resulting weighted QD:Ab ratio computed in this way for each bioconjugate peak matches well with both the global (average) QD:Ab ratio experimentally obtained by the simpler peak area ratio computation and the theoretical QD:Ab molar ratios assayed, which internally validates the procedure developed.

Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0-80 mg/kg of Zn, 5.4-60 mg/kg of Fe and 0.5-4.5 mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.

Solid phase speciation of chromium in dry dust deposition and road paint was determined using transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS). Spherical black carbon aggregates in dry dust deposition contained discrete nano-sized lead chromate (PbCrO 4 ) and zinc chromate (ZnCrO 4 ), which likely originated from yellow traffic paint and zinc chromate primer (corrosion resistant pigment), respectively based on their main applications. Road marking paint samples from auto roads included lead chromate particles whose size, shape, composition and crystal structure were similar to those in dry dust deposition. A slight difference was found at the particle boundary. Namely, lead chromate in traffic paint was encapsulated by silica-bearing matrix, while discrete lead chromate in the black carbon of dry deposition was rarely enclosed within silica-bearing matrix. The Cr K edge X-ray absorption near edge structure (XANES) spectrum for dry deposition showed the characteristic pre-edge resonance peak similar to the spectra for the Cr(VI) standard and road paint, but the lower intensity. The amount of Cr(VI) accounted for approximately 45% of the total Cr in the dust sample. The solid phase speciation of Cr observed using TEM and their valence states determined using XANES were consistent with the chemical speciation determined using the sequential extraction. The contribution of this study is that XANES was applied to identify Cr valance states in urban dust deposition and zinc chromate was found as a Cr(VI) phase in dry dust deposition using TEM. These study results provide novel data on Cr speciation and Cr(VI)-containing mineral phases in dry dust deposition and their potential sources. Based on the wide use of lead and zinc chromate, atmospheric contamination with these solid phase speciation of Cr(VI) is expected in other cities in the world., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A moisture-sensitive 2-acetyl-1-pyrroline zinc chloride complex (2AP-ZnCl 2 ) was successfully encapsulated by spray-chilling, using a hydrophobic moisture barrier as a practical way to protect the complex and to help facilitate its general use in food applications. Use of octacosane as wall material provided a flavor retention of 65.3%. The results from scanning electron microscopy (SEM) and X-ray micro-computed tomography (X-ray micro-CT) indicated desirable morphological characteristics of the matrix type microcapsules. Gas chromatography (GC) and absorbance spectroscopy were used for chemical quantitation of 2AP and ZnCl 2 , respectively, in the microcapsules. Results revealed no degradation of 2AP occurred as a result of the encapsulation process. This study is the first to demonstrate the feasibility of producing high quality microcapsules from labile flavor complexes by spray-chilling. The use of generally recognized as safe (GRAS) substances, including 2AP and ZnCl 2 , may allow for widespread commercial use of 2AP as a flavor ingredient., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Ischaemia-reperfusion injury (IRI) during various surgical procedures, including partial nephrectomy for kidney cancer or renal transplantation, is a major cause of acute kidney injury and chronic kidney disease. Currently there are no drugs or methods for protecting human organs, including the kidneys, against the peril of IRI. The aim of this study was therefore to investigate the reno-protective effect of Zn 2+ preconditioning in a clinically relevant large animal sheep model of IRI. Further the reno-protective effectiveness of Zn 2+ preconditioning was tested on normal human kidney cell lines HK-2 and HEK293. Anaesthetised sheep were subjected to uninephrectomy and 60 min of renal ischaemia followed by reperfusion. Sheep were preconditioned with intravenous injection of zinc chloride prior to occlusion. Serum creatinine and urea were measured before ischaemia and for 7 days after reperfusion. HK-2 and HEK293 cells were subjected to in vitro IRI using the oxygen- and glucose-deprivation model. Zn 2+ preconditioning reduced ischaemic burden determined by creatinine and urea rise over time by ~ 70% in sheep. Zn 2+ preconditioning also increased the survival of normal human kidney cells subjected to cellular stress such as hypoxia, hydrogen peroxide injury, and serum starvation. Overall, our protocol incorporating specific Zn 2+ dosage, number of dosages (two), time of injection (24 and 4 h prior), mode of Zn 2+ delivery (IV) and testing of efficacy in a rat model, a large preclinical sheep model of IRI and cells of human origin has laid the foundation for assessment of the benefit of Zn 2+ preconditioning for human applications.

Objectives: The purpose was to evaluate a combined effect of active ingredients contained in new toothpaste in reducing dentine hypersensitivity., Methods: The tested toothpaste contained active ingredients potassium nitrate (5.00%) and zinc citrate (0.50%). Pain to water stimulus and blowing air was reported on hypersensitive teeth and measured using the VAS (Visual Analogue Scale). The degree of pain to water stimulus was detected after each subject drank a few sips of water which was boiled to the room temperature. Data were collected on each subject's dental history., Results: A significant reduction in dentine hypersensitivity (26-29% after 2 weeks versus 40% after 4 weeks) was detected in the tested group. The controls also showed significant reduction to both stimuli, but at lower rate. A statistically significant difference to blowing air and water stimuli showed the highest impact for the tested group after 4 weeks (P = 0.033, P = 0.006)., Conclusion: This study supports the efficacy of the tested toothpaste in reducing the phenomenon of dentine hypersensitivity after 4 weeks of usage., (© 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

The retention of CdS/ZnS QDs on the epidermis has been confirmed to be one of the core procedures during the root uptake process. However, the retention mechanisms of QDs on the epidermis of woody plant were poorly understood for lacking of an appropriate QD quantitative method. In this study, a novel method for in situ determination of CdS/ZnS QDs retained on the root epidermis was established using synchronous nanosecond time-resolved fluorescence spectroscopy. No correlations between K f values of oleylamine-CdS/ZnS QDs retained on the epidermal tissues and the surface/bulk composition of mangrove root were observed (p > 0.05) due to the existence of endocytosis mechanisms during the QD uptake processes. Moreover, the difference of the CdS/ZnS QDs in water and further translocated to xylem/phloem of root rather than the combination with cell wall/membranes was the predominant reason that caused the K f values to follow the sequence of PEG-COOH-CdS/ZnS QDs < PEG-NH 2 -CdS/ZnS QDs ≪ oleylamine-CdS/ZnS QDs.

