Polymeric (O‐ethyl di­thio­carbonato)silver(I)

The title compound, [Ag(C₃H₅OS₂)]_n, is polymeric in the solid state and adopts a layered structure in which each Ag atom is five‐coordinated in a distorted trigonal‐bipyramidal geometry defined by four S atoms belonging to four different xanthate groups and by a neigbouring Ag atom [Ag⃛Ag = 3.0540 (8) Å]. Each S atom is three‐coordinated to one C and two Ag atoms. The structure can be envisaged as being formed by Ag₂(S₂COEt)₂ units in which every S atom is bonded to another Ag atom from a different unit and the Ag atoms are also bonded to two different S atoms of two other units. The result is a two‐dimensional network of condensed metallacycles of six or eight atoms.     

Cutaneous Photoprotective Activity of a Short‐term Ingestion of High‐Flavanol Cocoa: A Nutritional Intervention Study

In vivo and in vitro studies have shown that prolonged oral administration of flavanol‐rich cocoas extracts have photoprotective effects. The aim of the present study was to assess the photoprotective activity of short‐time administration of a new variety of naturally selected cocoa extract rich in bioactive compounds. We selected a cocoa powder particularly rich in polyphenols, flavanols, caffeine, theobromine and theophylline. We then investigated, in 10 healthy subjects, the photoprotective effects of one week of daily oral administration of two doses of such powder. Phototesting with solar simulated radiation was performed at baseline and after cocoa supplementation. Visual assessment of the minimal erythema dose and spectrophotometric measurement of the “a” parameter were done after 24 h from the irradiation. Oral daily supplementation of 1 g of high‐flavanol cocoa was not effective but a one‐week administration of 4–6 g of cocoa induced a statistically significant increase in the visual erythema threshold and a significant reduction in the “a” parameter. We demonstrated that a new variety of naturally selected cocoa extract, even when administered for a short time, retains a dose‐dependent photoprotective effect. These results are also indicative of the fact that topical sunscreens could be supplemented by a specific diet.     

Monitoring of Pollutants Content in Bottled and Tap Drinking Water in Italy

The concentration levels of thirteen organic pollutants and selected heavy metals were investigated in 40 plastics bottled and tap water samples. Some of the selected contaminants have an ascertained or suspected endocrine disrupting activity, such as Bisphenol A (BPA) and its analogs, and Bis 2-ethylhexyl phthalate (DEHP), which are used by industries as plasticizers. The most frequently detected pollutants were Bisphenol AF (BPAF) (detection frequency (DF) = 67.5%, mean 387.21 ng L⁻¹), DEHP (DF = 62.5%, mean 46.19 µg L⁻¹) and BPA (DF = 60.0%, mean 458.57 ng L⁻¹), with higher concentration levels found in tap waters. Furthermore, a possible level of exposure to thirteen pollutants via drinking water intake was calculated. Our findings show that, even though the occurrence of contaminants and heavy metals in drinking waters does not pose an immediate, acute health risk for the population, their levels should be constantly monitored and “hard-wired” into everyday practice. Indeed, the health impact to the continuous and simultaneous intake of a huge variety of xenobiotics from various sources by humans is complex and still not fully understood.     

Electron-beam lithography of cinnamate polythiophene films: conductive nanorods for electronic applications

We report the electron-beam induced crosslinking of cinnamate-substituted polythiophene proceeding via excited state [2+2]-cycloaddition. Network formation in thin films is evidenced by infrared spectroscopy and film retention experiments. For the polymer studied herin, the electron-stimulated process appears to be superior to photo (UV)-induced crosslinking as it leads to less degradation. Electron beam lithography (EBL) patterns cinnamate-substituted polythiophene thin films on the nanoscale with a resolution of around 100 nm. As a proof of concept, we fabricated nanoscale organic transistors using doped and cross-linked P3ZT as contact fingers in thin film transistors.

