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Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2,2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2,2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.

Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2,2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2,2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.

Unsaturated oxyallyl cations with a suitably positioned alkene bond undergo 5-exo-cyclization with the formation of vinylcyclopentane derivatives. Alkyne analogues provide allenes. The reaction proceeds with a moderate to excellent level of stereoselectivity and allows for asymmetric induction in the reaction with chiral substrate.

Unsaturated oxyallyl cations with a suitably positioned alkene bond undergo 5-exo-cyclization with the formation of vinylcyclopentane derivatives. Alkyne analogues provide allenes. The reaction proceeds with a moderate to excellent level of stereoselectivity and allows for asymmetric induction in the reaction with chiral substrate.

Unsaturated oxyallyl cations with a suitably positioned alkene bond undergo 5-exo-cyclization with the formation of vinylcyclopentane derivatives. Alkyne analogues provide allenes. The reaction proceeds with a moderate to excellent level of stereoselectivity and allows for asymmetric induction in the reaction with chiral substrate.

Unsaturated oxyallyl cations with a suitably positioned alkene bond undergo 5-exo-cyclization with the formation of vinylcyclopentane derivatives. Alkyne analogues provide allenes. The reaction proceeds with a moderate to excellent level of stereoselectivity and allows for asymmetric induction in the reaction with chiral substrate.

Unsaturated oxyallyl cations with a suitably positioned alkene bond undergo 5-exo-cyclization with the formation of vinylcyclopentane derivatives. Alkyne analogues provide allenes. The reaction proceeds with a moderate to excellent level of stereoselectivity and allows for asymmetric induction in the reaction with chiral substrate.

Предмет истраживања дисертације је развој модела мобилног здравства заснованог на wearable computing-у. Централни проблем који се разматра у докторској дисертацији је испитивање могућности примене и интеграције wearable computing-а, Интернета интелигентних уређаја (енг. Internet of Things, IoT), мобилних технологија и сервиса, big data аналитике и рачунарства у облаку за развој сервиса мобилног здравства. Фокус истраживања биће на примени сервиса мобилног здравства у области мерења, праћења и контроле стреса код студената. Увођењем Интернета интелигентних уређаја у мобилно здравство, у области контроле стреса, омогућава се прикупљање података са тела корисника путем сензора. Примена wearable уређаја у процесу контроле стреса лекарима или психолозима треба да омогући добијање информација о психофизичком стању корисника. Применом сервиса електронског здравства измерени подаци се прате, чувају и врши се анализа података. На основу аналитичких резултата могу сe креирати одговарајуће методе за контролу стреса и персонализоване превентивне здравствене поруке намењене корисницима. Предложен је модел мобилног здравства заснован на wearable computing-у који се састоји из система мобилног здравства, wearable система и сервиса за међусобну интеграцију компоненти и интеграцију са електронским здравством. Осим тога, модел обухвата интеграцију мобилног здравства са програмима формалног образовања. У екперименталном делу докторске дисертације предложени модел мобилног здравства заснован на wearable computing-у је имплементиран у образовном окружењу. Систем је евалуиран у реалном окружењу, током одбране завршних радова студената на Факултету организационих наука Универзитета у Београду. Резултати су показали да је коришћење мобилне апликације са садржајима за релаксацију утицало на смањење стреса код студената током одбране завршних радова., The subject of this thesis is development of mobile health model based on wearable computing. The main problem discussed in the thesis is to investigate the possibilities of implementation and integration of wearable computing, Internet of Things, mobile technologies and services, big data analytics, and Cloud computing for the development of mobile health services. By introducing the Internet of Things into mobile healthcare, in the field of stress control, it is possible to collect sensors’ data from the users’ body. The use of the wearable devices in the process of the stress control by physicians or psychologists should enable obtaining information on the psychophysical condition of the user. The measured data could be monitored, stored and analyzed using the e-health services. Appropriate methods for controlling stress and personalized preventive health messages for users can be created based on analytical results. The thesis proposes a mobile healthcare model based on wearable computing. It consists of a mobile healthcare system, wearable systems and services for interconnection of components and integration with electronic health services. In addition, the model includes the integration of mobile healthcare and formal education programs. In the experimental part of the thesis, the proposed model of mobile healthcare based on wearable computing has been implemented in an educational environment. The system was evaluated in a real environment, during the defense of students' thesis at the Faculty of Organizational Sciences, University of Belgrade. The results show that the use of a mobile application with relaxation content affected the reduction of stress among students during their thesis defense. In addition, this thesis outlines the role of the education system in the implementation of mobile healthcare. The approach to designing a course for smart healthcare engineers has been presented. Through key topics of the course, students should gain new skills and