A simple fluorescence turn-on sensor has been designed for the highly sensitive detection of glycoproteins on the basis of boronic acid functional polymer capped Mn-doped ZnS quantum dots (QDs@MPS@AAPBA). In the absence of glycoproteins, the fluorescence emission intensity of the QDs@MPS@AAPBA was relatively weaker due to the effective electronic transfer from the QDs to the boron moieties on its surface. While the glycoproteins were introduced into the system, an obvious fluorescence enhancement was observed. It was attributed to the boron moieties covalent binding glycans of the glycoproteins resulting in the electronic transfer process being inhibited. Under the optimal conditions, this fluorescent probe not only could be applied in a wide pH range of 5.0-9.0, but also the binding constants and detection limits of the QDs@MPS@AAPBA for horseradish peroxidase (HRP) and transferrin (TRF) were up to 7.23 × 10 6  M -1 , 1.53 × 10 7  M -1 and 1.44 × 10 -10  M, 3.36 × 10 -10  M, respectively. Finally, this proposed method has also been utilized for the TRF determination in serum without any complicated pretreatment and the recovery was in the range of 95.7%-103.0%. As a result, it is promising for application on the glycoproteins detection in complex biological samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

This article deals with health risks resulting from exposure to zinc and its inorganic compounds in industry. The main source of zinc exposure are fumes generated during thermal and chemical processes, mainly zinc oxide fume formed by immediate oxidation of metallic zinc vapor formed during high-temperature processes, as well as dust generated during the mechanical processing of zinc-containing materials. It is recognized that zinc ions are responsible for health effects of exposure to dust/fumes of the majority of zinc compounds, and the final effect of exposure depends on the degree of dispersion of dusts/fumes suspended in the air. Since the effects of exposure depends on the particle size, occupational exposure limits have began to be established separately for respirable and inhalable fractions. A critical effect of acute exposure to respirable fraction is a "fume fever" which in chronic exposure occurs as an effect associated with recurrent symptoms of acute poisoning. Impaired lung function and asthma symptoms are considered to be the main effects of exposure to inhalable fraction. Due to the limited number of the available data it is not possible to assess carcinogenicity, reproductive toxicity and teratogenicity of zinc and its compounds. The aim of the study was to analyze the major health hazards resulting from occupational exposure to zinc and its inorganic compounds in the context of their physico-chemical properties, a wide range of applications and occupational exposure data. Med Pr 2017;68(6):779-794., (This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.)

The aim of this study was to ascertain the effect of Zn-doping of dental adhesives and mechanical load cycling on the micromorphology of the resin-dentin interdiffusion zone (of sound and caries affected dentin). The investigation considered two different Zn-doped adhesive approaches and evaluated the interface using a doubled dye fluorescent technique and a calcium chelator fluorophore under a confocal laser scanning microscopy. Sound and carious dentin-resin interfaces of unloaded specimens were deficiently resin-hybridized, in general. These samples showed a rhodamine B-labeled hybrid layer and adhesive layer completely affected by fluorescein penetration (nanoleakage) through the porous resin-dentin interface. It was thicker after phosphoric acid-etching and more extended in carious dentin. Zn-doping promoted an improved sealing of the resin-dentin interface, a decrease of the hybrid layer porosity, and an increment of dentin mineralization. Load cycling augmented the sealing of the Zn-doped resin-dentin interfaces, as porosity and nanoleakage diminished, and even disappeared in caries-affected dentin substrata conditioned with EDTA. Sound and carious dentin specimens analyzed with the xylenol orange technique produced a clearly outlined fluorescence when resins were Zn-doped, due to a consistent Ca-mineral deposition within the bonding interface and inside the dentinal tubules. It was more evident when load cycling was applied on specimens treated with self-etching adhesives that were Zn-doped. Micropermeability at the resin-dentin interface diminished after combining EDTA pretreatment, ZnCl 2 -doping and mechanical loading stimuli on restorations. It is clearly preferable to include the zinc compounds into the bonding constituents of the self-etching adhesives, instead of into the primer ingredients. The promoted new mineral segments contributed to reduce or avoid both porosity and nanoleakage from the load cycled Zn-doped resin dentin interfaces. EDTA+SB-ZnCl 2 or SEB·Bd-Zn doping are preferred to treat caries-affected dentin surfaces. ZnO-doping encouraged for etch-and-rinse adhesives., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Background: Nanoparticle interactions with cellular membranes and the kinetics of their transport and localization are important determinants of their functionality and their biological consequences. Understanding these phenomena is fundamental for the translation of such NPs from in vitro to in vivo systems for bioimaging and medical applications. Two CdSe/ZnS quantum dots (QD) with differing surface functionality (NH 2 or COOH moieties) were used here for investigating the intracellular uptake and transport kinetics of these QDs., Results: In water, the COOH- and NH 2 -QDs were negatively and positively charged, respectively, while in serum-containing medium the NH 2 -QDs were agglomerated, whereas the COOH-QDs remained dispersed. Though intracellular levels of NH 2 - and COOH-QDs were very similar after 24 h exposure, COOH-QDs appeared to be continuously internalised and transported by endosomes and lysosomes, while NH 2 -QDs mainly remained in the lysosomes. The results of (intra)cellular QD trafficking were correlated to their toxicity profiles investigating levels of reactive oxygen species (ROS), mitochondrial ROS, autophagy, changes to cellular morphology and alterations in genes involved in cellular stress, toxicity and cytoskeletal integrity. The continuous flux of COOH-QDs perhaps explains their higher toxicity compared to the NH 2 -QDs, mainly resulting in mitochondrial ROS and cytoskeletal remodelling which are phenomena that occur early during cellular exposure., Conclusions: Together, these data reveal that although cellular QD levels were similar after 24 h, differences in the nature and extent of their cellular trafficking resulted in differences in consequent gene alterations and toxicological effects.

