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High resolution solid-state 29Si NMR spectroscopy of silicone gels used to fill breast prostheses.

We have used 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy to study the chemical structure of the silicone gels in virgin and explanted breast prostheses. Despite evidences of alteration in the morphological appearance of the silicone gel inside the breast prosthesis, our results do not reveal changes in the chemical nature and structure of the silicone gels after implantation. In addition to the main 29Si resonance peak at -22.26 ppm that corresponds to the resonance frequency of the D repeat unit of the polysiloxane chains, the high sensitivity of our NMR technique allows the detection of very low concentrations of silicone compounds. Within our experimental detection limit of 0.2%, no signal between -90 ppm and -150 ppm are observed. This indicates that no silica products are present inside the gel of the prostheses. Furthermore, our 29Si NMR spectra indicate differences in the chemical compositions of the silicone gels from different manufacturers.

Breast Implants↗

The influence of inorganic silicon (Si) on pituitary-thyroid axis.

The influence of silicon-treatment on the levels of TSH and thyroid hormones was studied in rats. Concentrations of thyrotropin (TSH), triiodothyronine (T3), and thyroxine (T4) were estimated in sera of rats receiving per os a soluble silicon compound--sodium metasilicate nonahydrate (Na2SiO3.9H2O), dissolved in the animals' drinking water. An increase in the TSH level in the tested group was observed, without statistically significant differences in T3 and T4 concentrations between the two groups of animals. The results provide evidence for the influence of silicon on the endocrine balance. They could also prove that this chemical element is capable of modifying the rate of some hormones' synthesis.

Animals↗

Imaging the cerebrovascular tree in the cadaveric head for planning surgical strategy.

OBJECTIVE: The objective of the study was to identify whether an integration of cadaveric dissections with preoperative imaging information may enable a better understanding of pathological anatomy, especially vascular lesions, and thus allow for greater precision in surgical planning. METHODS: We selected a computed tomographic contrast agent and experimentally determined the proportion of it that could mix compatibly with the silicone compound. The resultant mixture was injected into the cerebrovascular systems of six fresh human cadaveric heads. The specimens underwent computed tomography for the purpose of digital virtual exposures in parallel with laboratory dissections performed on these specimens. RESULTS: The 1:8 ratio of contrast agent to silicone rubber was determined to be appropriate for both computed tomography and subsequent laboratory dissection of the specimens. The blood vessels in computed tomographic scans demonstrated a higher attenuation than surrounding soft tissues. The opacity consistency of the injected vessels was a critical parameter for a clear three-dimensional rendering of the vascular structures in the natural surroundings of the skull base. Static and dynamic three-dimensional images of the cadaveric vascular tree were obtained as viewed through surgical corridors of various skull base approaches. CONCLUSION: We demonstrated a new cadaveric preparation model for imaging and dissection. This model allows for static and dynamic three-dimensional examination of the surgical anatomy from a neurosurgeon's perspective. It may facilitate the study of cerebrovascular system morphology/pathology in relation to the skull base as a tool for surgical planning.

Brain↗

Effect of the Nd:YAG laser on polymethylmethacrylate, HEMA copolymer, and silicone intraocular materials.

Recent trends of cataract extraction feature both small surgical wounds and preservation of posterior capsules. The development of safe, reliable, and flexible implant materials that can withstand near impact with a Nd:YAG laser during secondary posterior capsule discissions are required. An in vitro experiment was performed to analyze the effects of Nd:YAG laser irradiation on polymethylmethacrylate (PMMA), hydroxyethylmethacrylate (HEMA), hydroxyethylhydroxymethylmethacrylate (HEMA-MEMA) copolymer combination, and a silicone compound. The HEMA and HEMA-MEMA compounds were the least susceptible to Nd:YAG laser damage in this laboratory setting.

Acrylates↗

The action of excessive, inorganic silicon (Si) on the mineral metabolism of calcium (Ca) and magnesium (Mg).