This paper shows the development of an IoT system for students' stress management. The IoT system is developed in an open architecture and is an integral part of the educational ecosystem. The system is composed of two elements: the one that enables measurement of vital parameters for identifying stress in students, and the other for stress control. The system for stress control consists of a mobile health application featuring relaxation content. Such system should minimize the excitement and have an impact on reducing future stress. The IoT system for stress management was evaluated in a real environment, during students' thesis defense on Faculty of Organizational Sciences, University of Belgrade. The results show that time spent using mobile health application with relaxing content can reduce students' physiological arousal and excitement during thesis defense.

Smart healthcare is an emerging concept that relies on the synergy of various engineering concepts and intelligent technical innovations applicable to healthcare. Demand for smart healthcare engineers is anticipated to grow, hence, arising a need to educate profile engineers. The goal of this paper is to introduce an approach to designing a course for smart healthcare engineering education. Through the key topics of the course, students acquired new skills and knowledge from emerging technologies underlying smart healthcare. The proposed approach was evaluated at a graduate course at the Faculty of Organizational Sciences, University of Belgrade. The results indicate that there was a positive impact on the learning process as well as a positive learning experience.

Detaljnom analizom radne snage u poljoprivredi, koja je prikazana u ovom radu, može se zaključiti da su ruralna područja i poljoprivreda kao osnovna delatnost nekonkurentni, sa izrazitim teritorijalnim i regionalnim različitostima i specifičnostima. Na to ukazuje činjenica da su ruralna područja manje afirmativna za život i rad ljudi, zbog čega su prisutni nepovoljni trendovi vezani za starosnu, polnu i obrazovnu strukturu stanovništva. To se direktno odražava na produktivnost rada, koja je u ovom istraživanju prikazana kroz prosečan broj godišnjih radnih jedinica i u odnosu na države članice Evropske unije nepovoljna. Iz tih razloga, neophodno je da kroz mere agrarne i socijalne politike, a u skladu sa merama ekonomske politike, poljoprivreda i ruralna područja budu fokus interesovanja i podrške države.

Detaljnom analizom radne snage u poljoprivredi, koja je prikazana u ovom radu, može se zaključiti da su ruralna područja i poljoprivreda kao osnovna delatnost nekonkurentni, sa izrazitim teritorijalnim i regionalnim različitostima i specifičnostima. Na to ukazuje činjenica da su ruralna područja manje afirmativna za život i rad ljudi, zbog čega su prisutni nepovoljni trendovi vezani za starosnu, polnu i obrazovnu strukturu stanovništva. To se direktno odražava na produktivnost rada, koja je u ovom istraživanju prikazana kroz prosečan broj godišnjih radnih jedinica i u odnosu na države članice Evropske unije nepovoljna. Iz tih razloga, neophodno je da kroz mere agrarne i socijalne politike, a u skladu sa merama ekonomske politike, poljoprivreda i ruralna područja budu fokus interesovanja i podrške države.

The study was carried out in the AD Vršac vineyards, Serbia during the 2000- 2004 period. The vineyard was established in the location of Crvenka in 1989 with the row distance of 3 x 1 m. The vine was grown in rows with a two level cordon-shaped root to which a mixed cut was applied. The Italian Riesling variety was transplanted on the clones of various rootstocks of the Kober 5BB, clone 114 and 13; SO4 clone 31 and 74; Teleki 5C clones 6-16, 6-52, 6-53 i 10; 41B clones 86, 87 and 88. The study encompassed the clones 114 and 13 Kober 5BB and their properties were observed during the period of full vineyard fertility. The obtained results indicate that the used clones of the rootstocks positively affected the observed properties: grape yield, sugar content, total acid, glucoacidimetric index of the grape yield. The best results were detected in the clone 114, then in the clone 13 and at last in the Kober 5BB control that prevails in this location., Istraživanja su obavljena u periodu 2000-2004. godine u proizvodnom zasadu AD Vršački vinogradi. Vinograd je podignut 1989. godine na lokaciji Crvenka sa razmakom sadnje 3x1 m. Loza je gajena špalirski sa visokim stablom u vidu dvospratne kordunice uz primenu mešovite rezidbe. Vinska sorta rizling italijanski okalemljena je na klonovima različitih podloga kober 5BB, klon 114 i 13; SO4 klon 31 i 74; Teleki 5C klonovi 6-16, 6-52, 6-53 i 10; 41B klonovi 86, 87 i 88. Ovim istraživanjem bili su obuhvaćeni klonovi 114 i 13 kober 5BB, a praćena su i njihova svojstva u fazi pune rodnosti vinograda. Postignuti rezultati ukazuju da su primenjeni klonovi loznih podloga ispoljili pozitivan uticaj na praćena svojstva: količina prinosa, masa grozda, sadržaj šećera, ukupne kiseline i glukoacidimetrijski indeks zrelosti grožđa. Najbolje rezultate dao je klon 114, zatim klon 13 u odnosu na standardu varijantu lozne pologe kober 5BB koja je dominantna na ovoj locaji.

