Synthesis of iso-C-nucleoside analogues from 1-(methyl 2-O-benzyl-4,6-O- benzylidene-3-deoxy-α-D-altropyranosid-3-yl)but-3-yn-2-ones

1-(Methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-α-D-altropyranosid-3- yl)but-3-yn-2-one (3a) reacted with 3-amino-1H-1,2,4-triazole and 5-aminopyrazole-4-carboxylic acid derivatives in the presence of base to furnish the triazolo[1,5-a]pyrimidine (5) and the pyrazolo[1,5-a]pyrimidines (8a-d), respectively. Treatment of 1-(methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy- α-D-altropyranosid-3-yl)-4-phenyl-but-3-yn-2-one (3b) with cyanacetamide, 2-cyano-N-(4-methoxyphenyl)acetamide und N-aryl-3-oxo-butyramides afforded the substituted nicotinonitriles (11a-d). Furthermore, reaction of 3b with 2-benzimidazolyl-acetonitrile yielded the benz[4,5]imidazo[1,2-a]pyridine-4- carbonitrile (13). Deprotection of 8d in two steps afforded the 2-amino-N-benzyl-5-(methyl 3-deoxy-α-D-altropyranosid-3-yl-methyl) pyrazolo[1,5-a]pyrimidine-3-carboxamide (10). Compounds 5 and 11d were treated with AcOH/H2O to furnish the 5-(methyl 2-O-benzyl-3-deoxy-α-D- altropyranosid-3-yl-methyl)[1,2,4]triazolo[1,5-a]pyrimidine (6) and the 3-acetyl-1,2-dihydro-1-(4-methoxyphenyl)-6-(methyl 2-O-benzyl-3-deoxy-α-D- altropyranosid-3-yl-methyl)-4-phenylpyridin-2-one (12), respectively

3D freeform surfaces from planar sketches using neural networks

A novel intelligent approach into 3D freeform surface reconstruction from planar sketches is proposed. A multilayer perceptron (MLP) neural network is employed to induce 3D freeform surfaces from planar freehand curves. Planar curves were used to represent the boundaries of a freeform surface patch. The curves were varied iteratively and sampled to produce training data to train and test the neural network. The obtained results demonstrate that the network successfully learned the inverse-projection map and correctly inferred the respective surfaces from fresh curves

Nucleoside analogues from push-pull functionalized branched-chain pyranosides

The reaction of methyl 4,6-O-benzylidene-2-deoxy-α-D-erythro- hexopyranosid-3-ulose (1) with ethynylmagnesium bromide in tetrahydrofuran and subsequent trimethylsilylation yielded the methyl 4,6-O-benzylidene-2-deoxy-3-C- ethynyl-3-O-trimethylsilyl-α-D-ribo-hexopyranoside (3). Push-pull functionalization of 3 with N,N,N′,N′,N″,N″- hexamethylguanidinium chloride under basic conditions and following deprotection afforded the spiro{2,5-dihydro-3-dimethylamino-furan-2,8'-4',4'a,6',7',8',8'a- hexahydro-6'-methoxy-2'-phenyl-pyrano[3,2-d][1,3]dioxine}-5- ylidenemalononitrile (9). Furthermore, compound 1 reacted with N,N-dimethylformamide dimethylacetal to furnish methyl (E)-4,6-O-benzylidene-2- deoxy-2-dimethylaminomethylene-α-D-erythro-hexopyranosid-3-ulose (10). Treatment of 10 with methylhydrazine and amidines yielded (4S,5aR,8R,9aS)-2,5a, 6,9a-tetrahydro-4-methoxy-2-methyl-8-phenyl-4H-[1,3]dioxino[4',5':5,6]pyrano[4, 3-c]pyrazole (11a) and (2R,4aR,6S,10bS)-4,4a,6,10b-tetrahydro-6-methoxy-2- phenyl[1,3]dioxino[4',5':5,6]pyrano[4,3-d]pyrimidines 12, respectively. © 2006 Verlag der Zeitschrift für Naturforschung

Dimethylaminomethylene-α-D-xylo-hept-5-ulofuranurononitrile as building block in the synthesis of 'reversed' C-nucleoside analogues

