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Interfacial Behavior of Mixed Systems of Glycerylether-Modified Silicone and Polyoxyethylene-Modified Silicone.

Undecylglycerylether-modified silicone (GES; the glycerylether-type surfactant with a silicone segment and alkyl chains (carbon number, 11) as the hydrophobic portion) forms a molecular aggregate (M.A.) with a small amount of water. This M.A. is similar to the reversed hexagonal liquid crystal formed by alpha-mono long-chain alkylglycerylether (3-isooctadecyloxy-1,2-propanediol; GE). From the investigation of the phase behavior in the water/GES/polydimethylsiloxane (PDMS) ternary system, a wide three-phase region of water (W)+M.A.+oil (O) was observed. As this M.A. is insoluble in PDMS and easily orients in the interface between water and PDMS, the high water content silicone W/O emulsion using GES as a surfactant is well stabilized. However, as the PDMS content increased this W/O emulsion became less stable. In order to improve this stability, mixtures of GES and polyoxyethylene-modified silicone (PS) were applied to the silicone emulsion as co surfactant. By application of a PS with a methyl group at the end cap of the polyoxyethylene chain (PSM), the emulsion became most stable at a GES/PSM ratio of 1 : 2, and at the same time, the interfacial tension between the oil phase and the water phase became minimal. The reason for this was studied by the measurement of spin-lattice relaxation times (T(1)) of the alkyl chains of GES in the GES/PS/water system by (13)C NMR. We assumed that the W/O silicone emulsions were stabilized by the efficient orientation of the aggregates in the interface between the silicone phase and the water phase by using PSM as a cosurfactant. Copyright 2001 Academic Press.

Journal Article↗

Solution structure of hanatoxin1, a gating modifier of voltage-dependent K(+) channels: common surface features of gating modifier toxins.

The three-dimensional structure of hanatoxin1 (HaTx1) was determined by using NMR spectroscopy. HaTx1 is a 35 amino acid residue peptide toxin that inhibits the drk1 voltage-gated K(+) channel not by blocking the pore, but by altering the energetics of gating. Both the amino acid sequence of HaTx1 and its unique mechanism of action distinguish this toxin from the previously described K(+) channel inhibitors. Unlike most other K(+) channel-blocking toxins, HaTx1 adopts an "inhibitor cystine knot" motif and is composed of two beta-strands, strand I for residues 19-21 and strand II for residues 28-30, connected by four chain reversals. A comparison of the surface features of HaTx1 with those of other gating modifier toxins of voltage-gated Ca(2+) and Na(+) channels suggests that the combination of a hydrophobic patch and surrounding charged residues is principally responsible for the binding of gating modifier toxins to voltage-gated ion channels.

Amino Acid Motifs↗

Modifiable automata self-modifying automata.

One of the most important features of living beings that seems universal is perhaps their ability to be modified in a functional way. In order to modelize this characteristic, we designed automata with a finite number of instantaneous internal descriptions, with input(s) and output(s) and which are able to be functionally modified. The rules which govern the evolution of these automata (and the initial conditions) are randomly chosen at the beginning and once and for all. When such an automaton is linked by its input and output to a deterministic process, it always stabilizes and it then has the property to rebuild itself. Thus it made a function which is inverse of the external function. We demonstrate the prevalence of p = 1 length period and of tau = 0 transient length for automata with m instantaneous internal descriptions.

Animals↗

Biological properties of chemically modified insulins. I. Biological activity of proinsulin and insulin modified at A1-glycine and B29-lysine.

Beef insulin, pork proinsulin and four derivatives of beef insulin modified at the A1-B29 site on the molecular surface have been studied. Three derivatives had a synthetic crosslink between the A and B chains. Previous studies with these materials [2, 3 and 5] had demonstrated in vivo bioactivities which were much higher than those displayed in vitro. This paper reports experiments which explain this discrepancy. The analogues were administered at equimolar rates to anaesthetised greyhounds by a priming-dose constant infusion technique and the plasma concentrations achieved were estimated by radioimmunoassay. Proinsulin and the modified insulins were metabolised more slowly than insulin. Biopotency values, which related fall in plasma glucose concentration to the total administered dose of analogue, agreed broadly with published results of conventional in vivo bioassays. On the other hand, calculation of potency in relation to the serum concentration of analogue actually achieved, yielded results which agreed more closely with in vitro assay data. We conclude that for these analogues, reported discrepancies between in vitro and in vivo biopotencies can be largely explained by the different rates at which these materials are metabolised.