The influence of silicon treatment on the levels of calcium and magnesium in blood serum and tissues was studied in rats. The concentrations of both elements were estimated in samples of sera and tissues of rats receiving per os a soluble, inorganic silicon compound--sodium metasilicate nonahydrate (Na2SiO3.9H2O (REACHIM, USSR)), dissolved in the animals' drinking water. A decrease of magnesium concentration in serum was observed with accompanying elevation of registered calcemia. Moreover, a reduction of tissue calcium levels was found with a simultaneous increase of magnesium tissue pool. The results provide evidence for silicon involvement in mineral metabolism. It could result in a modification of pathological processes concerning bone tissue.

Animals↗

Volatile organic components in the Skylab 4 spacecraft atmosphere.

The volatile organic components in the spacecraft cabin atmosphere of Skylab 4 were trapped on a solid adsorbent at various times during the mission. In post-flight analyses, more than 300 compounds in concentrations from less than 1 ppb up to 8000 ppb could be detected by high-resolution gas chromatography. In the samples of the 11th, 47th, and 77th day of the mission, approximately 100 components in the molecular weight range of 58 to 592 were identified by mass spectrometry. Besides components known from other environments, such as alkanes, alkenes, and alkylated aromatic hydrocarbons, components typical for the human metabolism such as ketones and alcohols were found. Other typical components in the spacecraft atmosphere are fluorocarbons (freons) and various silicone compounds, mostly normal and cyclic methylsiloxanes.

Air Pollutants↗

Silicon metabolism. The interrelations of inorganic silicon (Si) with systemic iron (Fe), Zinc (Zn), and copper (Cu) pools in the rat.

The influence of silicon treatment on the levels of trace elements zinc (Zn), copper (Cu), and iron (Fe) in serum and tissues was studied in rats. The concentrations of silicon, iron, and zinc were estimated in samples of sera and tissues of rats receiving per os a soluble, inorganic silicon compound--sodium metasilicate nonahydrate (Na2SiO3.9H2O), dissolved in the drinking water. An increase of copper concentrations in liver and aortic walls in the experimental group was observed, with simultaneous reduction of zinc amounts in serum and all the tissue samples in the course of the experiment. The iron concentrations in the analyzed samples did not show any significant changes between both groups. The silicon levels in serum and in all the examined tissues were significantly higher in the tested group. The results provide evidence for the silicon interaction with copper and zinc, which could result in a number of metabolic process modifications, antiatheromatous activity among them.

Animals↗

Vibrational spectra of trimethylsilanol. The problem of the assignment of the SiOH group frequencies.

The assignment of the SiOH group vibrations of trimethylsilanol, which is still controversial, is proposed. This assignment is based on theoretical B3LYP force field scaled using the constants of the (CH3)3Si group optimized to fit experimental vibrational frequencies of (CH3)3SiF and (CD3)3SiF molecules as well as the OH stretching scale factor from methanol. The ab initio force field defined in this way gives a good agreement of the theoretical vibrational frequencies of trimethylsilanol with the positions of IR and Raman bands observed in the gas phase. This force field predicts the greatest contribution of the delta SiOH coordinates to the vibration with frequency of 804 cm(-1). The elimination of the coupling of the SiOH deformation with methyl rocking modes by the normal coordinate treatment of (CD3)3SiOH gives 832 cm(-1) for silanol deformation which is in a good agreement with the 834 cm(-1) value proposed earlier for the bending mode of free silanol groups. The geometry and force field of the open chain H3SiOH trimer is computed to model the change of the delta SiOH frequencies upon formation of the hydrogen-bonded polymers. This model predicts a significant shift of SiOH bending frequencies to the 1000-1200 cm(-1) range while those of SiOD to the 800-850 cm(-1) range. These predictions allow us to ascribe the 1087 cm(-1) band observed in the IR spectrum of crystalline (CH3)3SiOH and the Raman 775 cm(-1) band of the liquid (CH3)3SiOD to deformations of the hydrogen-bonded silanol groups.

