3,6-Di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione and bithiophene copolymer with rather disordered chain orientation showing high mobility in organic thin film transistors

Pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione or diketopyrrolopyrrole (DPP) is a useful electron-withdrawing fused aromatic moiety for the preparation of donor-acceptor polymers as active semiconductors for organic electronics. This study uses a DPP-furan-containing building block, 3,6-di(furan-2-yl)pyrrolo[3,4- c]pyrrole-1,4(2H,5H)-dione (DBF), to couple with a 2,2′-bithiophene unit, forming a new donor-acceptor copolymer, PDBFBT. Compared to its structural analogue, 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBT), DBF is found to cause blue shifts of the absorption spectra both in solution and in thin films and a slight reduction of the highest occupied molecular orbital (HOMO) energy level of the resulting PDBFBT. Despite the fact that its thin films are less crystalline and have a rather disordered chain orientation in the crystalline domains, PDBFBT shows very high hole mobility up to 1.54 cm 2 V-1 s-1 in bottom-gate, top-contact organic thin film transistors.

Solution processable poly(2,5-dialkyl-2,5-dihydro-3,6-di-2-thienyl- pyrrolo[3,4-c]pyrrole-1,4-dione) for ambipolar organic thin film transistors

Solution processable diketopyrrolopyrrole (DPP)-bithiophene polymers (PDBT) with long branched alkyl side chains on the DPP unit are synthesized. These polymers have favourable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for the injection and transport of both holes and electrons. Organic thin film transistors (OTFTs) using these polymers as semiconductors and gold as source/drain electrodes show typical ambipolar characteristics with very well balanced high hole and electron mobilities (μ h = 0.024 cm 2 V -1 s -1 and μ e = 0.056 cm 2 V -1 s -1). These simple and high-performing polymers are promising materials for ambipolar organic thin film transistors for low-cost CMOS-like logic circuits.

A statistical model for combustion resonance from a DI diesel engine with applications

Introduced in this paper is a Bayesian model for isolating the resonant frequency from combustion chamber resonance. The model shown in this paper focused on characterising the initial rise in the resonant frequency to investigate the rise of in-cylinder bulk temperature associated with combustion. By resolving the model parameters, it is possible to determine: the start of pre-mixed combustion, the start of diffusion combustion, the initial resonant frequency, the resonant frequency as a function of crank angle, the in-cylinder bulk temperature as a function of crank angle and the trapped mass as a function of crank angle. The Bayesian method allows for individual cycles to be examined without cycle-averaging|allowing inter-cycle variability studies. Results are shown for a turbo-charged, common-rail compression ignition engine run at 2000 rpm and full load.

5,7-di-N-acetyl-acinetaminic acid: A novel non-2-ulosonic acid found in the capsule of an Acinetobacter baumannii isolate

An Acinetobacter baumannii global clone 1 (GC1) isolate was found to carry a novel capsule biosynthesis gene cluster, designated KL12. KL12 contains genes predicted to be involved in the synthesis of simple sugars, as well as ones for N-acetyl-l-fucosamine (l-FucpNAc) and N-acetyl-d-fucosamine (d-FucpNAc). It also contains a module of 10 genes, 6 of which are required for 5,7-di-N-acetyl-legionaminic acid synthesis. Analysis of the composition of the capsule revealed the presence of N-acetyl-d-galactosamine, l-FucpNAc and d-FucpNAc, confirming the role of fnlABC and fnr/gdr genes in the synthesis of l-FucpNAc and d-FucpNAc, respectively. A non-2-ulosonic acid, shown to be 5,7-diacetamido-3,5,7,9-tetradeoxy-l-glycero-l-altro-non-2-ulosonic acid, was also detected. This sugar has not previously been recovered from biological source, and was designated 5,7-di-N-acetyl-acinetaminic acid (Aci5Ac7Ac). Proteins encoded by novel genes, named aciABCD, were predicted to be involved in the conversion of 5,7-di-N-acetyl-legionaminic acid to Aci5Ac7Ac. A pathway for 5,7-di-N-acetyl-8-epilegionaminic acid biosynthesis was also proposed. In available A. baumannii genomes, genes for the synthesis of 5,7-di-N-acetyl-acinetaminic acid were only detected in two closely related capsule gene clusters, KL12 and KL13, which differ only in the wzy gene. KL12 and KL13 are carried by isolates belonging to clinically important clonal groups, GC1, GC2 and ST25. Genes for the synthesis of N-acyl derivatives of legionaminic acid were also found in 10 further A. baumannii capsule gene clusters, and three carried additional genes for production of 5,7-di-N-acetyl-8-epilegionaminic acid.

