Redox-photosensitized aminations of 1,2-benzo-1,3-cycloalkadienes, arylcyclopropanes, and quadricyclane with ammonia

1,2,4-Triphenylbenzene and 2,2'-methylenedioxy-1,1'-binaphthalene successfully photosensitized the aminations of 1,2-benzo-1,3-cycloalkadienes, arylcyclopropanes, and quadricyclane with ammonia and primary amines in the presence of m- or p-dicyanobenzene, which gave the 4-amino-1,2-benzocycloalkenes, 3-amino-1-arylpropanes, and 7-amino-5-(p-cyanophenyl)bicyclo[2.2.1]hept-2-ene, respectively. A key pathway for the photosensitized amination is the hole transfer from the cation radicals of the sensitizers that were generated by photoinduced electron transfer to the electron acceptors to the substrates. Therefore, it was found that the relationships in oxidation potentials between the sensitizers and the substrates and the positive charge distribution of the cation radicals of the substrates were important factors for the efficient amination.     

High-resolution laser ablation inductively coupled plasma mass spectrometry used to study transport of metallic nanoparticles through collagen-rich microstructures in fibroblast multicellular spheroids

We have efficiently produced collagen-rich microstructures in fibroblast multicellular spheroids (MCSs) as a three-dimensional in vitro tissue analog to investigate silver (Ag) nanoparticle (NP) penetration. The MCS production was examined by changing the seeding cell number (500 to 40,000 cells) and the growth period (1 to 10 days). MCSs were incubated with Ag NP suspensions with a concentration of 5 μg mL⁻¹ for 24 h. For this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to visualize Ag NP localization quantitatively. Thin sections of MCSs were analyzed by LA-ICP-MS with a laser spot size of 8 μm to image distributions of ¹⁰⁹Ag, ³¹P, ⁶³Cu, ⁶⁶Zn, and ⁷⁹Br. A calibration using a NP suspension was applied to convert the measured Ag intensity into the number of NPs present. The determined numbers of NPs ranged from 30 to 7200 particles in an outer rim of MCS. The particle distribution was clearly correlated with the presence of ³¹P and ⁶⁶Zn and was localized in the outer rim of proliferating cells with a width that was equal to about twice the diameter of single cells. Moreover, abundant collagens were found in the outer rim of MCSs. For only the highest seeding cell number, NPs were completely captured at the outer rim, in a natural barrier reducing particle transport, whereas Eosin (⁷⁹Br) used as a probe of small molecules penetrated into the core of MCSs already after 1 min of exposure.

Fibroblast MCS could build up the barrier only for nanoparticles

     

Microwave spectroscopy of platinum monofluoride and platinum monochloride in the X 2Π(3/2) states

Platinum monofluoride (PtF) and platinum monochloride (PtCl) were detected in the gas phase using a source-modulated microwave spectrometer. The PtF and PtCl radicals were generated in a free space cell using the sputtering reaction from a platinum sheet placed on the inner surface of a stainless steel cathode through a dc glow discharge plasma of CF(4) and Cl(2), respectively, diluted with Ar. Rotational transitions were measured in the region between 150 and 313 GHz. Rotational, centrifugal distortion, and several fine- and hyperfine-structure constants were determined by a least-squares analysis. The observed fine-structure spectral patterns indicate that both PtF and PtCl radicals have the (2)Π(3/2) electronic ground states, while the related cyanide PtCN and hydride PtH radicals have the (2)Δ(5/2) electronic ground states.     

Synthesis of (−)‐Morphine: Application of Sequential Claisen/Claisen Rearrangement of an Allylic Vicinal Diol

A detailed exploration of the synthesis of (?)‐morphine based on sequential [3,3]‐sigmatropic rearrangements is described. The sequential Claisen/Claisen rearrangements of an allylic vicinal diol resulted in the stereoselective formation of the two contiguous carbon centers, including a sterically encumbered quaternary carbon, in a single operation. The two ethyl esters generated in this reaction were successfully differentiated during a subsequent Friedel–Crafts‐type cyclization. The (?)‐morphine double bond was introduced at a late stage in our first‐generation synthesis, but was formed at an earlier stage in the second‐generation synthesis, resulting in a more efficient route to the end product.     

Duality for a class of nondifferentiable mathematical programming problems

Two dual problems are proposed for the minimax problem: minimize max_y?Yφ(x, y), subject to g(x) ? 0. A duality theorem is established for each dual problem. It is revealed that these problems are intimately related to a class of nondifferentiable programming problems.     

Biexponential apparent diffusion coefficients in prostate cancer

Purpose

The purpose of this study was to investigate the need for biexponential signal decay modeling for prostate cancer diffusion signal decays with b-factor over an extended b-factor range.

Materials and Methods

Ten healthy volunteers and 12 patients with a bulky prostate cancer underwent line scan diffusion-weighted MR imaging in which b-factors from 0 to 3000 s/mm² in 16 steps were sampled. The acquired signal decay curves were fit with both monoexponential and biexponential signal decay functions and a statistical comparison between the two fits was performed.

Results

The biexponential model provided a statistically better fit over the monoexponential model on the peripheral zone (PZ), transitional zone (TZ) and prostate cancer. The fast and slow apparent diffusion coefficients (ADCs) in the PZ, TZ and cancer were 2.9±0.2, 0.7±0.2×10⁻³ mm²/ms (PZ); 2.9±0.4, 0.7±0.2×10⁻³ mm²/ms (TZ); and 1.7±0.4, 0.3±0.1×10⁻³ mm²/ms (cancer), respectively. The apparent fractions of the fast diffusion component in the PZ, TZ and cancer were 70±10%, 60±10% and 50±10%, respectively. The fast and slow ADCs of cancer were significantly lower than those of TZ and PZ, and the apparent fraction of the fast diffusion component was significantly smaller in cancer than in PZ.

Conclusions

Biexponential diffusion decay functions are required for prostate cancer diffusion signal decay curves when sampled over an extended b-factor range, providing additional, unique tissue characterization parameters for prostate cancer.     

Photomagnetic effect in molecular magnets based on nitrosyl complexes of ruthenium and rare-earth ions

The magnetic properties of new bifunctional molecular magnets based on nitrosyl complexes of ruthenium and thiacalix[4]arenes of rare-earth ions (Gd³⁺, Dy³⁺) have been investigated. A photoinduced decrease in the magnetization of the molecular magnet with rare-earth ions Gd³⁺ and the absence of a photomagnetic effect in crystals with rare-earth ions Dy³⁺ have been revealed at a temperature of 2 K. It has been found that, in the sample containing Dy³⁺ ions, the magnetization deviates by 6% from the calculated value for noninteracting ions. A comparison of the results obtained for two groups of isostructural samples, which differ only in the type of rare-earth ions, has demonstrated that the observed deviation of the magnetization is caused by the interaction of the orbital moment of the Dy³⁺ ions with the crystal field.