Development of a syn‐Selective Mannich Reaction of Aldehydes with Propargylic Imines by Dual Catalysis: Asymmetric Synthesis of Functionalized Propargylic Amines

Direct coupling of enolizable aldehydes with C‐alkynyl imines is realized affording the corresponding propargylic Mannich adducts of syn configuration, thus complementing previous methods that gave access to the anti‐isomers. The combination of proline and a urea Brønsted base cocatalyst is key for the reactions to proceed under very mild conditions (3–10 mol % catalyst loading, dichloromethane as solvent, ?20 °C, 1.2 molar equivalents of aldehyde) and with virtually total stereocontrol (syn/anti ratio up to 99:1; ee up to 99 %). Some possibilities of further chemical elaboration of adducts are also briefly illustrated.     

Sampling and digestion of waste mobile phones printed circuit boards for Cu,Pb, Ni,and Zn determination

Sampling is the most important procedure in arriving at the value of an electronic scrap. Inappropriate sampling makes other procedures, including assaying, valueless, as the sample must really represent the electronic scrap from which it was taken. The aim of this study was to develop the procedure to investigate the composition of heterogeneous printed circuit boards (PCBs) material and to show its applicability as well as its related limitations. The contents of Cu, Pb, Ni, and Zn in PCBs from wasted mobile phones were determined. Mixtures of aqua regia, hydrogen peroxide and hydrofluoric acid were applied to sample digestion. Open and closed vessel wet digestion with or without heating and microwave-assisted one was realized. For these purposes different sample amounts (0.2, 0.4, and 0.5 g) were applied and on the basis of calculated relative standard deviation values (RSD), the precision of repeated the most effective digestion was evaluated. The microwave-assisted wet digestion and mixture of aqua regia and hydrogen peroxide was found as the most effective one of the compared mixtures and applied conditions. A sample amount of 0.5 g was found as the most suitable. RSD values confirm the importance of electronic waste material sample preparation.     

Combined prostate diffusion tensor imaging and dynamic contrast enhanced MRI at 3T — quantitative correlation with biopsy

The purpose of this work was to compare diagnostic accuracy of Diffusion Tensor Imaging (DTI), dynamic contrast-enhanced magnetic resonance imaging (DCE MRI) and their combination in diagnosing prostate cancer. Twenty-five patients with clinical suspicion of prostate cancer underwent MRI, prior to transrectal ultrasound-guided biopsies. MRI data were correlated to biopsy results. Logistic regression models were constructed for the DTI parameters, DCE MRI parameters, and their combination. The areas under the receiver operator characteristic curves (AUC) were compared between the models. The nonparametric Wilcoxon signed rank test was used for statistical analysis. The sensitivity and specificity values were respectively 81% (74–87%) and 85% (79–90%) for DTI and 63% (55–70%) and 90% (85–94%) for DCE. The combination “DTI or DCE MRI” had 100% (97–100%) sensitivity and 77% (69–83%) specificity, while “DTI and DCE MRI” had 44% (37–52%) sensitivity and 98% (94–100%) specificity. The AUC for DTI+DCE parameters was significantly higher than that for either DTI (0.96 vs. 0.92, P=.0143) or DCE MRI parameters (0.96 vs. 0.87, P=.00187) alone. In conclusion, the combination of DTI and DCE MRI has significantly better accuracy in prostate cancer diagnosis than either technique alone.     

Characterization of nanochannel delivery membrane systems for the sustained release of resveratrol and atorvastatin: new perspectives on promoting heart health

Novel drug delivery systems capable of continuous sustained release of therapeutics have been studied extensively for use in the prevention and management of chronic diseases. The use of these systems holds promise as a means to achieve higher patient compliance while improving therapeutic index and reducing systemic toxicity. In this work, an implantable nanochannel drug delivery system (nDS) is characterized and evaluated for the long-term sustained release of atorvastatin (ATS) and trans-resveratrol (t-RES), compounds with a proven role in managing atherogenic dyslipidemia and promoting cardioprotection. The primary mediators of drug release in the nDS are nanofluidic membranes with hundreds of thousands of nanochannels (up to 100,000/mm²) that attain zero-order release kinetics by exploiting nanoconfinement and molecule-to-surface interactions that dominate diffusive transport at the nanoscale. These membranes were characterized using gas flow analysis, acetone diffusion, and scanning and transmission electron microscopy (SEM, TEM). The surface properties of the dielectric materials lining the nanochannels, SiO₂ and low-stress silicon nitride, were further investigated using surface charge analysis. Continuous, sustained in vitro release for both ATS and t-RES was established for durations exceeding 1 month. Finally, the influence of the membranes on cell viability was assessed using human microvascular endothelial cells. Morphology changes and adhesion to the surface were analyzed using SEM, while an MTT proliferation assay was used to determine the cell viability. The nanochannel delivery approach, here demonstrated in vitro, not only possesses all requirements for large-scale high-yield industrial fabrication, but also presents the key components for a rapid clinical translation as an implantable delivery system for the sustained administration of cardioprotectants.     

