Photochemical reactions of substituted cyclobutadieneiron tricarbonyl complexes with acetylenes

When mixtures of monosubstituted cyclobutadieneiron tricarbonyl complexes and propyne are irradiated, substituted toluenes are obtained. The composition of the isomeric mixture is influenced by the nature of the substituent in the metal complex. Electron-withdrawing groups produce mixtures containing a very large percent of the ortho isomer while electron-releasing groups yield mixtures rich in the para isomer. Complex mixtures of isomeric benzene compounds are obtained when substituted acetylenes are allowed to react with methyl- or isopropylcyclobutadieneiron tricarbonyl.     

Reducing reflected contributions to ear-canal distortion product otoacoustic emissions in humans

Distortion product otoacoustic emission (DPOAE) fine structure has been attributed to the interaction of two cochlear-source mechanisms (distortion and reflection sources). A suppressor presented near the 2f1-f2 frequency reduces the reflection-source contribution and, therefore, DPOAE fine structure. Optimal relationships between stimulus and suppressor conditions, however, have not been described. In this study, the relationship between suppressor level (L3) and stimulus level (L2) was evaluated to determine the L3 that was most effective at reducing fine structure. Subjects were initially screened to find individuals who produced DPOAE fine structure. A difference in the prevalence of fine structure in two frequency intervals was observed. At 2 kHz, 11 of 12 subjects exhibited fine structure, as compared to 5 of 22 subjects at 4 kHz. Only subjects demonstrating fine structure participated in subsequent measurements. DPOAE responses were evaluated in 1/3-octave intervals centered at 2 or 4 kHz, with 4 subjects contributing data at each interval. Multiple L3's were evaluated for each L2, which ranged from 20 to 80 dB SPL. The results indicated that one or more L3's at each L2 were roughly equally effective at reducing DPOAE fine structure. However, no single L3 was effective at all L2's in every subject.     

Synthesis and characterization of glucosamine-bound near-infrared probes for optical imaging

[structure: see text] Two novel near-infrared (NIR) fluorescent probes have been synthesized by linking a carbocyanine fluorophore and glucosamine through different linkers. These probes demonstrated a high quantum yield, low cytotoxicity, reversible pH-dependent fluorescence in the physiological pH range, and a decreased aggregation tendency in aqueous solutions. In vitro NIR optical imaging studies revealed cellular uptake and strong intracellular NIR fluorescence of these two probes in four breast epithelial cell lines.     

Resolutions of monomial almost complete intersections and generalizations

Let S=K[x₁,…,x_n] be a polynomial ring over a field kand let / be a monomial ideal of S. The main result of this paper is an explicit minimal resolution of kover R= S/Iwhen / is a monomial almost complete intersection ideal of S. We also compute an upper bound on the multigraded resolution of k over a generalization of monomial almost complete intersection ring.     

A Chemiluminescent Probe for HNO Quantification and Real‐Time Monitoring in Living Cells

Azanone (HNO) is a reactive nitrogen species with pronounced biological activity and high therapeutic potential for cardiovascular dysfunction. A critical barrier to understanding the biology of HNO and furthering clinical development is the quantification and real‐time monitoring of its delivery in living systems. Herein, we describe the design and synthesis of the first chemiluminescent probe for HNO, HNOCL‐1 , which can detect HNO generated from concentrations of Angeli's salt as low as 138 nm with high selectivity based on the reaction with a phosphine group to form a self‐cleavable azaylide intermediate. We have capitalized on this high sensitivity to develop a generalizable kinetics‐based approach, which provides real‐time quantitative measurements of HNO concentration at the picomolar level. HNOCL‐1 can monitor dynamics of HNO delivery in living cells and tissues, demonstrating the versatility of this method for tracking HNO in living systems.     

A Metallaphotoredox Strategy for the Cross‐Electrophile Coupling of α‐Chloro Carbonyls with Aryl Halides

Here, we demonstrate that a metallaphotoredox‐catalyzed cross‐electrophile coupling mechanism provides a unified method for the α‐arylation of diverse activated alkyl chlorides, including α‐chloroketones, α‐chloroesters, α‐chloroamides, α‐chlorocarboxylic acids, and benzylic chlorides. This strategy, which is effective for a wide variety of aryl bromide coupling partners, is predicated upon a halogen atom abstraction/nickel radical‐capture mechanism that is generically successful across an extensive range of carbonyl substrates. The construction and use of arylacetic acid products have further enabled two‐step protocols for the delivery of valuable building blocks for medicinal chemistry, such as aryldifluoromethyl and diarylmethane motifs.     

Functionalization of Polyethyleneimine with Hollow Cyclotriveratrylene and Its Subsequent Supramolecular Interaction with Doxorubicin

In this paper, a modified Cyclotriveratrylene was synthesized and linked to a branched Polyethylenimine, and this unique polymeric material was subsequently examined as a potential supramolecular carrier for Doxorubicin. Spectroscopic analysis in different solvents had shown that Doxorubicin was coordinated within the hollow-shaped unit of the armed Cyclotriveratrylene, and the nature of the host–guest complex revealed intrinsic Van der Waals interactions and hydrogen bonding between the host and guest. The strongest interaction was detected in water because of the hydrophobic effect shared between the aromatic groups of the Doxorubicin and Cyclotriveratrylene unit. Density functional theory calculations had also confirmed that in the most stable coordination of Doxorubicin with the cross-linked polymer, the aromatic rings of the Doxorubicin were localized toward the Cyclotriveratrylene core, while its aliphatic chains aligned closer with amino groups, thus forming a compact supramolecular assembly that may confer a shielding effect on Doxorubicin. These observations had emphasized the importance of supramolecular considerations when designing a novel drug delivery platform.     

Transition‐Metal‐Free Reductive Hydroxymethylation of Isoquinolines

A transition‐metal‐free reductive hydroxymethylation reaction has been developed, enabling the preparation of tetrahydroisoquinolines bearing C4‐quaternary centers from the corresponding isoquinolines. Deuterium labelling studies and control experiments enable a potential mechanism to be elucidated which features a key Cannizzaro‐type reduction followed by an Evans–Tishchenko reaction. When isoquinolines featuring a proton at the 4‐position are used, a tandem methylation‐hydroxymethylation occurs, leading to the formation of 2 new C?C bonds in one pot.