Hydrogen Bonding and Vaporization Thermodynamics in Hexafluoroisopropanol-Acetone and -Methanol Mixtures. A Joined Cluster Analysis and Molecular Dynamic Study

Binary mixtures of hexafluoroisopropanol with either methanol or acetone are analyzed via classical molecular dynamics simulations and quantum cluster equilibrium calculations. In particular, their populations and thermodynamic properties are investigated with the binary quantum cluster equilibrium method, using our in-house code Peacemaker 2.8, upgraded with temperature-dependent parameters. A novel approach, where the final density from classical molecular dynamics, has been used to generate the necessary reference isobars. The hydrogen bond network in both type of mixtures at molar fraction of hexafluoroisopropanol of 0.2, 0.5, and 0.8 respectively is investigated via the molecular dynamics trajectories and the cluster results. In particular, the populations show that mixed clusters are preferred in both systems even at 0.2 molar fractions of hexafluoroisopropanol. Enthalpies and entropies of vaporization are calculated for the neat and mixed systems and found to be in good agreement with experimental values.     

Transport engineering in microbial cell factories producing plant-specialized metabolites

Transport engineering strategies use altered expression of transporter proteins to change metabolite distribution within an organism. The production of plant specialized metabolites in microbial cell factories encounters a set of challenges that could benefit from the implementation of transport engineering technology. The range of challenges includes premature pathway termination due to secretion of intermediates, feedback inhibition due to inefficient export of final products, low yields in bioconversion processes due to inefficient import of precursors, and poor connectivity between subcellular compartments expressing different parts of complex biosynthetic pathways. We highlight the latest examples of transport engineering in microbial cell factories producing plant specialized metabolites, identify the current knowledge gap, and propose future research for advancing the field.     

Soliton interactions and Yang–Baxter maps for the complex coupled short-pulse equation

The complex coupled short-pulse equation (ccSPE) describes the propagation of ultrashort optical pulses in nonlinear birefringent fibers. The system admits a variety of vector soliton solutions: fundamental solitons, fundamental breathers, composite breathers (generic or nongeneric), as well as so-called self-symmetric composite solitons. In this work, we use the dressing method and the Darboux matrices corresponding to the various types of solitons to investigate soliton interactions in the focusing ccSPE. The study combines refactorization problems on generators of certain rational loop groups, and long-time asymptotics of these generators, as well as the main refactorization theorem for the dressing factors that leads to the Yang–Baxter property for the refactorization map and the vector soliton interactions. Among the results obtained in this paper, we derive explicit formulas for the polarization shift of fundamental solitons that are the analog of the well-known formulas for the interaction of vector solitons in the Manakov system. Our study also reveals that upon interacting with a fundamental breather, a fundamental soliton becomes a fundamental breather and, conversely, that the interaction of two fundamental breathers generically yields two fundamental breathers with a polarization shifts, but may also result into a fundamental soliton and a fundamental breather. Explicit formulas for the coefficients that characterize the fundamental breathers, as well as for their polarization vectors are obtained. The interactions of other types of solitons are also derived and discussed in detail and illustrated with plots. New Yang–Baxter maps are obtained in the process.     

Large-Field X-ray Imaging at SPring-8 BL20B2

The medium-length (215 m) bending-magnet beamline 20B2 is allocated to medical applications and various X-ray micro imaging techniques (e.g., angiography, computed tomography, phase contrast imaging and diffraction topography) [1 S. Goto, Nuclear Instruments and Methods in Physics Research A 467–468, 682–685 (2001).[Crossref], [Web of Science ®] , [Google Scholar]]. The unique properties of BL20B2 are high spatial coherence (large coherent length) and its wide beam cross-section, which come from its long beam transport path and bending magnet light source. The horizontal angular aperture of BL20B2 is 1.5 mrad, as in all bending magnet beamlines at SPring-8. The horizontal beam width at the end station is larger than 300 mm for a 215 m beamline length.     

Crystal and Molecular Structure Analysis of 2-Methylimidazole

Abstract  

The crystal structure of the title compound, C₄H₆N₂, has been determined using X-ray diffraction at 100 K. The crystal of 2-methylimidazole is in orthorhombic crystal system with space group P2₁2₁2₁ (Z = 4), lattice parameters: a = 5.9957(12) ?, b = 8.1574(16) ? and c = 9.7010(19) ?, V = 474.47(16) ?. The molecule of 2-methylimidazole is approximately planar. The maximum deviation from the least-squares imidazole plane, calculated for all non-H atoms is 0.006(2) ?. N–H···N hydrogen bonds link the molecules together, forming infinite chains of hydrogen bond pattern C(4) defined by the graph-set analysis. Two chains, which are almost antiparallel to each other, pass through each unit cell. The dihedral angle between the mean planes of molecules forming these intersecting chains is 76.90(4)°. No evidence was found for disorder of the hydrogen-bonding proton between the atoms N1 and N3. The significance of this study lies in the analysis of the interactions occurring via hydrogen bonds in this structure, as well as, in the comparison drawn between the molecular structure of 2-methylimidazole and those of several of other imidazole derivatives possessing a hydrogen atom in the N1 position.     

Delivery and subcellular targeting of dendrimer-based fluorescent pH sensors in living cells

Synthesis and targeted delivery of dendrimer-based fluorescent biosensors in living HeLa cells are reported. Following electroporation dendrimers are shown to display specific subcellular localization depending on their size and surface charge and this property is preserved when they are functionalized with sensing moieties. We analyze the case of double dendrimer conjugation with pH-sensitive and pH-insensitive molecules leading to the realization of ratiometric pH sensors that are calibrated in vitro and in living cells. By tuning the physicochemical properties of the dendrimer scaffold sensors can be targeted to specific cellular compartments allowing selective pH measurements in different organelles in living cells. In order to demonstrate the modularity of this approach we present three different pH sensors with tuned H(+) affinity by appropriately choosing the pH-sensitive dye. We argue that the present methodology represents a general approach toward the realization of targetable ratiometric sensors suitable to monitor biologically relevant ions or molecules in living cells.     

Accessible silanol sites - beneficial for the RP-HPLC separation of constitutional and diastereomeric azaspirovesamicol isomers

Different RP-HPLC columns (phenyl, conventional ODS, cross-linked C(18) and special end-capped C(8) and C(18) phases) were used to investigate the separation of four basic ionizable isomers. Using ACN/20mM NH(4)OAc aq., a separation was observed exclusively on RP columns with higher silanol activity at unusual high ACN concentration, indicating cation-exchange as main retention mechanism. Using MeOH/20mM NH(4)OAc aq., another separation at low MeOH concentrations was observed on both, RP columns with higher as well as RP columns with lower silanol activity, which is mainly based on hydrophobic interactions. The isomers were also separated on a bare silica column at higher MeOH content using NH(4)OAc. Since cation-exchange governs this retention, the elution order was different compared to the RP phases. A strong retention on the silica column was observed in ACN, which could be attributed to partition processes as additional retention mechanism.     

Cobalt(II) Complexes of Nitrile‐Functionalized Ionic Liquids

A series of nitrile‐functionalized ionic liquids were found to exhibit temperature‐dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C₁C_1CNPyr)₂(Tf₂N)₄] and [Co(C₁C_2CNPyr)₆][Tf₂N]₈, which were isolated from ionic‐liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt‐containing ionic liquids.