[Ir(3,4,7,8-Me4phen) (CH2=CH2)2Cl]: A very active catalyst precursor for hydrogen transfer from alcohols to unsaturated organic substrates

Some new complexes of the type Ir¹chel(CH₂=CH₂)₂Cl (chel = bipy; 4,4′-Me₂bipy; 4,4′-Ph₂bipy; phen; 5,6-Me₂phen; 4,7-Ph₂phen; 3,4,7,8-Me₄phen) behave as catalyst precursors for the hydrogen transfer from alcohols to ketones and Schiff bases. The most active of the complexes is the 3,4,7,8-Me₄phen derivative, which, at 83°C, gave turnovers of up to 2850 cycles/min with cyclohexanone, 2700 cycles/min with 4-tert-butylcyclohexanone and 5000 cycles/min with benzylidenaniline, at a catalyst concentration of 4 X 10⁻⁵ M and a KOH (cocatalyst) concentration of 8 X 10⁻⁴ M. Good catalytic activity was observed also at room temperature. Some catalytic activity was found at low substrate concentrations, even in the absence of KOH. The maximum stereoselectivity reached in the reduction of 4-tertbutylcyclohexanone was 97%, the trans-alcohol being formed.     

Harmonic Pinnacles in the Discrete Gaussian Model

The 2D Discrete Gaussian model gives each height function \({\eta : {\mathbb{Z}^2\to\mathbb{Z}}}\) a probability proportional to \({\exp(-\beta \mathcal{H}(\eta))}\), where \({\beta}\) is the inverse-temperature and \({\mathcal{H}(\eta) = \sum_{x\sim y}(\eta_x-\eta_y)^2}\) sums over nearest-neighbor bonds. We consider the model at large fixed \({\beta}\), where it is flat unlike its continuous analog (the Discrete Gaussian Free Field). We first establish that the maximum height in an \({L\times L}\) box with 0 boundary conditions concentrates on two integers M, M + 1 with \({M\sim \sqrt{(1/2\pi\beta)\log L\log\log L}}\). The key is a large deviation estimate for the height at the origin in \({\mathbb{Z}^{2}}\), dominated by “harmonic pinnacles”, integer approximations of a harmonic variational problem. Second, in this model conditioned on \({\eta\geq 0}\) (a floor), the average height rises, and in fact the height of almost all sites concentrates on levels H, H + 1 where \({H\sim M/\sqrt{2}}\). This in particular pins down the asymptotics, and corrects the order, in results of Bricmont et al. (J. Stat. Phys. 42(5–6):743–798, 1986), where it was argued that the maximum and the height of the surface above a floor are both of order \({\sqrt{\log L}}\). Finally, our methods extend to other classical surface models (e.g., restricted SOS), featuring connections to p-harmonic analysis and alternating sign matrices.     

Towards Enhanced MRI Performance of Tumor-Specific Dimeric Phenylboronic Contrast Agents

It is known that phenylboronic acid (PBA) can target tumor tissues by binding to sialic acid, a substrate overexpressed by cancer cells. This capability has previously been explored in the design of targeting diagnostic probes such as Gd- and ⁶⁸Ga-DOTA-EN-PBA, two contrast agents for magnetic resonance imaging (MRI) and positron emission tomography (PET), respectively, whose potential has already been demonstrated through in vivo experiments. In addition to its high resolution, the intrinsic low sensitivity of MRI stimulates the search for more effective contrast agents, which, in the case of small-molecular probes, basically narrows down to either increased tumbling time of the entire molecule or elevated local concentration of the paramagnetic ions, both strategies resulting in enhanced relaxivity, and consequently, a higher MRI contrast. The latter strategy can be achieved by the design of multimeric Gd^III complexes. Based on the monomeric PBA-containing probes described recently, herein, we report the synthesis and characterization of the dimeric analogues (Gd^III-DOTA-EN)₂-PBA and (Gd^III-DOTA-EN)₂F₂PBA. The presence of two Gd ions in one molecule clearly contributes to the improved biological performance, as demonstrated by the relaxometric study and cell-binding investigations.     

Influence of electrode composition on the second-order nonlinearity profile in thermally poled silica glass

Silica glass plates (Infrasil from Heraeus) have been thermally poled with different types of electrodes (evaporated or pressed-on) having different chemical compositions (Au, Al, n-doped Si or p-doped Si). We show for the first time to our best knowledge that the profile of the induced second-order nonlinearity strongly depends on the composition of electrodes used for the thermal poling process.     

Experimental observation of three-color optical quantum correlations

Quantum correlations among bright pump, signal, and idler beams produced by an optical parametric oscillator, all with different frequencies, are experimentally demonstrated. We show that the degree of entanglement between signal and idler fields is improved by using information on pump fluctuations. To our knowledge this is the first observation of three-color optical quantum correlations.     

