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The prostate is an accessory sex organ that secretes essential components of semen. High levels of Zn are found both in the prostate and its secretion. In the present study, the effects of environmental stress on zinc levels in the prostate were examined in Wistar male rats exposed to tributyltin chloride (TBTC), an environmental toxicant, by inductively coupled argon plasma–mass spectrometry (ICP-MS) for determination of Zn concentration in lobe-dissectioned specimens and micro-PIXE analysis for determination of site-specific distribution of Zn in prostatic sections. A single oral administration of TBTC to rats at a dose of 90 μmol/kg resulted 14 days later in a decrease in the Zn level in the dorsolateral prostate but not the ventral prostate. The TBTC did not affect the weight of the prostate tissue. Micro-PIXE imaging found Zn both in the lumen and the epithelium of the lateral prostatic tubules. PIXE spot analysis revealed that the epithelium of the control rat contained levels of Zn 4–fold higher than in the lumen and that Zn in the epithelium decreased selectively after TBTC exposure.

The pancreas is a large gland capable of both exocrine and endocrine functions; it releases digestive enzymes into the duodenum and hormones into the bloodstream. It is known that Zn plays a key role in the synthesis and action of insulin, one of the pancreatic hormones. However, elemental profiles of the pancreas are not well understood. Here, we examined precise distributions of elements in the pancreas of newborn and young rats by scanning microbeam particle induced X-ray emission (micro PIXE) analysis and compared the results to those of adult animals.

Micro PIXE analysis revealed a site-specific distribution of elements in the two major compartments of the pancreas, the exocrine (acinar tissue) and the endocrine portions (islets of Langerhans). The Zn concentrations in the pancreas of the newborn (six days), young (three weeks), and adult rats (ten weeks) were 11.3 ± 2.5 μg/g wet weight, 7.26 ± 0.36 μg/g wet weight, and 10.8 ± 1.1 μg/g wet weight, respectively. In newborn and young rats, Zn was detected mainly in the islets of Langerhans, while K and P were distributed more to the acinar tissues than the islet cells. The site-specific distributions of K, P, and Zn were more obvious in the adult animals.

Synchrotron radiation X-ray fluorescence (SR-XRF) using high energy incident X-rays was combined with micro-PIXE to analyze the renal distribution of Rb and essential elements in immature rats. The Rb concentrations in the kidneys of newborn (1 week old) and young (3 weeks old) rats were 4.19 ± 0.71 and 4.13 ± 0.30 µg/g, respectively, similar to those of adult rats. Rubidium as well as Zn was detected more in the cortex than the medulla, while Fe was concentrated in the outermost areas of the medulla of newborn rats. The renal structures of young rats achieved adult zonation into the cortex, the outer medulla and the inner medulla. Rubidium was high in the outer stripe of the outer medulla. Further analysis at higher resolution revealed Rb in the proximal tubules in the innermost part of the cortex. These results indicated that Rb was distributed downstream of the proximal tubules. This profile was similar to that of potassium, an Rb congener.

Investigation of the radiation-induced bystander effect plays an important role in the understanding of the mechanisms of radiation response after low-dose irradiation. Sphingomyelinase (SMase) was activated by radiation and required the metal element for its activation. For further elucidation of the bystander effect, we investigated the relationship between its induction by acid SMase and a factor secreted from the irradiated tumor cells. In the cell culture medium transfer experiment after irradiation at a dose of 0.1 Gy, cell death was induced in non-irradiated cells. However, when cells received prior treatment with SMase inhibitor, cell death was not induced. When fluctuations in the activation of SMase and metal elements were detected, both intracellularly and extracellularly after irradiation, an increase in SMase activity and Zn concentration occurred within the cells at 5 min and outside of the cells at 15 min after irradiation. This increase in zinc concentration at 15 min after irradiation was suppressed by treatment with SMase inhibitor. These results suggest that activation of SMase, which is related to the bystander effect, is dependent on zinc.

A total of 4269 beard samples were collected from the same person every day over a 12-year period and analyzed by PIXE using a standard-free method. It was found that the concentrations of copper and zinc showed certain short-term changes but did not show a noticeable long-term trend over the study period, with only iron showing a slightly decreasing tendency with age. All of these elements showed clear yearly variations with a cycle of a few years possibly due to periodic metabolic changes in the subject’s body or long-term changes in eating habits. In contrast, however, selenium showed clear seasonal variations. Its concentration significantly increased in the summer and decreased in the winter, just as was observed with arsenic and mercury. This suggests that most of the subject’s selenium intake was from marine products, whose supply and consumption were increased in the summer. These findings confirmed that beard analyses are useful not only for evaluating essential-element intake but also for estimating the relationship between the body-element concentrations and ingestion of certain foods.

