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Novel gamma-phase of titanium metal at megabar pressures.

Group IV transition metals titanium, zirconium, and hafnium are expected to transform from an ambient hexagonal close packed (hcp, alpha-phase) to a body centered cubic (bcc, beta-phase) at high pressures. This transition path is usually facilitated by the occurrence of an intermediate hexagonal phase (distorted bcc, omega-phase). The existence of a bcc phase in zirconium and hafnium at high pressures has been known for the past ten years; however, its occurrence in titanium has been theoretically predicted but never observed. We report a novel unexpected transformation in titanium metal from an omega phase to an orthorhombic phase (distorted hcp, gamma-phase) at a pressure of 116+/-4 GPa.

Journal Article↗

(NH4)2ZrGe3O9: a new microporous zirconogermanate.

A new microporous zirconogermanate, diammonium zirconium trigermanate, (NH(4))(2)ZrGe(3)O(9) (FDZG-2), analogous to wadeite (K(2)ZrSi(3)O(9)), was hydrothermally synthesized using ZrO(NO(3))(2).2H(2)O as the source of zirconium and 1,4-diaminobutane as a structure-directing agent. Single-crystal X-ray diffraction analysis reveals that the framework structure is built up of cyclic trigermanate units crosslinked by ZrO(6) octahedra. The Zr atom lies at a site with -3 symmetry and the unique N atom of the ammonium ion lies at a site with threefold symmetry. Large cages are observed, with two NH(4)(+) cations in each. The structure contains intersecting six- and three-membered ring (6MR and 3MR) channels, but only the 6MR channels can accommodate the NH(4)(+) ions.

Journal Article↗

Infrared spectra of U.S. automobile original finishes. VII. Extended range FT-IR and XRF analyses of inorganic pigments in situ--nickel titanate and chrome titanate.

The identification, analysis, and occurrence in U.S. automobile original finishes (1974-1989) of Nickel Titanate (yellow) and Chrome Titanate (yellow-orange) are described in this report. The titanate pigments are based on the rutile (titanium dioxide) structure and there are only minor differences between the infrared absorptions of rutile and the titanates. Titanate pigment absorptions in paint spectra can thus be easily mistaken for those of rutile. Each of the titanates, however, contains two elements in addition to titanium that can serve to distinguish them using elemental analyses. Fourier transform infrared (4000-220 cm(-1)) and X-ray fluorescence instruments were used in combination for the in situ analysis of the titanates. In addition to titanium, nickel, and antimony, the three main detectable elements comprising Nickel Titanate, all of the commercial products of this pigment that were examined also contained impurities of zirconium, niobium, and usually lead. These elements were also detected in most of the monocoats in which Nickel Titanate was identified, as well as in the Chrome Titanate pigments, and the zirconium to niobium ratio was found to exhibit a wide variation. Nickel Titanate is a relatively common pigment that was identified in nearly three dozen U.S. automobile yellow nonmetallic monocoats (1974-1989), while Chrome Titanate appears to have been used in only a few yellow and orange nonmetallic monocoats. The use of the titanate pigments likely increased after this time period as they were replacements for lead chromate pigments (last used in a U.S. automobile original finish in the early 1990s), and are more amenable for use in basecoat/clearcoat finishes than in monocoats. Minor distortions of the infrared absorptions of rutile, anatase, and the titanates obtained using accessories with diamond windows were noted, and their origins are discussed.

Journal Article↗

Isolation and structural characterization of 1-zirconacyclopent-3-yne, five-membered cyclic alkynes.

Stable five-membered cyclic alkynes were synthesized, isolated, and fully characterized. Divalent zirconium species, bis(cyclopentadienyl)zirconium(II) equivalent, reacted with (Z)-1,4-disubstituted 1,2,3-butatrienes [(Z)-R-CH=C=C=CH-R, 1a: R = (CH3)3Si-, 1b: R = tert-C4H9-] to give 1-zirconacyclopent-3-yne compounds (2a-b) in good yields. X-ray diffraction analysis revealed their five-membered cyclic structure with a sufficiently short triple bond to regard this compound as a metallacyclopentyne.

