Synthesis and photopolymerization of phosphonic acid monomers for applications in compomer materials

Novel methacrylate monomers bearing phosphonic acid groups 1 and 2 as well as new sulfur methacrylates 9 and 10 have been prepared in good yields from thiophenol. They have been fully characterized by ¹H‐NMR, ¹³C‐NMR, ³¹P‐NMR, and HRMS. Their copolymerization with a bis‐GMA : TEGDMA (1 : 1) blend has been investigated with photodifferential scanning calorimetry at 50°C with camphorquinone as a photoinitiator and ethyl 4‐(dimethylamino)benzoate (EDAB) as a coinitiator. The higher the content of acidic monomer 1 or 2 incorporated in the bis‐GMA : TEGDMA (1 : 1) blend, the lower the mixtures reactivity. The phosphonic acid group has been proved to be responsible for this drop of reactivity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development of low‐shrinkage composites based on novel crosslinking vinylcyclopropanes

Polymerization shrinkage of methacrylate‐based dental composites remains a major concern in restorative dentistry. Cyclic monomers that undergo ring‐opening polymerization are known to exhibit reduced polymerization shrinkage compared to methacrylates. In this article, the synthesis of four crosslinking 1,1‐disubstituted 2‐vinylcyclopropanes bearing rigid spacers is described. These monomers were synthesized by esterification of 1‐ethoxycarbonyl‐2‐vinylcyclopropane‐1‐carboxylic acid with the corresponding diols. The photopolymerization kinetics of these monomers was investigated by photo‐differential scanning calorimeter using bis(4‐methoxybenzoyl)diethylgermane as the photoinitiator. The synthesized vinylcyclopropanes (VCPs) were shown to be more reactive than the frequently used reactive diluent triethylene glycol dimethacrylate. Composites based on these VCPs showed good mechanical properties and exhibited a significantly reduced volumetric shrinkage and shrinkage stress compared to a corresponding dimethacrylate‐based restorative material. This work highlights the excellent potential of VCPs as alternatives to methacrylates in the development of low‐shrinkage dental composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45577.     

Mass Spectrometry-Based Proteomics Reveal Alcohol Dehydrogenase 1B as a Blood Biomarker Candidate to Monitor Acetaminophen-Induced Liver Injury

Acute liver injury (ALI) is a severe disorder resulting from excessive hepatocyte cell death, and frequently caused by acetaminophen intoxication. Clinical management of ALI progression is hampered by the dearth of blood biomarkers available. In this study, a bioinformatics workflow was developed to screen omics databases and identify potential biomarkers for hepatocyte cell death. Then, discovery proteomics was harnessed to select from among these candidates those that were specifically detected in the blood of acetaminophen-induced ALI patients. Among these candidates, the isoenzyme alcohol dehydrogenase 1B (ADH1B) was massively leaked into the blood. To evaluate ADH1B, we developed a targeted proteomics assay and quantified ADH1B in serum samples collected at different times from 17 patients admitted for acetaminophen-induced ALI. Serum ADH1B concentrations increased markedly during the acute phase of the disease, and dropped to undetectable levels during recovery. In contrast to alanine aminotransferase activity, the rapid drop in circulating ADH1B concentrations was followed by an improvement in the international normalized ratio (INR) within 10–48 h, and was associated with favorable outcomes. In conclusion, the combination of omics data exploration and proteomics revealed ADH1B as a new blood biomarker candidate that could be useful for the monitoring of acetaminophen-induced ALI.     

Inhibition of Very Long Chain Fatty Acids Synthesis Mediates PI3P Homeostasis at Endosomal Compartments

A main characteristic of sphingolipids is the presence of a very long chain fatty acid (VLCFA) whose function in cellular processes is not yet fully understood. VLCFAs of sphingolipids are involved in the intracellular traffic to the vacuole and the maturation of early endosomes into late endosomes is one of the major pathways for vacuolar traffic. Additionally, the anionic phospholipid phosphatidylinositol-3-phosphate (PtdIns (3)P or PI3P) is involved in protein sorting and recruitment of small GTPase effectors at late endosomes/multivesicular bodies (MVBs) during vacuolar trafficking. In contrast to animal cells, PI3P mainly localizes to late endosomes in plant cells and to a minor extent to a discrete sub-domain of the plant’s early endosome (EE)/trans-Golgi network (TGN) where the endosomal maturation occurs. However, the mechanisms that control the relative levels of PI3P between TGN and MVBs are unknown. Using metazachlor, an inhibitor of VLCFA synthesis, we found that VLCFAs are involved in the TGN/MVB distribution of PI3P. This effect is independent from either synthesis of PI3P by PI3-kinase or degradation of PI(3,5)P₂ into PI3P by the SUPPRESSOR OF ACTIN1 (SAC1) phosphatase. Using high-resolution live cell imaging microscopy, we detected transient associations between TGNs and MVBs but VLCFAs are not involved in those interactions. Nonetheless, our results suggest that PI3P might be transferable from TGN to MVBs and that VLCFAs act in this process.     