Rhodium(I)-complexes catalyzed the 1,4-conjugate addition of arylzinc chlorides to N -Boc-4-pyridone in the presence of chlorotrimethylsilane (TMSCl). A combination of [RhCl(C₂H₄)₂]₂ and BINAP was determined to be the most effective catalyst to promote the 1,4-conjugate addition reactions of arylzinc chlorides to N -Boc-4-pyridone. A broad scope of arylzinc reagents with both electron-withdrawing and electron-donating substituents on the aromatic ring successfully underwent 1,4-conjugate addition to N -Boc-4-pyridone to afford versatile 1,4-adducts 2-substituted-2,3-dihydropyridones in good to excellent yields (up to 91%) and excellent ee (up to 96%) when ( S )-BINAP was used as chiral ligand.

Nd 3 + -doped lead-free zinc phosphate glasses with the chemical compositions (60-x) NH 4 H 2 PO 4  + 20ZnO + 10BaF 2  + 10NaF + xNd 2 O 3 (where x = 0.5, 1.0, 1.5, 2.0 and 2.5 mol%) were prepared using a melt quenching technique. Vibrational bands were assigned and clearly elucidated by Raman spectral profiles for all the glass samples. Judd-Ofelt (J-O) intensity parameters (Ω λ : λ = 2, 4, 6) were obtained from the spectral intensities of different absorption bands of Nd 3 + ions. Radiative properties such as radiative transition probabilities (A R ), radiative lifetimes (τ R ) and branching ratios (β R ) for different excited states were calculated using J-O parameters. The near infrared (NIR) photoluminescence spectra exhibited three emission bands ( 4 F 3 /2 level to 4 I 13 /2 , 4 I 11 /2 and 4 I 9 /2 states) for all the concentrations of Nd 3 + ions. Various luminescence properties were studied by varying the Nd 3 + concentration for the three spectral profiles. Fluorescence decay curves of the 4 F 3 /2 level were recorded. The energy transfer mechanism that leads to quenching of the 4 F 3 /2 state lifetimes was discussed at higher concentration of Nd 3 + ions. These glasses are suggested as suitable hosts to produce efficient lasing action in NIR region at 1.05 μm., (Copyright © 2016 John Wiley & Sons, Ltd.)

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The mineral body exploited in Salafossa (Eastern Dolomites) was one of the largest lead/zinc-containing mineral deposits in Europe. Both metals were mainly present as sulphides (sphalerite, ZnS and galena, PbS). Mining activity started around 1550, but it was only around 1960 that the richest veins of the minerals were discovered. The mine closed in 1985, and concentrations of several trace metals, such as thallium (Tl), iron (Fe), manganese (Mn), lead (Pb) and zinc (Zn), were detected in the soils and plant samples (Biscutella laevigata L.) that were collected from eighteen sites selected outside the mine. B. laevigata is a pseudometallophyta species, and it often grows near mining areas where the soil's metal concentrations are significantly higher than those of soil with a natural geochemical background. The total metal concentrations in the plant tissue (roots and leaves of Biscutella laevigata) and in the soil samples - both bulk-soil and the B. laevigata root system (rhizo-soil) - were determined through Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The metal extractability and leachability of the soil samples were estimated using soil extractions with DTPA (Diethylenetriaminepentaacetic acid). In addition, metal mobility caused by rainwater runoff was estimated by using a leaching test with a dilute solution of H 2 SO 4 and HNO 3 . The results showed that metals were present in a chemical form available for uptake by the plants' roots. In fact, high concentrations of the metals were also found in the plant tissue (roots and leaves) of B. laevigata, and these concentrations were higher than those whose soils present natural geochemical background levels in the corresponding rhizo-soil. Thus, B. laevigata has shown a marked ability to bioaccumulate trace metals, especially Tl and, to a lesser extent, Zn, Pb, Fe and Mn, and it can influence metal mobility in the rhizo-soil. To assess the uptake and translocation processes of the trace metals, resulting in their bioaccumulation, two different indices were calculated: the enrichment factor in roots (EFr), as the ratio between the metal concentration in belowground biomass and in the respective rhizo-soil, and the translocation factor (TF), as the ratio between the metal concentration in the leaves and the corresponding roots. For both indices, values > 1 denoted enrichment of the metal in the roots or its translocation to the upper tissues. The results showed that EFr and TF were considerably high only for Tl, reaching a maximum value of 60 for EFr and 11.6 for TF. Conversely, the other investigated metals did not show significant bioaccumulation (EFr < 1), and they showed TF > 1 only at a few sites., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Zinc oxide nanoparticles (ZnO NPs) are one of the most abundantly applied nanomaterials in nanotechnology-based industries and they may cause unexpected environmental and health risks with their physicochemical transformations in the environment. Currently, there is still a lack of the in-depth understanding of the toxicity of aged ZnO NPs to aquatic organisms, particularly demanding quantitative analysis of the physicochemical transformations to distinguish their contributions in the toxicity assessment. For this purpose, therefore, we initiated the study of the toxicity of aged ZnO NPs to the model aquatic microalga, i.e. Chlorella vulgaris, and with the aid of spectroscopic tools for characterization and quantification of the physicochemical transformations, we scrutinized the toxicity variations for ZnO NPs with different aging times. As a result, we found that the toxicity altered in an abnormal manner with the aging time, i.e. the toxicity of aged ZnO NPs for 30 days showed the higher toxicity to the green alga than the fresh ZnO NPs or the ZnO NPs aged for longer time (e.g. 120 and 210 days). Through spectroscopic tools such as XRD, FTIR and Raman spectroscopy, we made both the qualitative and quantitative assessments of the physicochemical changes of the ZnO NPs, and confirmed that in the early stage, the toxicity mainly stemmed from the release of zinc ions, but with longer aging time, the neoformation of the nanoparticles played the critical role, leading to the overall reduced toxicity due to the less toxic hydrozincite and zinc hydroxide in the transformed compounds.