Supramolecular organization of toluidine blue dye in solid amorphous phases

Toluidine blue (TB) dye molecules are intensively utilized for large-area photophysics applications such as carcinoma detection, photoinactivation of bacteria, biosensors, and photovoltaic cells. Understanding the nature of the TB aggregation state becomes an essential point of the research process in order to know the structure-function relationship and to foresee technological applications of this class of metachromatic-dye molecules. However, no structural information on toluidine blue is available in the literature, maybe because of the poor crystalline character of the aggregate. Here, we present the first structural determination of TB organic molecules using the energy dispersive X-ray diffraction technique. The investigation highlights dimeric arrangements of stacked molecules in antiparallel fashion, forming a superstructure of two dimers in a transverse arrangement. The behavior of the TB higher aggregates indicates that these dye molecules, in spite of repulsion due to similar charge (cationic dyes), undergo self-aggregation to form helical conformations.     

Quantification of myocardial viability distribution with Gd(DTPA) bolus-enhanced, signal intensity-based percent infarct mapping

Introduction

A substantial, common shortcoming of the currently used semiautomated techniques for the quantification of myocardial infarct with delayed enhancement magnetic resonance imaging is the assumption that the whole myocardial slab that corresponds to the hyperenhanced tomographic area is 100% nonviable. This assumption is, however, incorrect. To resolve this conflict, we have recently proposed the signal intensity percent-infarct mapping method and validated it in an ex vivo, canine experiment. The purpose of the current study has been the validation of the signal intensity percent-infarct mapping method in vivo, using a porcine model of reperfused myocardial infarct.

Methods

In swines (n=6), reperfused myocardial infarct was generated occluding for 90 min by an angioplasty balloon either the left anterior descending or the left circumflex coronary artery. To obtain DE images, Gd(DTPA) enhanced inversion-recovery fast gradient-echo acquisitions were carried out on day 28 after myocardial infarction. Scanning started 15 min after intravenous injection of 0.2 mmol/kg Gd(DTPA). At the end of the MRI session, the animal was sacrificed and 2,3,5-triphenyltetrazolium chloride staining was used to validate the existence and to determine the accurate size of the myocardial infarct. Tissue samples were taken and stained with hematoxylin-eosin and Masson's trichrome for histological assessment of the infarct and the periinfarct zone. The signal intensity percent-infarct mapping data were compared with corresponding data from the delayed enhancement images analyzed with SI_remote+2S.D. thresholding, and with corresponding triphenyltetrazolium-chloride staining data using Friedman's repeated measure analysis of variance on ranks.

Results

The infarct volume determined by the triphenyltetrazolium chloride, SI_remote+2S.D. and signal intensity percent-infarct mapping methods was 3.04 ml [2.74, 3.45], 13.62 ml [9.06, 18.45] and 4.27 ml [3.45, 6.33], respectively. Median infarct volume determined by SI_remote+2S.D. significantly differed from that determined by triphenyltetrazolium chloride (P<.05). The Bland-Altman overall bias was 12.49% of the volume of the left ventricle. Median infarct volume determined by signal intensity percent-infarct mapping, however, did not differ significantly (NS) from that obtained by triphenyltetrazolium chloride. Signal intensity percent-infarct mapping yielded only a 1.99% Bland-Altman overall bias of the left ventricular volume.

Conclusions

This in vivo study in the porcine reperfused myocardial infarct model demonstrates that signal intensity percent-infarct mapping is a highly accurate method for the determination of the extent of myocardial infarct. MRI images for signal intensity percent-infarct mapping are obtained with the pulse sequence of conventional delayed enhancement imaging and are acquired within clinically acceptable scanning time. This makes signal intensity percent-infarct mapping a practical method for clinical implementation.     

Thermal decomposition kinetics of PrMO<Subscript>3</Subscript> (M = Ni or Co) ceramic materials via thermogravimetry

Thermogravimetric data using the non-isothermal kinetic models of Flynn and Wall and “Model-free Kinetics” were used to determine the activation energy to study the decomposition kinetics of the ligand groups with system’s metallic ions that takes part in the synthesis of PrMO₃ (M = Ni or Co). This activation energy was determined for the stage of highest decomposition of the organic matter to establish parameters in synthesis condition optimization and application of the proposed material.     

Synthesis of (+)-dumetorine and congeners by using flow chemistry technologies

An efficient total synthesis of the natural alkaloid (+)-dumetorine by using flow technology is described. The process entailed five separate steps starting from the enantiopure (S)-2-(piperidin-2-yl)ethanol 4 with 29% overall yield. Most of the reactions were carried out by exploiting solvent superheating and by using packed columns of immobilized reagents or scavengers to minimize handling. New protocols for performing classical reactions under continuous flow are disclosed: the ring-closing metathesis reaction with a novel polyethylene glycol-supported Hoveyda catalyst and the unprecedented flow deprotection/Eschweiler-Clarke methylation sequence. The new protocols developed for the synthesis of (+)-dumetorine were applied to the synthesis of its simplified natural congeners (-)-sedamine and (+)-sedridine.