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Schwann cell vulnerability to demyelination is associated with internodal length in tellurium neuropathy.

The frequency of demyelinated fibers in mixed nerve and cutaneous nerve and the relationship of the frequency of demyelination to internodal length were assessed in a model of tellurium neuropathy in the rat. Twenty-day-old Long-Evans rats were fed chow containing 1.25% elemental tellurium for seven days and subsequently killed at 34 or 41 days of age. Teased-fiber preparations revealed a higher frequency of demyelinated fibers in sciatic nerve (mixed nerve) than in sural nerve (cutaneous nerve). The frequency of demyelinated fibers was positively associated with internodal length in both nerves. The type of nerve (mixed or cutaneous) was not a significant predictor of the frequency of demyelinated fibers once internodal length had been taken into account. These data indicate that there is a hierarchy of vulnerability within the population of myelinating Schwann cells to tellurium toxicity, and that this hierarchy is related to internodal length. The hierarchy of vulnerability may reflect intrinsic differences among Schwann cells, such as the volume of myelin each cell is synthesizing and maintaining, or a gradient of unrecognized axonal abnormalities.

Animals↗

Chronic tellurium intoxication in rats.

(1) Accumulation of neuronal lipofuscin was clearly demonstrated in the chronic tellurium intoxication in young rats with histological, fluorescent and electron-microscopical methods; (2) The needle-shaped crystal in the neuronal lysosomes were demostrated to contain the tellurium with electron dispersive spectrophotometry analysis. (3) The vacuolation of the cytoplasm of Schwann cells was the initial pathological change noted in the tellurium peripheral neuropathy.

Animals↗

Pyridine-2,6-bis(thiocarboxylic acid) produced by Pseudomonas stutzeri KC reduces and precipitates selenium and tellurium oxyanions.

The siderophore of Pseudomonas stutzeri KC, pyridine-2,6-bis(thiocarboxylic acid) (pdtc), is shown to detoxify selenium and tellurium oxyanions in bacterial cultures. A mechanism for pdtc's detoxification of tellurite and selenite is proposed. The mechanism is based upon determination using mass spectrometry and energy-dispersive X-ray spectrometry of the chemical structures of compounds formed during initial reactions of tellurite and selenite with pdtc. Selenite and tellurite are reduced by pdtc or its hydrolysis product H(2)S, forming zero-valent pdtc selenides and pdtc tellurides that precipitate from solution. These insoluble compounds then hydrolyze, releasing nanometer-sized particles of elemental selenium or tellurium. Electron microscopy studies showed both extracellular precipitation and internal deposition of these metalloids by bacterial cells. The precipitates formed with synthetic pdtc were similar to those formed in pdtc-producing cultures of P. stutzeri KC. Culture filtrates of P. stutzeri KC containing pdtc were also active in removing selenite and precipitating elemental selenium and tellurium. The pdtc-producing wild-type strain KC conferred higher tolerance against selenite and tellurite toxicity than a pdtc-negative mutant strain, CTN1. These observations support the hypothesis that pdtc not only functions as a siderophore but also is involved in an initial line of defense against toxicity from various metals and metalloids.

Chemical Precipitation↗

Tellurium-induced dose-dependent impairment of antioxidant status: differential effects in cerebrum, cerebellum, and brainstem of mice.

The effect of various doses of sodium tellurite (0.4, 0.8, and 2.0 mg/kg body weight, orally) on the activity of antioxidant enzymes (glutathione peroxidase, glutathione reductase, glutathione-S-transferase, and catalase) and content of glutathione and thiobarbituric acid reactive substances (TBARSs) in the cerebrum, cerebellum, and brainstem of male albino mice was studied after 15 d of treatment. All of the doses of tellurium (0.4, 0.8, and 2.0 mg/kg body weight, orally) have depleted the activity of antioxidant enzymes and the content of glutathione dose dependently in the cerebrum, cerebellum, and brainstem and it was significant with the dose of 2.0 mg/kg. On the other hand, the 2.0-mg/kg dose of tellurium has significantly elevated the content of TBARSs in the cerebrum and cerebellum. The 0.8-mg/kg dose of tellurium has significantly depleted the activities of glutathione peroxidase in the cerebrum and brainstem, glutathione-Stransferase in the cerebrum and cerebellum, catalase in the brainstem, and the content of glutathione in the cerebrum and cerebellum. In contrast, this dose has significantly elevated the content of TBARSs in the cerebrum and cerebellum. However, the depletion in the activity of glutathione reductase with various doses of sodium tellurite was not significant in any brain part of mice. The result suggests that sodium tellurite differentially affects the antioxidant status within various parts of the mice brain.