Adipose Tissue↗

Bacterial adhesion measurements on soft contact lenses using a Modified Vortex Device and a Modified Robbins Device.

S. marcescens 8100 and P. aeruginosa 15442 were used to study bacterial adhesion to hydrogel contact lenses which had not been worn. Bacterial removal from unworn lens materials was assessed with a calibrated vortex device modified with a digital rpm readout and fitted with a test tube attachment (MVD). The MVD, which relies on a whirlpool-like force to remove the bacteria, showed that bacteria adhered to the same degree to etafilcon A, vifilcon A and polymacon lenses under standardized conditions. Tracking the isoenzyme patterns of these bacterial species over time showed instability of S. marcescens upon repeated passage. This instability was not evident with P. aeruginosa. Bacterial adhesion of P. aeruginosa 15442, to human worn and unworn etafilcon A materials was determined with a Modified Robbins Device. The MRD was closed off at both ends stopping medium and bacterial movement after 1 h of fluid flow over the lens surface. The results show that immediately following this 1-h period more bacteria adhere to unworn contact lenses than to worn lenses. However, bacterial counts were equivalent on worn and unworn lenses following 5 h of static incubation.

Bacterial Adhesion↗

Effect of air polishing on the fluoride release of (resin-modified) glass ionomer cements and of a polyacid-modified composite resin.

Eight different conventional and resin-modified glass ionomers as well as a polyacid-modified composite were air polished and their fluoride release was determined in comparison to untreated controls. The air polishing was done with two different devices at medium and maximum setting for powder and water. Ninety discs of 1.5 mm thickness and 7.0 mm diameter were produced from each cement. These discs were stored in 5 ml deionized water at 37 degrees C. After 1 day and 1, 4, 8, 12, and 16 weeks, the specimens were transferred into new vials with fresh deionized water. From the 4th week onward, the specimens (except for the untreated controls) were air polished on half of their upper and lower surfaces for 2 s each before being put into a new vial. After 20 weeks the fluoride released during the previous 4 weeks was determined with a fluoride ion-sensitive electrode. With the exception of Ketac-Cem, all cements released significantly more fluoride ions after air polishing, irrespective of the devices' settings. The differences in the amount of fluoride released among the investigated materials were greater than the changes in fluoride release patterns caused by air polishing. Air polishing increased the fluoride release by 20-60% in most of the materials investigated.

Cariostatic Agents↗

Development of gingivitis around aged restorations of resin-modified glass ionomer cement, polyacid-modified resin composite (compomer) and resin composite.

Resin-modified glass ionomer cements (RMGIC) and polyacid-modified resin composites (PMC, compomers) are two recently introduced material groups supposed to replace traditional cements in operative dentistry. The new restoratives release initially fluoride in different relatively high concentrations, which decrease gradually during the first weeks in vivo. Earlier studies showed a stronger subclinical inflammatory reaction around different conventional tooth colored restorative materials than around intact enamel. The aim of this study was to compare intra-individually the initiation of gingival inflammation around, aged RMGIC, PMC and resin composite restorations. Subgingivally located Class III restorations were placed in 17 patients. Each patient received one of each of the experimental materials. All patients were placed on an oral hygiene regime 1-year after finishing of the restorations. Gingivitis was induced during a one-week period without oral hygiene. The gingival condition was assessed by sampling of gingival crevicular fluid (GCF), registration of the amount of bacterial plaque and by registration of bleeding after gentle probing of the entrance of the gingival sulcus (SBI) on the experimental filling- and control-enamel surfaces at days 0 and 7. No differences were seen in plaque and gingival index scores between the materials at both days. The GCF increased significantly for all surfaces during the experimental gingivitis period. At day 7 significantly lower GCF was sampled around the enamel surfaces. In conclusion, the differences between the materials did not result in measurable differences concerning clinical or subclinical signs of gingivitis.