Fluorides↗

Palladium-catalyzed conjugate addition of organosiloxanes to alpha,beta-unsaturated carbonyl compounds and nitroalkenes.

The addition of aryltrialkoxysilanes to alpha,beta-unsaturated carbonyl compounds (ketones, aldehydes) and nitroalkenes in the presence of SbCl(3), TBAF, AcOH, and a catalytic amount of Pd(OAc)(2), in CH(3)CN at 60 degrees C, provides the corresponding conjugate addition products in moderate to good yields. The addition of equimolar amounts of SbCl(3) and TBAF is necessary for this reaction to proceed smoothly. The arylpalladium complex, which is generated by the transmetalation from a putative hypercoordinate silicon compound, is considered to be the catalytically active species.

Aldehydes↗

Masticatory efficiency.

A method for measuring masticatory efficiency is described as well as a mathematical formula expressing the masticatory efficiency as an index. A silicone compound was used as test material. The masticatory efficiency index was calculated as the mean of the best four out of five consecutive measurements of masticatory efficiency calculated from a specially designed formula.

Chemical Phenomena↗

Modeling of adhesion in tablet compression--I. Atomic force microscopy and molecular simulation.

Adhesion problems during tablet manufacturing have been observed to be dependent on many formulation and process factors including the run time on the tablet press. Consequently, problems due to sticking may only become apparent towards the end of the development process when a prolonged run on the tablet press is attempted for the first time. It would be beneficial to predict in a relative sense if a formulation or new chemical entity has the potential for adhesion problems early in the development process. It was hypothesized that favorable intermolecular interaction between the drug molecules and the punch face is the first step or criterion in the adhesion process. Therefore, the rank order of adhesion during tablet compression should follow the rank order of these energies of interaction. The adhesion phenomenon was investigated using molecular simulations and contact mode atomic force microscopy (AFM). Three model compounds were chosen from a family of "profen" compounds. Silicon nitride AFM tips were modified by coating a 20-nm iron layer on the surfaces by sputter coating. Profen flat surfaces were made by melting and recrystallization. The modified AFM probe and each profen surface were immersed in the corresponding profen saturated water during force measurements using AFM. The work of adhesion between iron and ibuprofen, ketoprofen, and flurbiprofen in vacuum were determined to be -184.1, -2469.3, -17.3 mJ. m(-2), respectively. The rank order of the work of adhesion between iron and profen compounds decreased in the order: ketoprofen > ibuprofen > flurbiprofen. The rank order of interaction between the drug molecules and the iron superlattice as predicted by molecular simulation using Cerius(2) is in agreement with the AFM measurements. It has been demonstrated that Atomic Force Microscopy is a powerful tool in studying the adhesion phenomena between organic drug compounds and metal surface. The study has provided insight into the adhesion problems occurring during tablet compression and a direction for continued study.

Adhesiveness↗

Kikuchi's histiocytic necrotizing lymphadenitis associated with ruptured silicone breast implant.

OBJECTIVE: In this report we explore the relationship between Kikuchi's necrotizing lymphadenitis (Kikuchi-Fujimoto disease, KD) and a leaky silicone breast implant. PATIENT: The simultaneous occurrence of KD and silicone lymphadenopathy in an axillary lymph node of a patient with a leaking silicone breast implant is reported. Since both KD and silicone implants have been implicated in autoimmune diseases, including systemic lupus erythematosus, serologic tests for antinuclear antibodies and rheumatoid factor were performed. RESULTS: Axillary lymph nodes showed both silicone lymphadenopathy, as well as classic morphologic and immunophenotypic features of KD. Screening tests for systemic autoimmune disorders were within normal range, suggesting that the unusual Kikuchi's-like immune reaction in one axillary lymph node was localized. The patient has no evidence of progressive immunologic disorders 3 years later. Subsequent lymph node biopsies showed silicone adenopathy with no evidence of KD. CONCLUSIONS: Our findings indicate that silicone compounds may be associated with transient abnormal immune reactions and lend further support to the hypothesis that KD represents an exuberant T-cell-mediated immune response to a variety of nonspecific stimuli.

