Ferromagnetic 2p-2p and 4f-2p Couplings in a Macrocycle from Two Biradicals and Two Gadolinium(III) Ions

A new ground triplet biradical 2′,4′,6′-triisopropylbiphenyl-3,5-diyl bis(tert-butyl nitroxide) (iPr₃BPBN) was prepared and characterized by means of room-temperature ESR spectroscopy displaying a zero-field splitting pattern together with a half-field signal. Complex formation with gadolinium(III) 1,1,1,5,5,5-hexafluoropentane-2,4-dionate (hfac) afforded a macrocycle [{Gd(hfac)₃(μ-iPr₃BPBN)}₂]. As the X-ray crystallographic analysis clarified, the biradical serves as a bridging ligand, giving a 16-membered ring, where each nitroxide radical oxygen atom is directly bonded to a Gd³⁺ ion. The magnetic study revealed that the iPr₃BPBN bridge behaved as a practically triplet biradical and that the Gd³⁺-radical magnetic coupling was weakly ferromagnetic. The exchange parameters were estimated as 2j_rad-rad/k_B > 300 K and 2J_Gd-rad/k_B = 1.2 K in the H = −2J S₁•S₂ convention. The DFT calculation based on the atomic coordinates clarified the ground triplet nature in metal-free iPr₃BPBN and the enhanced triplet character upon coordination. The calculation also suggests that ferromagnetic coupling would be favorable when the Gd-O-N-C(sp²) torsion comes around 100°. The present results are compatible with the proposed magneto-structure relationship on the nitroxide-Gd compounds.     

Synthesis of pyranopyrazoles using nano‐Fe‐[phenylsalicylaldiminemethylpyranopyrazole]Cl2 as a new Schiff base complex and catalyst

By the condensation reaction of benzaldehyde with ethyl acetoacetate, malononitrile and hydrazine hydrate in the presence of FeCl₂, a pyranopyrazole derivative was prepared which was then reacted with salicylaldehyde to afford nano‐Fe‐[phenylsalicylaldiminemethylpyranopyrazole]Cl₂ (nano‐[Fe‐PSMP]Cl₂). The prepared nano‐Schiff base complex was fully characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, differential thermogravimetry, scanning electron microscopy and UV–visible spectroscopy, and was used as an efficient and catalyst for the preparation of pyranopyrazoles.     

The Effects of Side-Chain Configurations of a Retro–Inverso-Type Inhibitor on the Human T-Cell Leukemia Virus (HTLV)-1 Protease

In this study, the effects of side-chain configurations of D-Ile residues of a retro–inverso (RI)-type inhibitor on the human T-cell leukemia virus type 1 (HTLV-1) protease containing a hydroxyethylamine dipeptide isostere were clarified. Prior to evaluation using the RI-type inhibitor, the effects of side-chain configurations of Ile residues of the substrate peptide on the HTLV-1 protease were examined to estimate the influence of side-chain configurations on enzyme activity. Based on the estimation of the influence of side-chain configurations on protease affinity, the RI-type inhibitors containing a D-allo-Ile residue in the corresponding substrate sequence, instead of a D-Ile residue, were synthesized via 9-fluorenylmethoxycarbonyl-based solid-phase peptide synthesis. Refolded recombinant HTLV-1 protease (1-116, L40I) was used for the simple and short evaluation of the inhibitory activities of the synthesized RI-type inhibitors. The results clearly indicated that mimicking the whole topology, comprising both the main- and side-chain structures of the parent inhibitor, is effective for the design of potent RI-modified protease inhibitors.     

Phosphorescence at Low Temperature by External Heavy-Atom Effect in Zinc(II) Clusters

Luminescent Zn^II clusters [Zn₄L₄(μ₃-OMe)₂X₂] (X=SCN ( 1 ), Cl ( 2 ), Br ( 3 )) and [Zn₇L₆(μ₃-OMe)₂(μ₃-OH)₄]Y₂ (Y=I⁻ ( 4 ), ClO₄⁻ ( 5 )), HL=methyl-3-methoxysalicylate, exhibiting blue fluorescence at room temperature (λ_max=416≈429 nm, Φ_em=0.09–0.36) have been synthesised and investigated in detail. In one case the external heavy-atom effect (EHE) arising the presence of iodide counter anions yielded phosphorescence with a long emission lifetime (λ_max=520 nm, τ=95.3 ms) at 77 K. Single-crystal X-ray structural analysis and time-dependent density-functional theory (TD-DFT) calculations revealed that their emission origin was attributed to the fluorescence from the singlet ligand-centred (¹LC) excited state, and the phosphorescence observed in 4 was caused by the EHE of counter anions having strong CH−I interactions.     

