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PubMed2004

Si-E (E = N, O, F) bonding in a hexacoordinated silicon complex: new facts from experimental and theoretical charge density studies.

The concept of hypervalency in molecules, which hold more than eight valence electrons at the central atom, still is a topic of constant debate. There is general interest in silicon compounds with more than four substituents at the central silicon atom. The dispute, whether this silicon is hypervalent or highly coordinated, is enlightened by the first experimental charge density determination and subsequent topological analysis of three different highly polar Si-E (E = N, O, F) bonds in a hexacoordinated compound. The experiment reveals predominantly ionic bonding and much less covalent contribution than commonly anticipated. For comparison gas-phase ab initio calculations were performed on this compound. The results of the theoretical calculations underline the findings of the experiment.

Journal Article↗
PubMed1995

Silicone breast implants: immunotoxic and epidemiologic issues.

Silicone gel implants for breast augmentation and reconstruction have been in use since 1962. Significant local complications include capsular contracture, rupture, gel "bleed", and spread of the implant material to regional lymph nodes (1-7) as well as histologic findings of foreign body granulomas in the capsular tissue and in lymph nodes (7-9). Through magnetic resonance spectroscopy and atomic emission spectroscopy, silicon compounds were found in the blood of some women with silicone breast implants; silicone and silica have also been found in liver (10). Well-publicized case reports have raised significant concerns regarding an association between implants and systemic disease. However, despite the availability of silicone implants for over 30 years, controlled epidemiological studies were not carried out until 1992. Currently available epidemiologic data are extremely limited. In part, because the majority of implants were used after 1981, the incidence of long-term problems is not yet known. In 1992, due to the unavailability of studies demonstrating the safety of implants, the U.S. Food and Drug Administration advised that silicone breast implants should be used only in reconstructive surgery and as part of clinical trials (11). This decision spurred a wave of research on the bioreactivity of silicone and clinical observations of patients with implants. Herein, we review the adverse immune effects following contact with silicone as well as the epidemiologic data available.

Animals↗
PubMed1998

[Silicone breast prosthesis and rheumatoid arthritis: a new systemic disease: siliconosis. A case report and a critical review of the literature].

Today the number of women receiving breast implants of silicone gel, for augmentation or reconstruction of the breast, is increasing. Silicon implants may cause local complications (such as capsular contracture, rupture, closed capsulotomy, gel "bleed", nodular foreign body granulomas in the capsular tissue and lymph nodes) or general symptoms. An adverse immune reaction with signs and symptoms of rheumatoid disorders is also possible, although an increased frequency of true autoimmune systemic connective tissue diseases is controversial. The US Food and Drug Administration advised that these silicone implants should be used only in reconstructive surgery and as part of clinical trials. Silicone is not an inert substance and silicone compounds were found in the blood and liver of women with silicone breast implants. The development of disease related to silicone implants would depend on genetic factors, so that only a very few women are potentially at risk. HLA-DR53 may be a marker of predisposed subjects. Breast-feeding by women with silicone implants should not be recommended for possible autoimmune disorders in the children. We report the case of an adult female patient with silicone breast implantation for bilateral mastectomy (performed 12 months before) and a unique syndrome characterized by low-grade fever, chronic fatigue, arthralgias of the hands, dysphagia, dry eye, increased level of rheumatoid factor and decreased value of complement C3 and C4. No increased erythrocyte sedimentation rate occurred, and no ANA, nDNA, ENA and AAT autoantibodies were evidence. A critical review of literature (source: MEDLINE 1980-1997) was performed and our case seems to be the first one reported in Italy. The internist should become familiar with the immunological disorders related to silicone breast implants, often so marked to require the explantation of the prostheses to improve symptomatology. However, perhaps due to the leak and spreading of silicone, the progression to a severe systemic involvement may remain despite the implant removal.

Adult↗
PubMed2005

Disproving a silicon analog of an alkyne with the aid of topological analyses of the electronic structure and ab initio molecular dynamics calculations.

A silicon compound has recently been synthesized that was claimed to exhibit the first realization of a silicon-silicon triple bond. We debate this classification on the basis of a thorough investigation of the nature of the chemical bond, using the rigorous topological analysis of the electron density as developed in Bader's atoms-in-molecules theory, that of the electron localization function and the related orbital-independent definitions of the bond order. Our results refer both to the ground-state geometry and to nonequilibrium configurations, which are accessed by the system in a room-temperature ab initio molecular dynamics simulation. We also use the reciprocal compliance force constant as an independent chemical descriptor. All the above procedures are in agreement and do not support the classification of the silicon-silicon central bond as triple. The characterization which consistently emerges from the present study is one in which two electron pairs participate in the bonding and the other pair belongs mainly to nonbonding regions.

Alkynes↗
PubMed1979

Calcification in augmentation mammoplasty.