In veterinary medicine, the management of malignant skin wounds is highly challenging. We conducted a study on seven case animals (four dogs and three cats) which presented with malignant skin wounds. All seven animals had signs and symptoms which were controlled following treatment with a modified Mohs paste. Upon obtaining informed consent from their owners, the animals requiring management of malignant wounds were enrolled in this study. The modified Mohs paste was prepared by mixing zinc chloride, zinc oxide starch powder, glycerin, and distilled water. The modified Mohs paste was topically applied to and left to remain on the malignant wounds for one hour, under controlled conditions. Once the paste was removed, the wounds were irrigated with a solution of sterile saline. At the first examination, the wounds of each animal were observed for signs of exudate, malodor, and bleeding. In every case, visible improvement was observed immediately after the modified Mohs paste treatment. Specifically, the size of the malignant wounds, and the number of times the dressing gauze required changing, significantly decreased (p < 0.05 and p < 0.01, respectively). The open malignant skin wounds caused by mammary gland tumors disappeared in two cases. The Mohs paste has been shown to be a viable option for the palliative treatment in canine and feline malignant skin wound management.

In this work, we established a fluorescence resonance energy transfer (FRET) system between ZnSe:Mn/ZnS quantum dots and Hypocrellin A (HA, a photosensitizer used for photodynamic therapy of cancer) in aqueous solution, excited by four-photon. Here, the QDs are the donors and the HA are the acceptors. The four-photon-excited fluorescence resonance energy transfer spectrum was obtained under 1300nm femtosecond laser pluses. The experimental results indicated that the highest efficiency of FRET can reach up to 61.3%. Furthermore, the viability test in cancer cells was further demonstrated for biological applications of FRET system. When FRET occurs the cell killing rate of the cancer cells will reach to 84.8% with the 1mM concentration of HA. Our work demonstrates that while the four-photon excited FRET system is promising in both optics and biological applications, is also needs further investigation.

Although mining and mineral processing industry is a vast source of heavy metal pollutants, the formation and behavior of micrometer- and nanometer-sized particles and their aqueous colloids entered the environment from the technological media has received insufficient attention to date. Here, the yield and characteristics of ultrafine mineral entities produced by routine grinding of the Pb-Zn sulfide ore (Gorevskoe ore deposit, Russia) were studied using laser diffraction analysis (LDA), dynamic light scattering (DLS) and zeta potential measurement, microscopy, X-ray photoelectron spectroscopy, with most attention given to toxic lead species. It was revealed, in particular, that the fraction of particles less that 1 μm in the ground ore typical reaches 0.4 vol. %. The aquatic particles in supernatants were micrometer size aggregates with increased content of zinc, sulfur, calcium as compared with the bulk ore concentrations. The hydrodynamic diameter of the colloidal species decreased with time, with their zeta potentials remaining about -12 mV. The colloids produced from galena were composed of 20-50 nm PbS nanoparticles associated with lead sulfate and thiosulfate, while the surface oxidation products at precipitated galena were largely lead oxyhydroxides. The size and zeta potential of the lead-bearing colloids decreased with time down to about 100 nm and from -15 mV to -30 mV, respectively. And, conversely, lead sulfide nanoparticles were mobilized before the aggregates during redispersion of the precipitates in fresh portions of water. The potential environmental impact of the metal-bearing colloids, which is due to the large-scale production and relative stability, is discussed., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This paper reports the effect of particle size on the thermoluminescence (TL) of undoped ZnS nanoparticles. ZnS nanoparticles were prepared using a chemical precipitation method in which mercaptoethanol was used as the capping agent. The nanoparticles were characterized by X-ray diffraction, field emission gun-scanning electron microscopy and high-resolution transmission electron microscopy. When the concentrations of mercaptoethanol used are 0, 0.005, 0.01, 0.015, 0.025, 0.040 and 0.060 M, the sizes of the nanoparticles are 2.86, 2.81, 2.69, 2.40, 2.10, 1.90 and 1.80 nm, respectively. Initially, the TL intensity of UV-irradiated ZnS nanoparticles increases with temperature, attains a peak value Im for a particular temperature Tm, and then decreases with further increases in temperature. The values of both Im and Tm increase with decreasing nanoparticle size. Whereas the activation energy decreases slightly with decreasing nanoparticle size, the frequency factor decreases significantly as the nanoparticle size is reduced. The order of kinetics for the TL glow curve of ZnS nanoparticles is 2. Expressions are derived for the dependence of activation energy (Ea) and Tm on nanoparticle size, and good agreement is found between the experimental and theoretical results., (Copyright © 2015 John Wiley & Sons, Ltd.)

The influence of the chirality of semiconductor nanocrystals, CdSe/ZnS quantum dots (QDs) capped with L- and D-cysteine, on the efficiency of their uptake by living Ehrlich Ascite carcinoma cells is studied by spectral- and time-resolved fluorescence microspectroscopy. We report an evident enantioselective process where cellular uptake of the L-Cys QDs is almost twice as effective as that of the D-Cys QDs. This finding paves the way for the creation of novel approaches to control the biological properties and behavior of nanomaterials in living cells.

