Selective oxidation of bulky organic sulphides over layered titanosilicate catalysts

The authors acknowledge the Czech Science Foundation (P106/12/G015) for the financial support.Selective oxidation of sulphides is a straightforward method of preparation of organic sulphoxides and sulphones, which are important chemical intermediates and building blocks of pharmaceuticals and agrochemicals. Oxidation of methylphenyl sulphide (MPS), diphenyl sulphide (Ph2S), and dibenzothiophene (DBTH) over lamellar titanosilicate catalysts with the MFI and UTL-derived topology was investigated with hydrogen peroxide as the oxidant. Lamellar titanosilicates combine the advantages of crystalline zeolites and mesoporous molecular sieves due to accessible active sites located on the external surface of their layers. The selectivity of the MPS oxidation to methylphenyl sulphoxide is driven by the diffusion restrictions in the catalyst. A methylphenyl sulphoxide selectivity of 95% at 40% conversion was achieved using the Ti-IPC-1-PI catalyst together with an outstanding TONtot = 1418 after 30 min. The selectivity can be adjusted also by dosing of the oxidant to keep its concentration low during the reaction. The silica-titania pillared TS-1-PITi catalyst showed the highest potential of the tested catalysts in oxidative desulphuration, easily oxidising the DBTH to dibenzothiothene sulphone.PostprintPeer reviewe

Raman Spectroscopic and SEM Analysis of Sodium-Zippeite

Raman at 298 and 77 K and infrared spectra of two samples of sodium-zippeite were studied and interpreted. U-O bond lengths in uranyl were calculated and compared with those inferred from the X-ray single crystal structure data of a synthetic sodium-zippeite analog. Hydrogen-bonding network in the studied samples is discussed. O-H…O bond lengths were calculated and compared with those predicted from the X-ray single crystal structure analysis

Selective oxidation of bulky organic sulphides over layered titanosilicate catalysts

The authors acknowledge the Czech Science Foundation (P106/12/G015) for the financial support.Selective oxidation of sulphides is a straightforward method of preparation of organic sulphoxides and sulphones, which are important chemical intermediates and building blocks of pharmaceuticals and agrochemicals. Oxidation of methylphenyl sulphide (MPS), diphenyl sulphide (Ph2S), and dibenzothiophene (DBTH) over lamellar titanosilicate catalysts with the MFI and UTL-derived topology was investigated with hydrogen peroxide as the oxidant. Lamellar titanosilicates combine the advantages of crystalline zeolites and mesoporous molecular sieves due to accessible active sites located on the external surface of their layers. The selectivity of the MPS oxidation to methylphenyl sulphoxide is driven by the diffusion restrictions in the catalyst. A methylphenyl sulphoxide selectivity of 95% at 40% conversion was achieved using the Ti-IPC-1-PI catalyst together with an outstanding TONtot = 1418 after 30 min. The selectivity can be adjusted also by dosing of the oxidant to keep its concentration low during the reaction. The silica-titania pillared TS-1-PITi catalyst showed the highest potential of the tested catalysts in oxidative desulphuration, easily oxidising the DBTH to dibenzothiothene sulphone.PostprintPeer reviewe

DNA end resection by Dna2–Sgs1–RPA and its stimulation by Top3–Rmi1 and Mre11–Rad50–Xrs2

The repair of DNA double-strand breaks (DSBs) by homologous recombination requires processing of broken ends. For repair to start, the DSB must first be resected to generate a 3′-single-stranded DNA (ssDNA) overhang, which becomes a substrate for the DNA strand exchange protein, Rad51 (ref. 1). Genetic studies have implicated a multitude of proteins in the process, including helicases, nucleases and topoisomerases. Here we biochemically reconstitute elements of the resection process and reveal that it requires the nuclease Dna2, the RecQ-family helicase Sgs1 and the ssDNA-binding protein replication protein-A (RPA). We establish that Dna2, Sgs1 and RPA constitute a minimal protein complex capable of DNA resection in vitro. Sgs1 helicase unwinds the DNA to produce an intermediate that is digested by Dna2, and RPA stimulates DNA unwinding by Sgs1 in a species-specific manner. Interestingly, RPA is also required both to direct Dna2 nucleolytic activity to the 5′-terminated strand of the DNA break and to inhibit 3′ to 5′ degradation by Dna2, actions that generate and protect the 3′-ssDNA overhang, respectively. In addition to this core machinery, we establish that both the topoisomerase 3 (Top3) and Rmi1 complex and the Mre11–Rad50–Xrs2 complex (MRX) have important roles as stimulatory components. Stimulation of end resection by the Top3–Rmi1 heterodimer and the MRX proteins is by complex formation with Sgs1 (refs 5, 6), which unexpectedly stimulates DNA unwinding. We suggest that Top3–Rmi1 and MRX are important for recruitment of the Sgs1–Dna2 complex to DSBs. Our experiments provide a mechanistic framework for understanding the initial steps of recombinational DNA repair in eukaryotes

