HPLC monitored synthesis of R2NCH2 substituted benzene derivatives used as (C,N)-ligands for organometallic compounds

2-(Diethylaminomethyl)phenyl bromide and 1,3-bis(dimethylaminomethyl)-benzene, useful ligands for the synthesis of hypervalent organometallic compounds, were prepared and characterized by NMR (¹H, ¹³C, 2D experiments) spectroscopy. Their synthesis was monitored by the HPLC method. The compounds were eluted on a Nucleosil 120 Si column (5 μm, 25×0.4 cm) with n-hexane at room temperature using a 1.0 ml/min flow-rate. The maximum values of absorbance for the studied compounds, excepting the diethylamine, were located in a narrow range around 212 nm, the wavelength used for their UV detection. The diethylamine was detected at 190 nm. The calibration curves are straight lines with correlation factors r>0.995. The HPLC data are in good agreement with those provided by NMR spectroscopy.     

Chemie von α-Aminonitrilen. 13. Mitteilung. Über die Bildung von 2-Oxoethyl-phosphaten (“Glycoladehyd-phosphaten”) aus rac-Oxirancarbonitril und anorganischem Phosphat und über (formale) Konstitutionelle Zusammenhänge zwischen 2-Oxoethyl-phosphaten und Oligo (hexo- und pentopyranosyl)nucleotid-Rückgraten

Chemistry of α-Aminonitriles. Formation of 2-Oxoethyl Phosphates (“Glycolaldehyde Phosphates”) from rac-Oxiranecarbonitrile and on (Formal) Constitutional Relationships between 2-Oxoethyl Phosphates and Oligo(hexo- and pentopyranosyl)nucleotide Backbones Oxiranecarbonitrile in basic acqueous solution at room temperature reacts regioselectively with inorganic phosphate to give the cyanohydrin of 2-oxoethyl phosphate (“glycolaldehyde phosphate”), a source of (the hydrate of) the free aldehyde, preferably in the presence of formaldehyde. In aqueous phosphate solution buffered to nearly neutral pH, oxiranecarbonitrile produces the phosphodiester of glycoladehyde as its bis-cyanohydrin in good yield. In contrast to mono- and dialkylation, trialkylation of phosphate with oxiranecarbonitrile is difficult, and the triester derivative is highly sensitive to hydrolysis. Glycolaldehyde phosphate per se is of prebiotic interest, since it had been shown [5] to aldomerize in basic aqueous solution regioselectively to rac-hexose 2, 4, 6-triphosphates and – in the presence of formaldehyde - mainly to rac-pentose 2, 4-diphosphates with, under appropriate conditions, rac-pentose 2, 4-diphosphates as the major reaction product. However, the question as to whether oxiranecarbonitrile itself has the potential of having been a prebiological natural constituent remains unanswered. Backbone structures of hexopyranosyl-oligonucleotides with phosphodiester linkages specifically between the positions 6′ → 4′, 6′ → 2′, or 4′ → 2′ of the sugar residues can formally be derived via the (hypothetical) aldomerization pathway, a combinatorial intermolecular aldomerization of glycoladehyde phosphate and bis(glycolaldehyde)-phosphodiester in a 1: 1 ratio. The constitutional relationships revealed by this synthetic analysis has played a decisive role as a selection criterion in the pursuit of our experimental studies toward a chemical etiology of the natural nucleic acids' structure. The Discussion in this paper delineates how the analysis contributed to the conception of the structure of p-RNA. The English Footnotes to Schemes 1–11 provide an extension of this summary.     

An efficient synthesis of acetylide/trimetal/acetylide molecular wires

Efficient syntheses are reported for incorporating trimetal units of the type M(3)(dpa)(4)(2+) (M = Cr, Co, Ni, and dpa = 2,2'-dipyridylamide) into polyalkynyl assemblies to give the prototypical bis-phenylacetylide complexes M(3)(dpa)(4)(CCPh)(2). Reactions of M(3)(dpa)(4)Cl(2) with LiCCPh have led only to mixtures of products which cocrystallize forming materials of the composition M(3)(dpa)(4)(CCPh)(x)()Cl(2)(-)(x)(). Here we report that acetonitrile complexes [M(3)(dpa)(4)(NCCH(3))(2)](PF(6))(2) react cleanly with LiCCPh in MeCN to afford the desired target molecules in 40-60% yield and in excellent purity. Isolation of the mixed ligand complex [Co(3)(dpa)(4)(NCCH(3))(CCPh)]PF(6) has been accomplished, which suggests that these reactions are stepwise and that it will be possible to synthesize mixed acetylide complexes (i.e., M(3)(dpa)(4)(CCR)(CCR')) via this method.     

On the diameter of planar curves and Fourier coefficients

Summary LetF denote a complex valued function on , which is absolutely continuous and periodic with a period 2. Its complex Fourier coefficientsc _n satisfy the inequality 2|c _n |d,n0, whered denotes the diameter of the closed planar curve defined byF. In this paper those functionsF are considered, which give equality for a specificn.

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Zusammenfassung Es seiF eine komplexwertige Funktion auf , die absolut stetig und periodisch ist mit einer Periode 2. Sie definiert eine geschlossene ebene Kurve. Zwischen ihrem Durchmesserd und den komplexen Fourierkoeffizientenc _n besteht die Ungleichung 2|c _n |d fürn0. Es werden jene FunktionenF betrachtet, für die in dieser Ungleichung, für ein gegebenesn, Gleichheit besteht.

