Highly sensitive electrochemical detection of living cells based on diamond microelectrode arrays

The new boron-doped nanocrystalline diamond microelectrode arrays (BNCD-MEAs) with 16 channels were designed to detect biological signals from some activated cancer cells. Upon recordings of the released H₂O₂ from cancer cells stimulated by ascorbic acid (AA), it can readily detect the reactive oxygen species (ROS) released from target cells, which will be helpful for the cancer cell recognition and also beneficial for further studying the cause of relevant disease.     

Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C‐Glycosylation Reactions at Room Temperature

Pairing a range of bis(aryl) zinc reagents ZnAr₂ with the stronger Lewis acidic [(ZnAr^F₂)] (Ar^F=C₆F₅), enables highly stereoselective cross‐coupling between glycosyl bromides and ZnAr₂ without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnAr^F₂ acts as a non‐coupling partner although its presence is crucial for the execution of the C(sp²)–C(sp³) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition‐metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases versus diarylzinc compounds (e.g. THF).     

Synthesis of Densely Packaged,Ultrasmall Pt02 Clusters within a Thioether‐Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Temperature

The gram‐scale synthesis, stabilization, and characterization of well‐defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X‐ray snapshots of Pt⁰₂ clusters, homogenously distributed and densely packaged within the channels of a metal–organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO₂ methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal clusters in solids for technically easier, cheaper, and dramatically less‐dangerous industrial reactions.     

Determination of Phenolic Endocrine Disruptors in Cosmetics by High-Performance Liquid Chromatography Mass Spectrometry

An analytical method for the simultaneous determination of bisphenol A, 4-t-octylphenol, 4-n-octylphenol, and 4-n-nonylphenol in cosmetic samples has been developed. These compounds have toxic effects on human health as they have shown to produce endocrine disrupting properties. Therefore, their presence in cosmetics should be avoided according to the current European Regulations on cosmetic products. The method is based on high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) detection. Standard addition calibration was used to avoid matrix effects. The limits of detection values ranged between 7 and 15?ng?mL^?1 (threefold of the residual standard deviation of regression lines). The proposed method was validated, and good recovery (90–106%) and repeatability values (2.7–8.2%) were obtained. Finally, the method was successfully applied to ten commercially available cosmetic samples. The good analytical features of the proposed method make it useful to carry out the quality control of cosmetic products and raw materials to assure the safety of users.     

Modelling hydrological data with and without long memory

The paper focuses on the problem of long-range dependence when analysing time series of hydrological data. Three time series are analysed: the monthly rainfall in the town of Florence, Italy; the daily minimum temperatures in the same town; and, finally, the daily water inflow to Lake Maggiore, Italy. Heuristic methods and maximum likelihood estimation of a parametric model are used to investigate the Hurst phenomena and to detect whether long-range dependence is present in any of the time series. We found that long-range dependence is not present in the first series but it is present in the last two. The daily water inflow to Lake Maggiore was modelled by a fractionally differenced arima model (farima) which contains a long-range dependence component. It is shown that the fit is much better than the one provided by more traditional arima models that do not have such a component.

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Sommario Lo studio considera il problema dell'identificazione dei fenomeni di dipendenza a lungo termine (long range dependence) nelle serie temporali di dati idrologici. Allo scopo sono state analizzate tre serie temporali, rispettivamente quella dei totali mensili di precipitazione rilevati alla stazione dell'Osservatorio Ximeniano de Firenze, quella delle temperature minime giornaliere per la stessa stazione e quella degli afflussi giornalieri al Lago Maggiore. Per identificare la presenza di fenomeni di dipendenza long range, attraverso la valutazione della consistenza del fenomeno di Hurst, sono stati utilizzati sia metodi euristici, sia la stima a massima verosimiglianza di un modello parametrico. Due delle tre serie analizzate sono risultate caratterizzate da tale dipendenza. Per la serie degli afflussi al Lago Maggiore, si è inoltre proceduto alla simulazione attraverso un modello arima a differenziazione frazionaria (farima), la cui struttura contiene una componente long-range. I risultati ottenuti, mostrano che tale modello fornisce risultati significativamente migliori dei tradizionali modelli arima, privi di tale componente.

     

2-Naphthol-phosphatidylethanolamine: A fluorescent phospholipid analogue for excited-state proton transfer studies in membranes

The fluorescence properties of the phospholipid derivative,N-[1-(2-naphthol)]-phosphatidylethanolamine (NAPH-PE), have been studied by steady-state and time-resolved fluorescence techniques. The new probe is a naphthol adduct of phosphatidylethanolamine. The emission spectrum of the fluorescent phospholipid depends on the pH and on the proton acceptor concentration as expected for a typical two-state excited-state proton transfer reaction. In ethanol solutions at an apparent pH of 6.7 and in the presence of acetate anion (0.14M), a biexponential decay is obtained from global analysis of the data. The lifetimes, ₁=3.9 ns and ₂=6.2 ns. are constant across the spectral region 350–460 nm. The decay-associated spectra and the species-associated spectra reproduce well the profiles reported for a two-state excited-state proton transfer reaction. The fluorescent phospholipid has been incorporated into dimyristoyllecithin and dipalmitoyllecithin vesicles. Although lower proton transfer is found, the reaction appears to be dependent on the gel-to-liquid-crystalline phase transition of the lipid membrane. In addition, the steady-state anisotropy of NAPH-PE measured as a function of temperature trace the phase transition of the two vesicle systems. Thus, it is shown that the physical state of the bilayer affects a reaction which takes place at the membrane surface. In the presence of acetate ions (0.3M), global analysis, performed in terms of fluorescence decay parameters, recovers preexponential coefficients that are consistent with an excited-state proton transfer reaction. The short lifetime drops from 3.9 to 0.44 ns without significant changes of the longer-lifetime component.     

Witnessing differences without redundancies

We show that elements suffice to witness the differences of pairwise distinct sets, and provide sufficient conditions for an infinite family of pairwise distinct sets to have a minimal collection of elements witnessing the differences between any two of its members.

     

Oxidative Cyclization of Iodo Ketones. Synthesis of 6-Oxa-5alpha-pregnane-3,20-dione

The steroidal delta- and gamma-iodo ketones 1 and 9 were converted to the cyclic hemiketals 3 and 10, by oxidation to the iodoso derivatives with m-CPBA. Spontaneous cyclization of the latter intermediates to the corresponding oxocarbenium ions, followed by stereoselective addition of water, rendered the hemiketals. Depending on the reaction conditions, the five-membered oxocarbenium ion derived from the gamma-iodo ketone 9 may add H(2)O or m-CPBA to give either the hemiketal or a Baeyer-Villiger type product 12, while the oxocarbenium derived from 1 gives exclusively the hemiketal. When the reaction was carried out in dry methanol, methyl ketals were formed. Use of this methodology allowed us to synthesize 6-oxa-5alpha-pregnanes with and without functionalization at C-19.     

Detection and quantitation of sulfonylurea herbicides in soil at the ppb level by capillary electrophoresis

A multi-residue analytical method based on solid-phase extraction enrichment combined with capillary electrophoresis (CE), using micellar electrokinetic capillary chromatography, was developed to isolate, recover and quantitate three sulfonylurea herbicides (chlorsulfuron, chlorimuron and metasulfuron) from soil samples. Optimization for CE separation was achieved using an overlapping resolution map scheme. The recovery of each herbicide was >80% and the limit of detection was 10 ppb. The capability of CE in providing quantitative analysis of sulfonylureas in soil samples at the ppb level has been demonstrated.