Solvation and axial ligation properties of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)

he solvation of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)[Zn(obtpp)], in twelve different solvents results in large red shifts of the B and Q bands of the porphyrin accompanied by enhanced absorbance ratios of the Q bands. These observations are ascribed to the destabilisation of the highest occupied molecular orbital a2u of the porphyrin arising from a flow of charge from the axial ligand to the porphyrin ring through the zinc(II) ion. The binding constants of adducts of [Zn(obtpp)] with neutral bases have been found to be an order of magnitude greater than those observed for the corresponding adducts of (5,10,15,20-tetraphenylporphyrinato)-zinc and vary in the order piperidine > imidazole > pyridine > 3-methylpyridine > pyridine-3-carbaldehyde. The enhanced binding constants and large spectral shifts are interpreted in terms of the electrophilicity of [Zn(obtpp)] induced by the electron-withdrawing bromine substituents in the porphyrin core. The structure of [Zn(obtpp)(PrCN)2] has been determined; it reveals six-co-ordinated zinc(II) with two long Zn–N distance [2.51(4), 2.59(3)Å]. The porphyrin is non-planar and displays a saddle-shaped conformation.

Structure of pregna-4,16-diene-7[alpha],14[alpha]-diol-3,20-dione

7a,14a-Dihydroxypregna-4,16-diene-3,20- dione, C21H2804, M r = 344.45, orthorhombic, P212121, a = 7.136 (1), b = 12.342 (1), c = 20.049 (3)/k, V= 1765.7 (3)/k 3, Z = 4, Dx = 1.295 g cm -3, A(Cu Kte) = 1.5418/k, /z = 6.7 cm- a, F(000) = 744, T = 293 K, R = 0.048 for 1345 observations. The A ring may be described as in a l a,2flhalf- chair conformation or a l a-sofa conformation. The B and C rings adopt normal chair conformations and the D ring has a 14a-envelope conforma tion. The molecules are held together by a hydrogen bond [0(3)...0(7)= 2.767 A].

