Supramolecular chirogenesis in zinc porphyrins: interaction with bidentate ligands,formation of tweezer structures,and the origin of enhanced optical activity

The complexation behavior, binding properties, and spectral parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral bidentate guests (diamines and amino alcohols) have been studied by means of UV-vis, CD, fluorescence, (1)H NMR, and ESI MS techniques. It was found that the guest structure plays a decisive role in the chirogenesis pathway. The majority of bidentate ligands (except those geometrically unsuitable) exhibit two major equilibria steps: the first guest ligation leading to formation of the 1:1 host-guest tweezer structure (K(1)) and the second guest molecule ligation (K(2)) forming the anti bis-ligated species (1:2). The second ligation is much weaker (K(1) > K(2)) due to the optimal geometry and stability of the 1:1 tweezer complex. The enhanced conformational stability of the tweezer complex ensures an efficient chirality transfer from the chiral guest to the achiral host, consequently inducing a remarkably high optical activity in the bis-porphyrin.     

Heterometallic d8–d10 Coupling of Rh(I) and M(0) (M=Pd,Pt) in a Sandwich Framework of π-Conjugated Ligands

A heterometallic M−M′ bond formation is a key to construct atomically precise bimetallic clusters and materials. However, it is sometimes not straightforward to construct a heterometallic M−M′ bond through conventional methods including redox condensation. Here, we found that a sandwich framework of π-conjugated unsaturated hydrocarbon ligands provides a unique coordination environment that facilitates unusual coupling of d⁸ Rh^I and d¹⁰ M⁰ (M=Pd, Pt). The molecular orbital analysis showed that the electron-accepting ability of the sandwich framework through back-donation allows the formation of a dσ-type Rh−Pd bond in a (d–d)¹⁸ electron system.     

Development of a stable isotope dilution UPLC‐MS/MS method for quantification of dexmedetomidine in a small amount of human plasma

Dexmedetomidine (Dex) is a selective central α2‐agonist with anesthetic properties and has been used in clinical practice for sedation in the intensive care unit (ICU) after operations. In this study, an analytical assay for the determination of Dex in a small amount of plasma was developed for the application to pediatric ICU trials. The quantification of Dex was constructed using the original stable isotope Dex‐d₃ for electrospray ionization‐tandem mass spectrometry (ESI‐MS/MS) in the selected reaction monitoring mode. A rapid ultra‐performance liquid chromatography technique was adopted using ESI‐MS/MS with a runtime of 3 min. Efficacious concentration levels (50 pg/mL to 5 ng/mL) could be evaluated using a very small amount of plasma (10 μL) from patients. The lower limit of the quantification was 5 pg/mL in the plasma (100 µL). For sample preparation, a solid‐phase extraction was used along with the OASIS‐HLB cartridge type. Recovery values ranged from 98.8 to 100.3% for the intra‐ [relative standard deviation (RSD), 0.9–1.3%] and inter‐ (RSD, 0.9–1.5%) day assays. A stable test had recovery values that ranged from 97.8 to 99.7% with an RSD of 1.0–1.9% for the process/wet extract, bench‐top, freeze–thaw and long‐term tests. This method was used to measure the Dex levels in plasma from pediatric ICU patients. In the clinical ICU trial, the small amount of blood (approximate plasma volume, 200 μL) remaining from blood gas analysis was reused and targeted for the clinical analysis of Dex in plasma. Copyright © 2013 John Wiley & Sons, Ltd.     

Alkyl Derivatives of Boehmite Having the Second Stage Structure

Abstract

The reaction of aluminum alkoxide in straight-chain primary alcohols at elevated temperatures yielded the alkyl derivatives of boehmite [AlO(OH)_1-x (OR) _x ], a class of intercalation compound where the guest moieties are covalently bonded to the host boehmite layers. The addition of small amounts of water to the reaction system yielded another phase having a larger basal spacing. XRD, IR, and elemental analysis showed that the products had the boehmite layer structure with the alkyl moieties incorporated between the boehmite layers. IR spectra of the products also exhibited bands due to hydrogen bonding between the boehmite layers. These results suggest that the products are the alkyl derivatives of boehmite having the second stage structure. Because water in the reaction medium facilitated the hydrolysis of intermediate aluminum alkoxides, the product with the second stage structure had smaller alkyl/Al ratio and therefore had smaller basal spacing than that expected from the corresponding first stage product.     