The study was carried out in the AD Vršac vineyards, Serbia during the 2000- 2004 period. The vineyard was established in the location of Crvenka in 1989 with the row distance of 3 x 1 m. The vine was grown in rows with a two level cordon-shaped root to which a mixed cut was applied. The Italian Riesling variety was transplanted on the clones of various rootstocks of the Kober 5BB, clone 114 and 13; SO4 clone 31 and 74; Teleki 5C clones 6-16, 6-52, 6-53 i 10; 41B clones 86, 87 and 88. The study encompassed the clones 114 and 13 Kober 5BB and their properties were observed during the period of full vineyard fertility. The obtained results indicate that the used clones of the rootstocks positively affected the observed properties: grape yield, sugar content, total acid, glucoacidimetric index of the grape yield. The best results were detected in the clone 114, then in the clone 13 and at last in the Kober 5BB control that prevails in this location., Istraživanja su obavljena u periodu 2000-2004. godine u proizvodnom zasadu AD Vršački vinogradi. Vinograd je podignut 1989. godine na lokaciji Crvenka sa razmakom sadnje 3x1 m. Loza je gajena špalirski sa visokim stablom u vidu dvospratne kordunice uz primenu mešovite rezidbe. Vinska sorta rizling italijanski okalemljena je na klonovima različitih podloga kober 5BB, klon 114 i 13; SO4 klon 31 i 74; Teleki 5C klonovi 6-16, 6-52, 6-53 i 10; 41B klonovi 86, 87 i 88. Ovim istraživanjem bili su obuhvaćeni klonovi 114 i 13 kober 5BB, a praćena su i njihova svojstva u fazi pune rodnosti vinograda. Postignuti rezultati ukazuju da su primenjeni klonovi loznih podloga ispoljili pozitivan uticaj na praćena svojstva: količina prinosa, masa grozda, sadržaj šećera, ukupne kiseline i glukoacidimetrijski indeks zrelosti grožđa. Najbolje rezultate dao je klon 114, zatim klon 13 u odnosu na standardu varijantu lozne pologe kober 5BB koja je dominantna na ovoj locaji.

Predmet istraživanja ovog rada je razvoj modela mobilnog zdravstva zasnovanog na wearable computing-u. Razvijeni model ima za cilj da pokaže jedan od načina integracije koncepata elektronskog zdravstva, mobilnog zdravstva, Interneta inteligentnih uređaja i wearable computinga. U radu je dat prikaz razvoja wearable sistema zasnovanog na uređajima i tehnologijama Interneta inteligentnih uređaja. Razvijeni sistem omogućava merenje otkucaja srca kod pacijenata. Kao podrška wearable sistemu razvijena je mobilna aplikacija koja pruža servise mobilnog zdravstva. Servisi treba da unaprede način pružanja zdravstvenih usluga, praćenje zdravstevnog stanja, sprovođenja preventivnih programa, smanjenje troškova pružanja zdravstvene zaštite i način na koji pacijent uzima aktivno učešće u brizi o svom zdravlju., The objective of this paper is development of mHealth model based on wearable computing. Developed model aim to demonstrate one way of integrating eHealth, mHealth, Internet of Things and wearable computing. The paper present the development of a system based on wearable devices and technologies of the Internet of Things. The developed system allows the measurement of the patient's heart rate. Mobile application that provides mobile health services is developed in support of wearable system. Those services needs to improve the way health services are delivered, health condition monitoring, and prevention programmes implementation, reduce the costs of health care delivery, and allow patient to take an active role in one's health care.