Pilottitutkimus apteekkien yksilöllisestä tupakoinninvieroituspalvelusta

Apteekkien yksilöllinen tupakoinninvieroituspalvelu on tupakoinnin lopettamiseen motivoituneille asiakkaille tarkoitettu maksullinen erikoispalvelu, joka sisältää 4–6 tapaamista vieroitusohjaajana toimivan farmaseutin tai proviisorin kanssa. Palvelu sisältää asiakkaalle räätälöityä neuvontaa, henkilökohtaisen vieroitussuunnitelman sekä seurantajakson. Apteekkien yksilöllinen tupakoinninvieroituspalvelu perustuu Isossa-Britanniassa kehitettyyn palvelumalliin, ja sitä on tarjottu suomalaisissa apteekeissa vuodesta 2006. Tämä pro gradu -tutkielma käsittelee apteekkien yksilöllisen tupakoinninvieroituspalvelun pilottitutkimusta, joka toteutettiin Suomen Apteekkariliiton ja Helsingin yliopiston farmasian tiedekunnan sosiaalifarmasian osaston yhteistyönä ja se kuului osana Hengitysliitto Heli ry:n koordinoimaa tupakasta vieroituksen hankekokonaisuutta. Tässä pro gradu -tutkielmassa tarkastellaan pilottitutkimuksessa saadun asiakasaineiston avulla apteekkien yksilöllisen tupakoinninvieroituspalvelumallin toimivuutta, asiakkaiden kokemuksia palvelusta, asiakkaiden onnistumista tupaakoinnin lopettamisessa sekä asiakkaiden kyvykkyyden tunteen kehittymistä palvelun aikana. Tässä interventiotutkimuksessa oli mukana 14 apteekkia, jotka rekrytoivat yhteensä 36 palveluasiakasta. Ennen asiakkaiden rekrytointia apteekit perehdytettiin palvelun tarjoamiseen. Apteekit tiedottivat pilottitutkimuksesta paikallisen terveydenhuollon lääkäreitä ja muita terveydenhuollon ammattilaisia, jotka voivat ohjata asiakkaita palveluun. Sosiaali- ja terveysministeriön pilottitutkimukselle myöntämä rahoitus mahdollisti asiantuntijapalkkion maksamisen apteekeille ja palvelun tarjoamisen asiakkaille ilmaiseksi tai pientä omakustannusosuutta vastaan. Asiakkaiden tupakoimattomana pysymistä sekä kokemuksia tupakoinninvieroituspalvelusta kartoitettiin kyselylomakkeilla, jotka asiakkaat saivat täytettäväkseen palvelun alussa sekä noin 3 kuukauden kohdalla palvelun alkamisesta. Asiakkaiden taustatiedot kerättiin ensimmäisen tapaamisen yhteydessä erillisille taustatietolomakkeille ja palvelun aikana tehtyjä huomioita niille tarkoitetuille kaavakkeille. Ensimmäisen kyselylomakkeen palauttaneista 28 henkilöstä 20 ja toisen kyselylomakkeen palauttaneista 17 henkilöstä 13 oli pysynyt tupakoimattomana (55,6 % ja 36,1 % kaikista asiakkaista). Kaikki tupakoinnin lopettaneet käyttivät jotakin tupakasta vieroituslääkettä. Tupakoinnin lopettaneilla asiakkailla kyvykkyyden tunne oli keskimääräistä parempi sekä palvelun alussa että koko palvelun ajan. Asiakkaat pitivät palvelua tarpeellisena ja apteekin vieroitusohjaajalta saatua tukea tärkeänä. Asiakkaat kokivat myös palvelun saamisen apteekista tärkeäksi. Noin 32 % ensimmäiseen kyselyyn vastanneista ja 41 % toiseen kyselyyn vastanneista oli valmis maksamaan palvelusta. Heidän ilmoittamansa maksuvalmius oli keskimäärin noin 45 euroa (10–100 euroa). Muusta terveydenhuollosta lähetettiin palveluun vain vähän tai ei lainkaan asiakkaita. Tästä syystä apteekit rekrytoivat asiakkaita myös ilman kontaktia muuhun terveydenhuoltoon. Palvelun 36 asiakkaasta noin 36 % oli pysynyt tupakoimattomana 3 kuukauden kohdalla. Verrokkiryhmä jouduttiin jättämään tutkimuksesta pois verrokkihenkilöiden rekrytoinnin epäonnistuttua. Tulos on kuitenkin vertailukelpoinen kansainvälisiin tutkimuksiin, joissa on saatu vastaavanlaisia tuloksia. Apteekkien yksilöllisestä tupakoinninvieroituspalvelusta saattaa olla hyötyä tupakoinnin lopettamisessa siihen motivoituneille henkilöille ja erityisesti henkilöille, jotka käyttävät lisäksi tupakasta vieroituslääkettä. Asiakkaat kokivat palvelun tärkeäksi ja tarpeelliseksi, mutta heikko maksuvalmius asettaa haasteita palvelun tarjoamiselle apteekeissa. Yhteistyömallia muun terveydenhuollon kanssa tulisi kehittää.

3,12-dinitro-5,10,15,20-tetraphenylporphyrin- an example of a twisted intramolecular charge-transfer system

he porphyrin ring in the title compound, 10,19-dinitro-2,7,12,17-tetraphenyl-21,22,23,24-tetraazapenta-cyclo[16.2.1.1(3,6).1(8,11).1(13,16)]tetracosa-1,3,5,7,9,11(23),-12,14,16,18(21),19-undecaene 0.5-dichloromethane solvate, C44H28N6O4.0.5CH2Cl2, adopts a saddle conformation with neighbouring pyrrole rings tilted with respect to each other. The two nitro groups are situated on alternate pyrrole rings and have their planes angled away from those of the pyrrole rings, thereby indicating that interaction between the porphyrin and nitro groups is slight.