Animals↗

Gene expression during tellurium-induced primary demyelination.

A compound may be "developmentally neurotoxic" because it interferes with a metabolic step exclusively or preferentially expressed during development in a particular class of neural cells. The initial metabolic specificity is often complicated by: (1) secondary responses in the affected cells, (2) involvement of other functionally-related cell types, and (3) the presence of compensatory and/or regenerative responses. In this context we study tellurium, which systemically blocks cholesterol biosynthesis at the squalene epoxidase step. Because of the high demand in developing peripheral nerves for newly synthesized cholesterol required for myelin assembly, this metabolic block leads to demyelination of the sciatic nerve. This insult is confounded by the fact that the myelin-forming Schwann cells do not upregulate their cholesterol biosynthetic pathway. This is contrary to expectations; liver (the main source of cholesterol for many tissues outside the nervous system) upregulates synthesis of cholesterol and overcomes the metabolic block. The shortage of cholesterol in Schwann cells results in an immediate secondary response down-regulation of steady-state mRNA levels for specific myelin proteins. Remyelination occurs after cessation of tellurium exposure. This model of primary demyelination allows study of Schwann-cell specific responses during the processes of myelin breakdown and subsequent steps leading to remyelination, without the complications of axonal degeneration and regeneration. Because tellurium specifically blocks the synthesis of a major required membrane component, it is also well suited for examining the coordinate control of membrane synthesis and assembly at the genomic level.

Animals↗

Separation and purification of 131I from tellurium material using ion exchange for preparing tetra-butyl ammonium iodide (131I).

A comparison of the distribution coefficients (Kd) of tellurium and iodine-131 (131I) between hydrochloric acid of various concentrations (without and in presence of 0.1 M thiourea) and the cation exchange resin (Dowex50WX8) was studied. The Kd of tellurium and 131I at different concentrations of thiourea in 0.1 M HCl on the Dowex50WX8 was also studied. The results clarified that the maximum uptake of tellurium was 98% on the Dowex50WX8, while the uptakes of 131I and thiourea are 1.96% and 70%, respectively. To purify 131I from thiourea (30%), which is not retained on Dowex50WX8, the remaining solution was shaken with different types of anion exchangers (Dowex21K, Dowex1X8, and Dowex1X2) within 60 min. The most suitable anion exchanger, which gave the maximum uptake of 131I (80%) was Dowex21K. Finally, 131I was re-extracted from Dowex21K into 5 mM TBAB with a separation yield of 98%. Quality control on the separated product of tetra-butyl ammonium iodide (131I) was carried out.

Journal Article↗

Experimental and theoretical investigations of tellurium(IV) diimides and imidotelluroxanes: X-ray structures of B(C6F5)3 adducts of OTe(mu-NtBu)2TeNtBu, [OTe(mu-NtBu)2Te(mu-O)]2 and tBuNH2.

The hydrolysis of (t)BuNTe(mu-N(t)Bu)(2)TeN(t)Bu (1) with 1 or 2 equiv of (C(6)F(5))(3)B.H(2)O results in the successive replacement of terminal imido groups by oxo ligands to give the telluroxane-Lewis acid adducts (C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)TeN(t)Bu (2) and [(C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)Te(mu-O)](2) (3), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The Te=O distance in 2 is 1.870(2) A. The di-adduct 3 involves the association of four (t)()BuNTeO monomers to give a tetramer in which both terminal Te=O groups [d(TeO) = 1.866(3) A] are coordinated to B(C(6)F(5))(3). The central Te(2)O(2) ring in 3 is distinctly unsymmetrical [d(TeO) = 1.912(3) and 2.088(2) A]. The X-ray structure of (C(6)F(5))(3)B.NH(2)(t)()Bu (4), the byproduct of these hydrolysis reactions, is also reported. The geometries and energies of tellurium(IV) diimides and imido telluroxanes were determined using quantum chemical calculations. The calculated energies for the reactions E(NR)(2) + Te(NR)(2) (E = S, Se, Te; R = H, Me, (t)Bu, SiMe(3)) confirm that cyclodimerization of tellurium(IV) diimides is strongly exothermic. In the mixed-chalcogen systems, the cycloaddition is energetically favorable for the Se/Te combination. The calculated energies for the further oligomerization of the dimers XE(mu-NMe)(2)EX (E = Se, Te; X = NMe, O) indicate that the formation of tetramers is strongly exothermic for the tellurium systems but endothermic (X = NMe) or thermoneutral (X = O) for the selenium systems, consistent with experimental observations.