Twenty-five cases of augmentation mammoplasty from among 1,600 routine mammograms were divided into paraffin and silicon compound groups. Calcification occurred in 11 cases and was seen in 75% of the paraffin group and 29% of the silicone group. The calcifications in the paraffin group were small, annular, and too numerous to be counted. They were diffusely distributed and tended to involve the lymph nodes. The calcifications in the silicone group were large, egg-shaped, localized, and fewer in number. Lymphadenopathy was rare. The two groups also differed in time elapsed between mammoplasty and mammography.

Adult↗
PubMed1983

[Perforation of the nasal septum of occupational origin].

Perforations of nasal septum as typical effects of exposure to certain hazards are a particular health problem among the diseases of upper respiratory tract mucous membranes (entry 10 on the list of occupational diseases). To obtain more data on etiopathogenetic factors and correlations between the clinical picture and exposure duration, the documentation of the patients in whom perforation was diagnosed during 1972-1979 was analysed epidemiologically. The examinations covered 185 workers of various industrial branches-salina, chemical plants, leather plants, tanneries, electroplating plants-who developed nasal septum perforation due to local effects of working environment irritants. In the test group the nasal septum was defected mostly in those exposed to chromium compounds (46.5%) and in salina workers (44.3%). In the remaining 9.2% of subjects the septum perforation resulted from exposure to arsenic, nickel, silicone compounds, cadmium, fluorine, soda and ammonia. The clinical course of the disease was presented as classified by industrial branch, occupational exposure, age and length of employment. In addition, procedures of diagnostics, certification and prevention were considered.

Abscess↗
PubMed1990

Investigations on the mechanism of the hypocholesterolemic action of 1-ethoxysilatrane.

Intraperitoneal administration of the nontoxic silicon compound, 1-ethoxysilatrane, to the rat did not cause proliferation of hepatic mitochondria or of endoplasmic reticulum, nor did it affect mitochondrial oxidative phosphorylation. The activities of cholesterol 7 alpha-hydroxylase in hepatic microsomes and of cholesterol oxidase in mitochondria respectively were unaffected by silatrane treatment. The rate of release of bile, whose composition remained unchanged, also was not increased in silatrane-treated animals. The results indicated that the compound did not affect the pathway of cholesterol degradation. A progressive decrease in the activity of hepatic microsomal 3-hydroxy-3-methylglutaryl coenzyme A (HMGCoA) reductase was observed on administration of the compound over a period of three weeks. Consistent with this, cholesterol biosynthesis in liver as measured by incorporation of radioactive precursors, acetate and water but not mevalonate, was significantly decreased in silatrane-treated animals. However, enzyme-linked immunosorbent assay revealed that the concentration of HMGCoA reductase protein was not decreased by the treatment indicating that inactivated enzyme was also present in such microsomes. Addition of silatrane to microsomes in the assay system did not cause inhibition indicating that the inactivation is by an indirect mechanism. It is concluded that the hypocholesterolemic action of the compound rested entirely on the inhibition of cholesterol biosynthesis in vivo by inactivation of the rate-limiting enzyme HMGCoA reductase.

AMP-Activated Protein Kinases↗
PubMed1998

Accommodation amplitude after lens refilling with injectable silicone by sealing the capsule with a plug in primates.

OBJECTIVE: To restore accommodation in primate eyes by refilling the lens capsule with injectable silicone compounds. MATERIALS AND METHODS: Eight eyes of 8 monkeys (Macaca fascicularis) were treated by the lens refilling procedure. To prevent leakage of the injected liquid silicone before it polymerized in the capsule in vivo, a silicone plug for sealing the capsular opening was developed. After endocapsular phacoemulsification following an upper minicircular capsulorhexis, the plug was introduced into the capsulorhexis opening. A silicone mixture was injected into the capsular bag through the delivery tube of the plug. Automated refractometry was performed 1 week and 3 months after surgery. Accommodation amplitude was determined as the difference between the refractions before and 1 hour after topical application of 4% pilocarpine chloride. RESULTS: Five of 8 eyes could be refilled. In 4 of 5 eyes, refraction could be measured. Accommodation amplitude ranged from 1.0 to 4.5 diopters, with a mean of 2.3 +/- 1.3 diopters (8.0 +/- 2.0 preoperative values). At 3-month examination, thick posterior capsule opacification precluded refractometry in all eyes. CONCLUSIONS: The lens refilling procedure with the use of a silicone plug for sealing the capsular opening was feasible in primate eyes. The accommodation amplitude attained was a small fraction of the value before surgery. This may result from the loss of so-called intracapsular accommodation, ie, active participation of lens fiber cells in accommodation. However, since the obtained accommodation may be sufficient for near vision after cataract surgery, this lens refilling procedure warrants further study. Elucidation of the mechanism of intracapsular accommodation may also be necessary.

Accommodation, Ocular↗
PubMed2001

Acupuncture granulomas.

Silicone compounds have recently been a source of controversy with regard to their potential role in the genesis of collagen vascular diseases. Foreign body reactions to injectable silicone were noted early in its cosmetic use and led to subsequent abandonment of this procedure. Here we report the first documented case of silicone granulomas to occur after acupuncture.

