Influence of increasing zinc contents in brass in the early stages of corrosion investigated by in-situ TM-AFM and SIMS

In-situ tapping mode atomic force microscopy (TM-AFM), a powerful, high-resolution imaging technique for determining the structure of surfaces and ex-situ secondary ion mass spectroscopy (SIMS), a multielement, high-depth-resolution method, were used to examine the influence of increasing zinc contents in brass in the early stages of corrosion. Four different samples (pure Cu, pure Zn, Cu/Zn=90/10 wt% and Cu/Zn=70/30 wt%) were studied in order to determine their chemical behaviour under various atmospheric conditions. The in-situ TM-AFM investigations were carried out in synthetic air with 60% relative humidity (RH) and 80% RH with 250 ppb SO(2). The samples for the ex-situ SIMS experiments were weathered over a period of 60 h in 80% RH and 250 ppb SO(2). The in-situ TM-AFM investigations have shown that an increasing Zn content in brass increases the corrosion rate.     

Tumorhemmende wirkstoffe, XIII [1] aromatisch carbocyclisch und heterocyclisch substituierte 2-perfluoralkylpyrimido[1,2-a]benzimidazole

The interaction of 2-aminobenzimidazole with the appropriate β-diketones carrying fluoroalkyl groupings has led to the 2-perfluoroalkylpyrimido[1,2-a]benzimidazoles as follows: 4-phenyl-, 4-(2'-naphthyl)-, 4-(3'-pyridyl)-, 4-(2'-furyl)-, and 4-(2,-thienyl)-2-trifluoromethylpyrimido[1,2-a]benzimidazole, and 4-(2'-thienyl)-2-(heptafluoropropylpyrimido [1,2-a]benzimidazole.     

PHOTOMOVEMENT RESPONSES OF THE HETEROTRICHOUS CILIATE Blepharisma Japonicum

Light-induced movement responses of the heterotrichous ciliate Blepharisma japonicum were studied by physiological experiments. Two photosensory responses could be identified. A step-up photophobic response is observed as a very rapid backward movement. Microbeam irradiations of individual cells showed that only the anterior part of the ciliate is able to perceive the light stimulus that mediates the phobic reaction. The action spectrum peaks at approximately 400 nm, which indicates that a blue light receptor is involved.
Positive photokinesis of Blepharisma could be shown as a forward movement that is accelerated by increasing the applied photon fluence rate. The steady state level of the velocity depends highly on wavelength and photon fluence rate of the actinic light. After specific inhibition of the phobic reaction bv 1 m/W NH₄⁺, photokinesis can be induced by microbeam irradiation at any part of the cell.
We isolated two main pigments by thin layer chromatography and characterized them as hypericin-like compounds: a red pigment that is obviously responsible for the red color of the ciliates (= blepharismin). and a yellow one with maximal absorption near 420 nm. The possible photoreceptor functions of these pigments are discussed.
We could not find in Blepharisma a distinct phototactic behavior which is so typical for the related ciliate Stentor.     

Synthese des Pyrrolizidin-Alkaloides (±)-Trachelanthamidin

Synthesis of the Pyrrolizidine Alkaloid (±)-Trachelanthamidine The important intermediate in the synthesis of the title compound 8 is the diastereoisomer mixture of ethyl 2-[2-(1,3 dioxolan-2-yl)ethyl]-5-oxopyrrolidine-3-carboxylate ( 3a/3b ) which was prepared from nitromethane, acrylaldehyde, and diethyl fumarate (Scheme). Its reduction (NaBH₄, t-BuOH, MeOH) gave exclusively the trans-alcohol 4a , which was converted to the protected pyrrolidine derivative 6 . The deprotection and reduction of 6 gave the pyrrolizidine alkaloid 8 , characterized as its hydrochloride.     

The Macrocyclic Spermidine Alkaloid (−)‐(S)‐Neoperiphylline: Revision of the Structure Based on the Total Synthesis

The total synthesis of the two isomeric macrocyclic enamides 2 and 17 is described. The precursor 14 was synthesized by means of template‐assisted macrocyclization (Scheme 2). Isomerization of 14 in the presence of [Fe(CO)₅] gave 2 and 17 (Scheme 4). Structure 2 was previously assigned to the alkaloid neoperiphylline. However, the synthetic 2 showed completely different properties compared to the earlier described data of the natural compound. Surprisingly, analytical data of the second synthetic product 17 were very close to those of the natural neoperiphylline. We conclude that the previously assigned structure of neoperiphylline is erroneous and should be corrected to that of (?)‐(4S,12Z)‐4‐phenyl‐9‐[(2E)‐3‐phenylprop‐2‐enoyl]‐1,5,9‐triazacyclotridec‐12‐en‐2‐one ( 17 ).     