Electrochemical detection of miRNA-222 by use of a magnetic bead-based bioassay

MicroRNAs (miRNAs, miRs) are naturally occurring small RNAs (approximately 22 nucleotides in length) that have critical functions in a variety of biological processes, including tumorigenesis. They are an important target for detection technology for future medical diagnostics. In this paper we report an electrochemical method for miRNA detection based on paramagnetic beads and enzyme amplification. In particular, miR 222 was chosen as model sequence, because of its involvement in brain, lung, and liver cancers. The proposed bioassay is based on biotinylated DNA capture probes immobilized on streptavidin-coated paramagnetic beads. Total RNA was extracted from the cell sample, enriched for small RNA, biotinylated, and then hybridized with the capture probe on the beads. The beads were then incubated with streptavidin–alkaline phosphatase and exposed to the appropriate enzymatic substrate. The product of the enzymatic reaction was electrochemically monitored. The assay was finally tested with a compact microfluidic device which enables multiplexed analysis of eight different samples with a detection limit of 7 pmol L^?1 and RSD?=?15 %. RNA samples from non-small-cell lung cancer and glioblastoma cell lines were also analyzed.     

On the determination of the point of fracture initiation by the load separation criterion in J-testing of ductile polymers

The application of an experimental approach based on the load separation criterion for the determination of the point of fracture initiation in a fracture test on a ductile polymer was critically examined. To this aim, the fracture process outlined by the application of this method was related to that described by the visual analysis of the fracture surfaces obtained in fracture tests on nominally identical specimens, in which different levels of crack extension were produced. The material examined was an acrylonitrile-butadiene-styrene (ABS) resin, and the fracture tests were performed at low loading rate on single-edge notched in bending specimens.The results demonstrated that this load separation criterion based methodology is a promising approach for the determination of the point of fracture initiation, and for material fracture resistance, J_Ic, evaluation. The method also has experimental simplicity and a high degree of repeatability.     

Trace elements in sediments and bioaccumulation in European silver eels (Anguilla anguilla L.) from a Mediterranean lagoon (SE Italy)

Samples of surface sediments and tissues (liver and muscle) of commercially available European silver eels (Anguilla anguilla L.) collected from Varano lagoon (Italy) were analysed to determine trace element contents. Univariate and multivariate analyses were performed to highlight both the differences between sampling sites and the influence of channel discharges. Atomic ratios indices for sediment data and biological enrichment factors (BEF) for eel tissues were calculated in order to evaluate the enrichment factor due to human activities. The highest levels of As (11.9?µg?g^?1) and Zn (14.1?µg?g^?1) were observed in the south-eastern zone of the lagoon, which is influenced by urban and agricultural discharges. The low levels of Hg observed in this study (0.04?µg?g^?1) led us to exclude both natural and human local sources of this element. Trace element concentrations of all elements were lower in muscle than in liver tissue. Significant enrichment of Cu and Zn was found in livers.     

Gold‐Decorated Chiral Macroporous Films by the Self‐Assembly of Functionalised Block Copolymers

We describe a new and very versatile method to place chosen chemical functionalities at the edge of the pores of macroporous materials. The method is based on the synthesis and self‐assembly of inorganic block copolymers (BCPs) having chiral rigid segments bearing controllable quantities of randomly distributed functional groups. The synthesis of a series of optically active block copolyphosphazenes (PP) with the general formula [N?P(R‐O₂C₂₀H₁₂)_0.9(FG)_0.2]_n‐b‐[N?PMePh]_m (FG=‐OC₅H₄N ( 6 ), ‐NC₄H₈S ( 7 ), and ‐NC₄H₈O ( 8 )), was accomplished by the sequential living cationic polycondensation of N‐silylphosphoranimines, using the mono‐end‐capped initiator [Ph₃P?N?PCl₃][Cl] ( 3 ). The self‐assembly of the phosphazene BCPs 6 – 8 led to chiral porous films. The functionality present on those polymers affected their self‐assembly behaviour resulting in the formation of pores of different diameters (D_n=111 ( 6 ), 53 ( 7 ) and 77 nm ( 8 )). The specific functionalisation of the pores was proven by decorating the films with gold nanoparticles (AuNPs). Thus, the BCPs 6 and 7 , having pyridine and thiomorpholine groups, respectively, were treated with HAuCl₄, followed by reduction with NaBH₄, yielding a new type of block copolyphosphazenes, which self‐assembled into chiral porous films specifically decorated with AuNPs at the edge of the pores.