Adult↗

Antibodies to cholesterol: biological implications of antibodies to lipids.

Injection of silicone gel or silicone oil intraperitoneally into BALB/c mice induced the formation of antibodies that reacted by ELISA with highly purified crystalline cholesterol and, to a much lesser extent, antibodies that reacted with a phospholipid (dimyristoyl phosphatidylglycerol). Although IgM and IgG antibodies to cholesterol were detected, the titers of IgG antibodies were low when compared with IgM. The titers of IgM antibodies to cholesterol in certain sera exhibited activities that reached baseline values at dilutions as high as 1:5000, thus making them equivalent to titers that have been previously published for ascites fluid containing murine monoclonal antibodies to cholesterol. The antibodies to cholesterol induced by silicone compounds are indistinguishable in their binding to crystalline cholesterol from naturally-occurring antibodies to cholesterol in normal human serum. They are also indistinguishable from antibodies induced by a proposed vaccine to cholesterol that is currently in late preclinical development for prevention of hypercholesterolemia in humans. The anti-cholesterol vaccine, which consists of liposomes heavily laden with cholesterol as an antigen and lipid A as an adjuvant, induces antibodies that react with low density lipoproteins (LDL) and opsonize them for removal by liver macrophages. It appears that silicone gel or silicone oil causes recruitment and adsorption of cholesterol at the injection site, and also serves as an adjuvant that may have immunostimulant properties similar to lipid A for inducing antibodies to lipids. Antibodies to lipids such as cholesterol or phospholipids are not harmful to intact cell membranes because of steric hindrance from surrounding lipids and larger macromolecules that block binding of the antibodies.

Animals↗

The effect of silicon (Si) on lipid parameters in blood serum and arterial wall.

The influence of silicon treatment on the levels of lipid parameters of blood serum and aortic wall was studied in rats. The concentrations of total cholesterol, phospholipids, triglycerides, HDL-cholesterol, LDL-cholesterol, and HDL-phospholipids were measured in sera of rats receiving per os a soluble, inorganic silicon compound--sodium metasilicate nonahydrate (Na2SiO3.9H2O)--dissolved in the drinking water. In the aortic tissue levels of total cholesterol, triglycerides and phospholipids were estimated. An increase in HDL-cholesterol and HDL-phospholipid concentrations, with a simultaneous decrease of LDL-cholesterol and triglyceride levels, was observed in the sera of the tested group. The levels of total cholesterol and phospholipids in the sera, as well as the concentrations of lipids in the aortic walls, showed no significant differences. The results obtained could provide evidence for the existence of an additional mechanism of silicon antiatheromatous action, concerning the modification of activity of enzymatic systems involved in lipids metabolism.

Animals↗

[Effect of the enteric sorbent noolit on the psychoemotional status in mice].

The enterosorbent noolit (representing a mineral matrix base with immobilized lithium and silicon compounds) significantly affects the psychoemotional state of mice with depression model induced by prolonged social emotional stress. Noolit administration produces a pronounced anxiolytic and antidepressant effect and reduced the level of behavioral deficiency in the test animals.

Animals↗

Chemistry of the aromatic 9-germafluorenyl dianion and some related silicon and carbon species.