The sweet aroma of success: Modification of products for new markets in the case of TORQ by Di Bella Coffee

In 2002, Phillip Di Bella’s childhood passion for coffee and keen entrepreneurial spirit led him to establish a small coffee roasting warehouse in in the inner suburbs of Brisbane (Di Bella, 2012). With a keen sense of direction and passion for his coffee products and providing unparalleled customer service, Di Bella Coffee quickly grew to become a key player in the coffee roasting scene. This passion for the ultimate coffee experience is evident in the firm’s logo ‘Di Bella Coffee Inspires Passion’. Phillip Di Bella stated that ‘the common denominator of this company is about inspiration and passion. We are not a coffee company, we are a people company. You know, are we inspiring you from the moment you walk in the door to the moment you leave. If you are not feeling inspired then we haven’t done our job properly as a company’. Fundamentally, providing the ultimate coffee experience, as detailed in the following case is one in which focuses on the coffee consumption experience, not the coffee itself. Over that last 10 years Di Bella Coffee has constantly strived for the ultimate coffee, while expanding business operations into the booming Asian coffee market, establishing headquarters in Shanghai in 2010. In 2011, Di Bella Coffee commenced their second international venture with the launch of operations in India (Di Bella Coffee, 2012); followed shortly by the creation of a new category of coffee, set to revolutionise to coffee industry. The fusion of two traditional forms of coffee; espresso coffee and instant coffee, to create a third category- espresso instant, led to the development of TORQ by Di Bella.

Crystal structure of poly[[di-mu2-aqua-aquasodium] 4-amino-3,5,6-trichloropyridine-2-carboxylate trihydrate], the sodium salt of the herbicide picloram

In the structure of the title complex [[Na(H2O)3]+ (C6H2Cl3N2O2)-^ . 3(H2O)]n, the Na salt of the herbicide picloram, the cation is a polymeric chain structure, based on doubly water-bridged NaO5 trigonal bipyramidal complex units which have in addition, a singly-bonded monodentate water molecule. Each of the bridges within the chain which lies along the a cell direction is centrosymmetric with Na...Na separations of 3.4807(16) and 3.5109(16)Ang. In the crystal, there are three water molecules of solvation and these, as well as the coordinated water molecules and the amino group of the 4-amino-3,5,6-trichloropicolinate anion are involved in extensive inter-species hydrogen-bonding interactions with carboxyl and water O-atoms as well as the pyridine N-atom. Among these association is a centrosymmetric cyclic tetra-water R4/4(8) ring , resulting in an overall three-dimensional structure.

Beta-Turn Conformations In Crystal-Structures Of Model Peptides Containing Alpha,Alpha-Di-N-Propylglycine And Alpha,Alpha-Di-N-Butylglycine

The crystal state conformations of three peptides containing the alpha, alpha-dialkylated residues, alpha,alpha-di-n-propylglycine (Dpg) and alpha,alpha-di-n-butylglycine (Dbg), have been established by x-ray diffraction. Boc-Ala-Dpg-Ala-OMe (I) and Boc-Ala-Dbg-Ala-OMe (III) adopt distorted type II beta-turn conformations with Ala (1) and Dpg/Dbg (2) as the corner residues. In both peptides the conformational angles at the Dxg residue (I: phi = 66.2 degrees, psi = 19.3 degrees; III: phi = 66.5 degrees, psi = 21.1 degrees) deviate appreciably from ideal values for the i + 2 residue in a type II beta-turn. In both peptides the observed (N...O) distances between the Boc CO and Ala(3) NH groups are far too long (I: 3.44 Angstrom; III: 3.63 Angstrom) for an intramolecular 4 --> 1 hydrogen bond. Boc-Ala-Dpg-Ala-NHMe (II) crystallizes with two independent molecules in the asymmetric unit. Both molecules IIA and IIB adopt consecutive beta-turn (type III-III in IIA and type III-I in IIB) or incipient 3(10)-helical structures, stabilized by two intramolecular 4 --> 1 hydrogen bonds. In all four molecules the bond angle N-C-alpha-C' (tau) at the Dxg residues are greater than or equal to 110 degrees. The observation of conformational angles in the helical region of phi,psi space at these residues is consistent with theoretical predictions.

