Gadolinium‐Decorated Silica Microspheres as Redox‐Responsive MRI Probes for Applications in Cell Therapy Follow‐Up

The redox microenvironment within a cell graft can be considered as an indicator to assess whether the graft is metabolically active or hypoxic. We present a redox‐responsive MRI probe based on porous silica microparticles whose surface has been decorated with a Gd‐chelate through a disulphide bridge. Such microparticles are designed to be interspersed with therapeutic cells within a biocompatible hydrogel. The onset of reducing conditions within the hydrogel is paralleled by an increased clearance of Gd, that can be detected by MRI.     

Pseudopeptide‐Based Hydrogels Trapping Methylene Blue and Eosin Y

We present herein the preparation of four different hydrogels based on the pseudopeptide gelator Fmoc‐l ‐Phe‐d ‐Oxd‐OH (Fmoc=fluorenylmethyloxycarbonyl), either by changing the gelator concentration or adding graphene oxide (GO) to the water solution. The hydrogels have been analysed by rheological studies that demonstrated that pure hydrogels are slightly stronger compared to GO‐loaded hydrogels. Then the hydrogels efficiency to trap the cationic methylene blue (MB) and anionic eosin Y (EY) dyes has been analyzed. MB is efficiently trapped by both the pure hydrogel and the GO‐loaded hydrogel through π–π interactions and electrostatic interactions. In contrast, the removal of the anionic EY is achieved in less satisfactory yields, due to the unfavourable electrostatic interactions between the dye, the gelator and GO.     

Analysis of the effects of catalytic bleaching on cotton

Hydrogen peroxide can be catalyzed to bleach cotton fibers at temperatures as low as 30°C by incorporating dinuclear tri-μ-oxo bridged manganese(IV) complex of the ligand 1,4,7-trimethyl-1,4,7-triazacyclononane (MnTACN) as the catalyst in the bleaching solution. The catalytic system was found to be more selective under the conditions applied than the non-catalytic H₂O₂ system, showing better bleaching performance while causing slightly lower decrease in degree of polymerization (DP) of cellulose. In order to gain fundamental knowledge of the bleach effect on cotton fibers and cellulose as its main component, especially after catalytic bleaching, X-ray Photoelectron Spectroscopy (XPS) was used to study surface chemical effects. The Washburn method was applied to investigate wetting properties, and liquid porosity was used to obtain pore volume distribution (PVD) plots. Parallel analyzes performed on model cotton fabric, i.e. “clean” cotton fabric stained with morin - a pigment regularly found in native cotton fiber, helped to differentiate between pigment oxidation and other bleaching effects produced on the (regular) industrially scoured cotton fabric. Bleaching was not limited to the chemical action but also affected cotton fiber capillary parameters most likely due to the removal of non-cellulosic materials as well as chain-shortened cellulose.     

Vascular endothelial and smooth muscle cell culture on NaOH-treated poly(epsilon-caprolactone) films: a preliminary study for vascular graft development

Tissue engineering offers the potential of providing vessels that can be used to replace diseased and damaged native blood vessels. The endothelization of a synthetic vascular graft minimizes the failures associated with blood clotting and platelet activation. The aim of this study was to culture vascular-derived endothelial and smooth muscle cells on both untreated and NaOH-treated poly(epsilon-caprolactone) (PCL) films, a biocompatible and bio-resorbable polymer, and to evaluate the behavior of both cell types as a preliminary study for vascular graft development. PCL films were prepared by hot pressing; characterized by DSC, IR, SEM, and scanning force microscopy; and treated with NaOH to increase the surface hydrophilicity before cell culture. Endothelial and smooth muscle cells, isolated from pig cava vein, were characterized by immunofluorescence and confocal microscopy studies of endothelial nitric oxide synthase and alpha-smooth muscle actin. Good adhesion, growth, viability and morphology of both the endothelial and smooth muscle cells on PCL films were obtained, but a light stimulation of mitochondrial activity was observed during short culture times. NaOH treatment improved the adhesion and enhanced the proliferation in both cell types. This verified the possible use of this modified polymer as a support in the preparation of a synthetic vascular graft. [Diagram: see text] SEM micrograph of smooth muscle cells cultured on NaOH-treated PCL film. (Original magnification: 1000x).     

Relaxation response of polymers containing highly flexible side groups monitored by broadband dielectric spectroscopy

The relaxation behavior of poly(5-acryloxymethyl-5-methyl-1,3-dioxacyclohexane), a polymer containing highly flexible side groups, is studied by broadband dielectric spectroscopy in the frequency and temperature ranges 10(-1)-10(9) Hz and 123-473 K, respectively. Above the glass transition temperature T(g) the dielectric loss in the frequency domain exhibits a prominent alpha absorption, followed in increasing order of frequencies by two secondary absorptions called beta and gamma. At temperatures slightly higher than T(g), the a relaxation is well separated from the beta, but as temperature increases overlapping between both relaxations augments forming an alphabeta absorption in the vicinity of 420 K. This latter absorption displays a shoulder on its high-frequency side corresponding to the y relaxation. The strength of the a relaxation decreases with increasing temperature, eventually vanishing at the temperature at which the alphabeta absorption is formed. The time retardation spectra of the isotherms are calculated and further used to facilitate the deconvolution of the overlapping relaxations. The fact that the temperature dependence of the beta relaxation also describes that of the alphabeta absorption suggests that both relaxations have the same nature. It seems that as temperature increases, the a relaxation feeds on the beta absorption until its complete disappearance. The gamma relaxation, in turn, seems to increase at the expense of the alphabeta process at high temperature.     