The hard tissues of cephalopod, namely statoliths were analyzed with PIXE for the Japanese common squid Todarodes pacificus of the Sea of Japan origin in order to examine the relationship between the amount of trace elements in statoliths and environmental temperature of the squid habitat. Calcium, iron, zinc. copper and strontium were detected in the statoliths. Negative relationship was observed between Sr concentration in statoliths and environmental temperature. On the contrary to Sr, Fe and Zn concentration in statoliths related positively with environmental temperature. These observations revealed that the statoliths would be a useful thermometer for reconstructing the environmental temperature of cephalopod habitat as seen in the hard tissues of other marine organisms.

This review is in general about group 12 elements and their small microclusters. In this part, after presenting an extensive literature survey of the electric dipole polarizability studies of the Zn, Cd and Hg atoms, we specifically target zinc-containing small clusters, beginning with the Zn₂ dimer, the Zn₃ trimer, higher Zn_n clusters and the neutral, cationic and anionic zinc oxide clusters: ZnO, ZnO⁺ and ZnO^-. We tabulated experimental and theoretical results for the spectroscopic constants (dissociation energy D_e or D₀, bond length r_e, fundamental frequency w_e, anharmonicity constant w_ex_e and dipole moment μ_e) of the diatomic clusters and the first and second ionization potentials IP₁ and IP₂ and electron affinity EA of the species reviewed.

La_0.8Sr_0.2MnO₃ (LSMO)/Zn composites were prepared by bonded method. The phase structure, electrical transport and low-field magnetoresistance (LFMR) characteristics have been investigated. The binder segregated mostly at the grain boundaries. The bonded composites exhibited enhanced LFMR, which was attributed to the enhanced intergrain spin-polarized tunneling behavior.

Calcium ferrite nanoparticles (NPs), doped with Zinc in the range of 10–50mol%, were synthesized through a solution combustion method using citrus Limon extract as a reducing agent, followed by calcination at 500^∘C. The synthesized samples are characterized with different techniques. Bragg reflections confirmed the formation of orthorhombic crystal structure. The shifting of the peak toward higher angle side is observed with increase in the dopant concentration. The surface exhibited irregular shapes and sized NPs with pores and voids in their morphology. The direct energy band gap increases from 2.91 to 2.97eV with increase in Zinc concentration. Further, magnetic and dielectric properties were carried out to know their importance in the high-frequency devices. Magnetic parameters, such as saturation magnetization (M_s), remanence (M_r), and coercivity (H_c) values, are discussed. M_s, M_r and H_c increase with increase in dopant concentration upto 30mol% and thereafter decreases. The dielectric studies revealed a decreasing dielectric constant from 2.98 to 1.84 as the dopant concentration increased. These findings suggest the potential use of these samples in memory devices and high-frequency applications.

Zn powder has been used for many years as anticorrosive pigments in various paints. In this work, the nano-sized Zn powder was synthesized by wire explosion method in deionised water and ethanol. The morphology of the prepared powders was observed by field emission-scanning electron microscopy (FE-SEM) and the oxidation of the powders was determined using energy-dispersive X-ray spectroscopy (EDS). The size of particles was estimated from transmission electron microscopy (TEM) and FE-SEM. Dispersion properties of the as-prepared Zn nanoparticles in ethanol were evaluated by Turbiscan lab device. It is found that Zn nanoparticle prepared in ethanol had spherical shape with average particles size ~150 nm while the one prepared in water had a mixture of hexagonal and spherical shape. Ethanol can reduce the oxidation of Zn nanoparticles in comparison with water. Stability of Zn nanoparticles dispersed in ethanol exhibited the agglomeration in the dispersion.

The crystal structure of zinc metal deviates from the ideal hexagonal close packing structure by a significantly increased axial ratio (c/a). The local atomic structure of zinc metal is investigated using the total scattering atomic pair distribution function (PDF) analysis based on X-ray powder diffraction data collected at ambient conditions. The X-ray total scattering PDF analysis confirms that the crystal structure of zinc can be described in terms of wurtzite structure, but with an anomalously atomic displacement parameters $U_{33}$, indicating a significant displacement disorder along the $c$-axis. For the long $r$-range PDF refinements, the thermal motion of zinc shows a notable anisotropy as expressed by the ratio $U_{33}$/$U_{11}$ of 2.5 at ambient conditions. This average distortion level along the $c$-axis, was not reflected locally for the features below 5.0 Å as it fits the high $r$ region. Based on PDF refinements over different $r$-ranges, we measure an interesting increase of the $U_{33}$ value with decreasing the $r$-range of the refinement. This suggests that the local structure features in zinc metal differ from the average structure ones.