Daphnia magna were exposed to nano-sized CdSe/ZnS quantum dots (QDs) having three different surface coatings. QDs were investigated for their aqueous stability in the test media (hard reconstituted laboratory water) and for their uptake, elimination, and in-vivo dissolution. Positively charged QDs (QEI) and negatively charged QDs (QSH) were electrostatically stable, whereas neutrally charged QDs (QSA) showed aggregation and sedimentation over 48-h. After 24h of exposure to QDs (100μg/L as total Cd), the D. magna whole body Cd concentration significantly increased with no mortality for all QDs. Uptake patterns differed among the three coatings and Cd concentration reached 1460±50, 1014±99, and 584±81μg Cd/g dry wt for QEI, QSH, and QSA, respectively. Significant amounts of QEI and QSA (40% and 43%, respectively) remained in the D. magna after 24h of depuration, while 89% QSH were readily excreted within the initial 1h of the depuration stage. Soluble Cd was released from QDs during both the uptake and depuration. Release of Cd was higher in QEI and QSA than QSH, possibly resulting from the longer retention of QEI and QSA in the D. magna than QSH. These results imply that the surface charge of QDs plays a significant role in both the exposure to organisms and the in-vivo dissolution of nanoparticles., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Background: Inhaled zinc has been found in association with cardiopulmonary toxicity. However, limited human epidemiologic studies are available. This study analyzed the association between covariate-adjusted cardiovascular (CVD) mortality rates and zinc compound air releases in the United States., Methods: We conducted an ecological analysis on the association between zinc compound air releases for 1991-2000 using the Toxics Release Inventory database and average age-adjusted CVD mortality for 2006-2010, adjusting for race/ethnicity composition and several health and socioeconomic factors. Models were estimated for males and females and for metropolitan and nonmetropolitan counties., Results: Zinc compound air releases were positively associated with increased adjusted CVD mortality rates in all four models (β=0.0085, p<0.0001 for males in nonmetropolitan counties; β=0.0093, p<0.0001 for males in metropolitan counties; β=0.0145, p<0.0001 for females in nonmetropolitan counties; and β=0.0098, p<0.0001 for females in metropolitan counties). Results were largely robust to various sensitivity analyses., Conclusion: This study provides epidemiological evidence for possible CVD health impacts of inhaled zinc in the United States. Although the strongest effect was found for females in nonmetropolitan counties, the associations were consistent in nonmetropolitan or metropolitan counties for both genders., (Copyright © 2015 Elsevier Inc. All rights reserved.)

The supply of Cd, Cu, Fe, Pb, Zn, and Tl into a wetland in the industrial area of Upper Silesia, southern Poland via atmospheric precipitation and dust deposition has been counterbalanced by the biogenic metal sulfide crystallization in microsites of the thin (<30 cm) peat layer, despite the overall oxidative conditions in the wetland. Disequilibrium of the redox reactions in the peat pore water (pH 5.4-6.2) caused by sulfate-reducing microorganisms has resulted in the localized decrease in Eh and subsequent precipitation of micron- and submicron-sized framboidal pyrite, spheroidal ZnS and (Zn,Cd)S, and galena as revealed by high-resolution scanning electron microscopy (SEM)/energy dispersive spectrometer (EDS). Saturation index for each sulfide is at a maximum within the calculated Eh range of -80 and -146 mV. Lead was also immobilized in galena deposited in fungal filaments, possibly at a higher Eh. Thallium (up to 3 mg kg(-1)) in the peat strongly correlates with Zn, whereas Cu (up to 55 mg kg(-1)) co-precipitated with Pb. The metal sulfides occur within microbial exudates, which protect them from oxidation and mechanical displacement. Vertical distribution of toxic metals in the peat layer reflects differences in pollution loads from atmospheric deposition, which has been much reduced recently.

The potential uptake and trophic transfer of nanoparticles (NP) is not well understood so far and for ZnO NP the data presented in peer-reviewed literature is limited. In this paper the influence of surface functionalization on the uptake and depuration behavior of ZnO NP, ZnO-OH NP and ZnO-octyl NP in D. magna was studied. Bulk ZnO particles (≤5 μm) and ZnCl2 were used as references for uptake of particles and dissolved species of Zn, respectively. Furthermore, the trophic transfer of ZnO NP and ZnO-octyl NP from daphnids (Daphnia magna) to zebra fish (Danio rerio) was studied. For ZnO NP and ZnO-octyl NP fast uptakes in D. magna were observed, whereas no measurable uptake took place for ZnO-OH NP. Lower body burden of ZnCl2 was found compared to both ZnO NP and ZnO-octyl. Contrary, the body burden for bulk ZnO was higher than that of ZnO NP but lower than ZnO-octyl. The higher body burdens found for functionalized ZnO-octyl NP than for non-functionalized ZnO NP showed that that the functionalization of the NP has a high influence on the uptake and depuration behavior. Though no mortality was observed, the resulting body burdens were 9.6 times (ZnO NP) and 47 times (ZnO-octyl NP) higher than toxic levels reported for zinc in D. magna. Consequently, the zinc recovered in the animals was not solely due to soluble zinc, but agglomerates/aggregates of ZnO NP or ZnO-octyl NP contributed to the body burdens. The trophic transfer study showed uptake of both ZnO NP and ZnO-octyl NP reaching more than tenfold higher levels than those obtained through aqueous exposure in other studies. This study contributes to expand the available data on uptake behavior of differently functionalized ZnO NP in D. magna and the potential trophic transfer from zooplankton to fish., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In the current work, using ZnSe ZnS quantum dots (QDs) as representative nanoparticles, the affinities of seven anticancer drugs for bovine serum albumin (BSA) were studied using fluorescence resonance energy transfer (FRET). The FRET efficiency of BSA-QD conjugates can reach as high as 24.87% by electrostatic interaction. The higher binding constant (3.63×10(7)Lmol(-1)) and number of binding sites (1.75) between ZnSe ZnS QDs and BSA demonstrated that the QDs could easily associate to plasma proteins and enhance the transport efficacy of drugs. The magnitude of binding constants (10(3)-10(6)Lmol(-1)), in the presence of QDs, was between drugs-BSA and drugs-QDs in agreement with common affinities of drugs for serum albumins (10(4)-10(6)Lmol(-1)) in vivo. ZnSe ZnS QDs significantly increased the affinities for BSA of Vorinostat (SAHA), Docetaxel (DOC), Carmustine (BCNU), Doxorubicin (Dox) and 10-Hydroxycamptothecin (HCPT). However, they slightly reduced the affinities of Vincristine (VCR) and Methotrexate (MTX) for BSA. The recent work will not only provide useful information for appropriately understanding the binding affinity and binding mechanism at the molecular level, but also illustrate the ZnSe ZnS QDs are perfect candidates for nanoscal drug delivery system (DDS)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Objectives: Zinc salts are formulated into oral health products as antibacterial agents, yet their interaction with enamel is not clearly understood. The aim was to investigate the effect of zinc concentration [Zn(2+)] on the in vitro demineralization of enamel during exposure to caries-simulating conditions. Furthermore, the possible mechanism of zinc's action for reducing demineralization was determined., Methods: Enamel blocks and synthetic hydroxyapatite (HAp) were demineralized in a range of zinc-containing acidic solutions (0-3565ppm [Zn(2+)]) at pH 4.0 and 37°C. Inductively coupled-plasma optical emission spectroscopy (ICP-OES) was used to measure ion release into solution. Enamel blocks were analysed by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and HAp by X-ray diffraction (XRD) and neutron diffraction (ND)., Results: ICP-OES analysis of the acidic solutions showed a decrease in [Ca(2+)] and [PO4(3-)] release with increasing [Zn(2+)]. FTIR revealed a α-hopeite (α-Zn3(PO4)2.4H2O)-like phase on the enamel surfaces at >107ppm [Zn(2+)]. XRD and ND analysis confirmed a zinc-phosphate phase present alongside the HAp., Conclusions: This study confirms that zinc reduces enamel demineralization. Under the conditions studied, zinc acts predominantly on enamel surfaces at PO4(3-) sites in the HAp lattice to possibly form an α-hopeite-like phase., Clinical Significance: These results have a significant implication on the understanding of the fundamental chemistry of zinc in toothpastes and demonstrate its therapeutic potential in preventing tooth mineral loss., (Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Indoor exposures to metals arise from a wide variety of indoor and outdoor sources. This study investigates the impact of humid indoor conditions on the bioaccessibility of Zn in dust, and the transformation of Zn species during weathering. House dust samples were subjected to an oxygenated, highly humid atmosphere in a closed chamber for 4 to 5 months. Zinc bioaccessibility before and after the experiment was determined using a simulated gastric acid extraction. Bulk and micro X-ray absorption structure (XAS) spectroscopy was used to speciate Zn in dust. Exposure to humid conditions led to a significant increase in Zn bioaccessibility in all samples, which was due to a redistribution of Zn from inorganic forms toward the organic pools such as Zn adsorbed on humates. ZnO readily dissolved under humid conditions, whereas ZnS persisted in the dust. Elevated humidity in indoor microenvironments may sustain higher Zn bioaccessibility in settled dust compared to drier conditions, and part of this change may be related to fungal growth in humid dust. These results help to explain the greater bioaccessibility of certain metals in house dust compared to soils.