EFFECTS OF EXCITED-STATE PROTON TRANSFER ON THE PHOSPHORESCENCE OF TYROSINE-PHOSPHATE COMPLEXES

Abstract Phosphate anions quench the fluorescence of tyrosine at room temperature as a result of an excited-state proton transfer. At 77 K in frozen solutions the fluorescence of tyrosine is still quenched by phosphate anions but the phosphorescence emission is enhanced. No tyrosinate phosphorescence is detected. A mechanism is proposed to explain these results: excited-state proton transfer from tyrosine to phosphates is followed by intersystem crossing in tyrosinate anions with subsequent back-transfer of the proton in the triplet state.     

Orientation and order in thin films of a combined liquid crystalline polymer

The order in thin films of a combined liquid crystalline polymer is studied by X-ray reflection. Films of thicknesses of less than 200 nm on float glass are investigated as a function of temperature. The polymer with mesogenic groups in the main and side-chains exhibits smectic and cholesteric mesophases. Measurements in the smectic phases show a Bragg peak and smectic layers are oriented parallel to the substrate. The sample is thus macroscopically ordered by the influence of substrate and free surface. The film surface is very smooth after spincoating; surface roughness is typically 0.8 nm. First annealing of samples leads to a significant roughening of the free surface; roughness increases to 2.1 nm. Order as a function of film thickness depends on the interaction of the polymer with the substrate and free surface. These interactions give rise to a typical correlation length of perturbations in smectic ordering.     

Optimizing control of simulated moving beds--linear isotherm

A new optimization based adaptive control strategy for simulated moving beds (SMBs) is proposed. A linearized reduced order model, which accounts for the periodic nature of the SMB process, is used for online optimization and control. The manipulated variables are the four inlet flow rates, the outputs are the raffinate and extract concentrations. Concentration measurements at the raffinate and extract outlets are used as the feedback information. The state estimate from the periodic Kalman filter is used for the prediction of the outlet concentrations over a chosen horizon. Predicted outlet concentrations are the basis for the calculation of the optimal input adjustments, which maximize the productivity and minimize the desorbent consumption subject to constraints on product purities. The realization of this concept is discussed and the implementation on a virtual eight column SMB platform is assessed, in the case of binary linear systems. For a whole series of typical plant disturbances it is shown that the proposed approach is effective in minimizing off-spec products and in achieving optimal SMB operation, also in the case where there are significant model uncertainties.     

Organic/inorganic hybrid vesicles based on a reactive block copolymer

Presented in this communication is a novel hybrid vesicle with a cross-linked polyorganosiloxane wall based on a new reactive block copolymer, poly(ethylene oxide)-block-poly(3-(trimethoxysilyl)propyl methacrylate) (PEO-b-PTMSPMA), which was synthesized by atom transfer radical polymerization. The vesicles were prepared first by self-assembly of the block copolymer in a selective solvent, and then the PTMSPMA block was subjected to hydrolysis and polycondensation reaction to fix vesicle wall in the presence of triethylamine as a catalyst. Transmission electron microscopy, scanning electron microscopy, NMR, and light scattering have been used to characterize the vesicles.     

Amidine als Zwischenprodukte bei Umamidierungsreaktionen. 9. Mitteilung über Umamidierungsreaktionen

Amidines as Intermediates in Transamidation Reactions By loss of water in the presence of p-toluenesulfonic acid/xylole N-aminoalkyllactames form bicyclic amidines. The corresponding N-alkylaminoalkyl-lactames' react to bicyclic amidinium salts or to transamidated products, ring-enlarged by the N-alkylamino residue, respectively (s. Scheme 1). The bicyclic amidines and amidinium salts are partially hydrolyzed by KOH/H₂O to lactames (s. Scheme 2). Which of the two possible isomeric lactames are formed is discussed.