Zum Mechanismus der thermischen Abspaltung von Chlorwasserstoff aus Polyvinylchlorid. 9. mitt.: Zur struktur der verzweigungen in polyvinylchlorid

The reduction of PVC and of copolymers from vinyl chloride and 2-chloropropene with lithium aluminium hydride occurs in a nearly quantitative manner. A selective reduction of the tertiary chlorine atoms in the copolymers, using lithium deuteride, cannot be observed by means of n.m.r. spectroscopy. The amount of CH₃-groupins the reduced samples was determined by i.r. spectroscopic compensation against polymethylene. The number of methyl groups determined in the copolymers agrees well with the copolymer composition found by n.m.r. spectroscopy. The experimental results of the determination of branches and of the thermal degradation indicate no tertiary chlorine atoms in PVC; therefore, one can assume another structure of branches in PVC.     

Matrix‐assisted laser desorption/ionization mass spectrometry of synthetic polymers. VI. Analysis of phenol–urea–formaldehyde cocondensates

Phenolic resoles can be regarded as copolymers of phenol and formaldehyde that are distributed in the chain length and the number of methylol groups per molecule. While other spectroscopic methods like FTIR and NMR only give average structures, MALDI–TOF mass spectrometry is able to resolve the oligomer distribution of phenolic resoles. Using 2,5‐dihydroxybenzoic acid or 2,4,6‐trihydroxyacetophenone as matrices, MALDI–TOF spectra are obtained where each oligomer peak can be assigned to a particular chemical structure. Thus, the degree of polymerization and the number of reactive methylol groups can be determined. For urea‐modified resoles, in addition to phenol–formaldehyde and urea–formaldehyde structures, for the first time, phenol–urea–formaldehyde cocondensate structures can be identified directly. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2540–2548, 2003     

Towards artificial intelligence at scale in the chemical industry

In the Industry 4.0 era, the chemical industry is embracing broad adoption of artificial intelligence (AI) and machine learning (ML) methods. This article provides a holistic view of how the industry is transforming digitally towards AI at scale. First, a historical perspective on how the industry used AI to aid humans in better decision-making is shown. Then state-of-the-art AI research addressing industrial needs on reliability and safety, process optimization, supply chain, material discovery, and reaction engineering is highlighted. Finally, a vision of the plant of the future is illustrated with critical components of AI-ready culture, model life cycle management, and renewed role of humans in chemical manufacturing.     

Efficient Modular Synthesis of Isomeric Mono‐ and Bispyridyl[2.2]paracyclophanes by Palladium‐Catalyzed Cross‐ Coupling Reactions

Pyridyl‐substituted [2.2]paracyclophanes build a multifunctional structural motif that is useful in material chemistry, catalysis and for luminescent structures. Nonetheless, there is still a lack of general methods for the synthesis of these structures tolerating easily accessible bromides as well as different isomeric pyridyl groups. Hence the coupling of functionalized [2.2]paracyclophanes with various substituted and functionalized pyridyl derivatives was achieved using Stille, Suzuki and Kumada coupling conditions. Hereby the Stille coupling of a [2.2]paracyclophane is presented as a versatile reaction for the formation of heteromeric [2.2]paracyclophane‐containing biaryl structures.

     

Doublecortin May Play a Role in Defining Chondrocyte Phenotype

Embryonic development of articular cartilage has not been well understood and the role of doublecortin (DCX) in determination of chondrocyte phenotype is unknown. Here, we use a DCX promoter-driven eGFP reporter mouse model to study the dynamic gene expression profiles in mouse embryonic handplates at E12.5 to E13.5 when the condensed mesenchymal cells differentiate into either endochondral chondrocytes or joint interzone cells. Illumina microarray analysis identified a variety of genes that were expressed differentially in the different regions of mouse handplate. The unique expression patterns of many genes were revealed. Cytl1 and 3110032G18RIK were highly expressed in the proximal region of E12.5 handplate and the carpal region of E13.5 handplate, whereas Olfr538, Kctd15, and Cited1 were highly expressed in the distal region of E12.5 and the metacarpal region of E13.5 handplates. There was an increasing gradient of Hrc expression in the proximal to distal direction in E13.5 handplate. Furthermore, when human DCX protein was expressed in human adipose stem cells, collagen II was decreased while aggrecan, matrilin 2, and GDF5 were increased during the 14-day pellet culture. These findings suggest that DCX may play a role in defining chondrocyte phenotype.     