The vibration characteristics of an aluminum surface subjected to ultrasonic waves were investigated with a combination of numerical simulation and experimental testing. The wetting behavior of solder droplets on the vibrating aluminum surface was also examined. The results show that the vibration pattern of the aluminum surface is inhomogeneous. The amplitude of the aluminum surface exceeds the excitation amplitude in some zones, while the amplitude decreases nearly to zero in other zones. The distribution of the zero-amplitude zones is much less dependent on the strength of the vibration than on the location of the vibration source. The surface of the liquid solder vibrates at an ultrasonic frequency that is higher than the vibration source, and the amplitude of the liquid solder is almost twice that of the aluminum surface. The vibration of the surface of the base metal (liquid solder) correlates with the oxide film removal effect. Significant removal of the oxide film can be achieved within 2s when the amplitude of the aluminum surface is higher than 5.4 μm or when the amplitude of the liquid solder surface is higher than 10.2 μm., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The biogeochemistry and bioavailability of cadmium, released during sphalerite weathering in soils, were investigated under contrasting agricultural scenarios to assess health risks associated with sphalerite dust transport to productive soils from mining. Laboratory experiments (365 d) on temperate and sub-tropical soils amended with sphalerite (<63 μm, 0.92 wt.% Cd) showed continuous, slow dissolution (0.6-1.2% y(-1)). Wheat grown in spiked temperate soil accumulated ≈38% (29 μmol kg(-1)) of the liberated Cd, exceeding food safety limits. In contrast, rice grown in flooded sub-tropical soil accumulated far less Cd (0.60 μmol kg(-1)) due to neutral soil pH and Cd bioavailability was possibly also controlled by secondary sulfide formation. The results demonstrate long-term release of Cd to soil porewaters during sphalerite weathering. Under oxic conditions, Cd may be sufficiently bioavailable to contaminate crops destined for human consumption; however flooded rice production limits the impact of sphalerite contamination., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Pseudomorphs of barite (BaSO4) and Cd-rich ZnS after whewellite (CaC2O4·H2O) occur within remnants of Scots pine bark tissues in the peat layer of a poor fen located near a zinc smelter in south Poland. A two-step formation of the pseudomorphs is postulated based on SEM observations: (1) complete dissolution of whewellite, possibly caused by oxalotrophic bacteria, and (2) subsequent bacterially induced precipitation of barite and spheroidal aggregates of ZnS together with galena (PbS) in voids left by the dissolved whewellite crystals. Local increase in pH due to microbial degradation of whewellite, elevated concentrations of Zn(II) and Ba(II) in pore water due to the decomposition of atmospheric particles of sphalerite and barite in the acidic (pH 3.5-3.8) environment, oxidation of S species during drying and rewetting of the peat layer, and subsequent partial reduction of sulfate anions by sulfur-reducing bacteria were all factors likely involved in the crystallization of ZnS and barite in the microenvironment of the post-whewellite voids.

An amorphous Zn biomineralization ("white mud"), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.