Epoxidation of Allylic Alcohols with Hydrogen Peroxide Catalyzed by [PMO12O40]3-[C5H5N+(CH2)15CH3]3

Applicatims a Mo- and W-based heteropoly acids (HPA) as a catalyst in the oxidation of olefins have extensively been investigated¹. However, a patent work is only attempted concerning the evoxidatim of olefins with H₂0₂ by HPA²⁾ since the oxirane ring is cleaved because of a strong acidity of HPA itself. Herein, an effective epoxidatim of some allylic alcohols with H₂0₂ by a new Mo-species (MPCP), which was prepared from 12-molybdatophosphoric acid (H₃PMo₁₂0₄₀) and cetylpyridinium chloride (C₅H₅N (CH₂), ₁₅CH₃- C1^-) under two-phase conditions using chloroform as an organic solvent, is described.     

Crystal structures and magnetic properties of nitroxide radical-coordinated copper(II) and cobalt(II) complexes

Transition Metal Chemistry - The crystal structures and magnetic properties of three coordination compounds constructed from various nitroxide radicals L and MII(hfac)2(H2O)2 building blocks...     

Control of Axial Chirality by Planar Chirality Based on Optically Active [2.2]Paracyclophane

Optically active X-shaped molecules based on the planar chiral [2.2]paracyclophane building block were prepared, in which di(methoxy)terphenyl units were stacked on the central benzene rings. At 25 °C, anisolyl rings freely rotate in solution, while in the crystal form, they are fixed by intramolecular CH–π interactions, thereby leading to the expression of the axial chirality, i.e., propeller chirality was exhibited by the planar chiral [2.2]paracyclophane moiety. The X-shaped molecule exhibited good circularly polarized luminescence (CPL) profiles with moderate Φ_PL and a large g_lum value in the order of 10⁻³ at 25 °C, in solution. In contrast, at −120 °C, dual CPL emission with opposite signs was observed. According to the theoretical studies, the rotary motion of the anisolyl units is suppressed in the excited states, and so emission from two isomers could be observed. These results demonstrate that the axial chirality was controlled by the planar chirality, leading ultimately to propeller chirality.     

Dual Chemical Modification of a Polytheonamide Mimic: Rational Design and Synthesis of Ion‐Channel‐Forming 48‐mer Peptides with Potent Cytotoxicity

Polytheonamide B ( 1 ) is a natural peptide that displays potent cytotoxicity against P388 mouse leukemia cells (IC₅₀=0.098 nm ). Linear 48‐mer 1 is known to form monovalent cation channels on binding to lipid bilayers. We previously developed a fully synthetic route to 1 , and then achieved the design and synthesis of a structurally simplified analogue of 1 , namely, dansylated polytheonamide mimic 2 . Although the synthetically more accessible 2 was found to emulate the channel function of 1 , its cytotoxicity was decreased 120‐fold. Herein, the chemical preparation and biological evaluation of seven analogues 3 – 9 of 2 are reported. Compounds 3 – 9 were modified at their N terminus and/or the side chain of residue 44 of 2 to alter their physicochemical properties. The total synthesis of 3 – 9 was accomplished in a unified fashion by a combination of solid‐phase and solution‐phase chemistry. Systematic evaluation of the hydrophobicities, single‐channel currents, ion‐exchange activities, and cytotoxicities of 3 – 9 revealed that their hydrophobicities are correlated with the total magnitude of ion exchange and determine their cytotoxic potency. Consequently, the most hydrophobic analogue 9 exhibited the lowest IC₅₀ value, which is comparable to that of 1 . Therefore, these results clarified that the bioactivity of the polytheonamide‐based peptides can be rationally controlled by changing their hydrophobicity at the N and C termini of the 48‐amino‐acid sequence.