Journal Article↗

92Nb-(92)Zr and the Early Differentiation History of Planetary Bodies.

The niobium-92-zirconium-92 ((92)Nb-(92)Zr) extinct radioactive decay system (half-life of about 36 million years) can place new time constraints on early differentiation processes in the silicate portion of planets and meteorites. Zirconium isotope data show that Earth and the oldest lunar crust have the same relative abundances of (92)Zr as chondrites. (92)Zr deficits in calcium-aluminum-rich inclusions from the Allende meteorite constrain the minimum value for the initial (92)Nb/(93)Nb ratio of the solar system to 0.001. The absence of (92)Zr anomalies in terrestrial and lunar samples indicates that large silicate reservoirs on Earth and the moon (such as a magma ocean residue, a depleted mantle, or a crust) formed more than 50 million years after the oldest meteorites formed.

Journal Article↗

Active immobilized antibiotics based on metal hydroxides.

The water-insoluble hydroxides of zirconium (IV), titanium (IV), titanium (III), iron (II), vanadium (III), and tin (II) have been used to prepare insoluble derivatives of a cyclic peptide antibiotic by a facile chelation process. Testing of the antibacterial activities of the products against two gram-positive and two gram-negative bacteria showed that in the majority of cases the water-insoluble antibiotics remained active against those bacteria susceptible to the parent antibiotic. The power of the assay system has been extended by the novel use of colored organisms to aid determinations where the growth of normal organisms could not be distinguished from the appearance of the supporting material. Insoluble derivatives of neomycin, polymyxin B, streptomycin, ampicillin, penicillin G, and chloramphenicol were prepared by chelation with zirconium hydroxide, and these derivatives similarly reflected the antibacterial activities of the parent compounds. Several of the metal hydroxides themselves possess antibacterial activity due to complex formation with the bacteria. However, the use of selected metal hydroxides can afford a simple, inexpensive, and inert matrix for antibiotic immobilization, resulting in an antibacterial product that may possess slow-release properties. The mechanisms by which the metal hydroxide-antibiotic association-dissociation may occur are discussed.

Anti-Bacterial Agents↗

Immobilization with metal hydroxides as a means to concentrate food-borne bacteria for detection by cultural and molecular methods.

The application of nucleic acid amplification methods to the detection of food-borne pathogens could be facilitated by concentrating the organisms from the food matrix before detection. This study evaluated the utility of metal hydroxide immobilization for the concentration of bacterial cells from dairy foods prior to detection by cultural and molecular methods. Using reconstituted nonfat dry milk (NFDM) as a model, two food-borne pathogens (Listeria monocytogenes and Salmonella enterica serovar Enteritidis) were concentrated from 25-ml samples by the sequential steps of clarification and high-speed centrifugation (designated primary concentration) and immobilization with zirconium hydroxide and low-speed centrifugation (designated secondary concentration). Sample volume reduction after immobilization with zirconium hydroxide was 50-fold, with total bacterial recoveries ranging from 78 to 96% of input for serovar Enteritidis and 65 to 96% of input for L. monocytogenes. Immobilized bacteria remained viable and could be enumerated by standard cultural procedures. When followed by RNA extraction and subsequent detection by reverse transcription (RT)-PCR, detection limits of 10(1) to 10(2) CFU/25 ml of reconstituted NFDM were achieved for both organisms. The bacterial-immobilization step was relatively nonspecific, resulting in recovery of >50% of the input cells when evaluated on a panel of representative bacterial strains of significance to foods. The method could be adapted to more complex dairy products, such as whole milk and ice cream, for which bacterial recoveries after immobilization ranged from 64 to >100%, with subsequent RT-PCR detection limits of >/=10(2) CFU/ml for whole milk and >/=10(1) CFU for ice cream for both serovar Enteritidis and L. monocytogenes. The bacterial-immobilization method is easy, rapid, and inexpensive and may have applications for the concentration of a wide variety of food-borne bacteria prior to detection by both conventional and alternative methods.