C60 nanocrystals thin film with controlled density

In this paper, C₆₀ nanocrystals thin film with monocrystal thickness was prepared using a liquid-liquid interface. C₆₀ nanocrystals dispersion prepared by reprecipitation method was added to n-hexane/water interface to form a thin film. The film was transferred onto an ITO substrate. Surface morphology of the film was studied by scanning electron microscope (SEM) and atomic force microscope (AFM) measurements. It was found that the density of the film increase with increasing the deposition number of layers with maintaining the monocrystal thickness.     

Synthesis and odor properties of Phantolide analogues

Phantolide analogues 1a–1d were newly synthesized to evaluate their odor profiles. The enantiomers of 1a and 1b were also synthesized. Both (S) enantiomers of 1a and 1b had musk odor although weakly, and but neither of the (R) enantiomers 1a and 1b had musk odor. During the investigations, we encountered the undesirable racemization in Friedel-Crafts reaction of the intermediate (S)-5.     

The B–C and C–C bonds as preferred electron source for H-bond and Li-bond interactions in complex pairing of C<Subscript>4</Subscript>B<Subscript>2</Subscript>H<Subscript>6</Subscript> with HF and LiH molecules

Ab initio calculations were used to analyze the interaction of C₄B₂H₆ with HF and LiH molecules at the mp2/6-311++g(2d,2p) computational level. Interaction of C₄B₂H₆ with HF results to H–F···H–C and C–B···H–F, C–C···H–F hydrogen bond as well as B–H···H–F dihydrogen bond complexes. Also interaction of C₄B₂H₆ with LiH results to B–C···LiH, C–C···LiH and B–H···LiH lithium bond as well as C–H···H–Li dihydrogen complexes. In the both cases, complexes involving interaction of HF or LiH with peripheral B–C and C–C bonds of the C₄B₂H₆ backbone have greater stabilities. The structures of complexes have been analyzed using AIM and NBO methodologies.     

Chemical preparation and characterization of fibrous poly(3-methylthiophene) decorated by TiO2 nanoparticles

In this article, we report on the chemical oxidative polymerization of 3-methylthiophene (3MTh) in a concentrated TiO₂/CHCl₃ homogeneous suspension with an oxidant/monomer mole ratio of 3 at room temperature. According to the scanning electron microscopy images, in this condition, poly(3-methylthiophene) (P3MTh) was prepared with fibrous morphology decorated by nano-dimensional TiO₂ particles. P3MTh/TiO₂ was also characterized by Fourier transform infrared spectroscopy and X-ray diffraction techniques. It was found that no aggregation of nanoparticles occurred during the polymerization process. In addition, the thermal stability of P3MTh/TiO₂ nanocomposite was investigated by thermogravimetric analysis and compared with that of an analogously prepared neat P3MTh. The thermal degradation of P3MTh in the temperature range of 300–550°C decreases significantly due to the presence of the TiO₂ nanoparticles in the polymer composite.     

Hydrodynamic control of droplet division in bifurcating microchannel and its application to particle synthesis

We describe herein a microfluidic system for active and precise control of droplet division at a bifurcation point in a microchannel. Water-in-oil or oil-in-water droplets, which were initially formed at a T-junction, were introduced into the bifurcation point, and then divided into two daughter droplets. By continuously introducing 'tuning flow' into the downstream of one of the branch channels, and by controlling the flow rates distributed into the two branch channels, the sizes of the daughter droplets could be precisely tuned. The ratio of the volumetric flow rates into the branch channels was estimated by regarding the microchannel network as a resistive circuit. In addition, we performed synthesis of monodispersed polymer particles with controlled sizes utilizing the presented system. The ability to hydrodynamically control the droplet sizes will open new possibilities not only for producing useful emulsions, but also for conducting controlled chemical and biochemical reactions in a confined space.