One- electron transfer properties and herbicidal activity of diquaternary salts of 2,4-di-(4-pyridyl)-1,3,5-triazines

Diquaternary salts of 2,4-di-(4-pyridyl)-1,3,5-triazines have been prepared. The salts can be regarded as reversible one electron transfer systems with redox potentials (E₀) of about ?0·44 V in the pH range 7·0–8·5. 2,4-Bis-(4-methyl-4-pyridinio)-1,3,5-triazinediium dihalides are effective post-emergent herbicides at application rates of 4–6 kg/hectare.     

Carotinoid-Glycosylester 4. Mitteilung. Synthese von 8′-Apo-β-carotin-8′-säure-(β-D-glucosyl)ester und Vitamin-A-säure-(β-D-glucosyl)ester

Carotenoid Glycosyl Esters Synthesis of β-D -Glucosyl 8′-Apo-β-carotene-8′-oate and β-D -Glucosyl Vitamin-A-oate (β-D -Glucosyl Retionate) β-D -glucosyl 8′-apo-β-carotene-8′-oate (III) and β-D -glucosyl vitamin-A-oate (VI) were regio- and stereoselectively synthesized in high yields from the N-acylimidazoles I and IV, respectively, or from the N-acyltriazoles II and V, respectively, and unprotected β-D -glucose, according to the method described for the synthesis of di(β-D -glucosyl) 8,8′-diapo-carotene-8,8′-dioate [1]. It seems that this method can generally be applied for the synthesis of β-D -glucosyl esters of polyene carboxylic acids.     

Säurekatalysierte Umsetzungen von 2- Vinylanilin-Derivaten mit 1-Benzyl- und 1-Methylpiperidin-4-on: Eine Elegante Synthese Neuer Polycyclischer Indol-Derivate

Acid-Catalyzed Reactions of 2-Vinylaniline Derivatives with 1-Benzyl- and 1-Methylpiperidin-4-one: An Elegant Synthesis of New Polycyclic Indole Derivatives The reaction of 2-vinylaniline derivatives with 1-benzylpiperidin-4-one or 1-methylpiperidin-4-one in toluene at temperatures between 115 and 120° with toluene-4-sulfonic acid as catalyst leads in good yields to a new class of polycyclic indole derivatives (Scheme 1, Table 1). The structure of the new diastereoisomerically pure racemic compounds 1–5 is determined by NMR-spectroscopic methods. A reaction mechanism proceeding via cyclization of enamine 9 , leading to a racemic, tricyclic reactive intermediate 10 , and subsequent intramolecular 1,5-dipolar cyclization as key steps in proposed for the formation of octahydropyrido[4′,3′:4]cyclobut[1,2-b]indoles 1–5 . The scope and limitations of the new method are discussed (see Table 2).     

Optimal control of capital injections by reinsurance in a diffusion approximation

In this paper we consider a diffusion approximation to a classical risk process, where the claims are reinsured by some reinsurance with deductible b ∈ [0,b?], where b = b? means “no reinsurance” and b = 0 means “full reinsurance”. The cedent can choose an adapted reinsurance strategy (b _t ) _{t ≥0}, i.?e. the deductible can be changed continuously. In addition, the cedent has to inject fresh capital in order to keep the surplus positive. The problem is to minimise the expected discounted cost over all admissible reinsurance strategies. We find an explicit expression for the value function and the optimal strategy using the Hamilton–Jacobi–Bellman approach. Some examples illustrate the method.     

Geometry optimization in ab initio SCF calculations. VII. Proton affinities and ion structures calculated with floating orbital geometry optimization (FOGO)

The FOGO method is used to calculate absolute proton affinities of the molecules H₂, HF, NH₃, H₂O, CH₃OH, C₂H₅OH, H₂O₂, CH₂O, CO, and CH₂CO. Comparison with experimental values demonstrates that the geometrical and energetical data resulting from this type of ab initio calculation are of chemical accuracy. Predictive data for higher energy isomers, such as hydroxymethylene and ethynol are given as possible aid for the identification of these species.     

Carotinoid-Glycosylester. 3. Mitteilung. Die synthese von crocetin-di-(β-D-glucosyl)-ester. Eine neue methode zur selektiven veresterung von ungeschützter β-D-glucose

Carotenoid Glycosyl Esters. The Synthesis of Crocetin-di-(β-D -glucosyl) Ester. A New Method for the Selective Esterification of Unprotected β-D -Glucose The naturally occurring crocetin-di-(β-D -glucosyl) ester is easily synthesized by the reaction of crocetin-di-imidazolide or crocetin-di-(1,2,4-triazolide) and unprotected β-D -glucose in pyridine in presence of a base (Scheme 4). Under the described experimental conditions the esterification takes place exclusively at the anomeric C-atom and furthermore produces only the β-anomer. It is the first time that an unprotected carbohydrate has been used for the selective synthesis of glucosyl esters at the anomeric C-atom. This represents the major advantage of this new method.     

Determination of cluster composition in heteroaggregation of binary particle systems by flow cytometry

Cluster composition in aggregation processes of multiple particle species can be dynamically determined by flow cytometry if particle populations are fluorescently labeled. By flow cytometric single particle analysis, aggregates can be characterized according to the exact amount of constituent particles, allowing the detailed and separate quantification of homo- and heteroaggregation. This contribution demonstrates the application of flow cytometry for the experimental detection of heteroaggregation in a binary particle mixture of oppositely charged polystyrene (PS) particles and Rhodamine-B labeled melamine-formaldehyde (MF-RhB) particles. Experiments with different particle concentration, temperature, mixing mode, ionic strength and particle mixing ratio are presented. Aggregation kinetics are enhanced with increasing particle concentration and temperature as well as by increased shear of mixing. These results represent well-known behavior published in previous investigations and validate the performance of flow cytometry for probing heteroaggregation processes. Physical insight with a novel level of detail is gained by the quantification of de- and restabilization phenomena. At low ionic strength, "raspberry"-type aggregates with PS cores are formed by primary heteroaggregation. At moderate particle number ratios, these aggregates are electrostatically destabilized and form more complex aggregates in a secondary heteroaggregation process. At high particle number ratios (> or =50:1), the raspberry-type aggregates are electrostatically restabilized and secondary heteroaggregation is prevented. The dynamic change of aggregate charge was verified by zeta-potential measurements. The elevation of salt concentration over several orders of magnitude retards aggregation dynamics, since attractive interparticle forces are diminished by an electrostatic double layer. This indicates that heteroaggregation induced by attractive interparticle forces is faster than aggregation due to random Brownian motion. Destabilization at high ionic strength is facilitated by charged ions and no longer by MF-RhB coverage. This results in a species independent one step aggregation process.     

On semilocally simply connected spaces

The purpose of this paper is: (i) to construct a space which is semilocally simply connected in the sense of Spanier even though its Spanier group is non-trivial; (ii) to propose a modification of the notion of a Spanier group so that via the modified Spanier group semilocal simple connectivity can be characterized; and (iii) to point out that with just a slightly modified definition of semilocal simple connectivity which is sometimes also used in literature, the classical Spanier group gives the correct characterization within the general class of path-connected topological spaces.While the condition “semilocally simply connected” plays a crucial role in classical covering theory, in generalized covering theory one needs to consider the condition “homotopically Hausdorff” instead. The paper also discusses which implications hold between all of the abovementioned conditions and, via the modified Spanier groups, it also unveils the weakest so far known algebraic characterization for the existence of generalized covering spaces as introduced by Fischer and Zastrow. For most of the implications, the paper also proves the non-reversibility by providing the corresponding examples. Some of them rely on spaces that are newly constructed in this paper.