Modified Crack Closure Integral (MCCI) For 3-D Problems Using 20-Noded Brick Elements

The Modified Crack Closure Integral (MCCI) technique based on Irwin's crack closure integral concept is very effective for estimation of strain energy release rates G in individual as well as mixed-mode configurations in linear elastic fracture mechanics problems. In a finite element approach, MCCI can be evaluated in the post-processing stage in terms of nodal forces and displacements near the crack tip. The MCCI expressions are however, element dependent and require a systematic derivation using stress and displacement distributions in the crack tip elements. Earlier a general procedure was proposed by the present authors for the derivation of MCCI expressions for 3-dimensional (3-d) crack problems modelled with 8-noded brick elements. A concept of sub-area integration was proposed to estimate strain energy release rates at a large number of points along the crack front. In the present paper a similar procedure is adopted for the derivation of MCCI expressions for 3-d cracks modelled with 20-noded brick elements. Numerical results are presented for centre crack tension and edge crack shear specimens in thick slabs, showing a comparison between present results and those available in the literature.

Modified crack closure integral (MCCI) for 3-d problems using 20 noded brick elememnts

The Modified Crack Closure Integral (MCCI) technique based on Irwin's crack closure integral concept is very effective for estimation of strain energy release rates G in individual as well as mixed-mode configurations in linear elastic fracture mechanics problems. In a finite element approach, MCCI can be evaluated in the post-processing stage in terms of nodal forces and displacements near the crack tip. The MCCI expressions are however, element dependent and require a systematic derivation using stress and displacement distributions in the crack tip elements. Earlier a general procedure was proposed by the present authors for the derivation of MCCI expressions for 3-dimensional (3-d) crack problems modelled with 8-noded brick elements. A concept of sub-area integration was proposed to estimate strain energy release rates at a large number of points along the crack front. In the present paper a similar procedure is adopted for the derivation of MCCI expressions for 3-d cracks modelled with 20-noded brick elements. Numerical results are presented for centre crack tension and edge crack shear specimens in thick slabs, showing a comparison between present results and those available in the literature.

Chiral synthons from carvone .20. Stereo- and enantiospecific total synthesis of (-)-valeranone

Stereo- and enantiospecific total synthesis of the irregular sesquiterpene, valeranone, starting from S-6-methylcarvone employing a hydrindanone to decalone ring expansion methodology, is described.

Structural and optical properties of nonpolar (11-20) a-plane GaN grown on (1-102) r-plane sapphire substrate by plasma-assisted molecular beam epitaxy

We report the structural and optical properties of a-plane GaN film grown on r-plane sapphire substrate by plasma-assisted molecular beam epitaxy. High resolution X-ray diffraction was used to determine the out-of-plane and in-plane epitaxial relation of a-plane GaN to r-plane sapphire. Low-temperature photoluminescence emission was found to be dominated by basal stacking faults along with near-band emission. Raman spectroscopy shows that the a-GaN film is of reasonably good quality and compressively strained. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nucleation and growth characteristics of cavities during the early stages of tensile creep deformation in a superplastic zirconia-20 wt% alumina composite

Constant-stress tensile creep experiments on a superplastic 3-mol%-yttria-stabilized tetragonal zirconia composite with 20 wt% alumina revealed that cavities nucleate relatively early during tensile deformation. The number of cavities nucleated increases with increasing imposed stress. The cavities nucleate at triple points associated largely with an alumina grain, and then grow rapidly in a cracklike manner to attain dimensions on the order of the grain facet size. It is suggested that coarser-grained superplastic ceramics exhibit lower ductility due to the ease in formation of such grain boundary facet-cracks and their interlinkage to form a macroscopic crack of critical dimensions.

First-principles electronic structure of the delafossites ABO(2) (A=Cu, Ag, Au; B=Al, Ga, Sc, In, Y): evolution of d(10)-d(10) interactions

While bonding between d(10) atoms and ions in molecular systems has been well studied, less attention has been paid to interactions between such seemingly closed shell species in extended inorganic solids. In this contribution, we present visualizations of the electronic structures of the delafossites ABO(2) (A = Cu, Ag, Au) with particular emphasis on the nature of d(10)-d(10) interactions in the close packed plane of the coinage metal ion. We find that on going from Cu to Ag to Au, the extent of bonding between A and A increases. However, the structures (in terms of distances) of these compounds are largely determined by the strongly ionic 13,11 0 interaction and for the larger B ions Sc, In and Y, the A atoms are sufficiently well-separated that A-A bonding is almost negligible. We also analyze some interesting differences between Ag and Au, including the larger A-O covalency of the Au. The trends in electronic structure suggest that the Ag and Au compounds are not good candidate transparent conducting oxides. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Minimizing buffer requirements under rate-optimal schedule in regular dataflow networks