3-O-Benzyl-6-deoxy-1,2-O-isopropylidene-6-(dimethylaminomethylene) -α-D-xylo-hept-5-ulofuranurononitrile (1) was reacted with amidinium salts, S-methylisothiouronium sulfate, and guanidinium chloride, respectively, in the presence of bases to furnish the 4-(3-O-benzyl-1,2-O-isopropylidene- α-D-xylo-tetrofuranos-4-yl)pyrimidine-5-carbonitriles 2 and the 4-(1,2-O-isopropylidene-α-D-glycero-tetr-3-enofuranos-4-yl) pyrimidine-5-carbonitriles 3, respectively. Treatment of 1 with ethyl 5-aminopyrazole-4-carboxylates yielded the ethyl 7-(3-O-benzyl-1,2-O- isopropylidene-α-D-xylo-tetrofuranos-4-yl)-6-cyanopyrazolo[1,5-a] pyrimidine-3-carboxylates 4 and the ethyl 7-amino-6-(3-O-benzyl-1,2-O- isopropylidene-α-D-xylo-pentofuranuronoyl)pyrazolo[1,5-a] pyrimidine-3-carboxylates 5, respectively. Reaction of 1 with 2-benzimidazolylacetonitrile in the presence of sodium methanolate afforded 1-amino-2-(3-O-benzyl-1,2-O-isopropylidene-α-D-xylo-pentofuranuronoyl) benzo[4,5]imidazo[1,2-a]pyridine-4-carbonitrile (6) and 1-amino-2-(3-deoxy-1,2- O-isopropylidene-α-D-glycero-pent-S-enofuranuronoyl)benzo[4,5]imidazo[1, 2-a]pyridine-4-carbonitrile (7). © 2006 Verlag der Zeitschrift für Naturforschung

The Spectral Properties of Pitted Impact Deposits on Vesta as Seen by the Dawn VIR Instrument

Pitted impact deposits (PIDs) on Vesta have been shown to exhibit distinct spectral characteristics with respect to their surrounding host deposits and other typical Vestan areas regarding the first major pyroxene absorption near 0.9 μm. The PIDs, especially those in the ejecta blanket of the large crater Marcia, show higher reflectance and pyroxene band strength with respect to their impact deposit surroundings. This study complements the spectral characterization of the PIDs on Vesta with Visible and Infrared Spectrometer observations obtained by NASA’s Dawn mission. In particular, we focus on the second major pyroxene absorption near 1.9 μm. We analyze nine PIDs in the ejecta blanket of the crater Marcia, as well as PIDs within the crater-fill deposits of the craters Marcia, Cornelia, and Licinia. We find that the second pyroxene absorption behaves in similar ways as the first major pyroxene absorption. The PIDs in Marcia’s ejecta blanket show higher reflectance and pyroxene band strength with respect to their immediate impact deposit surroundings. The PIDs present in the crater-fill deposits of Marcia, Cornelia, and Licinia, however, do not show such spectral characteristics. This is also consistent with previous observations of the first pyroxene absorption band. Based on the experimental results of other studies, we speculate that the observed spectral distinctness arises from an oxidation process in the interior of impact deposits, where Fe cations migrate within their host pyroxene grains. Thus, the surfaces of (melt-bearing) impact deposits might be different from their interiors, apart from space-weathering effects

Autonomous on-board data processing and instrument calibration software for the SO/PHI

The extension of on-board data processing capabilities is an attractive option to reduce telemetry for scientific instruments on deep space missions. The challenges that this presents, however, require a comprehensive software system, which operates on the limited resources a data processing unit in space allows. We implemented such a system for the Polarimetric and Helioseismic Imager (PHI) on-board the Solar Orbiter (SO) spacecraft. It ensures autonomous operation to handle long command-response times, easy changing of the processes after new lessons have been learned and meticulous book-keeping of all operations to ensure scientific accuracy. This contribution presents the requirements and main aspects of the software implementation, followed by an example of a task implemented in the software frame, and results from running it on SO/PHI. The presented example shows that the different parts of the software framework work well together, and that the system processes data as we expect. The flexibility of the framework makes it possible to use it as a baseline for future applications with similar needs and limitations as SO/PHI.Comment: Conference: SPIE Astronomical Telescopes + Instrumentatio, Software and Cyberinfrastructure for Astronomy

Chronic Sinusitis: The Empiric Treatment Strikes Back: Is CRS Directly Caused by Infectious Agent(s)?

Chronic sinusitis leads to unresolved infection and inflammation resulting in tissue remodeling, then further propagates the vicious cycle of deterioration and dysfunction of the sinuses’ natural defense mechanisms, and yet another cycle of infection and mucosal injury. Antibiotic therapy targeting pathogens classically implicated in sinusitis could augment the risk of therapeutic failure through the natural selection of resistant and/or virulent pathogens, especially in the presence of Gram-negative E. coli. Our recent demonstration of highly pathogenic E. coli, detected through intraoperative biopsy of sinus tissue, allowed the resolution of chronic sinusitis symptoms upon E. coli targeted therapy. The isolated E. coli carried three genes, each coding biofilm formation, which may, in part, account for the chronicity of E. coli sinusitis. We recommend that, patients with chronic sinusitis be considered for intraoperative biopsy for unusual pathogens, therefore allowing targeted therapy. In the future, use of vaccines and biofilm inhibitors might be an effective therapeutic consideration