Animals↗

In vitro testing of ten bone cements after different time intervals from polymerization.

Biological response of cells to implanted bone cement is a fundamental but often neglected issue in successful cemented implants. In this study, ten acrylic bone cements for orthopedics were assayed using two different in vitro testing methods on L929 cells. The cements were mixed as prescribed, cured for either 1 h or 7 days and then extracted in minimum essential medium (MEM) according to the ISO standard for the preparation of samples. For the evaluation of cytotoxicity, the neutral red uptake assay (NRU) and the incorporation of propidium iodide (PI) were used to detect the viability/death of cells. The two methods were shown to be well correlated (p < 0.0001) in the case of both the 1-h and the 7-day extracts. Two cements, i.e. CERIM LT and CMW2, were found to be toxic after 1-h curing through both the spectrophotometric NRU assay and the cytofluorometric assay with PI. After 7-day curing, these two cements, as well as the Zimmer-low viscosity cement, were toxic according to the NRU assay. The toxic effect of all the cements disappeared after dilution of extracts 1:2 with MEM, except in the case of CERIM LT. In the search for the component inducing the toxic effect, the possible contribution of the residual monomer was discarded on the basis of literature data and the influence of various other factors was analyzed, including the contrast medium (barium sulphate or zirconium dioxide) and the concentrations of N,N-dimethyl-paratoluidine and of benzoyl peroxide (< 1% or > or = 1%). Unlike zirconium dioxide, barium sulphate was found to damage the cells at the 1-h endpoint. Benzoyl peroxide at concentration > or = 1% was found to affect cells at the same endpoint, whereas dimethylparatoluidine had no effect regardless of the proportion.

Animals↗

The influence of bone and bone cement debris on counterface roughness in sliding wear tests of ultra-high molecular weight polyethylene on stainless steel.

Studies of explanted hip prostheses have shown high wear rates of ultra-high molecular weight polyethylene (UHMWPE) acetabular cups and roughening of the surface of the metallic femoral head. Bone and bone cement particles have also been found in the articulating surfaces of some joints. It has been proposed that bone or bone cement particles may cause scratching and deterioration in the surface finish of metallic femoral heads, thus producing increased wear rates and excessive amounts of wear debris. Sliding wear tests of UHMWPE pins on stainless steel have been performed with particles of different types of bone and bone cement added. Damage to the stainless steel counterface and the motion of particles through the interface have been studied. Particles of bone cement with zirconium and barium sulphate additives and particles of cortical bone scratched the stainless steel counterface. The cement particles with zirconium additive produced significantly greater surface damage. The number of particles entering the contact and embedding in the UHMWPE pin was dependent on particle size and geometry, surface roughness and contact stress. Particles are likely to cause surface roughening and increased wear rates in artificial joints.

Bone Cements↗

[Development of new synthetic method using organometallic complexes and an application toward natural product synthesis].

Recently, many organometallic complexes, such as palladium, nickel, ruthenium, titanium complexes and others, were used for synthetic organic chemistry. We have developed many novel synthetic methods using these organometallic complexes for synthetic organic chemistry. As the organometallic complexes, nickel, chromium, molybdenum, ruthenium, zirconium, titanium, and palladium complexes, were used. Furthermore, bimetallic complexes having silicon-tin and silicon-zirconium bonds were investigated. On the other hand, utilization of gases in synthetic organic chemistry has been also developed. 1 atm pressure of gases such as CO, CO(2), N(2), ethylene and acetylene, could be used and the reaction procedure is very simple, that a balloon filled with a gas is connected on the top of the flask. Using our novel synthetic methods, we have synthesized many natural products and biologically active substances, such as cephalotaxin, mesembrine, tubifoline, strychnine, stemoamide, lycopodine, pumiliotoxin C, beta-lactam, carbapenam and benzodiazepinone derivatives.

