The Isolation of Single MMX Chains from Solution: Unravelling the Assembly–Disassembly Process

Herein, we provide a systematic theoretical and experimental study of the structural and optical properties of MMX (M=metal, X=halide) chains. The influence of solvent, temperature, and concentration has been analyzed to find suitable parameters for initial building‐block associations in solution. By using density functional calculations, we have computed the dissociation energy of different MMX oligomers (up to the tetramer) in the gas phase. On the basis of these findings, we discuss the most likely disassembly scenario and propose a new interpretation of these compounds. We also calculated the charge redistribution that occurs upon MM+XMMX binding in vacuum. Time‐dependent density functional theory (TDDFT) is used to calculate the UV/visible spectra of different MMX chains up to the tetramer in the gas phase. The implications of these theoretical findings in the analysis of our experiments are discussed in the text. The overall body of data presented suggests a new way of looking at such linear structures. By taking into account these new data, we have been able to isolate single/few MMX chains on mica.     

Room‐Temperature Columnar Mesophases in Triazine–Gold Thiolate Metal–Organic Supramolecular Aggregates

Supramolecular mono‐ and dinuclear liquid‐crystalline gold(I) aggregates have been synthesized by means of hydrogen bond interactions of 2,4,6‐triarylamino‐1,3,5‐triazine with thiolate moities of gold metalloacids [Au(PR₃)(SC₆H₄COOH)] or [μ‐(binap){Au(SC₆H₄COOH)}₂], in 1:1 and 2:1 molar ratio, respectively. All of the supramolecular aggregates display a stable columnar hexagonal mesophase (Col_h) at room‐temperature. The supramolecular arrangement within the columns consists of the one‐dimensional stacking of triazine units, with the core of the attached metallic thioacid fragments acting as the fourth branch. The phosphine‐containing moieties of the metallic thioacid protrude out in the aliphatic continuum. These complexes do not show metallophilic interactions, but this strategy appears very promising for the future design of room‐temperature LC mesophases containing interacting metallic fragments.     

Capturing Linear Intermediates and C-Terminal Variants during Maturation of the Thiopeptide GE2270

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Evolution of crystal and amorphous fractions of poly[(R)-3-hydroxybutyrate] upon storage

Quantitative thermal analysis of the evolution of crystal and amorphous fractions of poly[(R)-3-hydroxybutyrate] (PHB) upon storage at room temperature is detailed in this contribution. Conventional and temperature-modulated calorimetry were used to quantify the crystallinity, as well as the mobile and rigid amorphous fractions, of an initially partially crystallized PHB, subsequently maintained at 25 °C for various times. PHB undergoes progressive crystallization during storage, with an increase in crystal fraction (w _C) from the initial w _C = 0.35 up to w _C = 0.71 attained after 1 year of storage. Crystallization is accompanied by vitrification of rigid amorphous segments, which leads to a noteworthy increase of the overall fraction of the material that is solid at room temperature, leaving only a mobile amorphous fraction w _A = 0.04 after 1 year at 25 °C. The quantitative thermal analysis allowed to clarify the kinetics of evolution of both the ordered and unordered fractions of PHB upon storage, which leads to a severe deterioration of material’s properties.     

Characterization of silver sulfadiazine-loaded solid lipid nanoparticles by thermal analysis

The aim of this study is the solid-state characterization of solid lipid nanoparticles (SLN) based on Compritol^® 888 (C888) and Lutrol^® F68 (F68), loaded with silver sulfadiazine (AgSD), used to develop sponge-like dressings to treat chronic skin ulcers such as decubitis and leg ulcers. Silver compounds like AgSD, in fact, are used to prevent and/or to treat wound colonization that could impair healing, also in the case of antibiotic-resistant bacteria. Thermal analysis, with support from powder X-ray diffractometry and Fourier transform infrared spectroscopy, is used to characterize lipid and drug bulk, unloaded and drug-loaded SLN. In particular, differential scanning calorimetry is used to investigate the degree of crystallinity and the solid-state modification of lipid, two parameters correlated to drug incorporation and drug release rates. The solid-state characterization demonstrates AgSD entrapment in C888 as a core enclosed into F68 shell. AgSD SLN are also stored at different temperatures 25 and 37 °C, respectively, to study the effect of storage conditions, that induce an increase of the lipid crystallinity index correlated to drug release from the lipid matrix.     