In the modern world the use of information and communication technologies, computer networks and systems based on such technologies are the determinants of efficiency and operating performance in healthcare. This paper deals with the concepts of electronic and mobile health and opportunities of their implementation in the healthcare systems. This paper will analyze the factors that influence the acceptance of mobile healthcare services among employees in health institutions. The main goal of this paper was to analyze the possibilities of using mobile healthcare services in health institutions, as well as to analyze the predictors for successful implementation of mobile health services. The research results indicate a high level of knowledge regarding the usefulness and availability of services among healthcare workers in health institutions, which is the prerequisite for a successful implementation of mobile health in the healthcare system.

The work indicate some of the key determinants of national minorities in Serbia. Special attention is devoted to the analysis of the basic characteristics of minorities in border municipalities, which are characterized by, among other things, homogenization and concentration of these communities that are the subject of our work. Serbia today is not among countries with significant ethnic heterogeneity and divisions, the total population of the country's share of national minorities is much lower than many countries in Eastern Europe. Testing characteristics of minority communities in these municipalities and territorial distribution by socio-demographic determinants show their differentiation in this regard. Different factors such as demographic, socio-cultural, historical and ethnic influence on a number of areas of social life of minorities., U radu se ukazuje na neke od osnovnih determinanti nacionalnih manjina u Srbiji. Posebna pažnja posvećena je analizi osnovnih obeležja manjina u pograničnim opštinama, koje odlikuje, između ostalog, homogenizacija i koncentracija ovih zajednica koje su predmet našeg rada. Današnja Srbija ne spada u red država sa izraženom etničkom heterogenošću i podeljenošću, u ukupnom stanovništvu zemlje udeo nacionalnih manjina je znatno manji od mnogih država Istočne Evrope. Ispitivanje obeležja manjinskih zajednica u navedenim opštinama i teritorijalni razmeštaj na osnovu socio-demografskih determinanti ukazuju na njihovu diferencijaciju u tom pogledu. Različiti faktori, kao što su demografski, sociokulturni, istorijski i etnički, utiču na niz sfera društvenog života manjina.

Domino reactions of ketones with molecular oxygen in the presence of potassium hydroxide and potassium t-butoxide afford cyclic hydroperoxy acetals (3,5-dihydroxy-1,2-dioxanes). Mixed endoperoxides can also be obtained in a three-component reaction of two ketones and oxygen.

Domino reactions of ketones with molecular oxygen in the presence of potassium hydroxide and potassium t-butoxide afford cyclic hydroperoxy acetals (3,5-dihydroxy-1,2-dioxanes). Mixed endoperoxides can also be obtained in a three-component reaction of two ketones and oxygen.

Domino reactions of ketones with molecular oxygen in the presence of potassium hydroxide and potassium t-butoxide afford cyclic hydroperoxy acetals (3,5-dihydroxy-1,2-dioxanes). Mixed endoperoxides can also be obtained in a three-component reaction of two ketones and oxygen.

Domino reactions of ketones with molecular oxygen in the presence of potassium hydroxide and potassium t-butoxide afford cyclic hydroperoxy acetals (3,5-dihydroxy-1,2-dioxanes). Mixed endoperoxides can also be obtained in a three-component reaction of two ketones and oxygen.

Domino reactions of ketones with molecular oxygen in the presence of potassium hydroxide and potassium t-butoxide afford cyclic hydroperoxy acetals (3,5-dihydroxy-1,2-dioxanes). Mixed endoperoxides can also be obtained in a three-component reaction of two ketones and oxygen.