Acetylene↗

In search of a 24 hours per day artificial kidney.

Wearable, 24 hrs per day, 7 days per week artificial kidneys are being developed. Patients will benefit from more even control of physiologic parameters than can be obtained with conventional intermittent dialysis. Improvement in economic and social circumstances will result. Both hemodialysis and peritoneal dialysis techniques are being miniaturized. Small REDY cartridges containing urease, zirconium phosphate, hydrouse zirconium oxide and activated carbon are being utilized to regenerate dialysate. Hemodialyzers will be worn on the forearm and include long, wide, low resistance series blood flow paths to reduce the potential for thrombosis. Peritoneal effluent is regenerated and filtered by the sorbent cartridge and automatically cycled back into the peritoneal cavity.

Animals↗

Restoration of posterior implants using a new ceramic material.

This article discusses posterior implant restorations made of an advanced, high-tech ceramic called zirconium oxide (also called In-Ceram Zirconia). This material, which is second in hardness only to diamond, was originally applied to industrial applications where metal components failed. Zirconium oxide is extremely hard, wear resistant, and chemically inert, and in combination with the In-Ceram technique, the first all-ceramic material recommended for posterior bridges.

Aluminum Oxide↗

Potentiometric/turbidometric titration of antiperspirant actives.

A titration procedure that simultaneously monitors the pH and turbidity of an antiperspirant solution during neutralization with sodium hydroxide was developed to characterize antiperspirant actives. Aluminum chloride, aluminum chlorohydrate (ACH), and aluminum zirconium glycine complex (AZG) gave distinctive pH/turbidity profiles. The activated forms of aluminum chlorohydrate (ACH') and aluminum zirconium glycine complex (AZG') produced more turbidity than the non-activated forms. On an equimolar basis, AZG' produced more turbidity than any of the antiperspirant actives tested.

Deodorants↗

Comparison of in vitro tensile bond strengths of luting cements to metallic and tooth-colored posts.

The aim of this study was to compare the tensile bond strength of tooth-colored ceramic and carbon-fiber post materials as well as titanium and stainless steel post materials luted with three different kinds of luting cements. Disks of alloy post materials were polished with 600-grit SiC paper, air abraded, and ultrasonically cleaned. Ceramic surfaces were pretreated with hydrofluoric acid and silanized. Panavia F, Vitremer, and ProTec Cem cements were bonded to the post specimens and placed in a humidor for 24 hours. Specimens were placed in a jig, and the debonding values were obtained using a universal testing machine. Means and standard deviations were analyzed by two-way ANOVA. Panavia F provided the highest bond strengths for all types of post materials. ProTec Cem bonded more strongly to stainless steel and titanium than to zirconium oxide. Vitremer results were the lowest. Bonds to carbon-fiber post materials were weaker than to metallic post materials, but stronger than to zirconium oxide. In general, higher bond strengths resulted in a higher percentage of cohesive failures.

Acid Etching, Dental↗

Infrared laser sclerostomies.

Four solid-state lasers with three fiberoptic delivery systems were used to perform laser sclerostomies in an acute-injury rabbit model and in fresh human globes. The lasers used were continuous-wave neodymium:yttrium aluminum garnet (YAG, 1.06 microns) and pulsed holmium:yttrium scandium galliam garnet (YSGG) (2.10 microns), erbium:YSGG (2.79 microns), and erbium:YAG (2.94 microns). Thermal damage to tissue and total laser energy required to produce sclerostomies decreased with increasing wavelength. In human tissue using a 600-microns fused silica fiberoptic, maximum thermal damage (greater than or equal to 100 microns) was noted at 1.06 microns with a total energy of 21 J at a power density of 2.5 kW/cm2. In addition, focal damage to the iris and ciliary body was noted at this wavelength. The least amount of thermal damage (15-20 microns) and lowest total energies needed were found at 2.94 microns. A 250-microseconds pulse length and pulse radiant exposures of 3.6 J/cm2 and 14.3 J/cm2 were used for the low hydroxyl-fused silica (500 microns) and zirconium fluoride (250 microns) fiberoptics, respectively. Although zirconium fluoride fibers have high through-put efficiencies that facilitate study of laser tissue interactions at 2.94 microns, problems encountered with fragility and solubility of the bare tip in aqueous media limit its usefulness. A high attenuation rate with the low hydroxyl-fused silica fiber limited its usable length to 35 cm at 2.94 microns. Tissue damage during sclerostomy formation was minimized at 2.94 microns, reaching a maximum at 1.06 microns. Minimizing tissue damage theoretically could decrease subconjunctival scarring and filtration failure.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