First observation of the hyperfine structure of an excited quintet state in liquid solution

After pulsed photoexcitation of a new fullerene-linked bisnitroxide, a well resolved transient EPR spectrum is detected which is assigned to an excited quintet spin state generated by spin coupling of the nitroxides and the fullerene excited triplet.     

Multi-residue screening of chlorinated and brominated compounds from aquaculture samples using matrix solid-phase dispersion--gas chromatography-mass spectrometry

An effective multiresidual method for the trace analysis of fifteen compounds from a diverse group of pesticides, polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyl (PCBs) and polybrominated biphenyl (PBBs) in aquaculture feed is described. The analytical procedure is based on the matrix solid-phase dispersion (MSPD) of feed sample and subsequent elution with hexane. The MSPD process was evaluated using an asymmetrical experimental design 2(3)3(2)//9. Factors such as C18 sorbent amount, kind of adsorbents, solvent volume and elution mode were considered. The results suggest that the operational MSPD conditions are elution with pressure, 1 g of C18, basic alumina as adsorbent and 30 mL of hexane. The overall method including MSPD procedure and GC coupled to mass spectrometry (MS/MS) has been applied to several samples of aquaculture feed and marine species. Precision and accuracy of the analytical method were determined using the reference material from the International Atomic Energy Agency (IAEA-406), showing a good agreement to the referenced values.     

Time-resolved electron paramagnetic resonance of photoinduced ion pairs in blends of polythiophene and fullerene derivatives

Substituted polythiophene and triethylenglycolpyrrolidino-C(60) blends are examined by time-resolved electron paramagnetic resonance (TR-EPR) at different temperatures. TR-EPR spectra recorded on the microsecond time scale after a short laser pulse are assigned to polythiophene and fullerene radical ion pairs, generated by electron transfer from the excited state of polythiophene to fullerene. At low temperatures, TR-EPR spectra show polarized lines with an antiphase emission/absorption pattern. The origin of the polarization pattern is described in the frame of spin correlated radical pair theory, in which two unpaired electron spins (on radical cation and anion, respectively) interact through isotropic spin exchange and anisotropic dipolar interactions. The polarization pattern is accounted for assuming a singlet excited state as the precursor of the charge-separated state. Spectral simulations yield dipolar and spin exchange coupling constants between unpaired electrons of the radical ion pair. Their values correspond to a mean distance between opposite charges of 22 A. When the temperature is increased, the spectra gradually loose their antiphase character and eventually consist of a signal totally in emission. This behavior is explained by a polarization mechanism involving a spin-selective charge recombination (ST(-1) mixing). The polarization pattern at different temperatures is examined in detail, and its generating mechanism is discussed.     

High temperature structures and orientational disorder in compressed solid nitrogen

An experimental study of the phase transitions at high temperature in compressed solid nitrogen has been performed using Raman spectroscopy. Knowledge of the equilibrium phase diagram in the region of the ordered epsilon phase and the two disordered delta and deltaloc phases, at pressures between 10 and 20 GPa, has been extended up to 500 K. The Raman scattering line shape and line width of the active vibrons has been measured accurately, along isobaric scans, across the phase transitions. Analysis of the width and of its different behavior with increasing temperature in the three phases led to more precise conclusions about the nature of the disorder in the different phases. Observation of an evident shoulder in the nu2 band of the deltaloc phase suggests the possibility that sites of two different symmetries may be occupied by the disk molecules in this structure.     

A flow-through microfluidic chip for continuous dielectrophoretic separation of viable and non-viable human T-cells

Effective methods for rapid sorting of cells according to their viability are critical in T cells based therapies to prevent any risk to patients. In this context, we present a novel microfluidic device that continuously separates viable and non-viable T-cells according to their dielectric properties. A dielectrophoresis (DEP) force is generated by an array of castellated microelectrodes embedded into a microfluidic channel with a single inlet and two outlets; cells subjected to positive DEP forces are drawn toward the electrodes array and leave from the top outlet, those subjected to negative DEP forces are repelled away from the electrodes and leave from the bottom outlet. Computational fluid dynamics is used to predict the device separation efficacy, according to the applied alternative current (AC) frequency, at which the cells move from/to a negative/positive DEP region and the ionic strength of the suspension medium. The model is used to support the design of the operational conditions, confirming a separation efficiency, in terms of purity, of 96% under an applied AC frequency of 1.5 × 10⁶ Hz and a flow rate of 20 μl/h. This work represents the first example of effective continuous sorting of viable and non-viable human T-cells in a single-inlet microfluidic chip, paving the way for lab-on-a-chip applications at the point of need.