Unusual sensitivity to the concentration of ethanol in the boron trifluoride/ethanol-catalyzed synthesis of 5,10,15,20-tetrakis-(4-cyano-2,6-dimethylphenyl)porphyrin by the lindsey method

The boron trifluoride/ethanol-catalyzed condensation of 4-cyano-2,6-dtmethylbenzaldehyde 1b with pyrrole by the Lindsey method to give the new, ortho-disubstituted 5,10,15,20-tetrakis(4-cyano-2,6-dimethylphenyl)porphyrin 2 was found to be highly sensitive to the concentration of ethanol. In the absence of ethanol the yield of porphyrin is only 1%. Yields can be increased to 20–25% with ethanol concentrations of 0.05–0.1% (v/v) but they decrease rapidly at higher concentrations of ethanol. Optimized procedures for the preparation of both 1b and 2 are described and the newly synthesized molecules are characterized by nmr (¹H and ¹³C), mass spectra and elemental analysis.     

Anwendungsbreite der reduktiven Kupplung aromatischer Aldimin-Derivate mit niedervalenten Titan-Reagenzien zu 1,2-Diarylethylendiaminen

Scope and Limitations of the Reductive Coupling of Aromatic Aldimine Derivatives with Formation of 1,2-Diarylethylenediamine Units, Using Low-Valent Titanium Reagents Besides the adducts from lithium amides to aromatic aldehydes, iminium salts, animals, and N-silylimines of aromatic aldehydes are coupled by the black suspension obtained from TiCL₄ and Mg turnings in tetrahydrofuran (THF). The 1,2-diarylethylenediamines with tertiary and primary amino groups thus obtained are formed with no or only moderate diastereoselectivity (products 4a–d (Scheme 2) and 5–e (Scheme 3), respectively); the amine component may contain a strained ring or additional heteroatoms as in azetidin, bis(2-methoxyethyl)amine, piperazine, morpholine, and thiomorpholine (products 6a–e ; Table 1). By an in-situ procedure, ethylenediamines exclusively trans-diaryl-substituted piperazine and perhydro-1,4-diazepine derivatives (products 7a–f ; Table 2). Enantiomerically pure monocyclic trans,cis-5-alkyl-2,-3-diaryl-piperazines and diazabicyclo[4.3.0]nonanes and -[4.4.0]decanes are obtained by employing suitable diamines prepared from the amino acids (S)-alanine, (S)-phenylalanine, (S)-proline and from (S,S)- or (R,R)-cyclohexane-1,2-diamine, respectively (products 11a–i , 7e ; Table 4). The configuration of all products are derived from the high-field NMR spectra, some of which are discussed in detail (Figs. 1 and 2, Tables 3 and 5); all new compounds are fully characterized by their physical data. Depending upon the structure of the components employed, the yields of purified products range from as low as 7% to essentially quantitative.     

The Quintile Share Ratio in location analysis

The inequality measure “Quintile Share Ratio” (QSR or sometimes S80/S20) is the primary income inequality measure in the European Union’s set of indicators on social cohesion. An important reason for its adoption as a leading indicator is its simplicity. The Quintile Share Ratio is “The ratio of total income received by the 20% of the population with the highest income (top quintile) to that received by the 20% of the population with the lowest income (lowest quintile)”. The QSR concept is used in this paper in the context of obnoxious facility location where the inequality is in distances to the obnoxious facility. The single facility location problem minimizing the QSR is investigated. The problem is investigated for continuous uniform demand in an area such as a disk, a rectangle, and a line; when demand is generated at a finite set of demand points; and when the facility can be located anywhere on a network. Optimal solution algorithms are devised for demand originating at a finite set of demand points and at nodes of the network. Computational experiments demonstrate the effectiveness of the algorithms.     

Effect of crystal orientation on picosecond-laser bulk microstructuring and Raman lasing in diamond

In the paper we report on picosecond-laser bulk microstructuring and stimulated Raman scattering (SRS) in type IIa single-crystal diamond in the course of multipulse irradiation at λ=532 nm wavelength using an advanced ps-laser system equipped with additional setups for on-line video imaging and photoluminescence spectra measurements. The effect of crystal orientation (relative to the incident laser beam) on (i) optical breakdown thresholds, (ii) character of bulk modifications, and (iii) generation of stimulated Raman scattering in diamond during irradiation with picosecond pulses of different durations (τ ₁=10 ps and τ ₂=44 ps) is studied. It is shown that the processes of laser-induced breakdown in the bulk of diamond (at the backside of the crystals) and bulk microstructure growth are governed by the dielectric breakdown mechanism. It is found that generation of high-order stimulated Raman scattering in diamond crystals has a considerable effect on the threshold of laser-induced breakdown and bulk microstructuring. Conditions of the efficient SRS lasing are determined, depending on the pulse duration and the direction ([100] and [110]) of the laser beam incidence. A method of local temperature measurements in the bulk of diamond based on the Stokes-to-anti-Stokes intensity ratio in the recorded SRS spectra is proposed, its applicability to determine a “pre-breakdown” temperature of diamond during multipulse ps-laser irradiation is discussed.     

