Synthesis and Characterization of Hydrophilic Trityl Radical TFO for Biomedical and Biophysical Applications

Tetrathiatriarylmethyl (TAM, trityl) radicals have found wide applications as spin probes/labels for EPR spectroscopy and imaging, and as polarizing agents for dynamic nuclear polarization. The high hydrophilicity of TAM radicals is essential for their biomedical applications. However, the synthesis of hydrophilic TAM radicals (e.g., OX063) is extremely challenging and has only been reported in the patent literature, to date. Herein, an efficient synthesis of a highly water-soluble TAM radical bis(8-carboxyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)-mono-(8-carboxyl-2,2,6,6-tetrakis(2-hydroxyethyl)benzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)methyl (TFO), which contains four additional hydroxylethyl groups, relative to the Finland trityl radical CT-03, is reported. Similar to OX063, TFO exhibits excellent properties, including high water solubility in phosphate buffer, low log P, low pK_a, long relaxation times, and negligible binding with bovine serum albumin. On the other hand, TFO has a sharper EPR line and higher O₂ sensitivity than those of OX063. Therefore, in combination with its facile synthesis, TFO should find wide applications in magnetic resonance related fields and this synthetic approach would shed new light on the synthesis of other hydrophilic TAM radicals.     

Ultrafast study of inter‐ and intrachain energy transfer in a core–polymer

Interchain interactions can play a positive role in reaching amplified spontaneous emission in an interesting core–polymer system where the donor (side chains) and the acceptor (core) are chemically linked together. Different degree of interchain interactions modifies the photophysical characteristics of the polymer. By means of transient absorption spectroscopy we show that the stimulated emission from the core decreases passing from solid state to concentrated solution and it is almost absent in the diluted solution. The conformational rearrangements of the core–polymer chain in solution limits the efficiency of the intrachain Förster energy transfer mechanism. The free chain rotations decrease the exciton hopping along the conjugated chains, the ratio between donor and acceptor moieties in the polymer, and change the relative orientation of the transition dipoles of the donor and acceptor causing a strong decrease of energy transfer efficiency and subsequently of the gain. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 965–969     

Recent Progress on Infrared Photoacoustic Spectroscopy Techniques

Abstract

Analogous to most new methods in science, photoacoustic spectroscopy (PAS) grew out of an advance in technology, in this case the dramatic improvement in novel light sources, modulators, and acoustic detectors, as well as signal recovery electronics, which in turn was made possible by the development of modern PAS techniques. PAS is a promising technique that can be used to analyze and characterize a broad variety of objects (gaseous, solid, and liquid samples). In the present review, the recent development of infrared PAS limited to the general area of gas-phase analysis techniques since 1990 is summarized, with special emphasis on the development of new or enhanced analytical methodologies based on the use of the photoacoustic (PA) effect to improve the sensitivity of PAS by enhancing signal or reducing noise levels, with regard to PA systems, applications, and conclusions. The applications of these novel PA methods are mainly concerned with molecular spectroscopic, industrial, atmospheric, environmental, chemical and biological, and medical and clinical analysis. New prospects and challenges in various application fields of PAS technique are described.     

Vacancy-like defects in nanocrystalline SnO2: influence of the annealing treatment under different atmospheres

The study of electronic and chemical properties of semiconductor oxides is motivated by their several applications. In particular, tin oxide is widely used as a solid state gas sensor material. In this regard, the defect structure has been proposed to be crucial in determining the resulting film conductivity and then its sensitivity. Here, the characteristics of vacancy-like defects in nanocrystalline commercial high-purity tin oxide powders and the influence of the annealing treatment under different atmospheres are presented. Specifically, SnO₂ nanopowders were annealed at 330 °C under three different types of atmospheres: inert (vacuum), oxidative (oxygen) and reductive (hydrogen). The obtained experimental results are discussed in terms of the vacancy-like defects detected, shedding light to the basic conduction mechanisms, which are responsible for gas detection.     

Analysis of the Chemical Composition of Red Pigments and Inks for the Characterization and Differentiation of Contemporary Prints

Prints are one of the most popular artistic forms. They consist of an original matrix that is printed on a paper support. The stamps are part of a series, and each series is composed of a particular number of prints. Many contemporary prints are made using oil inks and synthetic pigments (reds and yellows). Inks are mainly composed of pigments (organic or inorganic) and a binding medium. The analysis of inks has the potential to facilitate and complement the identification of stamps of different origins.

Fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscopy-Energy Dispersive X-ray (SEM-EDX) are techniques that are typically available in museums and centers related to the study of works of art. Both can be classified as micro-destructive and provide complementary information about the organic and some inorganic compounds (FTIR), and the elemental composition (SEM-EDX). In this article, the two techniques were used to analyze the composition of red ink in prints. As a result of these analyses, it was possible to distinguish among nearly all of the pigments and inks, indicating that the composition of the red ink can be reliably used to differentiate between stamps of different origins in a series of prints.     

