Lewis Acid Mediated Vinyl‐Transfer Reaction of Alkynes to N‐Alkylimines by Using the N‐Alkyl Residue as a Sacrificial Hydrogen Donor

A variety of N‐alkyl‐α,α‐dichloroaldimines were vinylated by terminal acetylenes in the presence of Lewis acids such as In(OTf)₃ or BF₃ ? OEt₂ and hexafluoroisopropanol (HFIP) as an additive. The reaction proceeds at ambient temperature and leads to geometrically pure allylic β,β‐dichloroamines. This approach is complementary to previously reported transition‐metal‐catalyzed vinyl‐transfer methods, which are not applicable to aliphatic imines and are restricted to imines that contain an electron‐withdrawing nitrogen substituent. In the present approach, terminal alkynes were used as a source of the vinyl residue, and the N‐alkyl moiety of the imine acts as a sacrificial hydrogen donor. The additional advantage of this methodology is the fact that no external toxic or hazardous reducing agents or molecular hydrogen has to be used. This new methodology nicely combines a C(sp²)? C(sp) bond formation, hydride transfer, and an unusual cleavage of an unactivated C? N bond, thereby giving rise to functionalized primary allylic amines. A detailed experimental study supported by DFT calculations of the mechanism has been done.     

Analysis of xylene in aqueous media using needle‐trap microextraction with a carbon nanotube sorbent

This paper describes a new extraction technique with needles and a sorbent based on carbon nanotubes to analyze trace amounts of three isomers of xylenes in aqueous samples. In this research, results have been compared with one commercial sorbent. The synthesized sorbent was prepared using sol–gel technology and was packed into 20 gauge needles, and the same size needle was used for packing the commercial sorbent. In the extraction process, a purge and trap sampling methodology is developed, so purging and trapping cycles were performed by a sampling pump. Optimized conditions for standard xylene samples have been obtained, and eight urine samples from workers that were exposed to xylene in the workplace were collected and analyzed. Experimental parameters such as limits of detection and quantification were investigated, and these two parameters were <1 μg/L.     

A Hemi‐metallocene Chromium Catalyst with Trimethylaluminum‐Free Methylaluminoxane for the Synthesis of Disentangled Ultra‐High Molecular Weight Polyethylene

Recently, it has been shown that by using a single‐site catalytic system having titanium as a metallic center, it is possible to tailor the entanglement density in the amorphous region of a semi‐crystalline ultra‐high molecular weight polyethylene (UHMWPE). This route provides the possibility to make high‐modulus, high‐strength uniaxially and biaxially drawn tapes and films, without using any solvent during processing. In this publication, it is shown that a single‐site catalyst having chromium as metallic center, proposed by Enders and co‐workers, can also be tuned to provide control on the entanglement density during synthesis of the UHMWPE. However, to achieve the goal some modifications during the synthesis are required. The synthesized polymers can be processed in the solid state below the equilibrium melting temperature, resulting in uniaxially drawn tapes having tensile strength and modulus greater than 3.5 N/tex and 200 N/tex, respectively. Rheological studies have been performed to follow the increase in entanglement density in melt state with time.

     

Baroque glass mosaics from the Capela de São João Baptista (Chapel of Saint John the Baptist,Lisbon): unveiling the glassmaking records

For the first time, 18th‐century glass mosaics from the Capela de São João Baptista (Chapel of St. John the Baptist, Lisbon) were analysed by Raman microscopy (RM). This masterpiece in baroque mosaic art had one of its major contributors the most famous glassmaker in Rome, Alessio Mattioli. Mattioli was celebrated because of the opacity of his mosaics and the astonishing number of hues he was able to produce for mosaic decorating Saint Peter's Basilica in Rome. This study had two goals in mind: (1) characterising the materials involved in the manufacture of these glass mosaics and (2) lengthening the understanding of what was left of Mattioli's glassmaking records. As expected the mosaics presented a high ratio of crystalline phases, making RM the ideal technique for non‐destructive analysis. The mosaics contained a white ‘background’ or opacifier added identified as Ca₂Sb₂O₇. The yellow tesserae are opacified with lead antimonate (Pb₂Sb₂O₇) and ternary oxides, structures related to lead antimonate but with other ions entering the position of Sb⁴⁺ (namely Sn⁴⁺). Those ternary oxides are pervasive in most colours, admixed with other colorants. The red, orange, pink and brown colours were accomplished with cuprous oxide (Cu₂O) and admixed with a ternary oxide to create the latter three colours. The red copper‐based colours were made according to the procedure to make a ruby copper glass and with the exception of the red colour; all mosaics exhibited a dark layer on each side of the mosaic, named scorzetta. This layer is the outcome of an oxidation reaction because of a quick cooling process and is composed of CuO. Finally the blue and green colours are accomplished with cobalt oxide and copper oxide, respectively, and the purple/black colour with manganese oxide. Copyright © 2015 John Wiley & Sons, Ltd.     