Journal Article↗

[Cd2(Te6O13)][Cd2Cl6] and Cd7Cl8(Te7O17): novel tellurium(IV) oxide slabs and unusual cadmium chloride architectures.

Initial attempts to prepare new Ln-Cd-Te-O-Cl compounds led to the isolation of two novel cadmium tellurium(IV) oxychlorides with two different types of structures, namely, [Cd(2)(Te(6)O(13))][Cd(2)Cl(6)] and Cd(7)Cl(8)(Te(7)O(17)). Both compounds feature novel polymeric tellurium(IV) oxide anions and unusual cadmium chloride substructures. The structure of [Cd(2)(Te(6)O(13))][Cd(2)Cl(6)] is composed of 1D [Cd(2)Cl(6)](2)(-) double chains and (002) [Cd(2)(Te(6)O(13))](2+) layers. The 1D Te(6)O(13)(2)(-) slab of the [Cd(2)(Te(6)O(13))](2+) layer is formed by TeO(3), TeO(4), and TeO(5) groups via corner- and edge-sharing, and it contains six- and seven-membered tellurium(IV) polyhedral rings. The structure of Cd(7)Cl(8)(Te(7)O(17)) features a 3D network with long-narrow tunnels along the b axis. The two types of structural building blocks are 1D [Te(7)O(17)](6)(-) anions and unusual corrugated [Cd(7)Cl(8)](6+) layers based on "cyclohexane-like" Cd(3)Cl(3) rings.

Journal Article↗

Preparation, Crystal Structures, and Isomerization of the Tellurium Diimide Dimers RNTe(&mgr;-NR')(2)TeNR (R = R' = (t)Bu; R = PPh(2)NSiMe(3), R' = (t)Bu, (t)Oct): X-ray Structure of the Telluradiazole Dimer [(t)Bu(2)C(6)H(2)N(2)Te](2).

The reaction of R'NHLi (R = (t)Bu, (t)Oct) with Ph(2)P(NSiMe(3))(2)Te(Cl)NPPh(2)NSiMe(3) in toluene at -78 degrees C, followed by warming to 23 degrees C, produces the tellurium diimide dimers RNTe(&mgr;-NR')(2)TeNR (2a, R' = (t)Bu, R = NPPh(2)NSiMe(3); 2b, R' = (t)Oct, R = NPPh(2)NSiMe(3)) and Ph(2)P(NHSiMe(3))(NSiMe(3)). X-ray analyses revealed that 2a and 2b have centrosymmetric structures containing a planar four-membered Te(2)N(2) ring and short exocyclic tellurium-nitrogen bond lengths (d(Te-N) = 1.900(5) and 1.897(4) or 1.905(4) Å for 2a and 2b, respectively). The exocyclic imido substituents adopt a trans arrangement with respect to the Te(2)N(2) ring. By contrast, the reaction of 2,4,6-(t)Bu(3)C(6)H(2)NHLi with Ph(2)P(NSiMe(3))(2)Te(Cl)NPPh(2)NSiMe(3) in toluene under similar conditions produces the telluradiazole ((t)Bu(2)C(6)H(2)N(2)Te)(2) (3), which exists as a weakly associated dimer in the solid state with intramolecular Te-N distances of 2.628(4) Å. The tellurium diimide dimer (t)BuNTe(&mgr;-N(t)Bu)(2)TeN(t)Bu (2c'), prepared by the reaction of TeCl(4) with (t)BuNHLi in a 1:4 molar ratio, consists of a folded Te(2)N(2) ring with exocyclic N(t)Bu groups in a cis orientation. The (1)H, (31)P, and (125)Te NMR spectra of 2a and 2b indicate that the trans isomers slowly transform into the corresponding cis isomers in solution. Crystals of 2b are triclinic, space group P&onemacr; (No. 2), with a = 13.304(3) Å, b = 16.927(3) Å, c = 13.292(5) Å, alpha = 98.94(2), beta = 109.27(2), gamma = 69.04(2) degrees, V = 2636(1) Å(3), and Z = 4. The final R and R(w) values were 0.034 and 0.033, respectively. Crystals of 2c' are orthorhombic, space group Pnma (No. 62), with a = 9.535(3) Å, b = 14.264(3) Å, c = 16.963(4) Å, V = 2307.1(9) Å(3), and Z = 4. The final R and R(w) values were 0.040 and 0.040, respectively. Crystals of 3 are monoclinic, space group P2(1)/n (No. 14), with a = 9.117(3) Å, b = 11.481(4) Å, c = 16.550(4) Å, beta = 97.76(2) degrees, V = 1716.5(8) Å(3), and Z = 4. The final R and R(w) values were 0.031 and 0.034, respectively.