The work indicate some of the key determinants of national minorities in Serbia. Special attention is devoted to the analysis of the basic characteristics of minorities in border municipalities, which are characterized by, among other things, homogenization and concentration of these communities that are the subject of our work. Serbia today is not among countries with significant ethnic heterogeneity and divisions, the total population of the country's share of national minorities is much lower than many countries in Eastern Europe. Testing characteristics of minority communities in these municipalities and territorial distribution by socio-demographic determinants show their differentiation in this regard. Different factors such as demographic, socio-cultural, historical and ethnic influence on a number of areas of social life of minorities., U radu se ukazuje na neke od osnovnih determinanti nacionalnih manjina u Srbiji. Posebna pažnja posvećena je analizi osnovnih obeležja manjina u pograničnim opštinama, koje odlikuje, između ostalog, homogenizacija i koncentracija ovih zajednica koje su predmet našeg rada. Današnja Srbija ne spada u red država sa izraženom etničkom heterogenošću i podeljenošću, u ukupnom stanovništvu zemlje udeo nacionalnih manjina je znatno manji od mnogih država Istočne Evrope. Ispitivanje obeležja manjinskih zajednica u navedenim opštinama i teritorijalni razmeštaj na osnovu socio-demografskih determinanti ukazuju na njihovu diferencijaciju u tom pogledu. Različiti faktori, kao što su demografski, sociokulturni, istorijski i etnički, utiču na niz sfera društvenog života manjina.

Fermentation and ripening specificity of traditional cheeses are predominantly directed by the natural microbial community present in milk selected by the cheese-making environment and technology. Therefore the traditional cheeses are unique products with specific microbiota biodiversity. There are several approaches for the identification of microbial population, however all of them have certain advantages and disadvantages. In this study the eligibility and performance of the Biolog phenotypic identification system (Biolog, Inc.) with GEN III microplates was tested. Parallel to this method, polymerase chain reaction with genus- and species-specific primers was performed. One hundred sixty-five isolates from nine types of artisan cheeses were isolated and analysed. Cheeses were produced from raw ewe’s milk in Slovenia, Bosnia and Herzegovina, Croatia and Serbia. The Biolog phenotypic identification system identified 90 isolates, but only 55 identifications acquired by the Biolog system were supported by polymerase chain reaction at a genus level and 28 at a species level. The obtained results showed that the reliability of commercial phenotypic identification systems was inadequate when analysing lactic acid bacteria isolates from natural, spontaneous fermentations and needs to be additionally corroborated by genotypic identification methods., Fermentacija i specifično zrenje sira najvećim je dijelom uvjetovano prirodnom mikrobnom zajednicom prisutnom u mlijeku, a koja se selekcionira uz pomoć sirarskog okoliša i tehnologije. Stoga su tradicionalni sirevi unikatni proizvodi sa specifičnom mikrobnom bioraznolikošću. Postoje različite mogućnosti identifikacije mikrobne populacije, međutim svi pristupi imaju svoje prednosti i nedostatke. U ovom istraživanju testirana je prikladnost i učinkovitost fenotipskog identifikacijskog sustava Biolog (Biolog, Inc.) s GEN III mikropločama. Usporedno je izvođena lančana reakcija polimeraze s rodom i vrstom specifičnih početnica. U ovom je istraživanju izolirano i analizirano ukupno 165 izolata porijeklom od devet vrsta tradicionalnih sireva. Sirevi su bili proizvedeni od sirovog ovčjeg mlijeka u Sloveniji, Bosni i Hercegovini, Hrvatskoj i Srbiji. Fenotipski identifikacijski sustav Biolog identificirao je 90 izolata. 55 identifikacija bilo je potvrđeno metodom lančane reakcije polimeraze na razini roda, a 28 na razini vrsta. Rezultati su pokazali da je pouzdanost komercijalnog fenotipskog identifikacijskog sistema neadekvatna kada se analiziraju izolati mliječno kiselinskih bakterija prirodnih i spontanih fermentacija. Taj identifikacijski sistem potrebno je dodatno potvrditi genotipskim identifikacijskim metodama.

