Highly Emissive Self‐Trapped Excitons in Fully Inorganic Zero‐Dimensional Tin Halides

The spatial localization of charge carriers to promote the formation of bound excitons and concomitantly enhance radiative recombination has long been a goal for luminescent semiconductors. Zero‐dimensional materials structurally impose carrier localization and result in the formation of localized Frenkel excitons. Now the fully inorganic, perovskite‐derived zero‐dimensional Sn^II material Cs₄SnBr₆ is presented that exhibits room‐temperature broad‐band photoluminescence centered at 540 nm with a quantum yield (QY) of 15±5 %. A series of analogous compositions following the general formula Cs_4?xA_xSn(Br_1?yI_y)₆ (A=Rb, K; x≤1, y≤1) can be prepared. The emission of these materials ranges from 500 nm to 620 nm with the possibility to compositionally tune the Stokes shift and the self‐trapped exciton emission bands.     

Hereditary nonpolyposis colorectal cancer: an approach to the selection of candidates to genetic testing based on clinical and molecular characteristics

OBJECTIVE: Identification of clinical and molecular characteristics associated with constitutional MLH1 and MSH2 mutations and definition of a stepwise strategy for the selection of colorectal cancer (CRC) patients amenable to MLH1 and MSH2 genetic testing. METHODS: 90 unrelated CRC patients were initially selected on the basis of either familial or early onset occurrence of CRC. They were screened for the presence of constitutional MLH1 and MSH2 mutations and for microsatellite instability (MSI). RESULTS: 16 pathogenetic mutations (9 MLH1 and 7 MSH2) were identified in 41% of Amsterdam hereditary nonpolyposis colorectal cancer (HNPCC) families, 5% of suspected HNPCC families, and 14% of sporadic early-onset CRC patients. The presence of the mutations correlated with MSI, with early age of onset and proximal location of the tumor, and with the presence of some extracolonic tumors of the HNPCC spectrum and/or multiple tumors in the family. CONCLUSIONS: Evaluation of clinical and molecular characteristics is useful for the identification of candidates to MLH1 and MSH2 mutational analysis and allows the application of a rational approach to genetic testing.     

An Extension of Itô's Formula for Anticipating Processes

In this paper we introduce a class of square integrable processes, denoted by L^F, defined in the canonical probability space of the Brownian motion, which contains both the adapted processes and the processes in the Sobolev space L^2,2. The processes in the class L^F satisfy that for any time t, they are twice weakly differentiable in the sense of the stochastic calculus of variations in points (r, s) such that r s t. On the other hand, processes belonging to the class L^F are Skorohod integrable, and the indefinite Skorohod integral has properties similar to those of the Ito integral. In particular we prove a change-of-variable formula that extends the classical Itô formula. Those results are generalization of similar properties proved by Nualart and Pardoux⁽⁷⁾ for processes in L^2,2.     

Spectroscopic,thermal, and X-ray diffraction studies of tetrakis(thiourea) palladium chloride bis (5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine dihydrate

The crystal and molecular structure of the title compound, ·[Pd(S=C(NH₂)₂)₄]Cl₂·2dmtp·2H₂O. has been determined and refined to a finalR=0.034. The cation is centrosymmetric with the Pd atom existing in a square planar geometry with two disparate Pd–S bond distances of 2.3129(9) and 2.292(1)Å. Interatomic parameters are reported for the first non-coordinated dmtp molecule; these suggest the predominance of a particular canonical form in the solid state. The lattice is stabilized via a series H-bonding contacts involving the thiourea. Cl^– and dmtp species. Crystals of [Pd(S=C(NH₂)₂)₄]Cl₂ · 2dmtp · 2H₂O are monoclinic with space groupP2₁/c, and unit cell dimensionsa=15.129(1),b=8.512(1),c=12.663(1) Å, =104.05(1)°.     

Sensitivity enhancement for the analysis of naproxen in tap water by solid-phase extraction coupled in-line to capillary electrophoresis

SPE coupled in-line to CE, as the strategy to enhance the concentration sensitivity in CE, has been used to enrich naproxen in tap water samples. In this study, a microcartridge containing an octadecyl silica (C18) sorbent was placed near the inlet within the separation capillary column. The optimum conditions were obtained when naproxen in an acidic aqueous solution (pH 3.5) was loaded into the capillary at 930 mbar for 30 min, and 20 mM ammonium acetate in methanol/water (70:30 v/v) was used as both an elution solution and a separation BGE. Under these conditions, the sensitivity was enhanced 1820-fold with respect to normal hydrodynamic injection, and the LOD achieved was 0.2 microg/L. To show the capability of the in-line SPE-CE method, tap water samples were analysed after a pretreatment consisting in an off-line C18-SPE procedure. The recovery of this procedure was higher than 80%. Under these conditions, naproxen could be detected at a concentration of 10 ng/L; so the potential of the procedure for the sensitive analysis of this type of drugs in water samples was demonstrated. Afterwards, these results were compared with those previously obtained for naproxen in water samples using different sample stacking techniques.     

Electrochemical rectification by redox-labeled bioconjugates: molecular building blocks for the construction of biodiodes

In the present work, we describe the properties of a bifunctional redox-labeled bioconjugate at electrode surfaces mediating the electron transfer across the electrode-electrolyte interface. We show that the assembly of ferrocene-labeled streptavidin on biotinylated electrodes results in a reproducible unidirectional current flow in the presence of electron donors in solution. Such rectifying films were built up by spontaneous binding of tetrameric streptavidin molecules to biotin centers immobilized on the electrode surface. Due to the high affinity of biotin to streptavidin, such bifunctional films completely bind any biotinylated compounds. The charge transport between donors in solution and the Au electrode is mediated by the ferrocene moieties, allowing us to develop a molecular rectifier. Our experimental results suggest that such redox-labeled proteins with a high binding capacity constitute a promising alternative to organic compounds used in molecular electronics.     

Investigation of the possible origins of sulfur in 19th century salted paper photographs by x‐ray fluorescence spectroscopy

An X‐ray fluorescence method to determine whether sulfur is present in 19th century photographs due to intentional toning or to environmental deterioration is proposed. In the 19th century salted paper print photographic process, AgCl formed on the surface of a sheet of paper was exposed to sunlight in contact with a negative, leading to the printing out of a Ag image that was fixed by immersing it in a sodium thiosulfate solution or hypo. The improper execution of the fixing in these photographs may result in the presence of sulfur, mostly manifested in image fading, irregular staining, and discoloration. Also, 19th century artists produced salted paper prints with a variety of image tonalities, for example, by using an artificially aged thiosulfate bath. The presence of sulfur in photographs may also be due to sulfur‐containing environmental pollutants. Therefore, knowledge about the location and amounts of sulfur is important to understand the artistic technique and/or the deterioration processes. In this study, the amounts of sulfur and the silver to sulfur signal ratios were determined for a salted paper print made in the laboratory following a 19th century procedure and for two artistic salted paper photographs using X‐ray fluorescence and standards prepared with different amounts of retained hypo and quantified by inductively coupled plasma atomic emission spectroscopy. The amounts of sulfur and the normalized silver to sulfur ratios for the artistic photographs were evaluated based on the results obtained in the samples prepared in the laboratory and in the context of the 19th century practices. Copyright © 2016 John Wiley & Sons, Ltd.