NMR Investigations on Di- and Tri-Azanaphthalenes Oriented in Liquid Crystals

Proton NMR spectra of 1,3-diazanaphthalene and 1,2,4-triazanaphthalene have been investigated in the nematic phase of three liquid crystals. The spectral analysis provided direct dipole-dipole couplings which have been used to derive the molecular structure. Geometry of the phenyl ring in both the molecules deviates from the regular hexagonal structure. Signs of the order parameter of the largest magnitude are opposite in liquid crystals with positive diamagetic anisotropies.

L'ecfrasis nel Piacere di Gabriele D'Annunzio

Tutkielman aiheena on ekfrasis Gabriele D'Annunzion romaanissa Il Piacere (1889). Lähtökohtana on selvittää, millaisissa muodoissa ekfrasis esiintyy romaanissa sekä miten ekfrasis vaikuttaa teoksen tulkintatradition esille tuomaan tematiikkaan. Pyrkimyksenä on myös selkeyttää ekfrasiksen käsitettä, jonka ongelmana ovat sanaan eri aikakausina liitetyt eri merkitykset. Tärkeimpiä lähdeteoksia ovat James A.W. Heffernanin Museum of Words (1993) ja W.J.T. Mitchellin Picture Theory (1994), Marinella Cantelmon Il Piacere dei leggitori: D'Annunzio e la comunicazione letteraria (1996) sekä John Hollanderin artikkeli "The Poetics of Ekphrasis" (1988). Tutkielman avainkäsitteenä on Heffernanin määritelmä, jonka mukaan ekfrasis on sanallinen esitys kuvallisesta esityksestä. Määritelmää sovellettaessa on otettu huomioon representaatiokäsityksen avautuminen, jolloin vastaanottaja, ympäristö etc. ovat osa esitystä. Korpuksen muodostavat tapahtumaympäristöä, taideteoksia, esineistöä ja henkilöhahmoja kuvaavat ekfrastiset katkelmat. Luokittelussa toimivat alakäsitteinä Valerie Robillardin kuvaileva, attributiivinen ja assosiatiivinen ekfrasis sekä Tamar Yacobin ekfrastinen vertaus. Analyysi osoittaa, että kuvaileva ekfrasis on yleisin, mutta vain kuvitteellisten teosten yhteydessä. Katkelmissa on näkyvissä ekfrasikselle luonteenomainen kerronnallinen impulssi. Ekfrasis osallistuu tunnetun ja uuden elementin vuoropuheluun ankkuroimalla kuvitteelliset taideteokset lukijalle tuttuun ympäristöön, jolloin myös uusi tulee toden kaltaiseksi. Attributiivinen ekfrasis takaa välittömän tunnistettavuuden. Henkilöhahmot, erityisesti keskeiset naishahmot, on määritelty ekfrastisten vertausten kautta. Ekfrasis ilmentää osaltaan naishahmojen vaihdettavuuden tematiikkaa. Kyseessä on myös toiseuden haltuunotto. Kuvallisen viittaussuhteen ansiosta ekfrasis toimii tehokeinona. Tekstuaalisena strategiana ekfrasis luo siteitä tapahtumien välille ja rytmittää teoksen vaiheita. Ekfrastiset katkelmat tarjoavat myös väylän vaihtoehtoiselle tulkinnalle haastamalla tekstin totuuskäsityksen. Kuvallinen ja sanallinen esitys tuovat tekstiin omat merkityksensä, jolloin merkityskenttä laajenee. Il Piacere on intertekstuaalinen kollaasi, jossa kokonaiskuva muodostuu eri elementtien vuorovaikutuksesta. D'Annunzion mielestä kauneus on taiteen ensisijainen tarkoitus, ja ekfrasis retorisena keinona on osa pyrkimystä tavoittaa täydellinen muoto.

