Tetraacylgermanes as highly efficient photoinitiators for visible light cured dimethacrylate resins and dental composites

Tetrabenzoylgermane 1 and various substituted tetrabenzoylgermanes 2 – 7 were investigated as visible light (VL) photoinitiators (PIs) for dental dimethacrylate resins and dimethacrylate‐based composites. The tetrabenzoylgermanes 1 – 7 show a very strong VL absorption between 400 and 450 nm. Substituents on the benzoyl chromophore strongly influence their properties such as melting point, solubility, absorption behavior, or PI reactivity. A good photobleaching behavior and a very high reactivity as VL PI was found in photo‐differential scanning calorimeter experiments for selected tetrabenzoylgermanes. Composite pastes containing only ～0.1 wt % of Ge‐PI exhibited a sufficient photocuring due to the high PI‐reactivity of the tetraacylgermanes. Among the investigated germane PIs, tetrakis(2‐methylbenzoyl)germane 2 shows the best performance as VL PI for restorative composites and enables the composites to be photocured using an LED with an emission maximum of 500 nm. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46115.     

Polymerization of cyclic monomers. VII. Synthesis and radical polymerization of 1,3‐bis[(1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzenes

1,3‐Bis[(1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzenes 1 [RO: CH₃O (a), C₂H₅O (b)] were synthesized by the esterification of the corresponding 1‐alkoxycarbonyl‐2‐vinylcyclopropane‐1‐carboxylic acids with resorcinol. The structure of the new vinylcyclopropanes was confirmed by elemental analysis and infrared (IR), ¹H nuclear magnetic resonance (¹H‐NMR), and ¹³C nuclear magnetic resonance (¹³C‐NMR) spectroscopy. The radical polymerization of difunctional 2‐vinyl‐cyclopropanes in bulk with 2,2′‐azoisobutyronitrile (AIBN) results in hard, transparent, crosslinked polymers. During the bulk polymerization of the crystalline bis[(1‐methoxycarbonyl‐2‐vinylcyclopropane‐1‐yl)carboxy]benzene 1a, an expansion in volume of about 1% took place. The radical solution polymerization of 1a resulted in a soluble polymer with pendant 2‐vinylcyclopropane groups. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1775–1782, 1999     

Ultrasonic Fabrication of Polymer Plate Reactors with a Surface Coating

Microreactors offer several advantages compared to the industrial scale when developing new chemical processes. Especially the production and investment costs are low if polymer microreactors are generated by ultrasonic processes. In order to observe the chemical reaction and the flow configuration, these microreactors need to be optically transparent, mechanically stable, and chemically inert to several reagents. The manufacturing process of a transparent polymer plate reactor with a chemically inert surface coating by ultrasonic fabrication is described. Experimental characterization of the microreactors showed that they are leak tight up to a pressure difference of at least 300 kPa and the mixing times are in the range of milliseconds.     

SIMULATION STUDIES OF THE REMOVAL OF WATER FROM ETHANOL BY A CATALYTIC DISTILLATION PROCESS

A new approach based on catalytic distillation (CD) technology was proposed to remove water from ethanol. Isobutylene was introduced to react with water in the CD column. The commercial software simulation tool Aspen Plus was used to investigate the effects of key design factors such as operating pressure and temperature, reactant ratios, reflux and distillate to feed ratios, number of separation and reaction stages, and feed and reaction zone location. It was found that the CD technology offers potential advantages of reduced energy consumption and reduced capital cost over traditional approaches for the removal of water from ethanol.     

Polybrominated diphenyl ethers in the sediments of the Great Lakes. 3. Lakes Ontario and Erie

Sediment cores were taken in 2002 in Lakes Ontario and Erie at four locations. A total of 48 sediment samples were characterized, dated using 210Pb, and analyzed for 10 congeners of polybrominated diphenyl ethers (PBDEs) including BDE209 as well as 39 congeners of polychlorinated biphenyls (PCBs). The surficial concentrations of nine tri- through hepta-BDE congeners (sigma9PBDE) are 4.85 and 6.33 ng g(-1), at sampling sites ON40 and ON30 in Lake Ontario, and 1.83 and 1.95 ng g(-1) at ER37 and ER09 in Lake Erie, respectively, based on dry sediment weight. The surficial BDE209 concentrations are 242 and 211 ng g(-1) at ON40 and ON30 and 50 and 55 ng g(-1) at ER37 and ER09. The sigma(9-) PBDEs fluxes to the sediment around 2002 are 147 and 195 pg cm(-2) year(-1) at ON40 and ON30 and 136 and 314 pg cm(-2) year(-1) at ER37 and ER09, respectively. The fluxes of BDE209 are 6.5 and 7.3 ng cm(-2) year(-1) at ON30 and ON40 and 3.7 and 8.9 ng cm(-2) year(-1) at ER37 and ER09, respectively. Dramatic increases in PBDE concentrations and fluxes upward toward the sediment surface and the present time are evident at both locations in Lake Ontario, while PCBs concentrations peak in the middle of sediment cores around the dated time of 1970s and 1960s. For both locations of Lake Erie, the increasing trends of both PBDEs and PCBs from the bottom to the surficial segments were distorted by sediment mixing. BDE209 is the most abundant congener among PBDEs in the sediments, constituting about 96 and 91% of the total PBDEs on mass basis in Lakes Ontario and Erie, respectively.     

Solubilization of fish muscle proteins with buffers containing sodium dodecyl sulfate

Summary The extraction of fish muscle protein using SDS containing solubilization buffers was studied varying the time and the temperature of solubilization, as well as pH and SDS concentration of the buffer. At pH < 6 the myofbrillar proteins were incompletely solubilized; temperatures of 80-100 °C resulted in protein degradation observable in the SDS-PAGE.Samples of fish muscle containing high amounts of formaldehyde (50 mmoles FA/kg wet weight) could only be solubilised at 100 °C; on the other hand it was possible to solubilize cooked and/or canned products under mild conditions (2% SDS, 1% 2-ME, pH 8.9, shaking for 2 h at 60 °C).