Journal Article↗

Experimental Investigations and Ab Initio Studies of Tellurium(II) Dithiolates, Te(SR)(2).

The reaction between Te(O(i)Pr)(4) and HSR offers a new and effective route to tellurium dithiolates, Te(SR)(2). Te(S(i)Pr)(2) (1) and Te(S(t)Bu)(2) (2) are stable compounds whereas Te(SPh)(2) (3) slowly decomposes at room temperature to give Te and Ph(2)S(2). IR spectra of 1-3 and ab initio calculations (HF/3-21G(d) and MP2 with double-zeta polarization effective core potential basis set) show nu(as)(Te-S) and nu(s)(Te-S) to be around 340 and 380 cm(-)(1), respectively. UV spectra exhibit similar lambda(max) (346-348 nm) for all three compounds, with the greater extinction coefficient of 3 accounting for its different and more intense color. Analysis of the molecular orbitals of the model compound Te(SCH(3))(2) shows that the phototransition is likely to be of n(p)(Te)-sigma(Te-S) type, thus rationalizing the instability of 3 when irradiated. Single-crystal X-ray diffraction of 1-3 revealed the following basic structural parameters: 1 d(av)(Te-S) 239.4(1) and d(av)(S-C) 183.8(5) pm, angle(STeS) 99.61(4) and angle(av)(TeSC) 105.8(3) degrees, tau(CSTeS) 77.0(2) and 90.3(2) degrees; 2 d(Te-S) 239.1(1) and d(S-C) 186.4(2) pm, angle(STeS) 103.88(2) and angle(TeSC) 107.6(1) degrees, tau(CSTeS) 78.01(8) degrees; 3 d(Te-S) 240.6(2) and d(S-C) 177.4(7) pm, angle(STeS) 100.12(6) angle(TeSC) 103.2(2) degrees, tau(CSTeS) 69.0(3) and tau(CCSTe) 81.6(6) degrees. Geometries of model compounds Te(SH)(2) and Te(SCH(3))(2) optimized at the MP2 level exhibit d(Te-S), angle(STeS), and tau(XSTeS) (X = H, C) values similar to those of 1-3. Natural bond orbital analysis revealed n(p)(S(1))-sigma(Te-S(2)) hyperconjugation as the cause for the CSTeS torsion angles being close to 90 or -90 degrees. Thermochemical calculations on the HF and MP2 level proved Te(SH)(4) to be unstable with respect to Te(SH)(2) and HSSH, thus rationalizing the reduction of Te(IV) to Te(II) when Te(O(i)Pr)(4) or TeO(2) are reacted with thiols. NMR spectra reveal ligand exchange reactions between different tellurium(II) dithiolates and between Te(SR)(2) and HSR'. These types of reaction offer other routes to tellurium(II) dithiolates.

Journal Article↗

Synthesis of single crystalline tellurium nanotubes with triangular and hexagonal cross sections.