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We report a theoretical study of the cyclopropanation reactions of EtZnCHI, (EtZn)₂CH EtZnCHZnI, and EtZnCIZnI radicals with ethylene. The mono-zinc and gem-dizinc radical carbenoids can undergo cyclopropanation reactions with ethylene via a two-step reaction mechanism similar to that previously reported for the CH₂I and IZnCH₂ radicals. The barrier for the second reaction step (ring closure) was found to be highly dependent on the leaving group of the cyclopropanation reaction. In some cases, the (di)zinc carbenoid radical undergoes cyclopropanation via a low barrier of about 5–7 kcal/mol on the second reaction step and this is lower than the CH₂I radical reaction which has a barrier of about 13.5 kcal/mol for the second reaction step. Our results suggest that in some cases, zinc radical carbenoid species have cyclopropanation reaction barriers that can be competitive with their related molecular Simmons-Smith carbenoid species reactions and produce somewhat different cyclopropanated products and leaving groups.

The synthesis of metallo derivatives (Ni, Zn) of phthalocyanines (pcs) obtained from 4,5-dicyanobenzomonoazacrown ether substituted with long alkyl chains (5a-d) are described. The new compounds have been characterized by elemental analysis, ¹H, ¹³C NMR, MS, IR and UV-vis spectroscopy techniques. The aggregation properties and alkali metal interaction of the pcs (6a-d and 7a-d) were investigated.

Pd(II), Co(II), Cu(II) and Zn(II) phthalocyanines with a tricarbethoxyethyl substituent on each benzo group were prepared from 4-(1,1,2-tricarbethoxyethyl)-phthalonitrile and the corresponding divalent metal salt at 170°C. Transesterification occurred when the reaction was carried out in pentanol. Treatment of the palladium complex with sodium ethoxide at room temperature and further acidification resulted with tetra(1,2-dicarboxyethyl)phthalocyaninatopal-ladium. Its UV-vis spectrum in aqueous solution indicated dimeric and monomeric species at pH ≈ 12, but at pH ≈ 6 only the dimeric form were present.

The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)₄), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)₄ and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.

5,15-substituted porphyrins are valuable compounds in bioorganic and materials chemistry. A new synthesis has been developed that employs 1,9-diformylation of a dipyrromethane, conversion of the diformyldipyrromethane to the bis(imino) derivative, and reaction of the bis(imino)dipyrromethane + a dipyrromethane to give the zinc-porphyrin bearing trans-AB-substituents. 1,9-diformylation was achieved via Vilsmeier reaction. Imination was achieved by treatment of the 1,9-diformyldipyrromethane with excess amine under neat conditions at room temperature. The porphyrin-forming reaction was carried out over 2 h in refluxing ethanol containing zinc acetate exposed to air. Oxidation of the intermediate porphyrinogen occurs aerobically. A complex composed of two bis(imino)dipyrromethanes and two zinc atoms was observed to form reversibly during the course of the reaction. A set of zinc-porphyrins with trans-AB-, A₂-, or A-substituents has been prepared in yields of ~30% (without detectable scrambling) with straightforward purification. The reaction is applicable to A/B substituent combinations of aryl/aryl, aryl/alkyl, and aryl/H.

Magnesium porphyrazinate substituted with eight (1-naphthyl) groups on the peripheral positions has been synthesized by cyclotetramerization of 3,4-(1-naphthyl)pyrroline-2,5-diimine, 4-(1-naphthyl)pyrroline-2,5-diimine in the presence of magnesium butanolate. Its demetalation by treatment with trifluoroacetic acid, resulted in a partially oxidized product, namely, octakis(1-naphthyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate led to the metallo derivatives, [octakis(1-naphthyl)-2-seco-2,3-dioxoporphyrazinato]M(II) (M = Cu, Zn or Co). These new compounds have been characterized by elemental analysis, together with FT-IR, ¹H NMR, UV-vis and mass spectral data.

Metal-free and metallophthalocyanines with four 9-anthroyl groups bound through ethylthio ester bridges on the periphery have been prepared. The new compounds were characterized by elemental analyses, ¹H NMR, IR, mass and UV-vis spectral data. The electronic spectra exhibit an intense π-π* transition of 9-anthroyl identity together with characteristic Q and B bands of the phthalocyanine core. Effect of metal ions on intensity of fluorescence spectra of phthalocyanine derivatives substituted with 9-anthroyl groups was investigated. The energy transfer to the phthalocyanine core and radiative decays of the 9-anthroyl emission and phthalocyanine core were examined.

The synthesis, spectroscopic and electrochemical properties of new phthalocyanines bearing four morpholine and four chloro units is reported. Two-step synthesis involved efficient nucleophilic substitution of 4,5-dichlorophthalonitrile as the key step. The free-base phthalocyanine and its several complexes have been characterized using UV-vis, IR, ¹HNMR, ¹³CNMR and mass spectroscopic data. Voltammetric and spectroelectrochemical studies show that while cobalt phthalocyanine gives both metal- and ring-based, diffusion-controlled, multi-electron and reversible/quasi-reversible redox processes, other complexes give ring-based, multi-electron and reversible/quasi-reversible redox processes.