Vladimir Pavlović

Light transmission through fiber post: The effect on adhesion, elastic modulus and hardness of dual-cure resin cement

OBJECTIVES The aim of this study was to investigate the effect of fiber post light transmitting ability to the continuity of resin cement-root dentin (C-RD) and resin cement-fiber post (C-FP) interface, elastic modulus and hardness of a dual-cure resin cement. METHODS Spectrophotometric measurements were applied for the determination of light transmission at coronal, middle and apical level as well as at the apical tip through Tech 21 X-OP (TECH) and DT Light Post (DT). Posts were cemented using dual-cured resin cement (Calibra). Roots were sectioned longitudinally through the post. Epoxy resin replicas were made and used to evaluate C-RD and C-FP interface under SEM. Modulus of elasticity (E) and Vickers hardness (VH) of the cement layer were assessed. RESULTS No light transmission was detected through TECH. Light transmission through DT decreased from coronal to apical and rose at the apical tip. TECH presented a significantly lower percentage of continuous C-RD and C-FP interface in comparison to DT. Coronal third of C-RD interface in TECH specimens had a significantly higher percentage of continuity than apical third. No regional differences in continuity of C-RD interface were found in DT specimens. E and VH were significantly lower when TECH was used, and decreased from coronal to apical for both posts. SIGNIFICANCE Cementation of fiber post with no light transmitting ability using a dual-cured resin cement resulted in lower E and VH of the cement layer, and lower percentage of continuous C-RD and C-FP interface in comparison to cementation of light transmitting fiber post.

A convenient synthesis of 1α- and 1β-hydroxycholesterol

Abstract An efficient procedure for the preparation of 1α-hydroxycholesterol 3-acetate 4 is described, which starts from cholesterol and involves as key steps transannular cyclization of the ten-membered ring ontaining (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one 1 to the oxetane derivative 1α,5-epoxy-5α-cholestan-3β-ol acetate 3, and opening of the four-membered ether ring in the latter compound. 1β-Hydroxycholesterol diacetate 9 was obtained by oxidation of 4 to the 1-oxo derivative 8, followed by metal hydride reduction and acetylation.

New androst-4-en-17-spiro-1,3,2-oxathiaphospholanes. Synthesis, assignment of absolute configuration and in vitro cytotoxic and antimicrobial activities

The reactions of 17α-hydroxyprogesterone with Lawessons reagent (LR) in toluene, CH(2)Cl(2) and/or CCl(4) gave, depending on the duration of the reaction, two diastereoisomeric androst-4-en-17-spiro-1,3,2-oxathiaphospholane-2-sulfide pairs 2a,b and 3a,b in approximately 7:3 ratio, differing in configuration at the phosphorus atom. A parallel analysis of heteronuclear 2D (1)H-(13)C spectra (HSQC and HMBC) and homonuclear 2D spectra (NOESY) enabled complete (1)H and (13)C assignments of each isomer. Also, analysis of NOESY correlations provided evidence for the preferred conformation. X-ray analysis of 3a confirmed the structure and absolute configuration on phosphorus. A pathway for the formation of 1,3,2-oxathiaphospholane ring was proposed. Cytotoxic activity in vitro was tested against three tumor cell lines (human cervix carcinoma HeLa cells and two human breast carcinoma MDA-MB-361 and MDA-MB-453 cells). Compound 3a and mixture 3a,b showed a moderate activity against HeLa and MDA-MB-453 cell lines while against MDA-MB-361 cell line all tested compounds exerted very weak cytotoxic effect. Antimicrobial activity against Gram-positive, Gram-negative bacteria and fungal cells, toxicity to brine shrimp Artemia salina, were evaluated. All tested compounds showed strong antifungal activity.

Synthesis of 4-Aryl-2-aminopyridine Derivatives and Related Compounds

Abstract A short, efficient, and high-yielding synthesis of 4-aryl-2-aminopyridine derivatives has been developed. The route employs two palladium-catalyzed processes, the Suzuki reaction and the Buchwald–Hartwig amination, as the key steps. The same approach has been used for preparation of the corresponding quinoline derivatives. In addition, a brief study of biological properties showed the anticancer potential of these compounds.

13,14-seco-steroids: A new type of modified steroids containing a nine-membered ring

Oxidations of 14 alpha-hydroxy-5 alpha-cholestan-3 beta-yl acetate (5) with lead tetraacetate under thermal or photolytic conditions or in the presence of iodine proceed mainly by fragmentation of the C(13)-C(14) bond to give as the primary products the 13,18-didehydro-13,14-seco derivative 6 and the (E)-Delta(12)-13,14-seco ketone 11, respectively. Further transformations of these compounds under conditions of their formation afforded, in addition, the acetoxy derivatives 7-9 (from 6), and the D-homo-C-nor compound 12 and (12R,13R)-epoxide 13 (from 11). Unexpectedly, the photolytic lead-tetraacetate oxidation of 5 resulted partly (to ca. 20%) in a reversible fragmentation involving scission and recombination of the C(8)-C(14) bond followed by formation of rite 14 beta,22-ether 10. Possible mechanisms for the observed transformations are discussed.