Preclinical evaluation of 188 Re-HYNIC-PSMA as a novel therapeutic agent

Journal of Radioanalytical and Nuclear Chemistry - In this study, optimized preparation, quality control, cell assessments and biostribution of 188Re-HYNIC-PSMA in normal rats and tumor bearing...     

Label-free PSA electrochemical determination by seed-mediated electrochemically-deposited gold nanoparticles on an FTO electrode

Journal of Solid State Electrochemistry - A facile and sensitive approach is introduced to precisely determine trace amounts of prostate specific antigen (PSA) by gold nanostructures deposited on...     

Preliminary Study of a 1,5-Benzodiazepine-Derivative Labelled with Indium-111 for CCK-2 Receptor Targeting

The cholecystokinin-2 receptor (CCK-2R) is overexpressed in several human cancers but displays limited expression in normal tissues. For this reason, it is a suitable target for developing specific radiotracers. In this study, a nastorazepide-based ligand functionalized with a 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelator (IP-001) was synthesized and labelled with indium-111. The radiolabeling process yielded >95% with a molar activity of 10 MBq/nmol and a radiochemical purity of >98%. Stability studies have shown a remarkable resistance to degradation (>93%) within 120 h of incubation in human blood. The in vitro uptake of [¹¹¹In]In-IP-001 was assessed for up to 24 h on a high CCK-2R-expressing tumor cell line (A549) showing maximal accumulation after 4 h of incubation. Biodistribution and single photon emission tomography (SPECT)/CT imaging were evaluated on BALB/c nude mice bearing A549 xenograft tumors. Implanted tumors could be clearly visualized after only 4 h post injection (2.36 ± 0.26% ID/cc), although a high amount of radiotracer was also found in the liver, kidneys, and spleen (8.25 ± 2.21%, 6.99 ± 0.97%, and 3.88 ± 0.36% ID/cc, respectively). Clearance was slow by both hepatobiliary and renal excretion. Tumor retention persisted for up to 24 h, with the tumor to organs ratio increasing over-time and ending with a tumor uptake (1.52 ± 0.71% ID/cc) comparable to liver and kidneys.     

Sweet Cherries as Anti-Cancer Agents: From Bioactive Compounds to Function

Sweet cherries (Prunus avium L.) are among the most appreciated fruits worldwide because of their organoleptic properties and nutritional value. The accurate phytochemical composition and nutritional value of sweet cherries depends on the climatic region, cultivar, and bioaccessibility and bioavailability of specific compounds. Nevertheless, sweet cherry extracts are highly enriched in several phenolic compounds with relevant bioactivity. Over the years, technological advances in chemical analysis and fields as varied as proteomics, genomics and bioinformatics, have allowed the detailed characterization of the sweet cherry bioactive phytonutrients and their biological function. In this context, the effect of sweet cherries on suppressing important events in the carcinogenic process, such as oxidative stress and inflammation, was widely documented. Interestingly, results from our research group and others have widened the action of sweet cherries to many hallmarks of cancer, namely metabolic reprogramming. The present review discusses the anticarcinogenic potential of sweet cherries by addressing their phytochemical composition, the bioaccessibility and bioavailability of specific bioactive compounds, and the existing knowledge concerning the effects against oxidative stress, chronic inflammation, deregulated cell proliferation and apoptosis, invasion and metastization, and metabolic alterations. Globally, this review highlights the prospective use of sweet cherries as a dietary supplement or in cancer treatment.     

Transition from a two-dimensional superfluid to a one-dimensional Mott insulator

A two-dimensional system of atoms in an anisotropic optical lattice is studied theoretically. If the system is finite in one direction, it is shown to exhibit a transition between a two-dimensional superfluid and a one-dimensional Mott insulating chain of superfluid tubes. Monte Carlo simulations are consistent with the expectation that the phase transition is of Kosterlitz-Thouless type. The effect of the transition on experimental time-of-flight images is discussed.