Single crystalline tellurium (Te) nanotubes with triangular cross sections were successfully synthesized for the first time by a simple approach of vaporizing tellurium metal and condensing the vapor in an inert atmosphere onto a suitable substrate. Tellurium gas was evaporated by heating at 350 degrees C and was condensed on the Si (100) substrate at 150-200 degrees C, in the downstream of argon (Ar) gas at a flow rate of 25 sccm for 10 min. This led to the production of nanotubes of triangular cross section along with some hexagonal ones. The formation of the nanotubes was highly dependent upon the structure of the substrate surface, Ar gas flow rate, and the deposition temperature. When the substrate is Si (111) or sapphire (0001) or when the argon flow rate is increased to 500 sccm, nanowires and nanorods were exclusively formed. Irrespective of the morphologies, all the observed Te nanostructures grew in a regular [0001] direction. The facile approach to nanotubes with a triangular cross section may facilitate some new applications as well as stimulate theoretical studies pertaining to the stability of this high-energy configuration.

Journal Article↗

A green chemical approach to the synthesis of tellurium nanowires.

Starch, an economical and safe carbohydrate, has been found to be not only an effective reducing agent but also a new morphology-directing agent for the synthesis of tellurium nanowires using commercial H2TeO4 precursor. The obtained tellurium nanowires are of single-crystal in nature, with an average diameter of approximately 25 nm and length up to 10 microm. A possible synthetic mechanism involves the chain-shaped bioorganic molecule acting as a template for the one-dimensional growth of inorganic tellurium. The effects of different chain-shaped structures and concentrations of biomolecules on the nanowire morphology have been investigated and different one-dimensional structures, including thick rods, short nanowires, bunched nanowires, and assembled spikelet structures, have been fabricated. These experimental results have been found to be useful in substantiating the proposed synthetic mechanism.

Journal Article↗

High-quality luminescent tellurium nanowires of several nanometers in diameter and high aspect ratio synthesized by a poly (vinyl pyrrolidone)-assisted hydrothermal process.

Large-scale selective synthesis of uniform single crystalline tellurium nanowires with a diameter of 4-9 nm, and microbelts with a width of 250-800 nm and tens of micrometers in length, can be realized by a poly (vinyl pyrrolidone) (PVP)-assisted hydrothermal process. The formation of tellurium nanowires and nanobelts in the presence of PVP is strongly dependent on the reaction conditions such as temperature, the amount of PVP, and reaction time. The results demonstrated that the keys for selective synthesis of Te nanobelts and nanowires are to modulate the growth rates of (100), (101), and (110) planes in the presence of PVP and to precisely control the reaction kinetics. High-quality luminescent ultrathin t-Te nanowires with a diameter of 4-9 nm display strong luminescent emission in the blue-violet region. This approach provides a facile route for the production of high-quality tellurium nanostructures with an interesting optical property. Furthermore, the synthesized ultrathin nanowires with deep blue color and nanobelts in gray color by this approach can be well dispersed in water or ethanol, making it possible for further engineering of their surfaces to prepare other hybrid core-shell nanostructures.

Journal Article↗

Dissociation study of tellurium cluster ions, Te(n)(+) (n = 25-85) using secondary ion mass spectrometry.

Dissociation pathways of tellurium clusters, Te(n)(+) (n = 25-85), were investigated by secondary ion mass spectrometry. Positively charged ions were generated from a tellurium sheet by bombardment with 10 keV xenon ion beam. Mass analyses of cluster ions were performed using a grand-scale sector mass spectrometer. In the first field-free region, Te(n)(+) (n = 25-80) had a large dissociation probability with five- and six-atom emission and Te(n)(+) (n = 50-85) had a slightly large dissociation probability with 10- and 11-atom emission. Five- and six-atom dissociation in the second field-free region could be also observed. These results were most likely due to the cluster emission processes for Te(n)(+), although sequential atom emission and cluster emission could not be distinguished by this type of experiments.

Spectrometry, Mass, Secondary Ion↗

Tellurium-induced myelinopathy in adult rats.

Tellurium is known to induce a neuropathy in young rats but not in adult rats. In the present study adult rats were fed a diet containing 1.25% tellurium every day for 30 days. By the end of this period, the rats moved with difficulty but did not show paralysis. Study of teased nerve fiber preparations in conjunction with light and electron microscopy revealed myelin abnormalities consisting of myelin bubbling, segmental demyelination, and remyelination. In some animals, these abnormalities had a patchy distribution, affecting several adjoining nerve fibers in sciatic nerves, brachial plexus, and spinal roots. The intramyelinic edema sometimes was associated with splitting of the axons.

