Increasing the Reactivity of Amides towards Organometallic Reagents: An Overview

The nucleophilic addition of carbon nucleophiles to amides has traditionally been a difficult task, both due to reactivity and selectivity problems. When successful, these processes would represent straightforward routes towards carbonyl‐type or amine compounds, depending on the fate of the generated tetrahedral intermediate. The direct addition of nucleophiles to amides for the preparation of ketones has been studied and applied to the syntheses of several natural products. On the other hand, the addition of nucleophiles to amides to obtain substituted amines represented a major challenge, and only scattered applications on particular substrates have appeared. Initial improvements were based on the activation of amides by introduction of particular substituents, such as in N‐methoxy amides (Weinreb amides) or electron‐withdrawing groups able to increase the carbon nucleophilicity. Although these strategies facilitate the introduction of nucleophiles, chemoselectivity issues arise when additional electrophilic moieties (i.e., carbonyls) are present, thus decreasing the versatility of the methods. In recent years, important advancements towards fully chemoselective methods have been realized. The capture of tetrahedral intermediates with acids generates highly electrophilic iminium species able to undergo chemoselective additions of various nucleophiles, thus accessing substituted amines. Alternatively, the in situ generation of an iminium triflate ion allows highly chemoselective additions of nucleophiles, yielding amines, ketones or ketimines. Also thioamides can be used as precursors of ketones or α‐substituted amines. The success of the above methodologies is further showcased by the application in various syntheses of natural products or biologically active molecules.

     

The Role of Higher Lying Electronic States in Charge Photogeneration in Organic Solar Cells

The role of excess photon energy on charge generation efficiency in bulk heterojunction solar cells is still an open issue for the organic photovoltaic community. Here, the spectral dependence of the internal quantum efficiency (IQE) for a poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b]­dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)]:6,6‐phenyl‐C₆₁‐butyric acid methyl ester (PCPDTBT:PC60BM)‐based solar cell is derived combining accurate optoelectronic characterization and comprehensive optical modeling. This joint approach is shown to be essential to get reliable values of the IQE. Photons with energy higher than the bandgap of the donor material can effectively contribute to enhance the IQE of the solar cell. This holds true independently of the device architecture, reflecting an intrinsic property of the active material. Moreover, the nanomorphology of the bulk heterojunction plays a crucial role in determining the IQE spectral dependence: the coarser and more crystalline, the lesser the gain in IQE upon high energy excitation.     

Bioaccumulation of dioxin-like substances and selected brominated flame retardant congeners in the fat and livers of black pigs farmed within the Nebrodi Regional Park of Sicily

An observational study was designed to assess the bioaccumulation of polychlorodibenzodioxins (PCDD) and polychlorodibenzofurans (PCDF), dioxin-like polychlorobiphenyls (DL-PCB), and 13 selected polybromodiphenylethers (PBDE) in autochthonous pigs reared in the Nebrodi Park of Sicily (Italy). Perirenal fat and liver samples were drawn from animals representative of three different outdoor farming systems and from wild pigs and then analyzed for the chemicals mentioned previously. The highest concentrations of PCDD + PCDF and DL-PCB were detected in the fat (0.45 and 0.35 pg World Health Organization toxicity equivalents [WHO-TE] per g of fat base [FB], respectively) and livers (12.7 and 3.28 pg WHO-TE per g FB) of the wild group, whereas the free-ranging group showed the lowest levels (0.05 and 0.03 pg WHO-TE per g FB in fat and 0.78 and 0.27 pg WHO-TE per g FB in livers). The sum of PBDE congeners was highest in wild pigs (0.52 ng/g FB in fat and 5.64 ng/g FB in livers) and lowest in the farmed group (0.14 ng/g FB in fat and 0.28 ng/g FB in livers). The contamination levels in fat and livers of outdoor pigs had mean concentration values lower than those levels reported for intensively indoor-farmed animals. In wild pigs, bioaccumulation was associated with their free grazing in areas characterized by bush fires. The results of this study aid to emphasize the quality of the environment as a factor to guarantee food safety in typical processed pig meat products, specifically from outdoor and extensive Nebrodi farming systems.     