Acupuncture Therapy↗
PubMed2001

Direct determination of silicon in powdered aluminium oxide by use of slurry sampling with in situ fusion graphite-furnace atomic-absorption spectrometry.

A direct method for determination of silicon in powdered high-purity aluminium oxide samples, by slurry sampling with in situ fusion graphite-furnace atomic-absorption spectrometry (GF-AAS), has been established. A slurry sample was prepared by 10-min ultrasonication of a powdered sample in an aqueous solution containing both sodium carbonate and boric acid as a mixed flux. An appropriate portion of the slurry was introduced into a pyrolytic graphite furnace equipped with a platform. Silicon compounds to be determined and aluminium oxide were fused by the in situ fusion process with the flux in the furnace under optimized heating conditions, and the silicon absorbance was then measured directly. The calibration curve was prepared by use of a silicon standard solution containing the same concentration of the flux as the slurry sample. The accuracy of the proposed method was confirmed by analysis of certified reference materials. The proposed method gave statistically accurate values at the 95% confidence level. The detection limit was 3.3 microg g(-1) in solid samples, when 300 mg/20 mL slurry was prepared and a 10 microL portion of the slurry was measured. The precision of the determination (RSD for more than four separate determinations) was 14% and 2%, respectively, for levels of 10 and 100 microg g(-1) silicon in aluminium oxide.

Aluminum Oxide↗
PubMed2006

The role of molecular modeling in bionanotechnology.

Molecular modeling is advocated here as a key methodology for research and development in bionanotechnology. Molecular modeling provides nanoscale images at atomic and even electronic resolution, predicts the nanoscale interaction of unfamiliar combinations of biological and inorganic materials, and evaluates strategies for redesigning biopolymers for nanotechnological uses. The methodology is illustrated in this paper through reviewing three case studies. The first one involves the use of single-walled carbon nanotubes as biomedical sensors where a computationally efficient, yet accurate, description of the influence of biomolecules on nanotube electronic properties through nanotube-biomolecule interactions was developed; this development furnishes the ability to test nanotube electronic properties in realistic biological environments. The second case study involves the use of nanopores manufactured into electronic nanodevices based on silicon compounds for single molecule electrical recording, in particular, for DNA sequencing. Here, modeling combining classical molecular dynamics, material science and device physics, described the interaction of biopolymers, e.g., DNA, with silicon nitrate and silicon oxide pores, furnished accurate dynamic images of pore translocation processes, and predicted signals. The third case study involves the development of nanoscale lipid bilayers for the study of embedded membrane proteins and cholesterol. Molecular modeling tested scaffold proteins, redesigned apolipoproteins found in mammalian plasma that hold the discoidal membranes in the proper shape, and predicted the assembly as well as final structure of the nanodiscs. In entirely new technological areas such as bionanotechnology, qualitative concepts, pictures and suggestions are sorely needed; these three case studies document that molecular modeling can serve a critical role in this respect, even though it may still fall short on quantitative precision.

Biosensing Techniques↗
PubMed2004

Effects of inorganic substances on water splitting in ion-exchange membranes; II. Optimal contents of inorganic substances in preparing bipolar membranes.

An approach to enhancing the water-splitting performance of bipolar membranes (BPMs) is introducing an inorganic substance at the bipolar (BP) junction. In this study, the immobilization of inorganic matters (i.e., iron hydroxides and silicon compounds) at the BP junction and the optimum concentration have been investigated. To immobilize these inorganic matters, novel methods (i.e., electrodeposition of the iron hydroxide and processing of the sol-gel to introduce silicon groups at the BP junction) were suggested. At optimal concentrations, the immobilized inorganic matters significantly enhanced the water-splitting fluxes, indicating that they provide alternative paths for water dissociation, but on the other hand possibly reduce the polarization of water molecules between the sulfonic acid and quaternary ammonium groups at high contents. Consequently, the amount of inorganic substances introduced should be optimized to obtain the maximum water splitting in the BPM.

Journal Article↗
PubMedDate not supplied

For insulin infusion: a miniature precision peristaltic pump and silicone rubber reservoir.

This paper describes a miniature precision peristaltic pump and a silicone rubber reservoir developed for the infusion of insulin in diabetic subjects. The ability of the 100-ml reservoir to maintain sterility of its contents over 26 refilling cycles (48 days) is demonstrated. Accelerated bench tests on 10 pumps over 30 days indicate an accuracy of +/- 1% on flow rate whether measured over 10 min or 24 h and with or without 1 atm of outlet back pressure. Comparison of calibrations made before and after 58 animal and clinical tests of 6--71 days' duration showed a percentage difference in calibration that varied with a mean +/- SD of 0.05 +/- 3.09%. Microscopic examination of pump tube samples after 21 days of clinical use indicated redistribution of surface material without evidence of particle spallation. Samples subjected to accelerated wear equivalent to 620 days of clinical use showed extensive luminal surface modification and particulate deposits on downstream filters. These were identified by X-ray spectroscopy as silicon compounds.

Animals↗