Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)] is reported. Grinding of the complex induced a photoluminescent color change, which was restored by exposure to a solvent. This cycle was repeated 20 times with no color degradation in the emissions. Their optical properties, X-ray crystallographic analysis, IR, and XRD measurements strongly suggested that the change in the molecular arrangement is responsible for this mechanochromic property. Intermolecular aurophilic bondings presumably play a key role in the altered emission.     

A highly efficient hybrid method for calculating the hydration free energy of a protein

We develop a new method for calculating the hydration free energy (HFE) of a protein with any net charge. The polar part of the energetic component in the HFE is expressed as a linear combination of four geometric measures (GMs) of the protein structure and the generalized Born (GB) energy plus a constant. The other constituents in the HFE are expressed as linear combinations of the four GMs. The coefficients (including the constant) in the linear combinations are determined using the three‐dimensional reference interaction site model (3D‐RISM) theory applied to sufficiently many protein structures. Once the coefficients are determined, the HFE and its constituents of any other protein structure are obtained simply by calculating the four GMs and GB energy. Our method and the 3D‐RISM theory give perfectly correlated results. Nevertheless, the computation time required in our method is over four orders of magnitude shorter.     

Palladium-catalyzed anti-hydrothiolation of 1-alkynylphosphines

[structure: see text]. Treatment of 1-alkynylphosphine with thiol in the presence of a catalytic amount of palladium acetate results in regio- and stereoselective anti-hydrothiolation, yielding the corresponding (Z)-1-phosphino-2-thio-1-alkene.     

Palladium-catalyzed direct arylation of aryl(azaaryl)methanes with aryl halides providing triarylmethanes

Direct arylation of aryl(azaaryl)methanes with aryl halides takes place at the benzylic position in the presence of a hydroxide base under palladium catalysis to yield triarylmethanes.     

Nickel-catalyzed 1,4-addition of trialkylboranes to alpha,beta-unsaturated esters: dramatic enhancement by addition of methanol

[reaction: see text] Nickel catalyst systems for 1,4-addition of trialkylboranes to alpha,beta-unsaturated esters have been developed. Addition of methanol was found to be essential for the alkylation reaction with 9-alkyl-9-BBNs.     

N-heterocyclic carbene ligands in cobalt-catalyzed sequential cyclization/cross-coupling reactions of 6-halo-1-hexene derivatives with Grignard reagents

[reaction: see text] N-Heterocyclic carbene/cobalt systems effectively catalyze sequential cyclization/cross-coupling reactions of 6-halo-1-hexene derivatives with trialkylsilylmethyl and 1-alkynyl Grignard reagents, which phosphine and amine ligands did not promote.     

Hybrid molecular material exhibiting single-molecule magnet behavior and molecular conductivity

Two unique materials based on Mn4 single-molecule magnet (SMM) clusters (ST=9) and integer or non-integer average valent platinum maleonitriledithiolate (mnt2-) complexes, [{MnII2MnIII2(hmp)6(MeCN)2}{Pt(mnt)2}2][Pt(mnt)2]2.2MeCN (1) and [{MnII2MnIII2(hmp)6(MeCN)2}{Pt(mnt)2}4][Pt(mnt)2]2 (2), were synthesized by the material diffusion method and electrochemical oxidation, respectively (hmp-=2-hydroxymethylpyridinate). 1 and 2 are comprised of four and six [Pt(mnt)2]n- units, respectively, in addition to a common MnII2MnIII2 double-cuboidal unit, [MnII2MnIII2(hmp)6(MeCN)2]4+ (hereinafter [Mn4]4+). Among the [Pt(mnt)2]n- units, two units in 1 and four units in 2 are coordinated with the [Mn4]4+ unit, forming a 1D chain of {-[Mn4]-[Pt(mnt)2]2-} for 1 and a discrete subunit of {[Pt(mnt)2]2-[Mn4]-[Pt(mnt)2]2} for 2. The other two [Pt(mnt)2]n- units, occupying void space of the packing, form a stacking column with the coordinating [Pt(mnt)2]n- units, finally constructing hybrid frames of aggregates consisting of [Mn4]4+ units and [Pt(mnt)2]n- units. Electronic conductivity measurements revealed that 1 is an insulator and 2 is a semiconductor with sigma=0.22 S.cm(-1) at room temperature and an activation energy of 136 meV. Detailed magnetic measurements proved that the [Mn4]4+ units in 1 and 2 behave as SMMs with an ST=9 ground state at low temperatures. There is no significant interaction between [Mn4]4+ units and [Pt(mnt)2]n- units, but interactions between localized spins of [Pt(mnt)2]n- were detected even in 2 at low temperatures where the conductivity is electronically insulated. 2 is the first example of a hybridized material exhibiting SMM behavior and electronic conductivity.     

Preparation of rapidly disintegrating tablets containing itraconazole solid dispersions

The disintegratability of tablets prepared from two types of solid dispersions containing the water-soluble polymer TC-5 and the enteric polymer HP-55 as an excipient were compared. The disintegratability was better in the tablets of solid dispersions containing non-water-soluble HP-55 than those containing TC-5. In consideration of the dissolubility of solid dispersions containing HP-55, the mean diameter of the solid dispersion (coating powder) must be controlled to 120 microm or less, but as this markedly increases the adhesion/aggregation tendency of the particles (angle of repose: 47 degrees ), control of the adhesion/aggregation tendency emerged as another problem. Therefore, surface-modification was performed in a high-speed agitating granulator using 0.1% light anhydrous silicic acid as a surface modifier, and marked improvement in the flowability was observed. This made continuous tableting using a rotary tablet machine possible even with the poorly flowable solid dispersions. Also, in tableting of the solid dispersions, no recrystallization of amorphous itraconazole by the tableting pressure was observed, and the tablets maintained satisfactory dissolubility. Moreover, it was possible to obtain the rapidly disintegrating tablets with very satisfactory properties, i.e., a tablet hardness of 30 N or higher and a disintegration time of 30 s or less, by the addition of croscarmellose as a disintegrant at 2% to the surface-modified solid dispersion and selection of the tableting pressure at 4.5 kN.