Synthesis of Lignans Based on a Borate-mediated One-pot Sequential Suzuki-Miyaura Coupling of Cyclic Boranes

Lignans are a group of polyphenolic phytochemicals that possess a large spectrum of chemical structures and biological activities. Here the syntheses of lignans – anwulignan, burseran, dehydroxycubebin, ruburisandrin B, and sesamin – are achieved based on a borate-mediated one-pot sequential Suzuki-Miyaura coupling of cis- and trans-fused bicyclic boranes, which were prepared by diastereoselective cyclic hydroboration of exo-cyclic diene with cyclopentyl- and thexylboranes, respectively. A one-pot sequential Suzuki-Miyaura coupling of each cyclic borate with various aryl bromides initiated by activation of the cyclic borane with the carbon nucleophile provided 2,3-dibenzylbutane derivatives with different aromatic substituents. Finally, the syntheses of naturally occurring lignans were accomplished in several steps from the products of Suzuki-Miyaura coupling.     

Synthesis of triphenylamine-based thiophene-(N-aryl)pyrrole-thiophene dyes for dye-sensitized solar cell applications

Two new triphenylamine-based metal-free organic dyes (TPTDYE-1 and TPTDYE-2) containing 1-(2,6-diisopropylphenyl)-2,5-di(2-thienyl)pyrrole as a new π-conjugated chromophore were synthesized for dye-sensitized solar cell (DSSC) applications. TPTDYE-1 containing three donor groups around the acceptor group was found to show relatively narrow absorption band from 300 nm to 470 nm while TPTDYE-2 having extended π–π delocalization between the donor and acceptor group showed broad absorption band from 300 nm to 550 nm. The electrochemical studies indicate that the HOMO–LUMO energy gap of TPTDYE-1 is considerably wider than that of TPTDYE-2. The dye-sensitized solar cell performance of each dye was investigated, and the TPTDYE-2-sensitized cell was found to show a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 75%, a short-circuit photocurrent density (J_sc) of 13.50 mA/cm², an open-circuit voltage (V_oc) of 0.72 V, and a fill factor (FF) of 0.69, corresponding to an overall conversion efficiency of 6.71% under simulated AM 1.5 irradiation (100 mW/cm²). Under the same condition the TPTDYE-1-sensitized cell showed the same IPCE value of 75% with a promising conversion efficiency of 6.00%, a J_sc of 11.11 mA/cm², a V_oc of 0.76 V, and a FF of 0.71.     

Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.     

Influence of constant magnetic field on electrodeposition of metals,alloys, conductive polymers,and organic reactions

The paper presents and summarizes some research on constant magnetic field effects in chemistry. Metals and alloys electrodeposited under constant magnetic field have greater thickness and smoother surface with finest grains. Metallic materials deposited under the influence of uniform magnetic field may have stronger corrosion resistance, than those obtained without the presence of magnetic field. Constant magnetic field also causes an increase of the electropolymerization rate and yield of some organic reactions. Our research also shows that the presence of constant magnetic field affects the electrodeposition process of alloys and their morphology to a great extent. The effects of magnetic field on metals, alloys, composites, polymers and other materials are due to the Lorentz force and the magnetohydrodynamic effect. It is possible that the further development of magnetoelectrodeposition will allow for using the constant magnetic field to improve the properties of metal coatings, alloys, polymers, and other materials in the industry.     

Examination of Polish Identity Documents by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was applied to the preliminary examination of Polish documents – passports and identity cards – for forensic purposes. Several security features of potentially high discrimination capability were selected at both the passports (Alphagram, serial number, the contour map of Europe, and emblem) and identity cards (kinegram, the date of birth, and emblem). Different elemental compositions were identified after comparing the spectra recorded from various measurement locations. It was possible to identify characteristic atomic emission from several elements (such as Ti, Ca, K, Fe, Cr, Mg, Na, La, Cd, Li, V, Al, Mn, Ni, and Cu) based on the type of document, issue date, and evaluated area. In the case of passports, the potentially good discriminators with unique elemental composition were identified, e.g., the serial number and the contour map of Europe printed with the use of intaglio printing technique. Identity cards with the cover of polycarbonate foil constitute a very difficult sample to analyze because of the foil’s influence on the laser ablation phenomenon. This study presents the potential of LIBS as an effective and useful technique to analyze Polish passports for forensic purposes. Its many advantages provide a good alternative to the analytical methods routinely used for the examination of these objects.     

Novel Simultaneous Determination of Calcium and Magnesium Based on Flow Injection Gradient Titration

A novel approach based on flow injection gradient titration is proposed for the simultaneous spectrophotometric determination of Ca and Mg based on parameters of a single signal. Two reagents, calmagite and EDTA, are used to perform the determinations. Calmagite is introduced into a sample to form complexes with the analytes and the solutions are introduced into the holding coil of a sequential injection system in the sequence: carrier, air, sample, EDTA, and sample. In the system, EDTA replaces calmagite to form more stable complexes in turn with Ca and Mg. Next, the flow is reversed and the mixture is directed to the detector where the signal is measured at 680?nm. The signal consists of two parts: a short plateau (the signal for the sum of absorbance of complexes of Ca and Mg with calmagite) and a peak (the signal corresponding to titration of both complexes using EDTA). The absorbance values measured at the plateau and appropriately measured peak width were applied to determine analytes using two-component calibration. The method was verified for the determination of analytes in synthetic samples and in a certified reference material of surface water. Using the developed method, Mg and Ca were determined within the concentration ranges of 0.5–5.0 and 1.0–10.0?mg?L^?1, with precision better than 2.2 and 4.2% (relative standard deviation) and accuracy of 7.0 and 6.8% (relative error). The detection limits were 0.1 and 0.3?mg?L^?1 for Mg and Ca, respectively. The method was applied to analysis of mineral water samples.     

Frustrated Helicity: Joining the Diverging Ends of a Stable Aromatic Amide Helix to Form a Fluxional Macrocycle

Macrocyclization of a stable two‐turn helical aromatic pentamide, that is, an object with diverging ends that are not prone to cyclization, was made possible by the transient introduction of disruptors of helicity in the form of acid‐labile dimethoxybenzyl tertiary amide substituents. After removal of the helicity disruptors, NMR, X‐ray crystallography, and computational studies show that the macrocycle possesses a strained structure that tries to gain as high a helical content as possible despite being cyclic. Two points of disruption of helicity remain, in particular a cis amide bond. This point of disruption of helicity can propagate along the cycle in a fluxional manner according to defined trajectories to produce ten degenerate conformations.