Large-grain synchronous dataflow graphs or multi-rate graphs have the distinct feature that the nodes of the dataflow graph fire at different rates. Such multi-rate large-grain dataflow graphs have been widely regarded as a powerful programming model for DSP applications. In this paper we propose a method to minimize buffer storage requirement in constructing rate-optimal compile-time (MBRO) schedules for multi-rate dataflow graphs. We demonstrate that the constraints to minimize buffer storage while executing at the optimal computation rate (i.e. the maximum possible computation rate without storage constraints) can be formulated as a unified linear programming problem in our framework. A novel feature of our method is that in constructing the rate-optimal schedule, it directly minimizes the memory requirement by choosing the schedule time of nodes appropriately. Lastly, a new circular-arc interval graph coloring algorithm has been proposed to further reduce the memory requirement by allowing buffer sharing among the arcs of the multi-rate dataflow graph. We have constructed an experimental testbed which implements our MBRO scheduling algorithm as well as (i) the widely used periodic admissible parallel schedules (also known as block schedules) proposed by Lee and Messerschmitt (IEEE Transactions on Computers, vol. 36, no. 1, 1987, pp. 24-35), (ii) the optimal scheduling buffer allocation (OSBA) algorithm of Ning and Gao (Conference Record of the Twentieth Annual ACM SIGPLAN-SIGACT Symposium on Principles of Programming Languages, Charleston, SC, Jan. 10-13, 1993, pp. 29-42), and (iii) the multi-rate software pipelining (MRSP) algorithm (Govindarajan and Gao, in Proceedings of the 1993 International Conference on Application Specific Array Processors, Venice, Italy, Oct. 25-27, 1993, pp. 77-88). Schedules generated for a number of random dataflow graphs and for a set of DSP application programs using the different scheduling methods are compared. The experimental results have demonstrated a significant improvement (10-20%) in buffer requirements for the MBRO schedules compared to the schedules generated by the other three methods, without sacrificing the computation rate. The MBRO method also gives a 20% average improvement in computation rate compared to Lee's Block scheduling method.

Influence of synthesis route on structural phase transition in YBa2−xLaxCu3Oy (0

The compounds YBa2−xLaxCu3Oy, with compositions (0-state reaction and characterised. Structural transition from orthorhombic to tetragonal phase occurred at (0.15-state reaction for x values up to 0.20. The ternary phase formation temperature is influenced by the starting materials used and ionic size considerations. These factors are shown to determine the composition at which the changeover from orthorhombic (superconducting) to tetragonal (non-superconducting) phase transition (O–T transition) occurs.

Sustainable biomass production for energy in selected Asian countries

This paper presents a synthesis of assessment of sustainable biomass production potential in six Asian countries-China, India, Malaysia, Philippines, Sri Lanka and Thailand, and is based on the detailed studies carried out in these countries under the Asian Regional Research Programme in Energy, Environment and Climate (ARRPEEC). National level studies were undertaken to estimate land availability for biomass production, identify and evaluate the biomass production options in terms of yield per hectare and financial viability, estimate sustainable biomass production for energy, and estimate the energy potential of biomass production in the six Asian countries. Sustainable biomass production from plantation is estimated to be in the range of 182.5-210.5, 62-310, 0.4-1.7, 3.7-20.4, 2.0-9.9 and 11.6-106.6 Mt yr(-1) for China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. The maximum annual electricity generation potential, using advanced technologies, from the sustainable biomass production is estimated to be about 27, 114, 4.5, 79, 254 and 195 percentage of the total electricity generation in year 2000 in China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. Investment cost for bioenergy production varies from US$381 to 1842 ha(-1) in the countries considered in this study; investment cost for production of biomass varies from US$5.1 to 23 t(-1). (C) 2003 Elsevier Ltd. All rights reserved.