Fermentation and ripening specificity of traditional cheeses are predominantly directed by the natural microbial community present in milk selected by the cheese-making environment and technology. Therefore the traditional cheeses are unique products with specific microbiota biodiversity. There are several approaches for the identification of microbial population, however all of them have certain advantages and disadvantages. In this study the eligibility and performance of the Biolog phenotypic identification system (Biolog, Inc.) with GEN III microplates was tested. Parallel to this method, polymerase chain reaction with genus- and species-specific primers was performed. One hundred sixty-five isolates from nine types of artisan cheeses were isolated and analysed. Cheeses were produced from raw ewe’s milk in Slovenia, Bosnia and Herzegovina, Croatia and Serbia. The Biolog phenotypic identification system identified 90 isolates, but only 55 identifications acquired by the Biolog system were supported by polymerase chain reaction at a genus level and 28 at a species level. The obtained results showed that the reliability of commercial phenotypic identification systems was inadequate when analysing lactic acid bacteria isolates from natural, spontaneous fermentations and needs to be additionally corroborated by genotypic identification methods., Fermentacija i specifično zrenje sira najvećim je dijelom uvjetovano prirodnom mikrobnom zajednicom prisutnom u mlijeku, a koja se selekcionira uz pomoć sirarskog okoliša i tehnologije. Stoga su tradicionalni sirevi unikatni proizvodi sa specifičnom mikrobnom bioraznolikošću. Postoje različite mogućnosti identifikacije mikrobne populacije, međutim svi pristupi imaju svoje prednosti i nedostatke. U ovom istraživanju testirana je prikladnost i učinkovitost fenotipskog identifikacijskog sustava Biolog (Biolog, Inc.) s GEN III mikropločama. Usporedno je izvođena lančana reakcija polimeraze s rodom i vrstom specifičnih početnica. U ovom je istraživanju izolirano i analizirano ukupno 165 izolata porijeklom od devet vrsta tradicionalnih sireva. Sirevi su bili proizvedeni od sirovog ovčjeg mlijeka u Sloveniji, Bosni i Hercegovini, Hrvatskoj i Srbiji. Fenotipski identifikacijski sustav Biolog identificirao je 90 izolata. 55 identifikacija bilo je potvrđeno metodom lančane reakcije polimeraze na razini roda, a 28 na razini vrsta. Rezultati su pokazali da je pouzdanost komercijalnog fenotipskog identifikacijskog sistema neadekvatna kada se analiziraju izolati mliječno kiselinskih bakterija prirodnih i spontanih fermentacija. Taj identifikacijski sistem potrebno je dodatno potvrditi genotipskim identifikacijskim metodama.

We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.

We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.

We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.

We recently reported the use of PSCl3 for the thiophosphorylation of alkylamines where the resulting N-thiophosphoramidate ions could be readily S-alkylated (Chem. Commun., 2011, 47, 6156-6158.). Herein we report the development of this methodology using amino acid, amino sugar, aminonucleoside and aniline substrates. The hydrolysis properties of N-thiophosphoramidate ions and their reactivities towards alkylating agents are also explored. In addition, we demonstrate the application of our approach to the preparation of a small library of compounds, including quinoline-based N,S-dialkylthiophosphoramidates which were tested for antileishmanial activity.

The design, synthesis and biological evaluation of a novel C, D-spirolactone analogue of paclitaxel is described. This is the first paclitaxel analogue without an oxetane D-ring that shows a significant cytotoxic effect (activity one order of magnitude lower than paclitaxel). More importantly, its cytotoxicity is a result of a different mechanism of action, involving mTOR inhibition-dependent autophagy instead of G(2)/M cell cycle arrest-dependent apoptosis.

The design, synthesis and biological evaluation of a novel C, D-spirolactone analogue of paclitaxel is described. This is the first paclitaxel analogue without an oxetane D-ring that shows a significant cytotoxic effect (activity one order of magnitude lower than paclitaxel). More importantly, its cytotoxicity is a result of a different mechanism of action, involving mTOR inhibition-dependent autophagy instead of G(2)/M cell cycle arrest-dependent apoptosis.

The design, synthesis and biological evaluation of a novel C, D-spirolactone analogue of paclitaxel is described. This is the first paclitaxel analogue without an oxetane D-ring that shows a significant cytotoxic effect (activity one order of magnitude lower than paclitaxel). More importantly, its cytotoxicity is a result of a different mechanism of action, involving mTOR inhibition-dependent autophagy instead of G(2)/M cell cycle arrest-dependent apoptosis.

The design, synthesis and biological evaluation of a novel C, D-spirolactone analogue of paclitaxel is described. This is the first paclitaxel analogue without an oxetane D-ring that shows a significant cytotoxic effect (activity one order of magnitude lower than paclitaxel). More importantly, its cytotoxicity is a result of a different mechanism of action, involving mTOR inhibition-dependent autophagy instead of G(2)/M cell cycle arrest-dependent apoptosis.