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Solubilisierung von Fischmuskelproteinen durch Natriumdodecylsulfathaltige Puffer

Zusammenfassung Der Einfluß von Solubilisierungszeit und -temperatur, des pH-Wertes und der SDS-Konzentration des Solubilisierungspuffers auf die Extraktion von Fischmuskelproteinen wurde überprüft. Bei pH-Werten < 6 wurden die myofbrillären Proteine nur unvollständig gelöst; Solubilisierungstemperaturen von 80 bis 100 °C führten zu einem in der SDS-PAGE sichtbaren Proteinabbau. Fischmuskelproben mit hohem Formaldehydgehalt (50 mmole FA/kg Feuchtgewicht) ließen sich nur bei 100 °C vollständig solubilisieren; demgegenüber gelang die weitgehende Solubilisierung gegarter und/oder sterilisierter Produkte unter milden Bedingungen (2% SDS, 1% 2-ME, pH 8,9; 2stündiges Schütteln bei 60 °C).

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Abbreviations FA formaldehyde - IEF isoelectric focusing - 2-ME 2-mercaptoethanol - PA polyacrylamide - PAGE polyacrylamide gel electrophoresis - pI isoelectric point - SDS sodium dodecyl sulfate - TMAO trimethylamine oxide - Tris Tris (hydroxymethyl)methylamine     

Flavonolglykoside der Pflaumen der Species Prunus domestica L. und Prunus salicina Lindley

Zusammenfassung Blätter wie Früchte von 6 SortenPrunus domestica-Pflaumen enthalten hauptsächlich 3-Rutinoside, in geringerer Konzentration 3-Glucoside und 3-Galaktoside von Kämpferol und Quercetin Bowie Quercetin-3-rhamnosid. Dagegen weisen Pflaumen vonPrunus salicina (2 untersuchte Sorten) Kämpferol-3,7-bisrhamnosid und Kämpferol-3-arabinosyl-7-rhamnosid als Hauptflavonole auf. Hierdurch ist eine Unterscheidung beider Arten leicht and sicher mög-lich. Weiterhin konnten inSalicina-Pflaumen Kämpfe-rol-3-rutinosid sowie Quercetin-3-rhamnosid, -xylosid,-glucosid, -galaktosid, --l-arabinofuranosid and -rutinosid, auch Quercetin-7-rhamnosid and Kämpferol-7-glucosid nachgewiesen werden.Die Gesamtgehalte an Flavonolglykosiden lagen bei den untersuchten Pflaumensorten vonPrunus domestica (P. salicina) bei 2500–3340 (7170, 10350) ppm in Blättern and 20–52 (8, 24) in Früchten, jeweils bezogen auf Frischgewicht.

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Flavonol glycosides of plums of the species Prunus domestica L. and Prunus salicina lindley12. Phenolics of fruits

Summary Leaves and fruits from 6 cultivars ofPrunus domestica plums contain mainly 3-rutinosides; in smaller concentrations the 3-glycosides and 3-galactosides of kaempferol and quercetin as well as quercetin-3-rhamnoside are present. On the other hand, in plums ofPrunus salicina (2 examined cultivars) main flavonols are kaempferol-3,7-bisrhamnoside and kaempferol-3arabinosyl-7-rhamnoside. Due to the difference in composition, differentiation of these species will be easy and reliable. Additionally kaempferol-3-rutinoside and quercetin-3-rhamnoside, -xyloside,-glucoside, -galactoside, --l-arabinofuranoside and-rutinoside, and also quercetin-7-rhamnoside and kaempferol-7-glucoside could be detected inP. salicina plums. The total content of flavonol glycosides in the investigated plums ofPrunus domestica (P. salicina) were based on fresh weight about 2500–3340 (7170, 10350) ppm in the leaves and 20–52 (8, 24) ppm in the fruits.

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11. Mitt.: Henning W, Herrmann K (1980) Z Lebensm Unters Forsch 170:433–444

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Auszug aus der Promotionsarbeit von W. Henning: Bestimmung der in Pflaumen, Kirschen, Pfirsichen and Aprikosen vorkommenden Flavonolglykoside unter Anwendung der Hochdruckflüssigkeitschromatographie. Diss. Univ. Hannover 1980     

Unique Crystal Structure of a Novel Surfactant Protein from the Foam Nest of the Frog Leptodactylus vastus

Breeding by releasing eggs into stable biofoams (“foam nests”) is a peculiar reproduction mode within anurans, fish, and tunicates; not much is known regarding the biochemistry or molecular mechanisms involved. Lv‐ranaspumin (Lv‐RSN‐1) is the predominant protein from the foam nest of the frog Leptodactylus vastus. This protein shows natural surfactant activity, which is assumed to be crucial for stabilizing foam nests. We elucidated the amino acid sequence of Lv‐RSN‐1 by de novo sequencing with mass‐spectrometry and determined the high‐resolution X‐ray structure of the protein. It has a unique fold mainly composed of a bundle of 11 α‐helices and two small antiparallel β‐strands. Lv‐RSN‐1 has a surface rich in hydrophilic residues and a lipophilic cavity in the region of the antiparallel β‐sheet. It possesses intrinsic surface‐active properties, reducing the surface tension of water from 73 to 61 mN m^?1 (15 μg mL^?1). Lv‐RSN‐1 belongs to a new class of surfactants proteins for which little has been reported regarding structure or function.