Dimerization of Colloidal Particles through Controlled Aggregation for Enhanced Properties and Applications

Devising syntheses capable of precisely manipulating matter on the nanoscale is central to many areas of research. The underlying motivation is fueled by the fact that at the nanometer scale, the property has a strong correlation with the structure. One such nanostructure that has accrued much attention is the dimer—a structure composed of two colloidal particles separated by a small gap. This Focus Review discusses how colloidal stability can be strategically manipulated to induce dimerization, together with effective purification steps to further improve yields. We conclude the article by providing representative examples for how dimers composed of plasmonic nanoparticles leads to structures with tunable optical properties and strong electric near‐fields, ideal for application in surface‐enhanced Raman spectroscopy.     

Allyl sulfides and α‐substituted acrylates as addition–fragmentation chain transfer agents for methacrylate polymer networks

The rapid and uncontrolled nature of network formation from di(meth)acrylate monomers produces high shrinkage stress and results in polymers with oftentimes brittle mechanical properties. Methods for regulating polymerization and network formation are sought. One option is the use of addition–fragmentation chain transfer (AFCT) agents, which are well known to control molecular weight and molecular weight distribution of monofunctional (meth)acrylates. A series of novel and previously described AFCT reagents were synthesized and screened with laser flash photolysis to determine reactivity. Well‐performing AFCT reagents were then tested in polymerizations with monofunctional and difunctional methacrylates. With monofunctional monomers, the molecular weight and polydispersity of the resultant linear polymers tend to decrease with the addition of AFCT agent. In copolymerization with dimethacrylate monomers, the AFCT agents were found to substantially lower and sharpen the glass transition. Sharpness of the glass transition is here indicative of a more regular and homogenous network. After coupling of the instruments, photorheology was performed simultaneously with real‐time IR to show an increase in monomer conversion at the time of gelation, which appears to have a positive effect on reducing shrinkage stress. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 394–406     

Unraveling σ and π Effects on Magnetic Anisotropy in cis‐NiA4B2 Complexes: Magnetization,HF‐HFEPR Studies,First‐Principles Calculations,and Orbital Modeling

By using complementary experimental techniques and first‐principles theoretical calculations, magnetic anisotropy in a series of five hexacoordinated nickel(II) complexes possessing a symmetry close to C_2v, has been investigated. Four complexes have the general formula [Ni(bpy)X₂]ⁿ⁺ (bpy=2,2′‐bipyridine; X₂=bpy ( 1 ), (NCS^?)₂ ( 2 ), C₂O₄^2? ( 3 ), NO₃^? ( 4 )). In the fifth complex, [Ni(HIM₂‐py)₂(NO₃)]⁺ ( 5 ; HIM₂‐py=2‐(2‐pyridyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazolyl‐1‐hydroxy), which was reported previously, the two bpy bidentate ligands were replaced by HIM₂‐py. Analysis of the high‐field, high‐frequency electronic paramagnetic resonance (HF‐HFEPR) spectra and magnetization data leads to the determination of the spin Hamiltonian parameters. The D parameter, corresponding to the axial magnetic anisotropy, was negative (Ising type) for the five compounds and ranged from ?1 to ?10 cm^?1. First‐principles SO‐CASPT2 calculations have been performed to estimate these parameters and rationalize the experimental values. From calculations, the easy axis of magnetization is in two different directions for complexes 2 and 3 , on one hand, and 4 and 5 , on the other hand. A new method is proposed to calculate the g tensor for systems with S=1. The spin Hamiltonian parameters (D (axial), E (rhombic), and g_i) are rationalized in terms of ordering of the 3 d orbitals. According to this orbital model, it can be shown that 1) the large magnetic anisotropy of 4 and 5 arises from splitting of the e_g‐like orbitals and is due to the difference in the σ‐donor strength of NO₃^? and bpy or HIM₂‐py, whereas the difference in anisotropy between the two compounds is due to splitting of the t_2g‐like orbitals; and 2) the anisotropy of complexes 1 – 3 arises from the small splitting of the t_2g‐like orbitals. The direction of the anisotropy axis can be rationalized by the proposed orbital model.     

DOSY NMR as a tool for predicting optimal conditions for hydrogel formation: The case of a hyperbranched polyglycidol cross‐linked with boronic acids

This article demonstrates the utility of DOSY NMR for the determination of the optimal conditions for the efficient covalent, reversible cross‐linking of macromolecules in water for hydrogel formation. The studied model system was hyperbranched polyglycidol (HbPGL) containing numerous diol groups in peripheral regions and two types of boronic acids, that is, B(OH)₄^? and benzene‐1,4‐boronic diacid, as cross‐linking agents. Diffusion coefficient changes of a polymer in solution, under the influence of various concentrations of cross‐linking agent and pH, which influences the equilibrium of the reaction between boronic acids and diols, were recorded. These data are consistent with the rheological properties, namely the G′_max(ω) of hydrogels prepared under analogous conditions, from more concentrated solutions of HbPGL. This approach appears to be promising as it facilitates avoiding the loss of a large amount of polymer that is necessary for the elaboration of appropriate conditions for network formation in aqueous media. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2171–2178