The homoprotocatechuate 2,3-dioxygenase from Arthrobacter globiformis (MndD) catalyzes the oxidative ring cleavage reaction of its catechol substrate in an extradiol fashion. Although this reactivity is more typically associated with non-heme iron enzymes, MndD exhibits an unusual specificity for manganese(II). MndD is structurally very similar to the iron(II)-dependent homoprotocatechuate 2,3-dioxygenase from Brevibacterium fuscum (HPCD), and we have previously shown that both MndD and HPCD are equally active towards substrate turnover with either iron(II) or manganese(11) (Emerson et al. in Proc. Natl. Acad. Sci. USA 105:7347-7352, 2008). However, expression of MndD in Escherichia coli under aerobic conditions in the presence of excess iron results in the isolation of inactive blue-green iron-substituted MndD. Spectroscopic studies indicate that this form of iron-substituted MndD contains an iron(III) center with abound catecholate, which is presumably generated by in vivo self-hydroxylation of a second-sphere tyrosine residue, as found for other self-hydroxylated non-heme iron oxygenases. The absence of this modification in either the native manganese-containing MndD or iron-containing HPCD suggests that the metal center of iron-substituted MndD is able to bind and activate 02 in the absence of its substrate, employing a high-valence oxoiron oxidant to carry out the observed self-hydroxylation chemistry. These results demonstrate that the active site metal in MndD can support two dramatically different 02 activation pathways, further highlighting the catalytic flexibility of enzymes containing a 2-His-1-carboxylate facial triad metal binding motif.

An aqueous method for the preparation of N,S-dialkyl thiophosphoramidates is reported. Thiophosphorylation of alkylamines was performed using SPCl3 in aqueous reaction media, and the resulting thiophosphoramidate-S-anions were S-alkylated with soft electrophiles. Ranges of amines and electrophiles were explored.

An aqueous method for the preparation of N,S-dialkyl thiophosphoramidates is reported. Thiophosphorylation of alkylamines was performed using SPCl3 in aqueous reaction media, and the resulting thiophosphoramidate-S-anions were S-alkylated with soft electrophiles. Ranges of amines and electrophiles were explored.

The presence of gene determinants for different bacteriocins has been already demonstrated in traditional Slovenian types of raw milk cheeses ‘Tolminc’ and ‘Kraški’. These genes were present also in the cultivable microbiota. In this research the aim was to establish how the presence of gene determinants for bacteriocins in microbial consortia is reflected in its antimicrobial activity. In addition, one of the goals was to determine whether the strains that carry gene determinants for bacteriocins have any competitive growth advantage in microbial population. Microbial consortium of ‘Tolminc’ cheese was propagated in milk and examined at the end of propagation its antimicrobial activity and the presence of gene determinants for bacteriocins. Comparison of the results obtained before and after propagation leaded to the conclusion that most of the strains possessing gene determinants for bacteriocins were unable to persist during propagation. The strains which did persist during propagation carried gene determinants for enterocins P, L50B and cytolysin. Antimicrobial activity of consortium before and after propagation was not substantially different and cannot be attributed to any of detected bacteriocins., Prisutnost genskih determinanti za stvaranje različitih vrsta bakteriocina već je ranijim istraživanjima utvrđena u slovenskim ovčjim sirevima “Tolminac” i “Kraški sir” koji se proizvode na tradicionalan način. Isti geni za izoliranu mikrobnu populaciju (konzorcij) također su potvrđeni i u kultiviranim uvjetima. U ovom radu pokušalo se utvrditi kako se prisutnost tih genskih determinanti u mikrobnom konzorciju odražava na njegovu antimikrobnu aktivnost. Osim toga, utvrđivao se i utjecaj bakterijskih sojeva koji nose gene za stvaranje bakteriocina na kompetitivnost rasta u mješovitoj populaciji. Mikrobni konzorcij izoliran iz sira “Tolminac” propagiran je u mlijeku 10 dana, nakon čega je utvrđena antimikrobna aktivnost kulture i prisutnost genskih determinanti za stvaranje bakteriocina. Usporedbom rezultata za sposobnost stvaranja bakteriocina prije i nakon precjepljivanja u mlijeku, utvrđen je gubitak te sposobnosti za većinu izoliranih sojeva. Sojevi koji su izdržali ponovljena precjepljivanja u mlijeku nosili su genske determinante za bakteriocine: enterocin P, enterocin L50B i citolizin. Antimikrobna aktivnost konzorcija prije i nakon precjepljivanja nije se značajno razlikovala te se ne može pripisati niti jednom od u ovom pokusu potvrđenih bakteriocina.