Aldehyde‐Assisted Hydrogen Transfer during the Formation of Hydride–Iridafurans from Alkynes and Aldehydes

The bis(ethylene) Ir^I complex [TpIr(C₂H₄)₂] ( 1 ; Tp=hydrotris(3,5‐dimethylpyrazolyl)borate) reacts with two equivalents of aromatic or aliphatic aldehydes in the presence of one equivalent of dimethyl acetylenedicarboxylate (DMAD) with ultimate formation of hydride iridafurans of the formula [TpIr(H){C(R¹)?C(R²)C(R³)O }] (R¹=R²=CO₂Me; R³=alkyl, aryl; 3 ). Several intermediates have been observed in the course of the reaction. It is proposed that the key step of metallacycle formation is a C? C coupling process in the undetected Ir^I species [TpIr{η¹‐O‐R³C(?O)H}(DMAD)] ( A ) to give the trigonal‐bipyramidal 16 e^? Ir^III intermediates [TpIr{C(CO₂Me)?C(CO₂Me)C(R³)(H)O }] ( C ), which have been trapped by NCMe to afford the adducts 11 (R³=Ar). If a second aldehyde acts as the trapping reagent for these species, this ligand acts as a shuttle in transfering a hydrogen atom from the γ‐ to the α‐carbon atom of the iridacycle through the formation of an alkoxide group. Methyl propiolate (MP) can be used instead of DMAD to regioselectively afford the related iridafurans. These reactions have also been studied by DFT calculations.     

MALDI-TOF mass spectrometric determination of intact phospholipids as markers of illegal bovine milk adulteration of high-quality milk

In the dairy industry one of the most common frauds is mixing high-value milk (sheep’s and goats’) with milk of lower value (cows’). This illegal practice has commercial, ethical, and serious sanitary consequences because consumers can be exposed to hidden allergens contained in the undeclared cows’ milk. Here, we investigated the possibility of using matrix-assisted laser-desorption/ionization (MALDI)-time of flight (TOF) mass spectrometry (MS) as a rapid, sensitive, and accurate technique for detection of milk adulteration by analysis of phospholipid profiles. Lipid extracts of pure raw milk, commercial milk, and binary mixtures of cows’ and goats’ milk and cows’ and sheep’s milk (the concentrations of each milk varied from 0 % to 50 %) were analyzed with α-cyano-4-chlorocinnamic acid as matrix. The abundance ratio of the ions at m/z 703 and m/z 706 was found to be species-correlated and was used as marker of cows’ milk in sheep’s and goats’ milk. Furthermore, the procedure could potentially be applied to cheese samples, because peaks at m/z 703 and 706 were also found in several commercial cheese samples. This approach proved to be an efficient, rapid, and inexpensive method of detecting milk fraud.

A comparison of four protocols for the immobilization of an aptamer on graphite composite electrodes

We have performed a comparative study on four protocols for the immobilization of the thrombin aptamer on a graphite-epoxy composite electrode with the aim to identify the most practical method for designing the corresponding impedimetric aptasensor. The protocols included (a) physical adsorption, (b) avidin-biotin affinity interaction, (c) electrochemical activation and covalent bonding via amide groups, and (d) electrochemical grafting using 4-carboxybenzenediazonium coupling. The properties of the sensing surface were probed by electrochemical impedance measurements in the presence of the (ferri/ferro)hexacyanide redox couple. An increase in the interfacial charge transfer resistance (R_ct) was noted in all cases after the aptamer-thrombin interaction had occurred. The selectivity of the aptasensor over common serum proteins was also systematically investigated. Physical adsorption resulted in the lowest detection limit of the probe (4.5 pM), while avidin-biotin interaction resulted in highest selectivity and reproducibility exhibiting a 4.9 % relative standard deviation at pM thrombin concentration levels.

Synthesis of 2,6-diaryl-1,2-dihydropyridines through a 6π-electrocyclization of N-sulfonylazatrienes

The development of an efficient synthetic method toward substituted 1,2-dihydropyridines from cinnamylideneacetophenones is reported. The key intermediates N-sulfonylazatrienes were synthesized through a TiCl₄-mediated direct condensation of primary sulfonamides with the substituted (E,E)-cinnamylideneacetophenones. The 6π-electrocyclization of these intermediates, catalyzed by a Lewis acid, selectively afforded the desired products in good yields.     

Dihydrobiphenylenes through Ruthenium‐Catalyzed [2+2+2] Cycloadditions of ortho‐Alkenylarylacetylenes with Alkynes

A new synthetic route to dihydrobiphenylenes has been developed. The process involves a mild Ru^II‐catalyzed [2+2+2] dimerization of ortho‐alkenylarylacetylenes or its more versatile variant, the Ru‐catalyzed [2+2+2] cycloaddition of ortho‐ethynylstyrenes with alkynes. Mechanistic aspects of this [2+2+2] cycloaddition are discussed.