Ferrocene Bioconjugates

In this review we present our recent contribution to the field of bioorganometallic chemistry of ferrocene. Ferrocene conjugates with biomolecules have been synthesized and characterized using IR and NMR (1H, 13C, COSY, NOESY, HMBC) spectroscopy, ESI-MS and HRMS. The bioconjugates of ferrocene with resveratrol (2) and mannose (10, 11, 14 and 15) were biologically evaluated for their potential inhibitory effect on HepG2 cancer cells (2) and E. coli adherence to the bladder epithelium (10, 11, 14 and 15). The oxalamide-bridged ferrocene 17 was sub¬jected to conformational analysis in solution and in the solid state, and tested for its gelation and cytotoxic activity. The mono- (30–32, 36–38, 42–45) and disubstituted ferrocene conjugates with natural amino acids (21–28, 33–35, 39–41, 48, 49, 62–65, 69–72) were subjected to the detailed conformational and DFT analyses in order to determine the turn-inducing potential of ferrocene scaffolds in the corresponding peptidomimetics. This work is licensed under a Creative Commons Attribution 4.0 International License

Trnje weekly magazine (1920.)

Nakon završetka Prvoga svjetskoga rata i propasti Austro-Ugarske Monarhije stvorena je nova država. Od samog početka traju prijepori o karakteru buduće države, a 1. prosinca 1918. godine regent Aleksandar proglašava Kraljevstvo SHS. Izbori za Ustavotvornu skupštinu nove države provedeni su tek krajem 1920. godine i na njima Komunistička partija Jugoslavije osvaja 59 mandata te tako postaje treća stranka po broju mandata u Ustavotvornoj skupštini. Vukovar je u to doba jako središte komunističkih ideja. Na općinskim izborima u ožujku 1920. godine vukovarski komunisti osvajaju polovicu mandata u gradskom zastupstvu. I na ponovljenim izborima u srpnju iste godine vukovarski komunisti osvajaju većinu mandata. Kako se približavaju izbori za Konstituantu, politička borba za glasače postaje sve oštrija. U listopadu 1920. godine u Vukovaru izlazi prvi broj tjednika »Trnje«, satirično- humorističnih novina koje izdaje Mjesna organizacija Komunističke partije radi propagande i diskvalifikacije političkih protivnika.Trnje was the first humoristic-satirical magazine in Vukovar. It had been published for only two months – from October to December of 1920. Trnje was a magazine of the local organization of the Communist Party and it served as a means of propaganda of the communist idea and to discredit political opponents. The analysis of articles published in it provides a picture of the political situation in Vukovar prior to the first parliament elections in the Kingdom of Serbs, Croats and Slovenes

Application of Infrared Spectroscopy in Honey Analysis

The chemical composition and sensory characteristics vary significantly within different honey types. In order to determine botanical origin of honey, it is necessary to conduct rather complicated and time consuming analytical methods. IR spectroscopy has not yet been experimentally explored for honey analysis in Croatia, so the aim of this study was to determine claimed botanical origin of honey using both, standard and alternative (IR spectroscopy) methods, for the purpose of their comparison, Altogether 144 samples of nine different unifloral honey types (black locust, sweet chestnut, lime, sage, heath, rosemary, lavender, mandarin and strawberry tree) were collected from different Croatian regions directly from the beekeepers. In order to confirm claimed botanical origin of collected honey samples, melissopalinological analysis, moisture and electrical conductivity measurements were conducted. Infrared spectra of honey samples were recorded using the ABB Bomem MB102 Fourier-transform infrared spectrometer (FT-IR spectrometer). Selected IR spectral regions were analyzed by multivariate data analysis, principal components analysis (PCA). Preliminary PCA of IR spectra showed significant clustering of the analyzed samples by botanical origin. The results of this study showed that IR spectroscopy provides reliable results, but also represents rapid and cheap analytical tool in comparison to commonly used standard analytical methods. This research has also provided the first insight in infrared spectra of Croatian honeys

Synthesis of the First Heteroannularly Substituted Ferrocene Amino Acid and Isomeric Carbamic Acid Derivatives Containing Chiral Centres

Syntheses of N- and C-protected derivatives of 1\u27-(1-aminoethyl)ferrocene-1-carboxylic acid (Fcca) and isomeric carbamic acid are reported. The first attempt to prepare N-Ac-Fcca (8) by cleavage of 1-[1-(acetamido)ethyl]-1\u27-(o-chlorobenzoyl)ferrocene (7) with t-BuOK/H2O/GLYME failed. Friedel-Crafts reactions of N-substituted (1-ferrocenylethyl)amines [Boc-Fea (5) and Ac-Fea (6)] with ClCOSMe/AlCl3 gave the corresponding heteroannularly substituted thioesters 9/10, which were hydrolyzed into Boc-Fcca/Ac-Fcca and esterified into Boc-Fcca-OMe (11)/ Ac-Fcca-OMe (12). In a multi-step sequence, bromoferrocene was transformed into 1’- brominated Fea (15), Boc-Fea (16) and Ac-Fea (17). Lithiation/ethoxycarbonylation of these bromine compounds gave the corresponding carbamic esters 18 and 19, instead of the expected Fcca esters. By lithiation/carboxylation and subsequent esterification, 5, 6, 16 and 17 were converted into the desired 11 and 12. 1\u27-Acetylferrocene-1-carboxylic acid (21) was transformed into oxime 22 and oxime-ester 23. Hydrogenation of this intermediate resulted in formation of Fcca-OMe (24) in very good yield. The structure of the compounds prepared was confirmed by HRMS and spectroscopic analyses