Phase segregation of metastable quenched liquid mixtures and the effect of the quenching rate

The effect of the quenching rate on the phase separation of partially miscible liquid mixtures is studied, showing that it may influence the growth rate of single-phase domains. In particular, the phase separation of metastable binary mixtures in the presence of strong emulsifiers appears to be heavily retarded. These effects constitute an important limitation to the phase transition extraction process introduced by the authors in previous works, which is based on the fact that phase separation of unstable mixtures is rapid, even in the presence of surface active compounds.     

Access to Enantiopure Advanced Intermediates en Route to Madangamines

The synthesis of enantiopure ABCE and ABCD tetracyclic advanced intermediates en route to madangamine alkaloids and studies for the construction of the triunsaturated 15-membered D ring of madangamine B and the saturated 13-membered D ring of madangamine E are reported.     

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Differential characters and cohomology of the moduli of flat connections

Let \(\pi {:}\, P\rightarrow M\) be a principal bundle and p an invariant polynomial of degree r on the Lie algebra of the structure group. The theory of Chern–Simons differential characters is exploited to define a homology map \(\chi ^{k} {:}\, H_{2r-k-1}(M)\times H_{k}({\mathcal {F}}/{\mathcal {G}})\rightarrow {\mathbb {R}}/{\mathbb {Z}}\), for \(k<r-1\), where \({\mathcal {F}} /{\mathcal {G}}\) is the moduli space of flat connections of \(\pi \) under the action of a subgroup \({\mathcal {G}}\) of the gauge group. The differential characters of first order are related to the Dijkgraaf–Witten action for Chern–Simons theory. The second-order characters are interpreted geometrically as the holonomy of a connection in a line bundle over \({\mathcal {F}}/{\mathcal {G}}\). The relationship with other constructions in the literature is also analyzed.

     

Recent advances and challenges in the recovery and purification of cellular exosomes

Exosomes are nanovesicles secreted by most cellular types that carry important biochemical compounds throughout the body with different purposes, playing a preponderant role in cellular communication. Because of their structure, physicochemical properties and stability, recent studies are focusing in their use as nanocarriers for different therapeutic compounds for the treatment of different diseases ranging from cancer to Parkinson's disease. However, current bioseparation protocols and methodologies are selected based on the final exosome application or intended use and present both advantages and disadvantages when compared among them. In this context, this review aims to present the most important technologies available for exosome isolation while discussing their advantages and disadvantages and the possibilities of being combined with other strategies. This is critical since the development of novel exosome‐based therapeutic strategies will be constrained to the effectiveness and yield of the selected downstream purification methodologies for which a thorough understanding of the available technological resources is needed.     

On the integrability of Degasperis–Procesi equation: Control of the Sobolev norms and Birkhoff resonances

We consider the dispersive Degasperis–Procesi equation $u_t?u_{xxt}?\mathtt{c}{u}_{xxx}+4\mathtt{c}{u}_x?u{u}_{xxx}?3u_x{u}_{xx}+4u{u}_x=0$ with $\mathtt{c}\in \mathbb{R}?\{0\}$. In [15] the authors proved that this equation possesses infinitely many conserved quantities. We prove that there are infinitely many of such constants of motion which control the Sobolev norms and which are analytic in a neighborhood of the origin of the Sobolev space $H^s$ with $s\ge 2$, both on $\mathbb{R}$ and $\mathbb{T}$. By the analysis of these conserved quantities we deduce a result of global well-posedness for solutions with small initial data and we show that, on the circle, the formal Birkhoff normal form of the Degasperis–Procesi at any order is action-preserving.     

Diagram,valence-to-core,and hypersatellite Kβ X-ray transitions in metallic chromium

We report on measurements of the Kβ diagram, valence-to-core (VtC), and hypersatellite X-ray spectra induced in metallic Cr by photon single and double K-shell ionization. The experiment was carried out at the Stanford Synchrotron Radiation Lightsource using the seven-crystal Johann-type hard X-ray spectrometer of the beamline 6-2. For the Kβ diagram and VtC transitions, the present study confirms the line shape features observed in previous works, whereas the K^hβ hypersatellite transition was found to exhibit a complex spectral line shape and a characteristic low-energy shoulder. The energy shift of the hypersatellite relative to the parent diagram line was deduced from the measurements and compared with the result of extensive multiconfiguration Dirac–Fock (MCDF) calculations. A very good agreement between experiment and theory was found. The MCDF calculations were also used to compute the theoretical line shape of the hypersatellite. A satisfactory agreement was obtained between the overall shapes of the experimental and theoretical spectra, but deviations were observed on the low- and high-energy flanks of the hypersatellite line. The discrepancies were explained by chemical effects, which were not considered in the MCDF calculations performed for isolated atoms.     

The effect of cationic groups on the stability of 19F MRI contrast agents in nanoparticles

Fluorine‐19 (¹⁹F)‐based contrast agents are increasingly used for magnetic resonance imaging. Conjugated to polymers, they provide an excellent quantitative imaging tool to detect the movement of the polymeric nanoparticles in vivo as there is no background signal in tissue. One of the challenges is the decline in signal intensity when the conjugated hydrophobic fluorinated functionalities aggregate. Therefore, a new fluorinated monomer was prepared from l ‐arginine that carries a 2,2,2‐trifluoroethyl functional group for imaging. The resulting monomer, 2,2,2‐trifluoroethylamide l ‐arginine methacrylamide (3FArgMA), was copolymerized with poly(ethylene glycol) methyl ether methacrylate (PEGMEMA), [2‐(2,3,4,6‐tetra‐O‐acetyl‐α‐d ‐mannopyranosyloxy)ethyl methacrylate or 1‐O‐methacryloyl‐2,3:4,5‐di‐O‐isopropylidene‐β‐d ‐fructopyranose, respectively, using poly(methyl methacrylate) macro‐reversible addition–fragmentation chain transfer polymerization agent. The resulting block copolymers, which varied in 3FArgMA content, were self‐assembled into micelles of hydrodynamic diameters from 25 to 60 nm. The permanently positively charged arginine functionality on the 3FArgMA displayed repulsive forces against aggregation enabling high spin–spin relaxation times (T₂) in acidic as well as alkaline solutions. However, the longer poly(ethylene glycol) side functionality in PEGMEMA enabled better steric stabilization (T₂~30 ms) while the short fructose side chain was not enough to maintain high T₂ values, in particular when a higher 3FArgMA content was used. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1994–2001     

The behavior of differential forms under purely inseparable extensions

Let F be a field of characteristic 2. In this paper we give a complete computation of the kernel of the homomorphism $H_2^{m+1}(F)?H_2^{m+1}(L)$ induced by scalar extension, where $L/F$ is a purely inseparable extension (of any degree), $H_2^{m+1}(F)$ is the cokernel of the Artin–Schreier operator $?:{\mathrm{\Omega }}_F^m?{\mathrm{\Omega }}_F^m/\mathrm{d}{\mathrm{\Omega }}_F^{m?1}$ given by: $x\frac{\mathrm{d}{x}_1}{x_1}\wedge ?\wedge \frac{\mathrm{d}{x}_m}{x_m}?(x^2?x)\frac{\mathrm{d}{x}_1}{x_1}\wedge ?\wedge \frac{\mathrm{d}{x}_m}{x_m}+\mathrm{d}{\mathrm{\Omega }}_F^{m?1}$, where ${\mathrm{\Omega }}_F^m$ is the space of absolute m-differential forms over F and d is the differential operator. Other related results are included.