Adult↗

Calorie restriction modifies the delayed-type hypersensitivity response to the hapten trinitrobenzenesulfonic acid and to hapten-modified syngeneic spleen cells.

We have studied the influence of different degrees of calorie restriction on the induction and the regulation of the delayed type hypersensitivity (DTH) response to trinitrobenzenesulfonic acid (TNBS) and TNBS-modified spleen cells (TNBS-SC), injected by the sc or the iv route. Immediately after weaning, BALB/c mice were placed on restricted diets for either 2 or 4 weeks and then the DTH response was induced. The results showed that a 37.5% restriction in the food supply significantly depressed the level of the DTH response induced by the sc injection of TNBS-SC. In contrast, a 25% restriction in the food supply was insufficient to depress the response. Calorie restriction did not modify the inhibitory influence of an iv injection of TNBS-SC on the DTH response. However, iv presensitization with free hapten or the simultaneous injection of TNBS-SC by the iv and the sc routes did not significantly depress the DTH response in calorie-restricted mice, indicating a defect in the inhibitory regulation of the DTH response in these dietary groups.

Animals↗

Comparison of in-vitro bond strengths between resin-modified glass ionomer, polyacid-modified composite resin, and giomer adhesive systems.

INTRODUCTION: The purpose of this in-vitro study was to compare the shear bond strength of orthodontic brackets bonded to tooth enamel with 4 adhesives: a commercially available giomer material, a polyacid-modified composite resin (PMCR), a resin-modified glass ionomer (RMGI), and a standard resin-based composite (RBC) adhesive. MATERIALS: Eighty extracted human molars were collected and divided into 4 groups (n = 20). Two stainless steel premolar brackets were bonded to each tooth with 1 of the 4 adhesives, according to each manufacturers' instructions. One bracket was tested for shear bond strength at 1 hour and the other at 7 days. A shear force was applied to the bracket/tooth interface with a chisel-shaped rod attached to a universal testing machine at a crosshead speed of 0.5-mm per minute until bracket failure. The force in newtons was recorded. Debonded enamel surfaces were examined under a stereomicroscope to assess the amount of residual adhesive. RESULTS: A 2-factor analysis of variance detected significant differences among adhesive types and time of load test. The Tukey HSD test determined that the RBC and the RMGI adhesives had significantly higher shear bond strength than the giomer and the PMCR materials at both 1 hour and 7 days. The chi-square test detected a significant difference in adhesive remnant index scores. The bracket/resin interface was the most common site of failure for all groups except the RMGI group. CONCLUSIONS: RMGI orthodontic cement provides acceptable bond strength in vitro. Further clinical research is needed to validate this laboratory finding.

Acrylic Resins↗

Ankylosing spondylitis and symptom-modifying vs disease-modifying therapy.

The main objectives of medical therapy in ankylosing spondylitis (AS) are to relieve pain, stiffness and fatigue and to prevent structural damage. The Assessment in Ankylosing Spondylitis Working Group has proposed different domains with specific instruments to assess the efficacy of therapeutic agents classified as symptom-modifying and disease-controlling antirheumatic drugs. Non-steroidal antiinflammatory drugs (NSAIDs) are still the first-line treatment in the management of AS, and they are effective in controlling symptoms such as pain and stiffness and maintaining mobility in many patients. A recent randomized trial suggested that the progression of radiological damage occurs less on continuous use of celecoxib compared with on-demand use. If such findings were confirmed by other studies, the therapeutic value of NSAIDs in AS may extend beyond symptom control. However, for each individual patient, the expected advantages of treatment with NSAIDs should be weighted against any possible gastrointestinal and cardiovascular disadvantages. Disease-modifying antirheumatic drugs (DMARDs) are widely used for second-line therapy in AS, but the evidence for their efficacy is poor. The term 'DMARD' has been borrowed from rheumatoid arthritis, and none of the DMARDs have been shown to prevent or significantly decrease the rate of progression of structural damage which is required to be qualified as a disease-controlling antirheumatic drug for AS. Sulphasalazine is the most extensively studied DMARD and studies suggest some degree of clinical benefit confined to peripheral joint involvement, but no evidence of benefit in axial disease. Methotrexate, which is the gold standard DMARD in rheumatoid arthritis, does not seem to have a substantial therapeutic effect in AS on axial or peripheral joint involvement. Leflunomide appears to exert little beneficial effect, if any, even on peripheral joint involvement. There is also good evidence that local therapy with corticosteroids is effective and may be used in selected patients. Oral corticosteroids may be somewhat effective in relieving the symptoms of AS, but this has not been formally studied. Small studies have reported favourable results with intravenous methylprednisolone pulse therapy, but the effect is temporary. Pamidronate and thalidomide have been used in some preliminary trials but need further studies to assess their potential role in treating AS patients resistant or intolerant to other forms of treatment. Treatment with tumour necrosis factor blockers is not discussed in this review.