Labortest zur Minimierung des Versuchsaufwandes bei Pilotfiltrationen

Investigating beer filtration using cellulose fibers requires appropriate methods. One aspect is the preparation of large scale trials. Starting from the filterability test according to Raible and based on the results of diverse pilot scale trials, a laboratory test was created. Apparatus, procedure and methods of assessing the results are described. The new test is qualified for reducing time and effort in upper scale trials, especially in case of varying filter aids compositions.     

A New Flame Retardant for Wood Materials Tested in Wood‐Plastic Composites

A new flame retardant based on an ammonium phosphonate is studied with respect to its thermal decomposition and its mode of action in wood‐plastic composites (WPCs). The measurements are carried out by means of fire tests (cone calorimeter) and pyrolysis investigations (thermogravimetry, infrared spectroscopy). The flame retardant acts mainly in the condensed phase by increasing the amount of residue formed by the wood part in the WPC. Additional flame dilution is achieved by the release of water, ammonia and carbon dioxide during the decomposition of the flame retardant.

     

Nitrogen budget for fescue pastures fertilized with broiler litter in Major Land Resource Areas of the southeastern US

The southeast US produces a tremendous number of broiler chickens (Gallus gallus), which in turn produce massive quantities of litter (manure and bedding materials). In the Southeast, litter is most often disposed of via land application to pastures, however, the ultimate fate of much of the applied nitrogen (N) is not known. We have constructed N budgets for three sites across the southeastern U.S. in an effort to determine how much of the applied N is useful for plant production and how much is left to be absorbed by the environment. Study sites were located in the Coastal Plain (Alabama), Piedmont (Georgia), and Cumberland Plateau (Tennessee) Major Land Resource Areas (MLRA) of the southeastern US. Litter was applied in the Spring of two consecutive years at a rate to supply 70 kg of available N ha^–1. The total amount of N applied ranged from 103 to 252 kg N ha^–1 depending on site and year. Nitrogen fluxes monitored in this study were broiler litter N, ammonia (NH₃) volatilization, denitrification, plant uptake, and leaching. Plant uptake represented the largest flux of applied N, averaging 43% of applied N. Losses due to NH₃ volatilization and denitrification combined were only 6% of applied N on average. Loss of N due to NO₃-N leaching appeared to be significant only at the Coastal Plain site where NO₃-N concentrations in the groundwater peaked at 38 mg N l^–1. We believe the majority of excess N shown in these budgets is likely accounted for by leaching losses and soil accumulation. Regardless of these assumptions and low gaseous losses, it is apparent that on average, 57% of applied N is destined for a fate other than plant uptake. The results of this study indicate that land-application of broiler litter at currently recommended rates has the potential for negative impacts on the environment of the southeastern U.S. in the long-term.     

Fullerene-based ruthenium catalysts: a novel approach for anchoring metal to carbonaceous supports. I. Structure

The influence of fullerenes and related support materials on the structural and catalytic properties of ruthenium was investigated. Catalysts based on C₆₀, raw fullerene black, extracted fullerene black, cathode deposit and graphite were prepared by an impregnation/activation procedure with Ru₃CO₁₂. The local co-ordination sphere of the resulting highly dispersed X-ray amorphous ruthenium was investigated by means of EXAFS. The dominating role of the presence of non-six-membered carbon rings on the structure and the stability of the Ru particles will be illustrated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polyphenolrückgewinnung aus Olivenölabwasser durch Einsatz von Membrantechnologie

Olive mill wastewater (OMW) is obtained as byproduct of oil production in large quantities after the olive harvest, mainly in the Mediterranean region. One problem is the high load of organic matter, such as phytotoxic polyphenols, which causes significant environmental problems. However, due to their antioxidant properties the use of these polyphenols is also popular in several industry branches, e.g. production of plastics, cosmetics and drugs. A combined wastewater treatment permits besides water purification also recovery of the polyphenolic compounds for industrial use. One possibility is membrane technology. An overview of research studies concerning polyphenol recovery from OMW using membrane technologies is given.