Dipotassio-9-germafluorenyl dianion (3b) was synthesized by reduction of 9,9-dichloro-9-germafluorene (4b) with sodium/potassium alloy in tetrahydrofuran. The X-ray crystal structure of 3b, like that for the analogous silicon compound 3a, shows C-C bond length equalization in the five-membered metallole rings and C-C bond length alternation in the six-membered benzenoid rings, indicating aromatic delocalization of electrons into the germole ring of 3b. Calculated nucleus independent chemical shift (NICS) values indicate that the five-membered ring is more aromatic than the six-membered rings in 3a and 3b. Derivatization of 3b with Me(3)SiCl gave 9,9-bis(trimethylsilyl)-9-germafluorene (5). Controlled oxidation of 3b yielded dipotassio-9,9'-digerma-9,9'-bifluorenyl dianion (6). Reaction of 6 with MeOH yielded 9,9'-digerma-9,9'-bifluorene (7). The X-ray structure of 6 indicates C-C bond length alternation in the five-membered rings. Thus dianion 6, like its silicon analogue 8, has the negative charges localized at metal atoms and no aromatic character. Dipotassio-9,9'-bifluorenyl dianion (9), the carbon analogue of 6, exhibits aromaticity with its X-ray crystal structure showing the C-C bond length equalization in both the five- and six-membered rings. Derivatization of 9 with MeI gave 9,9'-dimethyl-9,9'-bifluorene (10). The structure of 10 shows that the two fluorenyl rings are cis to each other with a torsional angle of 59 degrees and a long C-C single bond (1.60 A) connecting them.

Journal Article↗

Removal of siloxanes in biogases.

Methods for the removal of gaseous silicon compounds in biogases are presented. In laboratory studies, various solid adsorption materials and liquid absorption solutions were evaluated for their siloxane elimination efficiencies. Among the liquid sorbents studied, concentrated nitric acid and sulfuric acid were found to be especially potent siloxane removing agents at elevated temperature. Solid adsorbents tested include activated charcoal, carbopack B, Tenax TA, XAD II resins, molecular sieve 13X and silica gel. Apart from activated charcoal, silica gel showed especially high adsorption capacities of more than 100mg/g for siloxanes. Furthermore, excellent thermal regeneration of the loaded material was possible. The efficiency of silica gel in removing gaseous siloxanes was verified at a sewage treatment plant, where an adsorption bed with silica gel was used for biogas drying. Other gas pretreatment installations studied included refrigeration condensers and adsorbent beds of meadow ore for the catalytic removal of hydrogen sulfide. In contrast to biogas drying by refrigeration, which had a poor effect on siloxane content, the installation of meadow ore adsorption beds resulted in a significant siloxane reduction of 31-75%, depending on the site studied.

Adsorption↗

Whisker-reinforced dental core buildup composites: effect of filler level on mechanical properties.

The strength and toughness of dental core buildup composites in large stress-bearing restorations need to be improved to reduce the incidence of fracture due to stresses from chewing and clenching. The aims of the present study were to develop novel core buildup composites reinforced with ceramic whiskers, to examine the effect of filler level, and to investigate the reinforcement mechanisms. Silica particles were fused onto the whiskers to facilitate silanization and to roughen the whisker surface for improved retention in the matrix. Filler level was varied from 0 to 70%. Flexural strength, compressive strength, and fracture toughness of the composites were measured. A nano-indentation system was used to measure elastic modulus and hardness. Scanning electron microscopy (SEM) was used to examine the fracture surfaces of specimens. Whisker filler level had significant effects on composite properties. The flexural strength in MPa (mean +/- SD; n = 6) increased from (95+/-15) for the unfilled resin to (193+/- 8) for the composite with 50% filler level, then slightly decreased to (176+/-12) at 70% filler level. The compressive strength increased from (149+/-33) for the unfilled resin to (282+/-48) at 10% filler level, and remained equivalent from 10 to 70% filler level. Both the modulus and hardness increased monotonically with filler level. In conclusion, silica particle-fused ceramic single-crystalline whiskers significantly reinforced dental core buildup composites. The reinforcement mechanisms appeared to be crack deflection and bridging by the whiskers. Whisker filler level had significant effects on the flexural strength, compressive strength, elastic modulus, and hardness of composites.

Bisphenol A-Glycidyl Methacrylate↗