We investigated chemical determinants of the generation of chlorinated aromatic compounds (aromatic-Cls), such as polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs), in fly ash from municipal solid waste incineration. The influences of the following on aromatic-Cls formation in model fly ash (MFA) were systematically examined quantitatively and statistically: (i) inorganic chlorides (KCl, NaCl, CaCl2), (ii) base materials (SiO2, Al2O3, CaCO3), (iii) metal oxides (CuO, Fe2O3, PbO, ZnO), (iv) metal chlorides (CuCl2, FeCl3, PbCl2, ZnCl2), and (v) "coexisting multi-models." On the basis of aromatic-Cls concentrations, the ∑CBzs/∑PCBs ratio, and the similarity between distribution patterns, MFAs were categorized into six groups. The results and analysis indicated that the formation of aromatic-Cls depended strongly on the "coexistence condition", namely multimodels composed of not only metal chlorides, but also of metal oxides. The precise replication of metal chloride to oxide ratios, such as the precise ratios of Cu-, Fe-, Pb-, and Zn-chlorides and oxides, may be an essential factor in changing the thermochemical formation patterns of aromatic-Cls. Although CuCl2 acted as a promoter of aromatic-Cls generation, statistical analyses implied that FeCl3 also largely influenced the generation of aromatic-Cls under mixture conditions. Various additional components of fly ash were also comprehensively analyzed.

Fluorescence imaging technique has been used for imaging of biological cells and tissues in vivo. The Cd-free luminescent quantum dots conjugating with a cancer targeting ligand has been taken as a promising biocompatibility and low cytotoxicity system for targeted cancer imaging. This work reports the synthesis of fluorescent-doped core/shell quantum dots of water-soluble manganese-doped zinc sulfide. Quantum dots of manganese-doped zinc sulfide were prepared by nucleation doping strategy, with 3-mercaptopropionic acid as stabilizer at 90 in aqueous solution. The manganese-doped zinc sulfide nanoparticles exhibit strong orange fluorescence under UV irradiation, resistance to photo-bleaching, and low-cytotoxicity to HeLa cells. The structure and optical properties of nanoparticles were characterized by scanning electron microscope, X-ray diffraction, dynamic light scattering, and photoluminescence emission spectroscopy. Manganese-doped zinc sulfide nanoparticles conjugated with folic acid using 2,2'-(ethylenedioxy)-bis-(ethylamine) as the linker. The covalent binding of both 2,2'-(ethylenedioxy)-bis-(ethylamine) and folic acid on the surface of manganese-doped zinc sulfide nanoparticles probed by Fourier transform infrared spectroscopy detection. Furthermore, in vitro cytotoxicity assessment of manganese-doped zinc sulfide-folic acid probes use HeLa cells. The obtained fluorescent probes (manganese-doped zinc sulfide) were used for tumor targeting and imaging in vivo. The manganese-doped zinc sulfide-folic acid fluorescent probes which targeting the tumor cells in the body of nude mouse tumor model would emit orange fluorescence, when exposed to a 365 nm lamp. We investigate the biodistribution of the manganese-doped zinc sulfide-folic acid fluorescent probes in tumor mouse model by measuring zinc concentration in tissues. These studies demonstrate the practicality of manganese-doped zinc sulfide-folic acid fluorescent probes as promising platform for tumor targeting and imaging in vivo.

NaCl is a widely used chemical in food processing which affects sensory characteristics and safety; in fact, its presence is frequently essential for the proper preservation of the products. Because the intake of high contents of sodium is linked to adverse effects on human health, consumers demand foods with low-sodium content. A 1st step to reduce the use of salt would imply the proper application of this compound, reducing its levels to those technologically necessary. In addition, different chloride salts have been evaluated as replacers for NaCl, but KCl, CaCl2 , and ZnCl2 show the most promising perspectives of use. However, prior to any food reformulation, there is a need for exhaustive research before its application at industrial level. Salt reduction may lead to an increased risk in the survival/ growth of pathogens and may also alter food flavor and cause economic losses. This review deals with the technological, microbiological, sensorial, and health aspects of the potential low-salt and salt-substituted vegetable products and how this important segment of the food industry is responding to consumer demand., (© 2013 Institute of Food Technologists®)

In archaeology, the discovery of ancient medicines is very rare, as is knowledge of their chemical composition. In this paper we present results combining chemical, mineralogical, and botanical investigations on the well-preserved contents of a tin pyxis discovered onboard the Pozzino shipwreck (second century B.C.). The contents consist of six flat, gray, discoid tablets that represent direct evidence of an ancient medicinal preparation. The data revealed extraordinary information on the composition of the tablets and on their possible therapeutic use. Hydrozincite and smithsonite were by far the most abundant ingredients of the Pozzino tablets, along with starch, animal and plant lipids, and pine resin. The composition and the form of the Pozzino tablets seem to indicate that they were used for ophthalmic purposes: the Latin name collyrium (eyewash) comes from the Greek name κoλλυρα, which means "small round loaves." This study provided valuable information on ancient medical and pharmaceutical practices and on the development of pharmacology and medicine over the centuries. In addition, given the current focus on natural compounds, our data could lead to new investigations and research for therapeutic care.

To fully understand the biological and environmental impacts of nanomaterials requires studies that address both sublethal end points and multigenerational effects. Here, we use a nematode to examine these issues as they relate to exposure to two different types of quantum dots, core (CdSe) and core-shell (CdSe/ZnS), and to compare the effect to those observed after cadmium salt exposures. The strong fluorescence of the core-shell QDs allowed for the direct visualization of the materials in the digestive track within a few hours of exposure. Multiple end points, including both developmental and locomotive, were examined at QD exposures of low (10 mg/L Cd), medium (50 mg/L Cd), and high concentrations (100 mg/L Cd). While the core-shell QDs showed no effect on fitness (lifespan, fertility, growth, and three parameters of motility behavior), the core QDs caused acute effects similar to those found for cadmium salts, suggesting that biological effects may be attributed to cadmium leaching from the more soluble QDs. Over multiple generations, we commonly found that for lower life-cycle exposures to core QDs the parents response was generally a poor predictor of the effects on progeny. At the highest concentrations, however, biological effects found for the first generation were commonly similar in magnitude to those found in future generations.