Anti-Inflammatory Agents, Non-Steroidal↗

Improved chiral separation using achiral modifiers in cyclodextrin modified capillary zone electrophoresis.

The influence of achiral modifiers on the chiral separation of propranolol is examined by cyclodextrin modified capillary zone electrophoresis. The improved chiral separation of propranolol is by molecules previously identified in our group as forming ternary complexes with cyclodextrin and pyrene. The polarity, chain size and heteroatom composition of the functional groups on the comodifiers was systematically varied in order to study the influence of these variables on the separation of propranolol. The improved chiral separation is accompanied by a decrease in retention time. The decrease in retention time is suggestive of a decrease in the association of beta-cyclodextrin (beta-CD) with propranolol which was verified by calculation of apparent association constants using fluorometric methods.

Cyclodextrins↗

Comparative study of the physical properties of a polyacid-modified composite resin and a resin-modified glass ionomer cement.

OBJECTIVES: The physical properties of the resin-modified composite resin Dyract (Detrey Dentsply) and the resin-modified glass ionomer cement Fuji II LC (GC) were compared, and the effect of water sorption on these properties was studied. METHODS: Compressive, diametral compressive and flexural strengths were measured using specimens aged up to three months. The Vickers hardness and the water erosion were also determined. The specimens were stored at 37 degrees C under five different conditions, chosen to vary the water sorption of the samples. The results were analyzed using a multi-factor analysis of variance. RESULTS: Dry specimens of Dyract and Fuji II LC showed similar properties. However, the two materials behaved differently when stored in presence of water. In contrast to Fuji II LC, Dyract showed very little expansion for the first 24 h (1.5 +/- 0.3 and 0.03 +/- 0.01%, respectively), leached small quantities of ions and retained its mechanical strength. Those differences are related to their chemical composition. Fuji II LC is hydrophilic, as it contains polyHEMA. In the presence of water, Fuji II LC behaves like a hydrogel, but the network resulting from the copolymerization of acidic and UDMA monomers is less hydrophilic, and the effect of water on Dyract is retarded. SIGNIFICANCE: The significant properties of Dyract are determined by its composite character. This certainly represents some advantages, for instance, a higher mechanical strength, a better protection against initial dehydration and subsequent water effects. However, Dyract shows some disadvantages over Fuji II LC, like a lower amount of fluoride release or the interference of oxygen during polymerization.

Absorption↗

Effect of maturation on the fluoride release of resin-modified glass ionomer and polyacid-modified composite resin cements.

The effect of an early water contact on the fluoride release is studied for the resin-modified glass ionomer cements (RM-GIC) GC Lining LC, PhotacBond, Vitremer and Vitrebond and for the polyacid-modified composite resins (PAM-C) Variglass and Dyract. Six months fluoride release profiles were determined in regularly renewed water (37 degrees C), for the products directly after light curing and after 24 h maturation in a humid atmosphere (85% RH). ANOVA shows that both the short-term and the long-term fluoride release of a RM-GIC are influenced by this maturation. This indicates that direct water contact for this material should be avoided. For the RM-GIC a correlation is found between the initial fluoride release process and the long-term process. For the PAM-C materials, no differences in the fluoride release are found as a function of maturation, indicating that early water contact has no effect. The amounts of fluoride released by PAM-C are low compared to RM-GIC, which can affect their caries preventive potential. The results are explained on the basis of the setting reaction of both types of materials.

