TiF4-catalyzed direct amidation of carboxylic acids and amino acids with amines.

Unlike other metal fluorides, catalytic titanium tetrafluoride enhances the direct amidation of aromatic and aliphatic carboxylic acids and N-protected amino acids in refluxing toluene. While aromatic acids were converted to amides with 10 mol% of the catalyst within 24 h, aliphatic acids underwent a faster reaction (12 h), with lower catalyst loading (5 mol%). This protocol is equally efficient with alkyl and aryl amines providing a variety of carboxamides and peptides in 60-99% yields.

Titanium-Mediated Reduction of Carboxamides to Amines with Borane-Ammonia.

In this study, the successful titanium tetrachloride-catalyzed reduction of aldehydes, ketones, carboxylic acids, and nitriles with borane-ammonia was extended to the reduction (deoxygenation) of a variety of aromatic and aliphatic pri-, sec- and tert-carboxamides, by changing the stoichiometry of the catalyst and reductant. The corresponding amines were isolated in good to excellent yields, following a simple acid-base workup.

TiCl4-Catalyzed Hydroboration of Ketones with Ammonia Borane.

Investigation of a variety of Lewis acids for the hydroboration-hydrolysis (reduction) of ketones with amine-boranes has revealed that catalytic (10 mol %) titanium tetrachloride (TiCl4) in diethyl ether at room temperature immensely accelerates the reaction of ammonia borane. The product alcohols are produced in good to excellent yields within 30 min, even with ketones which typically requires 24 h or longer to reduce under uncatalyzed conditions. Several potentially reactive functionalities are tolerated, and substituted cycloalkanones are reduced diastereoselectively to the thermodynamic product. A deuterium labeling study and 11B NMR analysis of the reaction have been performed to verify the proposed hydroboration mechanism.

Room Temperature Reduction of Titanium Tetrachloride-Activated Nitriles to Primary Amines with Ammonia-Borane.

The reduction of a variety of aromatic and aliphatic nitriles, activated by a molar equivalent of titanium tetrachloride, has been achieved at room temperature using ammonia borane as a safe reductant. The corresponding methanamines were isolated in good to excellent yields following a simple acid-base workup.

COVID-19 vaccination knowledge, attitudes and practices among residents of Bosnia and Herzegovina during the third wave of COVID-19 outbreak.

Background: Bosnia and Herzegovina hasn't still developed and started any vaccination programs to contain the current COVID-19 outbreak and prevent further spreading and death from this disease. The aim of this study was to assess current knowledge, attitudes and practices towards COVID-19 vaccination during the third wave of the outbreak when the healthcare system is facing a collapse and to create a paradigm for developing vaccination programs in the country. Methods: his cross-sectional study was conducted by an anonymous online questionnaire based on a Congo study and Center for Disease Control and Prevention facts regarding COVID-19 vaccination during the third wave of the COVID-19 outbreak in the country. Results: In total, 570 subjects, mostly female 474 (83.1%), with a high school degree or lower 230 (40.3%), married 305 (53.5%), engaged in intellectual labor 302 (53.0%), from urban environment 531 (93.1%) and with a mean age of 35.28±11.35, were included in the study. The mean COVID-19 vaccination knowledge test score was 11.29±1.91. Being single (OR= 1.88, 95% 1.20-2.94) or in a relationship (OR=1.87, 95% 1.12-3.11), being engaged in intellectual labor (OR=1.59, 95% CI 1.06-2.37) and having a Master's degree or higher (OR=1.65, 95% CI 1.10-2.46) were associated with higher knowledge test scores. Only 264 (46.3%) subjects agreed that COVID-19 vaccination programs will prevail in a battle versus COVID-19 and only 36 (6.3%) were currently vaccinated against COVID-19. Higher knowledge regarding COVID-19 and its vaccination was determined as an independent predictor for vaccinating itself against COVID-19 (OR=23.09, 95% CI 11.94-44.68), as well as respecting socio-epidemiological measures such as avoidance of crowded places (OR=2.07, 95% CI 1.28-3.35) and wearing face mask (OR=6.95, 95% CI 2.07-23.29). Conclusions: Our study shows that Bosnia and Herzegovina population has poor knowledge, relatively pessimistic attitudes and a very low vaccinal rate against COVID-19 during the third wave of the outbreak which promotes COVID-19 vaccination hesitancy and further COVID-19 spreading and death toll. By activating proper socioepidemiological measures and educating population about COVID-19 and COVID-19 vaccination, as well as vaccination against COVID-19, the current situation could be changed.

