Modification of Polylactide Nonwovens with Carbon Nanotubes and Ladder Poly(silsesquioxane)

Electrospun nonwovens of poly(L-lactide) (PLLA) modified with multiwall carbon nanotubes (MWCNT) and linear ladder-like poly(silsesquioxane) with methoxycarbonyl side groups (LPSQ-COOMe) were obtained. MWCNT and LPSQ-COOMe were added to the polymer solution before the electrospinning. In addition, nonwovens of PLLA grafted to modified MWCNT were electrospun. All modified nonwovens exhibited higher tensile strength than the neat PLA nonwoven. The addition of 10 wt.% of LPSQ-COOMe and 0.1 wt.% of MWCNT to PLLA increased the tensile strength of the nonwovens 2.4 times, improving also the elongation at the maximum stress.     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Efficient Collocation Schemes for Singular Boundary Value Problems

We discuss an error estimation procedure for the global error of collocation schemes applied to solve singular boundary value problems with a singularity of the first kind. This a posteriori estimate of the global error was proposed by Stetter in 1978 and is based on the idea of Defect Correction, originally due to Zadunaisky. Here, we present a new, carefully designed modification of this error estimate which not only results in less computational work but also appears to perform satisfactorily for singular problems. We give a full analytical justification for the asymptotical correctness of the error estimate when it is applied to a general nonlinear regular problem. For the singular case, we are presently only able to provide computational evidence for the full convergence order, the related analysis is still work in progress. This global estimate is the basis for a grid selection routine in which the grid is modified with the aim to equidistribute the global error. This procedure yields meshes suitable for an efficient numerical solution. Most importantly, we observe that the grid is refined in a way reflecting only the behavior of the solution and remains unaffected by the unsmooth direction field close to the singular point.     

The plasticity of the Cu(H2O) 6 2+ Jahn-Teller complex affected by lattice strains and cooperative interactions

The EPR spectra evolution of Cs₂Zn_1?x Cu_x(ZrF₆)₂ · 6H₂O (x=0.01, 0.6, 0.8, and 1.0) in the temperature range 4.2–330 K and the x-ray structure analysis of the compound with x=1.0 in the range 150–327 K show that the Jahn-Teller (JT) complex Cu(H₂O)₆ coordination sphere undergoes a plastic deformation. The observed effect is due to the combined influence of small lattice strains existing in the paraphase and a new one appearing as a result of a ferroelastic phase transition and increasing with decreasing temperature below T _c . It is proved that both cooperative interactions between JT complexes and ferroelastic strain stabilize a certain JT configuration. The problem of instability of a JT configuration compressed at T ～ 265 K is discussed.     

Development in Synthesis,Electrochemistry, LB Moieties of Phenothiazine Based Units

A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique.     

Tracing Possible Structural Asymmetry of Silica Gel Used for Precoating Thin-Layer Chromatography Plates

JPC – Journal of Planar Chromatography – Modern TLC - We have previously described unexpected two-dimensionality in the thin-layer chromatographic separation of pairs of enantiomers of...     

Directed and elliptic flow in 197Au+197Au at intermediate energies

Directed and elliptic flow for the ¹⁹⁷Au+¹⁹⁷Au system at incident energies between 40 and 150 MeV per nucleon has been measured using the INDRA 4π multi-detector. For semi-central collisions, the excitation function of elliptic flow shows a transition from in-plane to out-of-plane emission at around 100 MeV per nucleon. The directed flow changes sign at a bombarding energy between 50 and 60 MeV per nucleon and remains negative at lower energies. Molecular dynamics calculations (CHIMERA) indicate sensitivity of the global squeeze-out transition on the σ _NN and demonstrate the importance of angular momentum conservation in transport codes at low energies.     

Orbital formal normal forms for general Bogdanov-Takens singularity

We solve completely the problem of classification of germs of complex planar vector fields with nilpotent singularity with respect to formal orbital equivalence.     

Deposition of boron nitride on graphite at 1300 K

A method for the deposition of BN onto graphite and other substrates is described. Boron trichloride (BCl₃) and ammonia (NH₃) diluted with Ar were used as reacting gases. The deposition process was carried out at 1300 K as well as lower temperatures in an open system at pressures of 1 atm. The consequences of the introduction of hydrogen to the system were considered. It was demonstrated that the replacement of argon with hydrogen increases the efficiency of the process as well as the theoretical rate of BN deposition. However, the acceleration of the deposition seems to be unprofitable, because the resulting supersaturation leads to the formation of an amorphous phase. The modification of the experimental conditions were proposed.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday