Diazoverbindungen. 72. (Diazoalkyl)phosphane – Synthese durch elektrophile Diazoalkansubstitution und oxidative Additionsreaktionen am Phosphor

Diazo Compounds. 72. Diazoalkylphosphanes – Synthesis by Electrophilic Diazoalkane Substitution and Oxidative Addition Reactions at Phosphorus Electrophilic diazoalkane substitution of the diazomethyl compounds 1a,b with the chloro phosphanes 2a-o in the presence of lithium diethylamide yields the diazoalkyl phosphanes 3a-z . Oxidative addition of oxygen, sulfur and selenium at phosphorus leads into the series of oxo, thioxo and selenoxo phosphanes having diazoalkyl substituents ( 4a-d, 5a-m and 7a-d ). The silyl group of 5n,o is cleaved by chromatography on aluminium oxide to yield the (diazomethyl)phosphane sulfides 6a,b .     

Measurements of the Refractive Index Increment on Hydroxyethyl Starch as a Basis for Absolute Molecular Weight Determinations

Solutions of hydroxyethyl starch are used as a blood plasma substitute. If their physiological efficiency is to be optimized, they need to be accurately characterized in terms of their molecular weight and its distribution. The absolute determination of molecular weight and molecular weight distribution by means of light scattering require a knowledge of the refractive index increment. Although numerous investigations of the refractive index increment of hydroxyethyl starch have already been published, the results vary significantly due to the use of different samples and the choice of different measuring parameters. There was therefore an urgent need to examine the extent to which the refractive index increment depends on molecular parameters, the experimental method used and the type of processing. Here it was found that different sample preparations result in different contents of solid matter, so that an exact determination of the quantity is required. Hydroxyethyl starches in the molecular weight range of about Mw = 200.000 g/mol and varying degrees of substitution between DS 0.38 and 0.50 which are regarded as optimal for clinical use give a refractive index increment of dn/dc^633nm = 0.146 = 0.005 cm³/g (solvent: H₂O/0.02% NaN₃; T = 25°C).     

Untersuchungen zu Mesityldimethylhalogensilanen als Schutzgruppenreagenzien für Alkohole

Investigation on Mesityldimethylhalosilanes as Protectiv Reagents for Alcohols The use of mesityldimethylhalosilanes as protecting reagents for steroid alcohols was investigated. The resistance of the obtained silyl ethers was tested in various media. The reaction pathway of the acidic hydrolyses of the silyl ethers is explained.     

Pre-adolescent children exhibit lower aerosol particle volume emissions than adults for breathing,speaking, singing and shouting

Speaking and singing are activities linked to increased aerosol particle emissions from the respiratory system, dependent on the utilized vocal intensity. As a result, these activities have experienced considerable restrictions in enclosed spaces since the onset of the COVID-19 pandemic due to the risk of infection from the SARS-CoV-2 virus, transmitted by virus-carrying aerosols. These constraints have affected public education and extracurricular activities for children as well, from in-person music instruction to children’s choirs. However, existing risk assessments for children have been based on emission measurements of adults. To address this, we measured the particle emission rates of 15 pre-adolescent children, all eight to ten years old, with a laser particle counter for the test conditions: breathing at rest, speaking, singing and shouting. Compared with values taken from 15 adults, emission rates for breathing, speaking and singing were significantly lower for children. Particle emission rates were reduced by a factor of 4.3 across all conditions, whereas emitted particle volume rates were reduced by a factor of 4.8. These data can supplement SARS-CoV-2 risk management scenarios for various school and extracurricular settings.     

Redox processes in pressurised smoked salmon studied by resonance Raman spectroscopy

Non-thermal food preservation technology is based on the application of high pressures up to 600 MPa. Here we report a resonance Raman (RR) spectroscopic analysis of smoked salmon meat after high pressure processing. High quality spectra, which can be obtained even from packed salmon without spectral interference of the packing foil, allow determining pressure-dependent irreversible changes of the main RR-active components of salmon meat, astaxanthin and myoglobin/haemoglobin. High pressure-treatment causes a decrease of the relative RR intensities of astaxanthin as probed with 514 nm excitation which is in line with a slight attenuation of the originally intense red colour of the salmon meat. 413-nm excited RR spectra indicate a heterogeneous broadening of astaxanthin bands accompanied by the formation of deoxy-myoglobin or deoxy-haemoglobin. The results suggest that pressure-treatment facilitates the oxidative degradation of astaxanthin coupled to the reduction of metmyoglobin (methaemoglobin).     

靴套的创新开发--QualiFlex靴套

对比了QualiFlex Q型,QualiFlex QX型、QualiFlex QV型三种聚胺酯材料靴套的性能,从而说明独特的QualiFlex靴套性能,使纸幅横幅水分的均匀性得到改善,纸幅出压榨干度得以维持恒定.     

Two-step enzymatic reaction for the synthesis of pure structured triacylglycerides

Structured triacylglycerides with medium-chain fatty acids (caprylic acid) in sn1- and sn3-positions and a long-chain unsaturated fatty acid (oleic or linoleic acid) in the sn2-position of glycerol (MLM) were synthesized by lipase catalysis in a two-step process. First, pure 2-monoacylglycerides (2-MG) were synthesized by alcoholysis of triacylglycerides (triolein, trilinolein, or peanut oil) in organic solvents with 1,3-regiospecific lipases (from Rhizomucor miehei, Rhizopus delemar, and Rhizopus javanicus). The 2-MG were purified by crystallization and obtained in up to 71.8% yield. These 2-MG were esterified in a second reaction with caprylic acid in n-hexane to form almost pure MLM. For 2-MG obtained from peanut oil, the final product contained more than 90% caprylic acid in the sn1- and sn3-positions, whereas the sn2-position was composed of 98.5% unsaturated long-chain fatty acids. Reaction conditions for both steps were optimized with respect to source and immobilization of lipase, water activity, and solvent.     

Structure–Activity Relationships of 2‐Sufonylpyrimidines as Quorum‐Sensing Inhibitors to Tackle Biofilm Formation and eDNA Release of Pseudomonas aeruginosa

Drug‐resistant Pseudomonas aeruginosa (PA) strains are on the rise, making treatment with current antibiotics ineffective. Hence, circumventing resistance or restoring the activity of antibiotics by novel approaches is of high demand. Targeting the Pseudomonas quinolone signal quorum sensing (PQS‐QS) system is an intriguing strategy to abolish PA pathogenicity without affecting the viability of the pathogen. Herein we report the structure–activity relationships of 2‐sulfonylpyrimidines, which were previously identified as dual‐target inhibitors of the PQS receptor PqsR and the PQS synthase PqsD. The SAR elucidation was guided by a combined approach using ligand efficiency and ligand lipophilicity efficiency to select the most promising compounds. In addition, the most effective inhibitors were rationally modified by the guidance of QSAR using Hansch analyses. Finally, these inhibitors showed the capacity to decrease biofilm mass and extracellular DNA, which are important determinants for antibiotic resistance.     

Sequestration and metabolism of protoxic pyrrolizidine alkaloids by larvae of the leaf beetle Platyphora boucardi and their transfer via pupae into defensive secretions of adults

Several neotropical leaf-beetles of the genus Platyphora ingest and specifically metabolize plant acquired pyrrolizidine alkaloids (PAs) of the lycopsamine type (e.g., rinderine or intermedine) and enrich the processed alkaloids in their exocrine defensive secretions. In contrast to the related palaearctic leaf beetles of the genus Oreina, which absorb and store only the non-toxic alkaloid N-oxides, Platyphora sequesters PAs exclusively as protoxic tertiary amines. In this study, the ability of P. boucardi larvae to accumulate PAs was investigated. Tracer studies with [¹⁴C]rinderine and its N-oxide revealed that P. boucardi larvae, like adult beetles, utilize the two alkaloidal forms with the same efficiency, but accumulate the alkaloid as a tertiary amine exclusively. Ingested rinderine is rapidly epimerized to intermedine, which is localized in the hemolymph and all other tissues; it is also detected on the larval surface. Like adults, larvae are able to synthesize their own alkaloid esters (beetle PAs) from orally administered [¹⁴C]retronecine and endogenous aliphatic 2-hydroxy acids. These retronecine esters show the same tissue distribution as intermedine. A long-term feeding experiment lasting for almost four months revealed that retronecine esters synthesized from [¹⁴C]retronecine in the larvae are transferred from larvae via pupae into the exocrine glands of adult beetles. Pupae contain ca. 45% of the labeled retronecine originally ingested, metabolized, and stored by larvae; ca. 12% of larval radioactivity could be recovered from the defensive secretions of adults sampled successively over two and a half months. Almost all of this radioactivity is found in the insect-made retronecine esters that are highly enriched in the defensive secretions, i.e., more than 200-fold higher concentration compared to pupae.