Electron beam lithography patterns selectively cinnamate-substituted polythiophene thin films via [2+2]-cycloaddition. A nanoscale organic field effect transistor is constructed using cross-linked and doped polythiophene as electrodes.     

Screening for illicit and medicinal drugs in whole blood using fully automated SPE and ultra‐high‐performance liquid chromatography with TOF‐MS with data‐independent acquisition

A broad forensic screening method for 256 analytes in whole blood based on a fully automated SPE robotic extraction and ultra‐high‐performance liquid chromatography (UHPLC) with TOF‐MS with data‐independent acquisition has been developed. The limit of identification was evaluated for all 256 compounds and 95 of these compounds were validated with regard to matrix effects, extraction recovery, and process efficiency. The limit of identification ranged from 0.001 to 0.1 mg/kg, and the process efficiency exceeded 50% for 73 of the 95 analytes. As an example of application, 1335 forensic traffic cases were analyzed with the presented screening method. Of these, 992 cases (74%) were positive for one or more traffic‐relevant drugs above the Danish legal limits. Commonly abused drugs such as amphetamine, cocaine, and frequent types of benzodiazepines were the major findings. Nineteen less frequently encountered drugs were detected e.g. buprenorphine, butylone, cathine, fentanyl, lysergic acid diethylamide, m‐chlorophenylpiperazine, 3,4‐methylenedioxypyrovalerone, mephedrone, 4‐methylamphetamine, p‐fluoroamphetamine, and p‐methoxy‐N‐methylamphetamine. In conclusion, using UHPLC–TOF‐MS screening with data‐independent acquisition resulted in the detection of common drugs of abuse as well as new designer drugs and more rarely occurring drugs. Thus, TOF‐MS screening of blood samples constitutes a practical way for screening traffic cases, with the exception of δ‐9‐tetrahydrocannabinol, which should be handled in a separate method.     

Electrochemical Magnetic Immunosensors for the Determination of Ceruloplasmin

Electrochemical immunosensors for ceruloplasmin (Cp) are reported for the first time. Two configurations involving magnetic beads (MBs) functionalized with Protein A or Streptavidin for immobilization of Cp antibodies were compared, using competitive immunoassay with synthesized alkaline phosphatase‐Cp conjugate. Upon capturing MBs‐immunoconjugates onto screen‐printed carbon electrodes, quantification of Cp was accomplished by DPV measurement of 1‐naphthol generated after 1‐naphthylphosphate addition. Linear ranges of calibration curves and detection limits were 0.1–1000 µg/mL and 0.040 µg/mL (Protein A‐MBs), and 0.025–20 µg/mL and 0.018 µg/mL (Strept‐MBs). Good results were obtained in the determination of Cp in spiked human serum samples.     

The Quenched Instationary Polymerization System, 5. The Peak Broadness as an Invariant Quantity of the Number,Molar Mass and Hyper Distributions

The total number, molar mass and hyper distributions generated by quenched instationary polymerization techniques are dominated by the radical chain length distribution (RCLD) whereas the contribution from the polymer chain length distribution (PCLD) is in most cases negligible. For the determination of the rate constant of propagation (k_p) the location of different extraordinary points of the distribution curves is determined by the use of the first and second derivatives. For the number, molar mass and hyper distributions these points are related in an unambiguous way to k_p[M]t_x and can be used to extract k_p. The choice of t_x (duration of the dark period, or an initiation period, or the sum of different periods) depends on the experimental conditions (δ‐pulse, incomplete pre‐effect, combination of periods differing in initiation extent) and is essential for the proper determination of k_p. The broadness of appearing peaks (introduced as the difference between two successive points of inflections) turned out to remain the same irrespective which type of distribution curve was analyzed. Analytical expressions for the peak broadness were derived for different types of quenched instationary polymerization conditions. For δ‐pulse initiation the broadness of the Poisson peak depends simply on the number of propagation steps that occurred whereas for non‐δ‐pulse initiation conditions the peak broadness is governed by the corresponding duration of the initiation period.