Picosecond-laser-induced structural modifications in the bulk of single-crystal diamond

Arrays of through laser-graphitized microstructures have been fabricated in type IIa single-crystal 1.2-mm-thick diamond plates by multipulse laser irradiation with 10-ps pulses at λ=532 nm wavelength. Raman and photoluminescence (PL) spectroscopy studies of the bulk microstructures have evidenced the diamond transformation to amorphous carbon and graphitic phases and the formation of radiation defects pronounced in the PL spectra as the self-interstitial related center, the 3H center, at 504 nm. It is found that the ultrafast-laser-induced structural modifications in the bulk of single-crystal diamond plates occur along {111} planes, known as the planes of the lowest cleavage energy and strength in diamond.     

Analytical in vitro approach for studying cyto- and genotoxic effects of particulate airborne material

In the field of inhalation toxicology, progress in the development of in vitro methods and efficient exposure strategies now offers the implementation of cellular-based systems. These can be used to analyze the hazardous potency of airborne substances like gases, particles, and complex mixtures (combustion products). In addition, the regulatory authorities require the integration of such approaches to reduce or replace animal experiments. Although the animal experiment currently still has to provide the last proof of the toxicological potency and classification of a certain compound, in vitro testing is gaining more and more importance in toxicological considerations. This paper gives a brief characterization of the CULTEX® Radial Flow System exposure device, which allows the exposure of cultivated cells as well as bacteria under reproducible and stable conditions for studying cellular and genotoxic effects after the exposure at the air–liquid or air–agar interface, respectively. A commercial bronchial epithelial cell line (16HBE14o-) as well as Salmonella typhimurium tester strains were exposed to smoke of different research and commercial available cigarettes. A dose-dependent reduction of cell viability was found in the case of 16HBE14o- cells; S. typhimurium responded with a dose-dependent induction of revertants. The promising results recommend the integration of cellular studies in the field of inhalation toxicology and their regulatory acceptance by advancing appropriate validation studies.     

Synthetic Potential of Fucosyltransferase III for the Synthesis of Fluorescent‐labeled Milk Oligosaccharides

Various fundamental biologic roles of milk oligosaccharides have been recognized; however, their structure‐affinity relationship is still not fully revealed. Herein, we describe the synthesis of the fluorescent‐labeled milk oligosaccharides 3‐(5‐dimethylaminonaphthalene‐1‐sulfonylamino)propyl β‐D‐galactopyranosyl‐(1→3)‐[α‐L‐fucopyranosyl‐(1→4)]‐2‐acetamido‐2‐deoxy‐β‐D‐glucopyranoside (1) and 3‐(5‐dimethylamino‐naphthalene‐1‐sulfonylamino)propyl β‐D‐galactopyranosyl‐(1→3)‐[α‐L‐fucopyranosyl‐(1→4)]‐β‐D-glucopyranoside (2) as useful tools for synthetic, analytic, and biologic applications. For the fucosylation of lactose and lacto‐N‐biose, the chemical and the enzymatic syntheses using fucosyltransferase III were compared.     

Thrombin contributes to the injury development and neurological deficit after acute subdural hemorrhage in rats only in collaboration with additional blood-derived factors

Background

Acute subdural hemorrhage (ASDH) is a severe consequence of traumatic brain injury. The occurrence of subdural blood increases the lethality of these patients independent of the amount of blood or elevated intracranial pressure. Thrombin is one of the potential harmful blood components. Possible harmful effects of thrombin are mediated via the Protease-activated-receptor-1 (PAR1) and thus, translating the acute Thrombin release after ASDH into cell loss. The objectives of the present study were twofold, namely to examine (1) the impact of direct thrombin inhibition in the acute phase after hemorrhage on the long-term histological and functional deficits and (2) the early inhibition of PAR1 activation by thrombin with the selective antagonist SCH79797 on lesion volume at 14 days after ASDH. The effects of thrombin on the lesion size were investigated in two separate experiments via (1) direct thrombin inhibition in the subdural infused blood (Argatroban 600 µg) as well as by (2) intraventricular injection of the PAR-1 antagonist SCH79797 (1 µg or 5 µg). Lesion volume and behavior deficits using a neurological deficit score and a motor function test (beam balance test) were analyzed as outcome parameters at 14 days after injury.

Results

59 Male Sprague–Dawley rats received a subdural infusion of 300 µl autologous blood or sham operation. Lesion volume at 14 days after ASDH tended to be smaller in the Argatroban-treated group when compared to the vehicle group (8.1?±?1.1 vs. 10.1?±?2.3 mm², n.s.). Motor deficits in the beam balance test were not significantly less severe in the Argatroban-treated group. Animals treated with SCH79797 also showed a trend towards dose-dependent decreased lesion volume in comparison to the vehicle-treated group (1 μg: 4.3?±?0.7 mm³; 5 μg: 3.8?±?1.1 mm³; vehicle: 6.5?±?2.0 mm³, n.s).

Conclusions

Thrombin inhibition in the subdural blood and local cerebral blockade of PAR-1 cause a tendency towards reduced lesion volume or functional recovery. All results show a trend in favor of the acute treatment on the outcome parameters. Our results suggests that thrombin could be an important blood-derived factor during acute subdural hemorrhage that translates its deleterious effects in concert with other blood-induced factors.