Approaches to the synthesis of novel photoactive side chain liquid crystalline polymers containing analogues of the cinnamate ester group

A series of chain liquid crystalline copolymers of 4-cyanophenyl 4′-(6-methacryloyloxyhexyloxy)benzoate and 2-methacryloyloxyethyl β-(1-naphthyl)-propenoate were prepared by free radical polymerization. The corresponding polyacrylates could not be prepared in the same way and an alternative method was used for their preparation involving the synthesis of copolymers of the mesogenic monomer and 2-hydroxyethyl acrylate followed by treatment of the resulting polymers with β-(1-naphthyl)propenoyl chloride. The materials are of interest as photoactive liquid crystalline polymers. The effect of introducing a bulky nonmesogenic group into a liquid crystalline copolymer generally lowers the clearing temperature and raises Tg but also gives rise to contrasting phase behaviour in these two series of polymers. Polymethacrylates which show mesomorphism have sharp transitions and continue to exhibit a highly ordered smectic phase over the bulk of their liquid crystal range. Polyacrylates, on the other hand, exhibit a weakening and broadening-out of their thermal transitions consistent with a lowering of order. These results emphasize the effect of the polymer backbone on phase behaviour.

Towards the total synthesis of mycaperoxide B: probing biosynthetic rationale

Studies towards the biomimetic synthesis of mycaperoxide B (1) are described. We have established the synthesis of four diastereoisomers of mycaperoxide B methyl ester (1a) by employing a Michael addition across an α,β-unsaturated ester precursor 2 as the key step. This result strongly suggestsstereocontrol in the addition of the hydroperoxide functionality to the E double bond and discloses the importance of choosing the correct geometry of the α,β-unsaturated double bond when attempting to synthesise mycaperoxide B. Four diastereoisomeric tetrahydrofurans derived from an intramolecular rearrangement of the 1,2-dioxolane enolate 12 were also isolated and characterised.

Emotional well-being and adjustment to vision loss in later life: a meta-synthesis of qualitative studies.

Purpose: To review perceived emotional well-being in older people with visual impairment and perceived factors that inhibit/facilitate psychosocial adjustment to vision loss. Method: The databases of MEDLINE, EMBASE, PsycINFO and CINAHL were searched for studies published from January 1980 to December 2010, which recruited older people with irreversible vision loss, and used qualitative methods for both data collection and analysis. Results sections of the papers were synthesised using a thematic-style analysis to identify the emergent and dominant themes. Results: Seventeen qualitative papers were included in the review, and five main themes emerged from the synthesis: 1) the trauma of an ophthalmic diagnosis, 2) impact of vision loss on daily life, 3) negative impact of visual impairment on psychosocial well-being, 4) factors that inhibit social well-being, and 5) factors that facilitate psychological well-being. We found the response shift model useful for explaining our synthesis. Conclusions: Acquired visual impairment can have a significant impact on older people's well-being and make psychosocial adjustment to the condition a major challenge. Acceptance of the condition and a positive attitude facilitate successful psychosocial adjustment to vision loss as well as social support from family, friends and peers who have successfully adjusted to the condition. [Box: see text].

Synthesis of a mononuclear oxidovanadium(V) complex by bridge-splitting of the corresponding binuclear precursor

The mononuclear oxidovanadium(V) complex VO(OEt)L (2), where L2- is the dianion of a diprotic tridentate ONO donor ligand, 2-hydroxyacetophenone-2-aminobenzoylhydrazone (H2L), has been synthesized by oxido-bridge splitting of the corresponding binuclear complex V2O3L2 (1) and structurally characterized by single crystal X-ray diffraction analysis, together with electrochemical and spectral studies. Splitting of the oxido-bridge was effected by refluxing 1 with excess triphenylphosphine in ethanol medium. The crystal structure of 2 is compared with that of the precursor binuclear complex 1.

One-pot three component reaction involving cyclohexyl isocyanide for the synthesis of furo[3,4-b]chromenes

On stirring an equimolar mixture of 4-oxo-4H-chromene-3-carbaldehyde, ninhydrin and cyclohexyl isocyanide in CH(2)Cl(2)-MeOH (7: 1) at room temperature produces 3-cyclohexylimino-1-(2-hydroxy-1,3-dioxo-2,3-dihydro-1H-inden-2-yl)-1,3-dihydro-9H-furo[3,4-b]chromen-9-one which on hydrolysis produces 1-(2-hydroxy-1,3-dioxo-2,3-dihydro-1H-inden-2-yl)-1H-furo[3,4-b]chromene-3,9-dione. The structure of the latter compound was confirmed by single crystal X-ray diffraction

Synthesis of ligands for use in actinide extraction

The invention discloses an improved process for the preparation of 2,2,5,5-tetrasubstituted hexane-1,6-dicarbonyl compounds, and in particular diethyl 2,2,5,5-tetramethylhexanedioate and dimethyl 2,2,5,5-tetramethylhexanedioate, by the alkylation of 1,2-difunctional ethane compounds with enolates of carbonyl compounds. The process provides higher yields and greater synthetic brevity than existing processes.