Surface roughness and color measurements of glazed or polished hybrid, feldspathic, and Zirconia CAD/CAM restorative materials after hot and cold coffee immersion.

BACKGROUND: The purpose of this study evaluates and compares the effect of surface roughness (Ra) and color stability on computer-aided design/computer-aided manufacturing (CAD/CAM) hybrid resin (Vita Enamic), feldspathic (Vitablocs® Mark II), and lithium disilicate Zirconia (Vita Suprinity) glazed or polished ceramics immersed in hot Arabic Qahwa and cold coffee. METHODS: A total of 96 standardized samples were prepared from CAD/CAM restorative materials. Half of the samples were polished as per the manufacturer's instructions using a porcelain polishing kit, and the other half were glazed. Samples were distributed and immersed in hot Arabian Qahwa and cold coffee followed by thermocycling. Ra measurements and color changes were conducted before and after immersion. SEM images were captured from each type of glazed or polished ceramic. One-way ANOVA paired Student's t-test, and Bonferroni test were conducted to detect significant difference between the groups. P > 0.05 was a significant level. RESULTS: Of all the tested samples, Ra increased without any significant difference; however, mean color changes (ΔE*) showed significant differences. An increase in Ra was noted for all the glazed and polished samples after immersion and thermocycling. However, differences were significant only in VM II. In addition, ΔE* was significant only in Vita Suprinity (VS) samples. For immersion groups, significant Ra changes were noticed in glazed samples, only in Vita Enamic (VE) with no ΔE*. In polished samples, mean Ra changes were observed in VM II and VS samples. Significant differences were also noticed in polished VE and VS subgroups of ΔE*. CONCLUSIONS: Ra affects all the tested samples, providing higher values on the polished specimens. The ΔE* caused by hot Arabic Qahwa and cold coffee on glazed or polished CAD/CAM restorative materials were clinically acceptable.

Effects of Khat on Surface Roughness and Color of Feldspathic and Zirconia Porcelain Materials under Simulated Oral Cavity Conditions.

Background and Objectives: Khat chewing is considered as a daily habit that is practiced by more than five million people globally. The effect of khat chewing on the surface roughness and the color stability of natural teeth and the material used in the fabrication of dental prosthesis remains unknown. This study was conducted to explore and compare the effect of khat homogenate (KH) on the surface roughness (Ra) and the average color changes (ΔE*) amongst natural teeth and selected shades from different porcelain types, namely, feldspathic metal ceramic (MC) VM13, computer-aided design/computer assisted manufacture (CAD/CAM) feldspathic (Vitablocs Mark II), and multilayer zirconia (Ceramill Zolid PS) porcelains. Materials and Methods: Seventy samples were prepared from natural teeth, feldspathic MC, CAD/CAM Vitablocs Mark II, and zirconia porcelain. The Ra values were measured using a profilometer and expressed in micrometers, whereas the ΔE* values were measured using VITA Easyshade® V spectrophotometer for all samples before and after frequent immersion and thermocycling in KH for 30 days. The surface topography was used to assess the materials surfaces (glazed or polished) after KH immersion by using a white light interferometry machine. Results: Results revealed that the Ra and the ΔE* values of the different types of tested porcelain were influenced by KH. The order of surface roughness values was glazed or polished MC > polished Zircon > polished Vitablocs Mark II > natural teeth. The lowest ΔE* values were recorded for glazed Vitablocs Mark II and MC, and the values could be arranged as polished zircon > natural teeth > glazed zircon > polished MC > polished Vitablocs Mark II. P values were significantly varied (< 0.001) among all the tested groups, except the zircon group (>0.05) for both Ra and ΔE*. Conclusion: KH significantly affected both surface parameter and color of glazed or polished porcelain materials and natural teeth.

Titanium tetrafluoride catalysis for the dehydrative conversion of diphenylmethanols to symmetric and unsymmetric ethers.

In contrast to the conversion of diphenylmethanol to the corresponding halides with an equivalent of titanium tetrachloride or -bromide, catalytic (50 mol%) titanium tetrafluoride converts benzhydrols in diethyl ether or dichloromethane to bis(benzhydryl) ethers within 0.5-1 h at room temperature. Cross ether formation with diphenylmethanols and primary aryl or aliphatic alcohols is achieved in the presence of 25 mol% TiF4 in refluxing toluene as solvent. A tentative mechanism involving a carbocation intermediate has been proposed.

Aryl carbonyls and carbinols as proelectrophiles for Friedel-Crafts benzylation and alkylation.