Background: A 4-year-old, 37 kg, male German shepherd developed hyperthermia, tachycardia, and agitation following consumption of ground meat found in the backyard of its owner. When presented to a veterinary clinic, plasma ethylene glycol (EG) testing was positive, and the dog was given ethanol and lactated Ringer's solution intravenously. Approximately 11 h postexposure the dog died., Discussion: Among tissues submitted for toxicological analysis, urine was negative for EG, ground meat was negative for certain drugs of abuse, and gastric contents were negative for zinc/aluminum phosphide and metaldehyde. Analysis of gastric contents by gas chromatography-mass spectrometry confirmed the presence of caffeine. Caffeine concentration in the ground meat was estimated at 1 %. Caffeine is a methylxanthine alkaloid with a reported canine oral median lethal dose (MLD(50)) of 140 mg/kg (range 120-200 mg/kg). A commercially available 200-mg tablet formulation of caffeine was considered to be a possible source but this was not confirmed. By conservative estimates, the dog would need to ingest approximately 500-550 g of the meat to reach the MLD(50). Acute intoxication affects the cardiovascular, pulmonary, neurologic, gastrointestinal, and metabolic systems. Although no tablet remnants were observed in the bait, tablets could have been crushed and/or dissolved. Other potential caffeine sources include guarana, brewed and concentrated coffee, and caffeine-containing beverages. Based on the history, clinical signs, and the detection of caffeine in the gastric contents and meat, a presumptive diagnosis of malicious caffeine poisoning was made. A suggested treatment regimen for caffeine intoxication in dogs is described. While few cases of accidental ingestion of caffeine by dogs have been described, the intentional use of a concentrated caffeine source to cause mortality in a dog has not been previously reported.

Blast furnace sludge (BFS), an industrial waste generated in pig iron production, typically contains high contents of iron and various trace metals of environmental concern, including Zn, Pb, and Cd. The chemical speciation of these metals in BFS is largely unknown. Here, we used a combination of synchrotron X-ray diffraction, micro-X-ray fluorescence, and X-ray absorption spectroscopy at the Zn K-edge for solid-phase Zn speciation in 12 BFS samples collected on a former BFS sedimentation pond site. Additionally, one fresh BFS was analyzed for comparison. We identified five major types of Zn species in the BFS, which occurred in variable amounts: (1) Zn in the octahedral sheets of phyllosilicates, (2) Zn sulfide minerals (ZnS, sphalerite, or wurtzite), (3) Zn in a KZn-ferrocyanide phase (K(2)Zn(3)[Fe(CN)(6)](2)·9H(2)O), (4) hydrozincite (Zn(5)(OH)(6)(CO(3))(2)), and (5) tetrahedrally coordinated adsorbed Zn. The minerals franklinite (ZnFe(2)O(4)) and smithsonite (ZnCO(3)) were not detected, and zincite (ZnO) was detected only in traces. The contents of ZnS were positively correlated with the total S contents of the BFS. Similarly, the abundance of the KZn-ferrocyanide phase was closely correlated with the total CN contents, with the stoichiometry suggesting this as the main cyanide phase. This study provides the first quantitative Zn speciation in BFS deposits, which is of great relevance for environmental risk assessment, the development of new methods for recovering Zn and Fe from BFS, and potential applications of BFS as sorbent materials in wastewater treatment.

A simple Schiff base type fluorescent receptor was prepared and evaluated for its fluorescence response to heavy metal ions. Receptor 1 exhibits an "off-on-type" mode with high selectivity in the presence of Zn(2+) ion. The addition of EDTA quenches the fluorescence of receptor 1-Zn(2+) complex, making receptor 1 a reversible chemosensor. The selectivity of 1 for Zn(2+) is the consequence of combined effects of CHEF, C=N isomerization and inhibition of ESIPT.

Zinc is one of the most widespread trace metals (TMs) in Earth surface environments and is the most concentrated TM in the downstream section of the Seine River (France) due to significant anthropogenic input from the Paris conurbation. In order to better identify the sources and cycling processes of Zn in this River basin, we investigated seasonal and spatial variations of Zn speciation in suspended particulate matter (SPM) in the oxic water column of the Seine River from upstream to downstream of Paris using synchrotron-based extend X-ray absorption fine structure (EXAFS) spectroscopy at the Zn K-edge. First-neighbor contributions to the EXAFS were analyzed in SPM samples, dried and stored under a dry nitrogen atmosphere or under an ambient oxygenated atmosphere. We found a sulfur first coordination environment around Zn (in the form of amorphous zinc sulfide) in the raw SPM samples stored under dry nitrogen vs an oxygen first coordination environment around Zn in the samples stored in an oxygenated atmosphere. These findings are supported by scanning electron microscopy and energy dispersive X-ray spectrometry observations. Linear combination fitting of the EXAFS data for SPM samples, using a large set of EXAFS spectra of Zn model compounds, indicates dramatic changes in the Zn speciation from upstream to downstream of Paris, with amorphous ZnS particles becoming dominant dowstream. In contrast, Zn species associated with calcite (either adsorbed or incorporated in the structure) are dominant upstream. Other Zn species representing about half of the Zn pool in the SPM consist of Zn-sorbed on iron oxyhydroxides (ferrihydrite and goethite) and, to a lesser extent, Zn-Al layered double hydroxides, Zn incorporated in dioctahedral layers of clay minerals and Zn sorbed to amorphous silica. Our results highlight the importance of preserving the oxidation state in TM speciation studies when sampling suspended matter, even in an oxic water column.

Low temperatures and frequent soil freeze-thaw in polar environments present challenges for the immobilisation of metals. To address these challenges we investigated the chemical forms of Pb, Zn and Cu in an Antarctic landfill, examined in vitro reaction kinetics of these metals and orthophosphate at 2 and 22 °C for up to 185 days, and subjected the products to freeze-thaw. Reaction products at both temperatures were similar, but the rate of production varied, with Cu-PO(4) phases forming faster, and the Zn- and Pb-PO(4) phases slower at 2 °C. All metal-orthophosphate phases produced were stable during a 2.5 h freeze-thaw cycle to -30 °C. Metal immobilisation using orthophosphate can be successful in polar regions, but treatments will need to consider differing mineral stabilities and reaction rates at low temperatures., (Copyright © 2011 Elsevier Ltd. All rights reserved.)