Polymer Fiber Probes Enable Optical Control of Spinal Cord and Muscle Function In Vivo

Restoration of motor and sensory functions in paralyzed patients requires the development of tools for simultaneous recording and stimulation of neural activity in the spinal cord. In addition to its complex neurophysiology, the spinal cord presents technical challenges stemming from its flexible fibrous structure and repeated elastic deformation during normal motion. To address these engineering constraints, we developed highly flexible fiber probes, consisting entirely of polymers, for combined optical stimulation and recording of neural activity. The fabricated fiber probes exhibit low‐loss light transmission even under repeated extreme bending deformations. Using our fiber probes, we demonstrate simultaneous recording and optogenetic stimulation of neural activity in the spinal cord of transgenic mice expressing the light sensitive protein channelrhodopsin 2 (ChR2). Furthermore, optical stimulation of the spinal cord with the polymer fiber probes induces on‐demand limb movements that correlate with electromyographical (EMG) activity.     

Use of compatible blends to fabricate carbon black composite vapor detectors

The aim of this work was the development of materials to be used in the field of gas sensing for the detection of organic vapors. Conductive sensors were prepared with carbon black filled blends of poly(vinyl chloride) and diol‐terminated poly(?‐caprolactone), an oligomeric plasticizer. For comparison, blends with di(2‐ethylhexyl)phthalate, a traditional low‐molecular‐weight plasticizer, were also prepared. All sensors were tested upon exposure to different organic vapors. In general, the plasticizer content affected the response rates of the sensors, and a linear variation of the relative resistance with the analyte concentration was observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1816–1821, 2004     

Determination of PCBs in fatty tissues by means of several detection techniques

Difficulties with harmonization of analytical procedures and consequently poor comparability of generated data represent in the Czech Republic the main reason for the delay in issuing of updated legislation for polychlorobiphenyls (PCBs) in foodstuffs. This study draws attention to possible errors (overestimations) that can occur during routine determination of these residues in the fat portion of biotic matrices. We demonstrate the gas Chromatographic (GC) conditions under which interfering contaminants such as phthalates and/or chlorinated pesticides can be separated from analytes. Discussion is focused on the advantages and drawbacks of GC with an electron capture detector, GC mass spectrometry and GC with an atomic emission detector. Various approaches used for calculation of PCBs contents are compared.

---

Bestimmung der PCB in Fettgeweben mittels verschiedener Detektionstechniken

Zusammenfassung Das Problem mit der Harmonisierung der analytischen Verfahren und der geringen Vergleichbarkeit der Angaben ist ein Hauptgrund der Verspätung in der neuen Legislative für PCB in Lebensmitteln in der Tschechischen Republik. Die Arbeit beschreibt die möglichen Fehler (Falsch-positive Fehler), die durch die routinierte Bestimmung von PCB-Rückständen in Fettanteilen der biologischen Materialien auftreten können. Es werden die gaschromatographischen Bedingungen beschrieben, unter denen die Interferenzen, wie z. B. Phthalaten und chlorierten Pesticiden, von Stoffen abgetrennt werden können. Die Vorteile und Nachteile der Methoden GC-ECD, GC-MS und GC-AED werden diskutiert. Die verschiedenen für die Kalkulation des PCB-Gehaltes angewendeten Annäherungen werden miteinander verglichen.

     

Prolonged muscular flaccidity: frequency and association with unilateral spatial neglect after stroke

A 21-month-old infant developed coma with hypotonia during a viral infection. Acyl CoA dehydrogenase deficiency was diagnosed on the basis of results of the chromatographic study of organic acids performed on a urine specimen collected during the acute episode. However, other disorders of mitochondrial and fatty acid oxygenation can generate similar symptoms. Emphasis is put on the need for collecting urine specimens in patients who develop alterations in consciousness and hypoglycemia without ketonuria during prolonged fasting or repeated vomiting due to a viral infection. Urine chromatography can suggest which enzyme is defective, although the diagnosis should always be confirmed by a study of fatty acid oxygenation in lymphocytes or fibroblasts.     

Photodegradable polyethylene

Polymer photodegradation can be achieved by introducing carbonyl groups which absorb radiations above the 300 mμ wavelength and thus are sensitized by solar or atmospheric radiations. We introduced these groups in polyethylene by oximation of aliphatic chain with photoactivated NOCI and hydrolysis of the oxime. Modified polymers show, during accelerated aging in Weather-O-Meter, a constant molecular weight decrease, which is directly proportional to the concentration of carbonyl groups.