Acrylic Resins↗

Effect of a neutral citrate solution on the fluoride release of resin-modified glass ionomer and polyacid-modified composite resin cements.

The effect of 0.01 mol/l citrate solution at pH = 7 on the fluoride release is compared for the resin-modified glass ionomer cements (RM-GIC) GC Lining LC, PhotacBond, Vitremer and Vitrebond and for the polyacid-modified composite resins (PAM-C) Variglass and Dyract by means of the six-month fluoride release profiles at 37 degrees C. The fluoride release of both RM-GIC and PAM-C increases in the neutral citrate solution as compared to water, which can be explained by the ability of citrate to complex metal ions and hence to degrade the glass as well as the polysalt matrix of the cement. Although RM-GIC release more fluoride than PAM-C in water as well as in citrate solution, the relative increase in fluoride release upon immersion in citrate solution is most pronounced for PAM-C. Whereas for the latter citrate affects both the short-term and long-term fluoride release, for RM-GIC only the long-term fluoride release is affected. This suggests that the action of citrate increases with decreasing importance of the polysalt formation in the hardening of the material. This could be explained on the basis of the difference in the chemical properties of the cement matrix.

Acrylic Resins↗

Carboranethiol-modified gold surfaces. A study and comparison of modified cluster and flat surfaces.

Four different carboranethiol derivatives were used to modify the surfaces of gold nanoparticles and flat gold films. The novel materials engendered from these modifications are extraordinarily stable species with surfaces that support self-assembled monolayers of 1-(HS)-1,2-C2B10H11, 1,2-(HS)2-1,2-C2B10H10, 1,12-(HS)2-1,12-C2B10H10, and 9,12-(HS)2-1,2-C2B10H10, respectively. Surprisingly, characterization of these materials revealed that a number of molecules of the carboranethiol derivatives are incorporated inside the nanoparticles. This structural feature was studied using a number of techniques, including X-ray photoelectron spectroscopy (XPS), UV-vis, and IR spectroscopies. Thermal desorption experiments show that carborane molecules detach and leave the nanoparticle surface mostly as 1,2-C2B10H10 isotopic clusters, leaving sulfur atoms bound to the gold surface. The surfaces of both the gold nanoparticles and the flat gold films are densely packed with carboranethiolate units. One carborane cluster molecule occupies an area of six to seven surface gold atoms of the nanoparticle and eight surface gold atoms of the flat film. XPS data showed that molecules of 1,12-(HS)2-1,12-C2B10H10 bind to the flat gold surface with only half of the thiol groups due to the steric demands of the icosahedral carborane skeleton. Electrochemical measurements indicate complete coverage of the modified gold surfaces with the carboranethiol molecules.

Boron Compounds↗

Anti-Candida and mode of action of two newly synthesized polymers: a modified poly (methylmethacrylate-co-vinylbenzoylchloride) and a modified linear poly (chloroethylvinylether-co-vinylbenzoylchloride) with special reference to Candida albicans and Candida tropicalis.