Investigations of urinary stone formation following persorption.

Persorption is the excretion in urine of particles that have been absorbed (persorbed) from the gastrointestinal tract. In experiments with rats the effect of Herbst was combined with the production of renal calcium oxalate sediments by the oral administration of ethylene glycol and acidification with ammonium chloride. We used this method to investigate whether persorbed corpuscula may represent nuclei of crystallization in the formation of renal calculi. Lead sulfide, zirconium silicate and 45Ca-labeled calcium oxalate crystals were used as persorbable model bodies. It became apparent that orally supplied lead sulfide and zirconium silicate crystals could be found in the urine and the kidneys but they did not function as crystallization centers in the calcium oxalate sediments. However, radioactive labeled calcium could be demonstrated histoautoradiographically within the renal concrements. Our experiments showed that persorbed calcium oxalate crystals can work as nuclei for stone formation.

Ammonium Chloride↗

Sorbent-filled hollow fibers for hemopurification.

Filled hollow fibers were prepared and evaluated for application in hemosorption. Powdered activated carbon, urease-carbon, and macroporous ion exchange resins were used as fillers in highly permeable cellulose acetate hollow fibers. The carbon-filled hollow fibers had better mass transfer properties than encapsulated carbon in solid form. Zirconium phosphate and 2 synthetic zeolites were tested for ammonium ion adsorption from buffered saline and Ringer's salt solutions. Synthetic zeolites were found to have higher specificity and capacity for ammonium ion adsorption than zirconium phosphate. Projections are that hemosorption devices utilizing urease, carbon, and zeolites could remove all nitrogenous waste metabolites currently being treated only by dialysis. Oxystarch and oxystarch derivatives were tested for direct urea adsorption and were found unsuitable for this application.

Adsorption↗

Temperature and pressure effects during erbium laser stapedotomy.

BACKGROUND AND OBJECTIVES: Laser-assisted stapedotomy has become a well-established alternative to the mechanical drilling method. The goal of this study is to quantify the mechanical and thermal tissue effects and to determine optimum erbium laser parameters for safe clinical treatment. STUDY DESIGN/MATERIALS AND METHODS: On an inner ear model, time-resolved pressure measurements and Schlieren optical flash photography were performed during the perforation of the stapes foot plate using an erbium laser at 2.79 microns. The laser radiation was transmitted via an optical zirconium fluoride fiber. The laser-treated foot plates were investigated by light microscopy and scanning electron microscopy to visualise the laser-induced tissue effects. RESULTS: Perforation of the stapes foot plate can be performed with a few erbium laser pulses with high precision and a thermal damage zone of < 10 microns. Strong pressure transients were found to be generated by the bone ablation process and the collapse of a vapor channel created in the perilymph after fenestration. CONCLUSION: From the comparison of the laser-induced pressure with the limit graph to avoid hearing defects published by Pfander, an unobjectionable use of the erbium laser is deduced for fluences < 10 J/cm2. The erbium laser seems to represent an ideal instrument for middle ear surgery with all the advantages (precision, fiber optic transportable, high ablation efficiency, safety) desired for clinical application.

Erbium↗