Friedel-Crafts benzylation/alkylation using benzylic, tertiary, and homobenzylic alcohols; aryl aldehydes, aryl ketones, and the highly challenging aryl carboxylic acids and esters as proelectrophiles has been achieved using borane-ammonia and TiCl4, greatly broadening the scope of useable substrates. Incorporation of deactivated aromatic proelectrophiles and specificity for substitution at the benzylic position are demonstrated in the synthesis of various di- and triarylalkane products. Dual protocols allow for the use of standard nucleophilic solvents (benzene, toluene, etc.) or for stoichiometric addition of more valuable nucleophiles including furans, thiophenes, and benzodioxoles.

Gingival health, plaque accumulation, and restoration outcomes in deciduous anterior teeth: evaluating zirconia crowns versus composite resin strip crowns.

BACKGROUND: Zirconia crowns, resembling crystals and with enamel-like aesthetics, are recent entrants in pediatric restorative dentistry. Despite growing use, their empirical efficacy remains under-explored. The aim of this study is to compare resin composite strip crowns and premanufactured zirconia crowns on primary maxillary incisors. METHODS: In the Pediatric Dental Clinics, 240 primary maxillary incisors (69 patients) were treated with either zirconia (120 teeth) or composite strip crowns (120 teeth). Evaluations of gingival health, plaque, secondary caries, restoration failure, and opposing teeth wear occurred at 3, 6, and 12-month intervals. RESULTS: At 3 months, zirconia crowns showed less gum bleeding (P=0.006) and plaque. Through 6 and 12 months, zirconia crowns exhibited fewer failures but higher opposing teeth wear. Strip crowns indicated greater tooth material loss. CONCLUSIONS: Zirconia crowns demonstrated superior gingival health and durability over composite resin strip crowns but caused increased wear on opposing teeth.

Catalyst- and Stoichiometry-Dependent Deoxygenative Reduction of Esters to Ethers or Alcohols with Borane-Ammonia.

A facile and selective room temperature deoxygenation of both aromatic and aliphatic carboxylic esters to ethers has been achieved by regulating the stoichiometry of the reductant, BH3-NH3, and the catalyst, TiCl4. This first, practical borane-mediated process is compatible with various potentially sensitive functional groups and is applicable to the deoxygenative ether formation from typically challenging aromatic acid esters. Substituting BF3-Et2O as the catalyst alters the reaction pathway, reducing the esters to alcohols. Mechanistic insights are provided by NMR spectroscopy, deuterium labeling, and kinetic isotope studies.

Balancing Lewis Acidity and Carbocation Stability for the Selective Deoxyhalogenation of Aryl Carbonyls and Carbinols.

Deoxyhalogenation of aryl aldehydes, ketones, carboxylic acids, and esters has been achieved utilizing an appropriate metal halide Lewis acid acting as a carbonyl activator and halogen carrier in combination with borane-ammonia as the reductant. Selectivity is accomplished by matching the stability of the carbocation intermediate with the effective acidity of the Lewis acid. Substituents and substitution patterns significantly influence the requisite solvent/Lewis acid combination. Logical combinations of these factors have also been applied for the regioselective conversion of alcohols to alkyl halides.

A Safer Reduction of Carboxylic Acids with Titanium Catalysis.

Ammonia-borane, shown previously to react with carboxylic acids under reflux to form primary amides, reduces acids to alcohols at room temperature in the presence of catalytic TiCl4. The process, which is tolerant of a variety of potentially reactive functional groups, including N-protected amino acids, can be employed for the selective reduction of acids in the presence of amides, nitriles and, to some extent, esters. Aliphatic acids can be selectively reduced in the presence of aromatic acids.

E-cigarettes and Vaping: A Smoking Cessation Method or Another Smoking Innovation?

The prevalence of using e-cigarettes (vaping) has risen rapidly since its introduction in 2007, mostly among male youth. Although research on the health risks of e-cigarettes is still limited, there is growing evidence of debilitating pulmonary conditions and general immune weakness from e-cigarettes, leading to various infections. Moreover, there are concerns that vaping could be used as a new model of cannabis consumption, increasing cannabis addiction among adolescents. With well-known health risks from traditional smoking, e-cigarettes are viewed as a safe way of smoking, appealing more to youth. Additionally, extensive e-cigarette marketing boosted by the internet and fame has resulted in worries that e-cigarettes can lead to a renormalization of cigarette smoking and can be used as a new method to consume vaporized drugs. Although the concern that e-cigarettes are as harmful as traditional smoking has been raised, youth and most healthcare providers remain relatively unaware. Therefore, this review explored the association between e-cigarettes and traditional smoking. With the introduction of e-cigarettes in the last two decades, the topic is still new and less studied. Therefore, this review will help us understand the topic to better care for e-cigarette smokers and reduce the increasing public health burden from vaping.