Polymeric antimicrobial agents represent a new and important direction that is developing in the field of antimicrobial agents. Antimicrobial activity of two newly synthesized polymers: a modified poly (methylmethacrylate-co-vinylbenzoylchloride) and a modified linear poly (chloroethylvinylether-co-vinylbenzoylchloride) have been investigated and found to be active. Both polymers have showed a broad antimicrobial activity against C. albicans and C. tropicalis. Minimal inhibitory concentrations (MIC's) for poly (methylmethacrylate-co-vinylbenzoyl chloride) were 100, 75 and 100 microg/ml in case of C. albicans (ATCC 2091), C. albicans (SC5314) and C. tropicalis, respectively. However, polycholoroethylvinylether-covinylbenzoylchloride inhibited C. albicans (ATCC 2091), C. albicans (SC5314) and C. tropicalis with minimum inhibitory concentration values (MIC's) of 150 microg/ml against the three tested Candida strains. Mode of action studies of both polymers on the medically important yeasts, C. albicans and C. tropicalis revealed that poly (methylmethacrylate-co-vinylbenzoylchloride) induced cytotoxicity, DNA damage, and altered cell permeability and morphology, which was manifested as aggregated and swollen yeast cells (C. albicans ATCC 2091) by fluorescent microscopy examination. Poly (chloroethylvinylether-co-vinylbenzoylchloride) increased cell permeability, and respiration for C. albicans and C. tropicalis. The tested polymers at 50 microg/ml had pronounced effects on C. albicans and C. tropicalis cell wall phosphopeptidomannane, proteins, sugars and phosphorus. Generally, the two polymers proved effective against the tested microorganisms, but growth inhibitory effect varied according to the composition of the polymer active group. Many investigators consider polymeric antimicrobial agents as a potential new approach for enhancing the efficiency of some existing antimicrobial agents, including prolonged activity, reduce their toxicity, as well as reduce the environmental issues associated with product use.

Antifungal Agents↗

Modified proenzymes as artificial substrates for proteolytic enzymes: colorimetric assay of bacterial collagenase and matrix metalloproteinase activity using modified pro-urokinase.

We describe a new principle for assessment of the activity of proteolytic enzymes of all classes and show the application of this principle for the quantitative assay of bacterial collagenase and human matrix metalloproteinases (MMPs). Central to this new principle is the presence of a proenzyme that can be activated into an active enzyme by a single proteolytic event. The regular activation sequence in the proenzyme is replaced using protein engineering by an artificial sequence recognized by the proteinase to be determined. The latter can act as an activator for the newly engineered proenzyme. In the present paper a simple colorimetric assay for the determination for MMPs is described based on this principle. With the aid of protein engineering, a modified pro-urokinase has been prepared in which the activation sequence normally recognized by plasmin (Pro-Arg-Phe-Lys upward arrowIle-Ile-Gly-Gly) has been replaced by a sequence expected to be recognized and hydrolysed by many MMPs (Arg-Pro-Leu-Gly upward arrowIle-Ile-Gly-Gly). The active urokinase resulting from activation of the modified pro-urokinase by a MMP could be measured either directly, using a specific chromogenic peptide substrate for urokinase, or indirectly via urokinase-catalysed plasminogen activation. The response of the assay to equal molar quantities of active MMPs decreases in the order MMP-2>MMP-9>MMP-1>MMP-3>MMP-7. The detection limit for MMP-9 was below 15 pM, corresponding to 3. 75x10(-15) mol per assay. Using the assay, increased MMP activity was detected in synovial tissue extracts from rheumatoid arthritis patients compared with those from osteoarthritis patients, and in stomach tumour extracts as compared with normal stomach tissue extracts.

Arthritis, Rheumatoid↗

The influence of finishing time on the marginal seal of a resin-modified glass-ionomer and polyacid-modified resin composite.

The aim of this study was to compare the effect of immediate and delayed finishing on the microleakage of encapsulated resin-modified glass-ionomer, Fuji II LC and a polyacid-modified resin composite, Dyract compomer at both the enamel and dentine margins. Standardized Class V cavities were prepared along the cemento-enamel junction on buccal and palatal surfaces of 24 freshly extracted non-carious premolars. Equal numbers of buccal and palatal cavities in each group were restored with Fuji II LC and Dyract compomer following the manufacturer's instructions. The groups with delayed finishing were restored 1 week earlier, stored in saline at 37 degrees C and finished on the same day as the groups with immediate finishing. The specimens were then thermocycled 500 times and subjected to dye penetration testing. The results showed that both materials leaked more at the dentine than enamel margins for both regimes of finishing methods. There was no statistical difference in the microleakage of Dyract finished immediately or later at enamel and dentine margins and Fuji II LC finished immediately or later in dentine. However, a statistical difference existed between the microleakage in Fuji II LC finished immediately and later in enamel.

Bicuspid↗