Synthesis of new semi-synthetic dipodands and tripodands from naturally occurring polyether ionophores

A new method to synthesize novel esters of Lasalocid acid 2-5 and of Monensin A, 7-9 (semi-synthetic di- and tripodands) is described. These new compounds are characterized by spectroscopic and microbiological methods.     

FT-IR study of the proton polarizability of hydrogen bonds and of the hydrogen-bonded systems in a di-Mannich base of 5,5′-dimethoxy-2,2′-biphenol

The mono- as well as the di-Mannich bases of 5,5′-dimethoxy-2,2′-biphenol are studied by FT-IR spectroscopy. It is shown that in these bases the protons remain localized at the phenol O atom. This result is in contrast to those obtained earlier for more acidic biphenols in which the protons are not localized but fluctuate and the relevant hydrogen bonds show large polarizability. An intense infrared continuum in the FT-IR spectrum of the mono-protonated di-Mannich base of 5,5′-dimethoxy-2,2′-biphenol demonstrates that the intramolecular hydrogen bond in this compound shows large proton polarizability.     

Random Perturbations of Matrix Polynomials

Journal of Theoretical Probability - A sum of a large-dimensional random matrix polynomial and a fixed low-rank matrix polynomial is considered. The main assumption is that the resolvent of the...     

Experimental Demonstration of SCM-PON Monitoring with Baseband Embedded OTDR

The combination of subcarrier multiplexing and passive optical networks can provide an efficient and cost-effective solution for fiber and wireless convergence in access networks. Moreover, to reduce operational expenditures, a reliable monitoring technique should provide in-service evaluation of the physical layer. Here, we perform the experimental demonstration of an SCM-PON system with baseband embedded optical time-domain reflectometer monitoring. Different modulation formats were tested to evaluate the penalty generated by the monitoring system. Based on the long-term evolution downlink test model (E-TM 3.1), our results show negligible power penalty while achieving a ~12-dB dynamic range with 10-m spatial resolution.     

A novel fluorescent silica tracer for biological silicification studies.

BACKGROUND: Biological silica production has drawn intense attention and several molecules involved in biosilicification have been identified. Cellular mechanisms, however, remain unknown mainly due to the lack of probes required for obtaining information on live specimens. RESULTS: The fluorescence spectra of the compound 2-(4-pyridyl)-5-((4-(2-dimethylaminoethylaminocarbamoyl)methoxy)phenyl)oxazole (PDMPO) are affected by the presence of >3.2 mM silicic acid. Increase in intensity and shift in the fluorescence coincide with the polymerization of Si. The unique PDMPO-silica fluorescence is explored here to visualize Si deposition in living diatoms. The fluorophore is selectively incorporated and co-deposited with Si into the newly synthesized frustules (the outer silica shells) showing an intense green fluorescence. CONCLUSIONS: We suggest that a fluorescence shift is due to an interaction between PDMPO and polymeric silicic acid. PDMPO is an excellent probe for imaging newly deposited silica in living cells and has also a potential for a wide range of applications in various Si-related disciplines, including biology of living organisms as diatoms, sponges, and higher plants, clinical research (e.g. lung fibrosis and cancer, bone development, artificial bone implantation), and chemistry and physics of materials research.     

Spectroscopic, semi-empirical and antimicrobial studies of a new amide of monensin A with 4-aminobenzo-15-crown-5 and its complexes with Na cation at 1:1 and 1:2 ratios

A new amide of monensin A with 4-aminobenzo-15-crown-5 (M-AM3) was synthesised and its ability to form complexes with Na⁺ cations was studied by ESIMS, ¹H, ¹³C and ²³Na NMR, FTIR and PM5 semi-empirical methods. ESI mass spectrometry indicates that in the gas phase M-AM3 amide forms complexes of 1:1 and 1:2 stoichiometry with Na⁺ cations. The formation of such complexes is also confirmed in the acetonitrile solution, in which the existence of equilibrium between two structures A and B is found, of which B structure is dominant. The structures of M-AM3 and its 1:1 and 1:2 complexes with Na⁺ cations are stabilised by various intramolecular hydrogen bonds, which are discussed in detail. The in vitro biological tests have demonstrated that the new M-AM3 amide shows good activity towards some strains of Gram-positive bacteria (MIC 25-50 μg/ml).     

Structure elucidation,complete NMR assignment and PM5 theoretical studies of new hydroxy‐aminoalkyl‐α,β‐unsaturated derivatives of the macrolide antibiotic josamycin

Four new hydroxy‐aminoalkyl derivatives of α,β‐unsaturated macrolide‐josamycin (2–5) have been synthesised and their structures have been studied by means of ¹H and ¹³C NMR and FT‐IR methods. Complete assignment of resonances in the ¹H and ¹³C NMR spectra has been made on the basis of ¹H? ¹³C HSQC, ¹H? ¹³C HMBC, ¹H? ¹H COSY, ¹H? ¹H NOESY 2D experiments. Spectroscopic data indicated that for the derivatives 3 and 4 some equilibrium between two different structures exists in contrast to derivatives 2 and 5. The lowest‐energy structures of the new derivatives of josamycin have been calculated and visualised by PM5 method at semi‐empirical level of theory, taking into account the NMR and FT‐IR data. The most significant differences between the structures of josamycin and its newly synthesised derivatives' were found in the conformation of the macrolide aglycone part and in the mutual orientation of the 4‐O‐isovalerylmycarosylmycaminose moiety relative to the aglycone part. PM5 semi‐empirical calculations indicated that the structures of the new macrolide derivatives are stabilised by rather weak intramolecular hydrogen bonds in agreement with spectroscopic data. Antimicrobial properties of the new derivatives 2–5 as well as those having an acetate group at C‐3 (6 and 7) were determined and compared to that of the parent macrolide antibiotic josamycin (1). Copyright © 2010 John Wiley & Sons, Ltd.     

The influence of protonation on molecular structure and physico-chemical properties of gossypol Schiff bases

Protonation of gossypol Schiff bases (S1 and S2), possessing different numbers of basic N-atoms, was studied using potentiometric, spectroscopic, ESI MS and PM5 methods. Titration of S1 and S2 with HClO(4), monitored by the FT-IR and (1)H NMR, indicated that the change from the enamine-enamine into the protonated imine-imine tautomeric form occurs at different Schiff base-H(+) ratio. The FT-IR and PM5 results show that for S1 the first protonation step occurs at Schiff base moiety whereas for S2 it is realised at N-atom of the morpholine. The formation of N(+)-HO hydrogen bond between morpholine moieties within S2 contributes to high pK(a(ACN)) = 22.65.