Synthesis and Reactions of Binuclear Diolefin Rhodium(I) Compounds bridged by Nitrogen Heterocycles, Crystal Structure of Dichloro-Di-1,5-Cyclooctadiene(Mu-Pyrazine)-Dirhodium(I) [[Rh(1,5-C8h12)Cl]2(Mu-C4h4n2)]

Binuclear complexes of rhodium(I) of the type [(dien)(X)Rh(μ-N-N)Rh(X)(dien)] (dien = 1,5-cyclooctadiene or norbornadiene; N-N = pyrazine, 4,4′-bipyridine or Phenazine and X = Cl or Br) with bridging heterocycles have been isolated and their reactions with carbon monoxide, 2,2′-bipyridine and 1,10-phenanthroline investigated. The crystal structure of [(COD)(Cl)Rh(μ-pyrazine)Rh(Cl)(COD)] has been determined.

Structure-reactivity correlation in inclusion complexes: deoxycholic acid di-tert-butyl thioketone

Ultraviolet irradiation of crystalline molecular inclusion complexes of deoxycholic acid with di-tert-butyl thioketone results in no reaction. The structure of the above complex has been determined via X-ray diffraction. The absence of expected photoreactions. namely, photoreduction and photooxidation, is rationalized on the basis of the X-ray structure analysis of the complex.

Structure of the K12 capsule containing 5,7-di-N-acetylacinetaminic acid from Acinetobacter baumannii isolate D36

The repeat unit of the K12 capsular polysaccharide isolated from the Acinetobacter baumannii global clone 1 clinical isolate, D36, was elucidated by means of chemical and spectroscopical methods. The structure was shown to contain N-acetyl-D-galactosamine (D-GalpNAc), N-acetyl-D-fucosamine and N-acetyl-L-fucosamine linked together in the main chain, with the novel sugar, 5,7-diacetamido-3,5,7,9-tetradeoxy-L-glycero-L-altro-non-2-ulosonic acid (5,7-di-N-acetylacinetaminic acid or Aci5Ac7Ac), attached to D-GalpNAc as a side branch. This matched the sugar composition of the K12 capsule and the genetic content of the KL12 capsule gene cluster reported previously. D-FucpNAc was predicted to be the substrate for the initiating transferase, ItrB3, with the Wzy polymerase making a α-D-FucpNAc-(1 → 3)-D-GalpNAc linkage between the repeat units. The three glycosyltransferases encoded by KL12 are all retaining glycosyltransferases and were predicted to form specific linkages between the sugars in the K12 repeat unit.

Predicting a new phase (T′′) of two-dimensional transition metal di-chalcogenides and strain-controlled topological phase transition

Single layered transition metal dichalcogenides have attracted tremendous research interest due to their structural phase diversities. By using a global optimization approach, we have discovered a new phase of transition metal dichalcogenides (labelled as T′′), which is confirmed to be energetically, dynamically and kinetically stable by our first-principles calculations. The new T′′ MoS2 phase exhibits an intrinsic quantum spin Hall (QSH) effect with a nontrivial gap as large as 0.42 eV, suggesting that a two-dimensional (2D) topological insulator can be achieved at room temperature. Most interestingly, there is a topological phase transition simply driven by a small tensile strain of up to 2%. Furthermore, all the known MX2 (M = Mo or W; X = S, Se or Te) monolayers in the new T′′ phase unambiguously display similar band topologies and strain controlled topological phase transitions. Our findings greatly enrich the 2D families of transition metal dichalcogenides and offer a feasible way to control the electronic states of 2D topological insulators for the fabrication of high-speed spintronics devices.

Hydrogen bonding with mono- and di-carbonyls

The electronic absorption and i.r. spectroscopic studies are reported for the hydrogen bonding systems involving alcohol and various ketones. It is shown that the hydrogen bonding abilities of ketones are determined by the extent of delocalization of the lone pair electrons in their non-bonding molecular orbitals. Evidence for the formation of very weak intermolecular hydrogen bonds between alcohol and the π-electron part of the dicarbonyls has also been presented from the i.r. studies in the 3400–3700 cm−1 region.