Asymmetric synthesis of peptides

The present invention provides a process comprising substitution of an acceptor molecule comprising a group -XC(O)- wherein X is O, S or NR8, where R8 is C1-6 alkyl, C6-12 aryl or hydrogen, with a nucleophile, wherein the acceptor molecule is cyclised such that said nucleophilic substitution at -XC (O)- occurs without racemisation. This process has particular application for the production of a peptide by extension from the activated carboxy-terminus of an acyl amino acid residue without epimerisation.

Synthesis of thiolated and acrylated nanoparticles using thiol-ene click chemistry: towards novel mucoadhesive materials for drug delivery

Thiol- and acrylate-functionalized nanoparticles have been synthesized from pentaerythritol tetrakis(3-mercapto-propionate) and pentaerythritol tetraacrylate using thiol-ene click chemistry. Using Raman and 1H NMR spectroscopy as well as Ellman's assay, it was demonstrated that excess pentaerythritol tetraacrylate in the feed mixture led to nanoparticles with free acrylate groups on their surface, whereas nanoparticles with thiolated surfaces could be synthesized using feed mixtures with excess pentaerythritol tetrakis(3-mercapto-propionate). The possibility of fluorescent labelling of thiolated nanoparticles has been demonstrated through their reaction with fluorescein-5-maleimide. The thiolated nanoparticles were found to be mucoadhesive and exhibited retention on mucosal surface of porcine urinary bladder.

Crystal design approaches for the synthesis of paracetamol co-crystals

Crystal engineering principles were used to design three new co-crystals of paracetamol. A variety of potential cocrystal formers were initially identified from a search of the Cambridge Structural Database for molecules with complementary hydrogen-bond forming functionalities. Subsequent screening by powder X-ray diffraction of the products of the reaction of this library of molecules with paracetamol led to the discovery of new binary crystalline phases of paracetamol with trans-1,4- diaminocyclohexane (1); trans-1,4-di(4-pyridyl)ethylene (2); and 1,2-bis(4-pyridyl)ethane (3). The co-crystals were characterized by IR spectroscopy, differential scanning calorimetry, and 1H NMR spectroscopy. Single crystal X-ray structure analysis reveals that in all three co-crystals the co-crystal formers (CCF) are hydrogen bonded to the paracetamol molecules through O−H···N interactions. In co-crystals (1) and (2) the CCFs are interleaved between the chains of paracetamol molecules, while in co-crystal (3) there is an additional N−H···N hydrogen bond between the two components. A hierarchy of hydrogen bond formation is observed in which the best donor in the system, the phenolic O−H group of paracetamol, is preferentially hydrogen bonded to the best acceptor, the basic nitrogen atom of the co-crystal former. The geometric aspects of the hydrogen bonds in co-crystals 1−3 are discussed in terms of their electrostatic and charge-transfer components.

Synthesis of prebiotic galactooligosaccharides from lactose using bifidobacterial β-galactosidase (BbgIV) immobilised on DEAE-Cellulose, Q-Sepharose and amino-ethyl agarose

The bifidobacterial β-galactosidase BbgIV was immobilised on DEAE-Cellulose and Q-Sepharose via ionic binding and on amino-ethyl- and glyoxal-agarose via covalent attachment, and was then used to catalyse the synthesis of galactooligosaccharides (GOS). The immobilisation yield exceeded 90 % using ionic binding, while it was low using aminoethyl agarose (25 – 28 %) and very low using glyoxal agarose (< 3 %). This was due to the mild conditions and absence of chemical reagents in ionic binding, compared to covalent attachment. The maximum GOS yield obtained using DEAE-Cellulose and Q-Sepharose was similar to that obtained using free BbgIV (49 – 53 %), indicating the absence of diffusion limitation and mass transfer issues. For amino-ethyl agarose, however, the GOS yield obtained was lower (42 – 44 %) compared to that obtained using free BbgIV. All the supports tried significantly (P < 0.05) increased the BbgIV operational stability and the GOS synthesis productivity up to 55 °C. Besides, six successive GOS synthesis batches were performed using BbgIV immobilised on Q-Sepharose; all resulted in similar GOS yields, indicating the possibility of developing a robust synthesis process. Overall, the GOS synthesis operation performance using BbgIV was improved by immobilising the enzyme onto solid supports, in particular on Q-Sepharose

Tropical climates at the Last Glacial Maximum: a new synthesis of terrestrial palaeoclimate data. I. Vegetation, lake-levels and geochemistry.

