Synthesis and structure of 1,3,5-tris(diorganohydroxysilyl)benzenes. Novel building blocks in supramolecular silanol chemistry

The 1,3,5-tris(diorganohydroxysilyl)benzenes 1,3,5-(HOR₂Si)₃C₆H₃ (TMSB, R = Me; TPSB, R = Ph) have been prepared and fully characterized by X-ray crystallography. The crystal structure of TMSB features pairwise connected layers, in which the molecules are involved in interlayer hydrogen bonding. The supramolecular hydrogen bond motif may be described as a 12-membered ring that adopts a chair conformation. TPSB forms an equimolar inclusion complex with water, which is associated via hydrogen bonding and apparently fills a void in the crystal packing. In this case, the supramolecular hydrogen bond motif may be described as an eight-membered ring. Two of the water molecules are also associated, giving rise to a water dimer entrapped in the silanol matrix. Besides the hydrogen bonds, the crystal structure of the TPSB·H₂O complex reveals intra- and intermolecular C-H··· π stacking of most of the phenyl groups. Electrospray mass spectrometry shows that TPSB undergoes supramolecular complex formation with a variety of N-donors such as 4-(dimethylamino)pyridine, N,N,N',N'-tetramethylethylenediamine, imidazole, 2-(dimethylamino)pyridine, and 2,2'-dipyridylamine.

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Permian brachiopods from the Baoshan and Simao Blocks in Western Yunnan, China

This paper describes and illustrates four Permian brachiopod assemblages (Assemblages A–D) from western Yunnan, southwest China. Assemblage A occurs in the basal part of the Yongde Formation in the Xiaoxinzhai section in the southern Baoshan Block and is assignable to the latest Artinskian or earliest Kungurian. Assemblage B occurs about 50 m stratigraphically above Assemblage A in the same section, and is of Chihsian (Kungurian–Roadian) age. Assemblage C was collected from the Yongde Formation in the Anpaitian section in the southern Baoshan Block and is most likely Roadian to Wordian in age. Assemblage D came from the Longtan Formation in the Simao Block and is of late Wuchiapingian in age. The brachiopod faunas from the Yongde Formation of the Baoshan Block, as a whole, is dominated by species characteristic of the Cathaysian Province, although some links with Peri-Gondwanan faunas are also evident. In contrast, Assemblage D from the Simao Block is characterised exclusively by taxa of the Cathaysian Province. New taxa described and illustrated are Neochonetes (Huangichonetes) inflatus n. sp. Costatumulus minor n. sp. and Celebetus yunnanensis n. sp.

Novel organotin and organotellurium complexes : building blocks for new materials?

The research produced a series of novel oranotin and organotellurium compounds that are potential building blocks for new materials. In particular, one carbonate cluster has practical applications in the fixation and recovery of carbon dioxide gas from the atmosphere.

Cracking and distortion of water jackets in engine blocks

This thesis investigated the cracking and distortion of water jackets in engine blocks. The Taguchi method was utilized to improve production process and in doing so, reducing the scrap of water jacket cores by over 60%. Further, by altering core material and pouring temperature, casting distortion was improved.

Polymeric colorants: Statistical copolymers of indigo building blocks with defined structures

Statistical copolymers of indigo (1a) and N-acetylindigo (1b) building blocks with defined structures were studied. They belong to the class of polymeric colorants. The polymers consist of 5,5′-connected indigo units with keto structure and N-acetylindigo units with uncommon tautomeric indoxyl/indolone (=1H-indol-3-ol/3H-indol-3-one) structure (see 2a and 2b in Fig. 1). They formed amorphous salts of elongated monomer lengths as compared to monomeric indigo. The polymers were studied by various spectroscopic and physico-chemical methods in solid state and in solution. As shown by small-angle-neutron scattering (SANS) and transmission-electron microscopy (TEM), disk-like polymeric aggregates were present in concentrated solutions (DMSO and aq. NaOH soln.). Their thickness and radii were determined to be ca. 0.4 and ca. 80 nm, respectively. From the disk volumes and by a Guinier analysis, the molecular masses of the aggregates were calculated, which were in good agreement with each other. Defined structural changes of the polymer chains were observed during several-weeks storage in concentrated DMSO solutions. The original keto structure of the unsubstituted indigo building blocks reverted to the more flexible indoxyl/indolone structure. The new polymers were simultaneously stabilized by intermolecular H-bonds to give aggregates, preferentially dimers. Both aggregation and tautomerization were reversible upon dissolution. The polymers were synthesized by repeated oxidative coupling of 1,1′-diacetyl-3,3′-dihydroxybis-indoles 5 (from 1,1′-diacetyl-3,3′-bis(acetyloxy)bis-indoles 6) followed by gradual hydrolysis of the primarily formed poly(N,N′-diacetylindigos) 7 (Scheme). N,N′-Diacetylbis-anthranilic acids 9 were isolated as by-products.

Lithium blocks 45Ca2+ uptake into platelets in bipolar affective disorder and controls.

The basal uptake of radiolabelled 45Ca2+ into platelets and the effect of 1 mM lithium on uptake was measured in manic (n = 13) and depressed (n = 15) patients with bipolar disorder and in controls (n = 13). Lithium was significantly associated with inhibition of uptake of 45Ca2+ into platelets in all three groups. There were no significant intergroup differences in either basal levels of calcium uptake or the effects of lithium on calcium uptake (analysis of variance).

Facile synthesis of guanidine functionalised building blocks

Three useful developments in the preparation of guanidines are presented herein. A collection of bis(Boc)aminoalkylguanidines (n=2, 3, 4 and 6; Boc=tert-butoxycarbonyl), known to be prone to cyclisation, have been synthesised and isolated without chromatography as shelf-stable sulfonate salts in good yield (up to 94%). Secondly, a selection of guanidines tethered to a range of other functional groups, including alkyne, alkene, alcohol, and azide, have been prepared in good yields with no requirement for a purification step, and thirdly an inexpensive, high-yielding (93%), and facile synthesis of N,N'-bis(Boc)guanidine, a key precursor for N,N'-bis(Boc)-N'-triflylguanidine, is described in which the need for chromatographic purification is again obviated.

Tokyo’s Dojunkai experiment: courtyard apartment blocks 1926–1932

Dojunkai apartments were constructed by the Japanese Government as a work of relief, after the Great Kanto Earthquake in Tokyo. These apartments were leading examples in concrete construction in Japan and were innovative in their exterior space design ideas and building organizational themes. Dojunkai apartments were designed not only as solutions to particular sites, but as possible models for the further development of well-planned, secure, and communal neighbourhood style residential developments. During 1920–1930, Japanese architects and designers were actively involved in experimenting with foreign concepts of urban remodelling and town planning. However while these town-planning concepts and theories were embraced by Japanese architects and town planners, the resultant apartment complexes suggest that they endeavoured to adapt and transform them to suit Japanese sensibilities and urban requirements. This paper examines the nature of these adaptations and transformations. The principles of exterior space design are deployed to examine and identify patterns in building arrangement and exterior space design for six selected Dojunkai apartments. This paper discusses the pre-existing models of urban planning in Japan to establish a relationship between the adopted foreign town-planning models and the pre-existing ideas of urban settlements in the Japanese society.