Solvent Vapor Annealing: An Efficient Approach for Inscribing Secondary Nanostructures onto Electrospun Fibers

Solvent vapor annealing (SVA) is originally developed to attain equilibrium nanostructures from microphase‐separated block polymer thin films. Interestingly, by carefully choosing a solvent vapor that can selectively mobilize the amorphous chains of a semicrystalline polymer while preserving the integrity of its crystalline structure, this study demonstrates that the SVA method can also be utilized to introduce hierarchical structures onto semicrystalline polymer‐based materials. This study on electrospun poly(ε‐caprolactone) (PCL) fibers clearly shows that acetone, a poor solvent for PCL, can effectively delocalize the amorphous chains and redeposit them onto the pre‐existing crystal edges, giving rise to secondary nanostructures inscribed onto the PCL fibers. In the past decade, various fiber fabrication methods and numerous fiber products are reported. The easy one‐step approach reported here provides new insight into the design and fabrication of structurally hierarchical polymeric materials.

     

New Poincaré-type inequalities

We present some Poincaré-type inequalities for quadratic matrix fields with applications e.g. in gradient plasticity or fluid dynamics. In particular, applications to the pseudostress–velocity formulation of the stationary Stokes problem and to infinitesimal gradient plasticity are discussed.     

Eigenvalue Characterization of Radial Operators on Weighted Bergman Spaces Over the Unit Ball

We study the so-called radial operators, and in particular radial Toeplitz operators, acting on the standard weighted Bergman space on the unit ball in ${\mathbb{C}^n}$ . They turn out to be diagonal with respect to the standard monomial basis, and the elements of their eigenvalue sequences depend only on the length of multi-indexes enumerating basis elements. We explicitly characterize the eigenvalue sequences of radial Toeplitz operators by giving a solution for the weighted extension of the classical Hausdorff moment problem, and show that the norm closure of the set of all radial Toeplitz operators with bounded measurable radial symbols coincides with the C*-algebra generated by these Toeplitz operators and is isomorphic and isometric to the C*-algebra of sequences that slowly oscillate in the sense of Schmidt.     

INTERVAL CARRIER FREE ELECTROPHORESIS FOR HIGH RESOLUTION PROTEIN PURIFICATION

Interval free flow zone electrophoresis is a new mode of free flow zone electrophoresis (FFZE), which facilitates purification of proteins and other molecular substances at very high resolution. It can be performed in the commercially available free flow electrophoresis (FFE) apparatus Octopus. The specimens are loaded and unloaded as usual with the help of a thin buffer film flowing between the two glass plates of the FFE. However, as long as electrical current is applied to a specimen, the medium flow is turned off and conditions of static column electrophoresis are simulated within the FFE device. Thereby electrohydrodynamic flow effects, which widen the sample bands migrating within the electric field, are eliminated while optimal heat removal from the thin buffer film is still possible and a sophisticated technique of harvesting of fractions remains available. Thus interval FFZE offers a gentle preparative method for purification of many kinds of charged molecular species such as proteins or dyes at very high resolution.     

A New Iron(II) Complex with Strongly Saddle Shaped Schiff Base like Ligand

The synthesis of two new Schiff base like ligands containing a 1, 8‐diaminonaphthalene unit in order to improve π–π interactions between the molecules is described. The corresponding iron(II), copper(II), and nickel(II) complexes were synthesized and characterized using NMR spectroscopy, magnetic measurements, and for the iron(II) complex X‐ray structure analysis. The crystal structure shows a strongly saddle shaped ligand. In contrast to related complexes with a phenylene unit that prefer an octahedral coordination sphere, this complex crystallizes pentacoordinate. The keto‐group of a neighboring complex serves as axial ligand resulting in the formation of infinite chains. Magnetic susceptibility measurements reveal nearly ideal curie behavior for the copper(II) and the iron(II) complex.     

High-Pressure Approach to the Synthesis of Optically Pure Methyl 4-Deoxyheptosides

Recently we have described¹ high pressure (4+2) cycloaddition of l-methoxybuta-1,3-diene (1)to 2,3-0-isopropylidene-D-glyceraldehyde (z), which gives rise to chiral cycloadducts 3 (Scheme). action was carried out under high-pressure conditions (22 kbar, 50°C. diethyl ether as solvent, 20 h, 80% yield)2 four diastereoisomeric adducts were formed in a ratio of 3a:3b:3c:3d=66:16:13:5. The reaction mixture was separated by column chromatography yielding two fractions which contained diastereoisomeric mixtures (3a+3b) and (3c+3d), respectively. Absolute configuration at the C-5 carbon atom in both mixtures was established by chemical correlation.' These results prompted us to use a mixture (3a+3b), being stereochemically pure at C-5 chiral center, in the synthesis of optically active methyl 4-deoxyheptosides (Scheme).     

Reactivity of Lewis Basic Platinum Complexes Towards Fluoroboranes

We herein report detailed investigations into the interaction of Lewis acidic fluoroboranes, for example BF₂Pf (Pf=perfluorophenyl) and BF₂Ar^F (Ar^F=3,5‐bis(trifluoromethyl)phenyl), with Lewis basic platinum complexes such as [Pt(PEt₃)₃] and [Pt(PCy₃)₂] (Cy=cyclohexyl). Two presumed Lewis adducts could be identified in solution and corresponding secondary products of these Lewis adducts were characterized in the solid state. Furthermore, the concept of frustrated Lewis pairs (FLP) was applied to the activation of ethene in the system [Pt(BPf₃)(CH₂CH₂)(dcpp)] (dcpp=1,3‐bis(dicyclohexylphosphino)propane; Pf=perfluorophenyl). Finally, DFT calculations were performed to determine the interaction between the platinum‐centered Lewis bases and the boron‐centered Lewis acids. Additionally, several possible mechanisms for the oxidative addition of the boranes BF₃, BCl_3, and BF₂Ar^F to the model complex [Pt(PMe₃)₂] are presented.     

Synthesis of Zwitterionic Cobaltocenium Borate and Borata‐alkene Derivatives from a Borole‐Radical Anion

Chemical single‐electron reduction of 1‐mesityl‐2,3,4,5‐tetraphenylborole ( 3 ) gave a stable radical anion [CoCp*₂][ 3 ] as shown in earlier investigations. Herein, we present the reaction of [CoCp*₂][ 3 ] with the 2,2,6,6‐tetramethylpiperidine‐N‐oxyl radical (TEMPO), a common radical trap. Instead of radical recombination, the reaction proceeds through a redox pathway involving oxidation of the borole radical anion combined with reduction of TEMPO. This electron‐transfer process is accompanied by a deprotonation reaction of the cobaltocenium counterion by the base TEMPO^? to give TEMPO‐H and a neutral cobalt(I) fulvene complex ( 7 ). The latter was not observed directly during the reaction, because it instantaneously reacts as a nucleophile attacking at the boron center of the in situ generated borole 3 to give the borate 6 . However, 7 was synthesized independently by deprotonation of [CoCp*₂][PF₆]. In addition, the obtained zwitterionic cobaltocenium borate 6 undergoes a photolytic rearrangement to form the borata‐alkene derivative 9 that thermally transforms to the chiral cobaltocenium borate 12 . Our investigations are based on spectroscopic evidence, X‐ray crystallography, elemental analysis, as well as DFT calculations.     

Reduction with Sulfur Dioxide

Abstract

A general method to reduce arene sulfonylchlorides to diarene disulfanes has been developped using sulfur dioxide and hydroiodic acid/quarternary ammonium salts as catalysts in a two - phase system.