Reshaping cortical activity with subthalamic stimulation in Parkinson's disease during finger tapping and gait mapped by near infrared spectroscopy

Exploration of motor cortex activity is essential to understanding the pathophysiology in Parkinson's Disease (PD), but only simple motor tasks can be investigated using a fMRI or PET. We aim to investigate the cortical activity of PD patients during a complex motor task (gait) to verify the impact of deep brain stimulation in the subthalamic nucleus (DBS-STN) by using Near-Infrared-Spectroscopy (NIRS). NIRS is a neuroimaging method of brain cortical activity using low-energy optical radiation to detect local changes in (de)oxyhemoglobin concentration. We used a multichannel portable NIRS during finger tapping (FT) and gait. To determine the signal activity, our methodology consisted of a pre-processing phase for the raw signal, followed by statistical analysis based on a general linear model. Processed recordings from 9 patients were statistically compared between the on and off states of DBS-STN. DBS-STN led to an increased activity in the contralateral motor cortex areas during FT. During gait, we observed a concentration of activity towards the cortex central area in the "stimulation-on" state. Our study shows how NIRS can be used to detect functional changes in the cortex of patients with PD with DBS-STN and indicates its future use for applications unsuited for PET and a fMRI

The Mre11-Nbs1 Interface Is Essential for Viability and Tumor Suppression

The Mre11 complex (Mre11, Rad50, and Nbs1) is integral to both DNA repair and ataxia telangiectasia mutated (ATM)-dependent DNA damage signaling. All three Mre11 complex components are essential for viability at the cellular and organismal levels. To delineate essential and non-essential Mre11 complex functions that are mediated by Nbs1, we used TALEN-based genome editing to derive Nbs1 mutant mice (Nbs1mid mice), which harbor mutations in the Mre11 interaction domain of Nbs1. Nbs1mid alleles that abolished interaction were incompatible with viability. Conversely, a 108-amino-acid Nbs1 fragment comprising the Mre11 interface was sufficient to rescue viability and ATM activation in cultured cells and support differentiation of hematopoietic cells in vivo. These data indicate that the essential role of Nbs1 is via its interaction with Mre11 and that most of the Nbs1 protein is dispensable for Mre11 complex functions and suggest that Mre11 and Rad50 directly activate ATM

Dussertite BaFe3+3(AsO4)2(OH)5 : a Raman spectroscopic study of a hydroxy-arsenate mineral

The mineral dussertite, a hydroxy-arsenate mineral of formula BaFe3+3(AsO4)2(OH)5, has been studied by Raman complimented with infrared spectroscopy. The spectra of three minerals from different origins were investigated and proved quite similar, although some minor differences were observed. In the Raman spectra of Czech dussertite, four bands are observed in the 800 to 950 cm-1 region. The bands are assigned as follows: the band at 902 cm-1 is assigned to the (AsO4)3- ν3 antisymmetric stretching mode, at 870 cm-1 to the (AsO4)3- ν1 symmetric stretching mode, and both at 859 cm-1 and 825 cm-1 to the As-OM2+/3+ stretching modes/and or hydroxyls bending modes. Raman bands at 372 and 409 cm-1 are attributed to the ν2 (AsO4)3- bending mode and the two bands at 429 and 474 cm-1 are assigned to the ν4 (AsO4)3- bending mode. An intense band at 3446 cm-1 in the infrared spectrum and a complex set of bands centred upon 3453 cm-1 in the Raman spectrum are attributed to the stretching vibrations of the hydrogen bonded (OH)- units and/or water units in the mineral structure. The broad infrared band at 3223 cm-1 is assigned to the vibrations of hydrogen bonded water molecules. Raman spectroscopy identified Raman bands attributable to (AsO4)3- and (AsO3OH)2- units