Animals↗

Teratogenicity of tellurium dioxide: prenatal assessment.

The effects of multiple maternal subcutaneous injections of tellurium dioxide (TeO2) suspended in olive oil (0-1,000 mumol/kg) from day 15 to day 19 of gestation were evaluated in the Wistar rat. External and internal soft-tissue examinations were performed on day 20 fetuses. Multiple maternal injections, at doses higher than 10 mumol/kg, resulted in a dose-related appearance of hydrocephalus, edema, exophthalmia, ocular hemorrhage, umbilical hernia, undescended testis, and small kidneys in fetuses on day 20 of gestation. At 500 mumol/kg, reduction in maternal weight gain was also observed. At this level, the incidence of the above anomalies was 100%. The 100 mumol/kg dose of Te, which did not produce apparent maternal toxic responses, resulted in a 100% incidence of hydrocephalus and edema but no fetal mortality. Thus, tellurium can be teratogenic to the rat fetus without concomitant maternal toxicity. Also, the fetal period may be more sensitive than the organogenic period for the induction of hydrocephalus. Such evidence is consistent with the development of the choroid plexus and an effect of TeO2 on the production/resorption of cerebrospinal fluid.

Abnormalities, Drug-Induced↗

Tellurium-labeled fatty-acid analogs: relationship of heteroatom position to myocardial kinetics.

To determine the effects of tellurium-heteroatom position on myocardial fatty-acid kinetics, a series of tellurium Te 123m-labeled heptadecanoic-acid analogs (123mTe-THDA) were evaluated in dogs. The left-anterior descending coronary artery was partially occluded, and 123mTe-THDA labeled at either the 5, 6, 9, 10, 11, 12, or 13 position from the carboxyl group was administered intravenously. In 24 dogs, the 123mTe activity in the ischemic and normal zones was monitored continuously for 3 h using miniature radiation detectors. There were no significant differences between the ischemic- and normal-wall 123mTe clearance rates for any of the compounds. There was minimal fractional 3-h myocardial clearance for the 123mTe-THDA labeled at the 5, 6, and 9 position (range of means, 0.02-0.05). There was significant clearance of 123mTe-THDA labeled at the 11, 12, and 13 position (range of means, 0.37-0.44). The myocardial clearance of the 123mTe-THDA labeled at the 10 position was intermediate between the two extremes. Thus, as the 123mTe heteroatom is placed further from the carboxyl portion of the molecule, there is a progressive increase in the myocardial clearance. Selection of the heteroatom position should depend on whether initial fatty-acid distribution or subsequent clearance rates are being studied.

Animals↗

Toxicity study in rats of a tellurium based immunomodulating drug, AS-101: a potential drug for AIDS and cancer patients.

Male and female Sprague Dawley rats were injected intraperitoneally for 4 weeks with ammonium trichloro (dioxyethylene-0-0'-) tellurate, an immunomodulating drug at doses ranging from 3 to 24 mg/kg/week. Routine laboratory examinations included body weight, food consumption, clinical chemistry and hematological examinations. At termination of the experiment, all rats were sacrificed and subjected to a detailed necropsy. Few mortalities were recorded during the course of the study. Clinical signs included hind limb paresis and paraphimosis. A garlic odor pervaded the room. Body weight and food consumption were adversely affected in a dose-related manner. Effects were elicited on the hematological system; changes being noted in the platelet and leukocyte counts as well. Clinical chemistry evaluation revealed signs of hepatoxicity, especially in the female treated groups. The level of beta-globulin was increased. At necropsy organs were found to have a grayish-blue discoloration. Tellurium related histopathological changes were observed in the eyes, liver, thymus, bone marrow, heart and kidneys. An attempt has been made to compare the toxicity of this drug with other tellurium-containing compounds. A good correlation was found. Novel effects of the drug were retinopathy and replacement of bone marrow by bony or fibrous tissue. The possibility that some of the effects may have been elicited due to selenium-vitamin E deficiency has been considered.

Acquired Immunodeficiency Syndrome↗