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Dedicated to my colleague for many years, Professor Eduard Stiefel

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This research was supported in part by the National Research Council of Canada A-7339     

Regiospecific synthesis of cepanolide,a cancer chemoprotective micronutrient found in green onions

The naturally occurring γ-hydroxy-β-sulfanylbutenolide cepanolide and a range of new analogues were synthesized in concise, regiospecific manner through the combined use of 2-silyloxyfuran oxyfunctionalization and tandem thio-Michael addition/elimination.     

A row–column addressed micromachined ultrasonic transducer array for surface scanning applications

Row–column addressed arrays for ultrasonic non-destructive testing (NDT) applications are analyzed and demonstrated in this paper. Simulation and experimental results of a row–column addressed 32 by 32 capacitive micromachined ultrasonic transducer (CMUT) array are presented. The CMUT array, which was designed for medical imaging applications, has a center frequency of 5.3 MHz. The CMUT array was used to perform C-scans on test objects with holes that have diameters of 1.0 mm and 0.5 mm. The array transducer has an aperture size of 4.8 mm by 4.8 mm, and it was used to scan an area of 4.0 mm by 4.0 mm. Compared to an N by N fully addressed 2-D array, a row–column addressed array of the same number of elements requires fewer (N instead of N²) pairs of interconnection and supporting electronic components such as pulsers and amplifiers. Even though the resulting field of view is limit by the aperture size, row–column addressed arrays and the row–column addressing scheme can be an alternative option of 2-D arrays for NDT applications.     

Imaging electron trajectories in a laser-wakefield cavity using betatron X-ray radiation

We demonstrate that betatron x-ray radiation accurately provides direct imaging of electrons trajectories accelerated in laser wakefields. Experimental far field x-ray beam profiles reveal that electrons can follow similar transverse trajectories with typical excursions of 1.5 microm+/-0.5 microm in the plane of laser polarization and 0.7 microm+/-0.2 microm in the plane perpendicular.     

Synchronization reveals topological scales in complex networks

We study the relationship between topological scales and dynamic time scales in complex networks. The analysis is based on the full dynamics towards synchronization of a system of coupled oscillators. In the synchronization process, modular structures corresponding to well-defined communities of nodes emerge in different time scales, ordered in a hierarchical way. The analysis also provides a useful connection between synchronization dynamics, complex networks topology, and spectral graph analysis.     

Extrinsic multiecho phase-contrast SSFP: evaluation on cardiac output measurements

Multiecho phase-contrast steady-state free precession (PC-SSFP) is a recently introduced sequence for flow quantification. In this multiecho approach, a phase reference and a velocity-encoded readout were acquired at different echo times after a single excitation. In this study, the sequence is validated in vitro for stationary flow. Subsequently, the sequence was evaluated on cardiac output measurements in vivo for through-plane flow in comparison to regular single gradient echo velocity quantification [phase-contrast spoiled gradient echo (PC-GE)]. In vitro results agreed with regular flow meters (RMS 0.1 cm/s). Cardiac output measurements with multiecho PC-SSFP on 10 healthy subjects gave on average the same results as the standard PC-GE. However, the limits of repeatability of PC-SSFP were significantly larger than those of PC-GE (2 l/min and 0.5 l/min, respectively, P=.001). The multiecho approach introduced some specific problems in vivo. The difference in echo times made the velocity maps sensitive for water-fat shifts and B(0)-drifts, which in turn made velocity offset correction problematic. Also, the addition of a single bipolar gradient cancelled the flow compensated nature of the SSFP sequence. In combination with the prolonged TR, this resulted in flow artifacts caused by high and pulsatile through-plane flow, affecting repeatability. Given the significantly lower repeatability of PC-SSFP, cardiac output in turn is less reliable, thus impairing the use of multiecho PC-SSFP.     

Dynamic contrast-enhanced MRI and MR diffusion imaging to distinguish between glandular and stromal prostatic tissues

Purpose

To compare peak enhancement (PE), determined from dynamic contrast-enhanced (DCE) magnetic resonance imaging (MRI) and the magnetic resonance (MR) directionally-averaged apparent diffusion coefficient () in glandular versus stromal prostatic tissues and, with this comparison, to infer if the hypothesis that gadolinium-DTPA (Gd-DTPA) does not enter healthy glands or ducts is plausible.

Materials and Methods

MRI, MR spectroscopic imaging, DCE MRI and MR diffusion were evaluated in 17 untreated subjects with suspected or proven prostate cancer. PE and were compared in glandular-ductal tissues [normal peripheral zone and glandular benign prostatic hyperplasia (BPH)] and stromal-low ductal tissues (central gland/mixed BPH and stromal BPH).

Results

The glandular-ductal tissues had lower PE [125±6.4 (% baseline)] and higher [1.57±0.15 (s/10⁻³ mm²)] than the stromal-low ductal tissues [PE=132±5.5 (% baseline) (P<.0008), =1.18±0.20 (s/10⁻³ mm²) (P<1×10⁻⁸)]. A statistical model based upon stepwise regression was generated and completely separated the tissue types: ductal Measure = 448+669× (s/10⁻³ mm²)−10.7×PE (1/%), R²=1.0 and P<8×10⁻¹⁰.

Conclusions

The very different MR results in the glandular-ductal versus stromal-low ductal tissues suggest that these tissues have different underlying structure. These results support the hypothesis that Gd-DTPA does not enter healthy prostatic glands or ducts. This may explain the higher PE and lower that previously have been reported in prostate cancer versus healthy tissue.