Design challenges of a 65 nm CMOS stacked folded differential PA structure for mobile communications

In this paper, a novel phase-locked loop (PLL) architecture with multiple charge pumps, which is used to design a fast-locking PLL and a low-phase-noise PLL, is proposed. The effective capacitance and resistance of the loop filter in terms of voltage is scaled up/down according to the locking status by controlling the magnitude and direction of the charge pump current. Two PLLs, one with a fast-locking characteristic and the other with a low-phase-noise characteristic, are designed and fabricated in a 0.35-μm CMOS process based on the proposed architecture. The fast-locking PLL has a locking time of less than 6 μs and a phase noise of −90.45 dBc/Hz at 1 MHz offset. The low-phase-noise PLL has a locking time of 25 μs, a phase noise of −105.37 dBc/Hz at 1 MHz offset, and a reference spur of −50 dBc. Both PLLs have an 851.2 MHz output frequency.     

Monomers for Adhesive Polymers, 10‐Synthesis,Radical Photopolymerization and Adhesive Properties of Methacrylates Bearing Phosphonic Acid Groups

Syntheses of eight novel methacrylates bearing phosphonic acid groups were synthesized in three to five steps. The interaction of these monomers with hydroxyapatite was investigated using ¹³C‐NMR spectroscopy. Free radical homopolymerizations were carried out in a mixture ethanol/water (2.5/1, v/v) using 2,2′azo(2‐methylpropionamidine) dihydrochloride as initiator. The copolymerization of these monomers with a mixture HEMA/GDMA (5/3, mol/mol) was investigated by photo‐DSC. Dentin shear bond strength measurements showed that 2‐methacryloyloxy‐3‐(1,1,2,2‐tetrafluoroethoxy)propylphosphonic acid 4b , 2,3‐dimethacryloyloxypropylphosphonic acid 18 and 3‐(methacryloyloxy)‐2,2‐(di[(dihydroxyphosphoryl)methyl])propyl methacrylate 23 are promising candidates for dental adhesives.

     

2D Percolation Design with Conductive Microparticles for Low‐Strain Detection in a Stretchable Sensor

Although a variety of stretchable strain sensors based on electrical percolation have been reported, stretchable sensors detecting low strains have been rarely demonstrated. This is because large stretchability of a strain sensor conflicts with high strain resolution at low strains. Here, the electrical percolation into 2D is confined and a strain sensor that is highly sensitive at low strains and simultaneously highly stretchable is presented. The 2D confinement of the electrical percolation is accomplished by a close‐packed monolayer assembly of conductive microparticles (MPs) on an elastomer substrate. The current profiles of the MP monolayer at low strains are in situ visualized using conductive atomic force microscopy. When the lattice of the MP monolayer is aligned vertically to the strain direction, the resistance is highly sensitive to low‐strain deformations (ε = 0 – 0.05), but the sensor has reasonable stretchability (ε = 0.3). The simultaneous achievement of the high sensitivity at low strains and the reasonable stretchability is explained by the relationship between the strain‐dependent current profile and the relative position changes of the MPs. A high‐precision pulse sensor clearly showing the representative peaks is demonstrated.     

Analytical investigation of the interactions between SC3 hydrophobin and lipid layers: elaborating of nanostructured matrixes for immobilizing redox systems

Hydrophobins are highly tensioactive fungal proteins with a pronounced affinity for interfaces and a propensity for self-assembly. Recently, these proteins were shown to be useful in retaining different molecules on solid surfaces. This finding offers a possibility for developing new functional materials, while creating the necessity of further research at a deeper mechanistic level. In this work, the mechanisms governing the surface phenomena were studied using native Schizophyllum commune hydrophobin (SC3) and lipid mono- and bilayers; the soft matter systems were used to get a handle on the interactive protein/interface effects at a molecular level. The results obtained indicated that the SC3/lipid membrane interactions were adjusted by protein conformational adaptation, allowing its incorporation into lipid matrixes; the incorporation of a chelating SC3 hydrophobin (PFA-SC3) in a monoolein cubic phase yielded a biomimetic, cell-like system of Cu(II) cation immobilization. This system, which is suitable for modifying electrode surface and monitoring the Cu(II)/Cu(0) redox process, may be of practical interest in switching and sensing.