The Antibacterial Activity of Coriolus versicolor Methanol Extract and Its Effect on Ultrastructural Changes of Staphylococcus aureus and Salmonella Enteritidis

The antibacterial activity of methanol extract obtained from fruiting body of industrially grown basidiomycete Coriolus versicolor was examined. The Minimum Inhibitory Concentration (MIC) values against various bacteria ranged from 0.625 to 20 mg mL-1. C. versicolor expressed bactericidal activity against both Gram-positive and Gram-negative bacteria. The growth curves of Staphylococcus aureus and Salmonella enterica serovar Enteritidis, measured at 630 nm, and confirmed with macrodilution method showed that the obtained extract could inhibit the growth of tested bacteria. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and the loss of 260-nm-absorbing material were used to examine the ultrastructural changes in bacteria induced by the extract. When S. aureus was exposed to the MIC of C. versicolor, elongated and malformed cells were observed by SEM, while S. Enteritidis treated cells appeared shorter and aggregated with ruptured cell walls. TEM revealed the formation of non-membrane-enclosed bodies and depleted inner content of S. aureus. Larger and irregular periplasmic space and deformed and scattered components of the cell envelope were observed in treated S. Enteritidis. The loss of 260-nm-absorbing material indicated that the disruptive action of the extract on cytoplasmic membrane was more pronounced in S. aureus than in S. Enteritidis treated cells. The UV and FTIR spectrophotometric analyses revealed diverse composition of C. versicolor extract and high content of total phenolics. Altogether, mushroom extracts could be used to develop nutraceuticals or drugs effective against pathogenic microorganisms.

Vertical distribution of natural radionuclides in soil: assessment of external exposure of population in cultivated and undisturbed areas.

In the present work, naturally occurring radionuclides ²³⁸U, ²³²Th and ⁴⁰K were measured in soil samples from the cultivated and undisturbed areas in Rudovci, municipality of Lazarevac, Serbia. There were three profiles, each profile divided into four horizons, giving the twelve soil samples. The specific activity of ²³⁸U, ²³²Th and ⁴⁰K in soil and sediment samples was determined by gamma spectrometry using the HPGe semiconductor detector. Obtained activity concentrations ranged from 28.0 to 44.0 Bq/kg for ²³⁸U, from 59.4 to 71.4 Bq/kg for ²³²Th and from 335.0 to 517.0 Bq/kg for ⁴⁰K. The evaluation of the radiological hazards originated from ²³⁸U, ²³²Th and ⁴⁰K in the samples, the absorbed dose rate (D) and the annual effective dose rate (E), calculated in accordance with the UNSCEAR 2000 report, are presented in this paper.

Thionation of Some α,β-Unsaturated Steroidal Ketones

The reactions of selected α,β-unsaturated steroidal ketones with Lawesson’s reagent (LR) in CH2Cl2 and toluene under the standard reaction conditions and with a combination of phosphorus pentasulfide with hexamethyldisiloxane (P4S10/HMDO) in 1,2-dichlorobenzene (ODCB) under microwave irradiation were investigated and for this purpose several cholestane, androstane and pregnane carbonyl derivatives were chosen. Depending on the reagent and the solvent, 19 new sulfur containing compounds, including dithiones 4c and 4d, α,β-unsaturated 3-thiones 3a-e, dimer-sulfides 2a-e, 1,2,4-trithiolanes 5a-e and phosphonotrithioates 6b-e were synthesized. All newly prepared compounds were characterized by IR, 1H- and 13C-NMR spectroscopy and elemental analysis.

Structure-reactivity relationship in 19-methyl-and 19-nor-5,10-secosteroids. Part 4. Intramolecular nitrone 1,3-dipolar cycloadditions

The (Z)-19-nor-5,10-secosteroidal ketone 11 reacts with hydroxylamine hydrochloride to give the (E)- and (Z)-oximes 12 and 13, while with N-methylhydroxylamine hydrochloride it undergoes transannular nitrone 1,3-dipolar cycloaddition to give isoxazolidines 14 and 15, and an estratriene derivative 16, originating from 14. The (E)-19-nor-5,10-seco-ketone 17 undergoes intramolecular nitrone 1,3-dipolar cycloaddition with both hydroxylamine hydrochloride and N-methylhydroxylamine hydrochloride to produce, with the former reagent, a single isoxazolidine 18, and with the latter, two regioisomers 22 and 23. The reaction and stereochemical courses of the above transformations are compared with those previously observed for the corresponding 19-methyl analogues. Copyright (C) 1996 Published by Elsevier Science Ltd.

Synthesis and characterization of a new type of levan-graft-polystyrene copolymer.

Novel macromolecular graft copolymers were synthesized by reaction of the hydroxyl groups of the microbial polysaccharide levan, produced using Bacillus licheniformis, with polystyrene (Lev-g-PS). Synthesis was performed by the free radical reaction using potassium persulfate (PPS) as initiator. The prepared copolymer was characterized by FTIR, SEM, TG/DTA, XRD and (13)C NMR. The influence of the different conditions (reaction temperature, air or nitrogen atmosphere, reaction time, type of amines and ascorbic acid (AA) concentration) on the grafting reaction was investigated. Results showed that maximum percentage of grafting (58.1%) was achieved at a reaction temperature 70°C, in a nitrogen atmosphere and using dimethylethanolamine (DMEA) as the amine activator. On the basis of the obtained results, the likely reaction mechanism was proposed. Synthesized copolymers have better thermal stability in comparison with their initial components. Copolymers such as Lev-g-PS could potentially have many applications, such as compatibilizers and material for membranes.