Distribution of toxic metals in organs of local cattle, sheep, goat and poultry from the West Bank, Palestinian Authority.

Graphite furnace atomic absorption spectrophotometry was used to measure the concentrations of Cu, Cd, Pb, and Zn in muscles and internal organs (liver, kidneys, heart, and lungs) of cattle, sheep goat and poultry sampled from local markets in the West Bank, Palestinian Authority. Mean levels of metals (dry weight basis) during this study were as follows: Cd: 0.34-0.57 microg/g, Pb: 0.2-4.7 microg/g, Cr: 0.44-3.62 microg/g and Cu: 1.03-217.9 microg/g. Muscles and internal organs of each species were found to have statistically different metal levels. Generally, livers and kidneys were found to have the highest levels of metals and muscles the lowest levels. When compared to each other, the four animal groups either did not show any significant differences or no clear trends. Compared to results reported in the literature, our results were comparable to or less than most of the studies reported from clean sites in different countries.

Genetic parameters for ewe productivity traits in the Columbia, Suffolk and Targhee breeds.

Estimates of repeatability and heritability were obtained for the following productivity traits of ewes: litter weight at birth (LWB) and weaning (LWW), litter size at birth (LSB), litter size alive at birth (NBA), litter size at weaning (LSW), neonatal survival rate (SRB) and preweaning survival rate (SRW). Phenotypic and genetic correlations were estimated for litter traits. The data set contained 6,394 ewe breeding records from three state stations over 10 yr on 1,731 ewes that were the progeny of 488 sires among three breeds (Columbia, Suffolk and Targhee). Pooled intra-station estimates of repeatability ranged from .11 to .22 for LWB and LWW among the three breeds. For litter size at birth, number born alive and litter size at weaning these estimates varied from .09 to .17 and for the survival traits (SRB and SRW) the variation was from .11 to .20. Intra-station estimates of heritability for the three breeds varied from .12 to .28 for LWB and LWW, and for LSB, NBA and LSW estimates varied from .05 to .35. Heritability estimates for survival traits (SRB and SRW) were low, ranging from .00 to .14. Phenotypic correlations among LWB, LWW, NBA and LSW ranged from .35 to .92 among the breed-station subclasses, with higher correlations occurring where a part-whole relationship existed. The study suggests that selection of ewes with high litter size at birth or at weaning and(or) litter weight at birth or at weaning will genetically improve total litter weight at weaning per ewe lambing.

Effects of the callipyge phenotype on serum creatinine, total cholesterol, low-density lipoproteins, very-low-density lipoproteins, high-density lipoproteins, and triacylglycerol in growing lambs.

The goals of this study were to investigate the effects of the callipyge (CLPG) phenotype on serum creatinine and lipid profiles of growing lambs. Preliminary studies in our laboratories indicated that creatinine may have utility in distinguishing the CLPG phenotype and that expression of the CLPG gene altered concentrations of serum total cholesterol (TC). As a result, in this study, we examined the influence of the CLPG gene on concentrations of creatinine, TC, very-low-density lipoproteins (VLDL), low-density lipoproteins (LDL), high-density lipoproteins (HDL), and triacylglycerol (TG) at varying stages of maturity in lambs. Ten homozygous (c/c) Polypay ewes were crossed with Dorset rams heterozygous for the CLPG gene (C/c). From this cross, 20 lambs (13 females and 7 males) were born, of which 11 were homozygotic (c/c) and 9 were heterozygotic (C/c; CLPG) based on muscle weights and longissimus dorsi (LD) area at slaughter. Blood samples were taken at monthly intervals and serum lipid constituents were assayed. At 1 mo of age, no differences (P > .05) in plasma lipids were detectable between phenotypes. However, at 2 mo age, CLPG lambs had higher (P < .01) concentration of TG, TC, HDL, and VLDL compared to homozygotic (c/c) lambs. Triglycerides and VLDL were elevated (P < .05) in CLPG lambs at 3 mo of age. By slaughter, no differences (P > .05) in serum lipid constituents were detectable between genotypes. Hence, the increase in serum TC is due to elevated levels of HDL and VLDL. These observations indicate that creatinine may be used to distinguish CLPG lambs and that the CLPG gene alters serum lipid profiles during the postnatal period.