Palaeodata in synthesis form are needed as benchmarks for the Palaeoclimate Modelling Intercomparison Project (PMIP). Advances since the last synthesis of terrestrial palaeodata from the last glacial maximum (LGM) call for a new evaluation, especially of data from the tropics. Here pollen, plant-macrofossil, lake-level, noble gas (from groundwater) and δ18O (from speleothems) data are compiled for 18±2 ka (14C), 32 °N–33 °S. The reliability of the data was evaluated using explicit criteria and some types of data were re-analysed using consistent methods in order to derive a set of mutually consistent palaeoclimate estimates of mean temperature of the coldest month (MTCO), mean annual temperature (MAT), plant available moisture (PAM) and runoff (P-E). Cold-month temperature (MAT) anomalies from plant data range from −1 to −2 K near sea level in Indonesia and the S Pacific, through −6 to −8 K at many high-elevation sites to −8 to −15 K in S China and the SE USA. MAT anomalies from groundwater or speleothems seem more uniform (−4 to −6 K), but the data are as yet sparse; a clear divergence between MAT and cold-month estimates from the same region is seen only in the SE USA, where cold-air advection is expected to have enhanced cooling in winter. Regression of all cold-month anomalies against site elevation yielded an estimated average cooling of −2.5 to −3 K at modern sea level, increasing to ≈−6 K by 3000 m. However, Neotropical sites showed larger than the average sea-level cooling (−5 to −6 K) and a non-significant elevation effect, whereas W and S Pacific sites showed much less sea-level cooling (−1 K) and a stronger elevation effect. These findings support the inference that tropical sea-surface temperatures (SSTs) were lower than the CLIMAP estimates, but they limit the plausible average tropical sea-surface cooling, and they support the existence of CLIMAP-like geographic patterns in SST anomalies. Trends of PAM and lake levels indicate wet LGM conditions in the W USA, and at the highest elevations, with generally dry conditions elsewhere. These results suggest a colder-than-present ocean surface producing a weaker hydrological cycle, more arid continents, and arguably steeper-than-present terrestrial lapse rates. Such linkages are supported by recent observations on freezing-level height and tropical SSTs; moreover, simulations of “greenhouse” and LGM climates point to several possible feedback processes by which low-level temperature anomalies might be amplified aloft.

Synthesis of linked heterocycles via use of bis-acetylenic compounds

Linked bis-pyrazoles, a pyrazolyl-isoxazole, a pyrazolyl-pyrimidine and a pyrazolyl-triazole were synthesized starting with commercially available 1,4-bis(trimethylsilyl)-1,3-butadiyne 1 or readily available bis-acetylenic diketone 22. A stepwise approach based on the use of 1 allowed the synthesis of nonsymmetrically substituted bis-pyrazoles and linked heterocycles with two different cores whereas a symmetric approach based on the use of 22 allowed a very short synthesis of symmetric bis-pyrazoles.

A flow reactor process for the synthesis of peptides utilizing immobilized reagents, scavengers and catch and release protocols

A general flow process for the multi-step assembly of peptides has been developed and this procedure has been used to successfully construct a series of Boc, Cbz and Fmoc N-protected dipeptides in excellent yields and purities, including an extension of the method to enable the preparation of a tripeptide derivative.

The greater whole: towards a synthesis of system dynamics and soft systems methodology

This paper makes a theoretical case for using these two systems approaches together. The theoretical and methodological assumptions of system dynamics (SD) and soft system methodology (SSM) are briefly described and a partial critique is presented. SSM generates and represents diverse perspectives on a problem situation and addresses the socio-political elements of an intervention. However, it is weak in ensuring `dynamic coherence'. consistency between the intuitive behaviour resulting from proposed changes and behaviour deduced from ideas on causal structure. Conversely, SD examines causal structures and dynamic behaviours. However, whilst emphasising the need for a clear issue focus, it has little theory for generating and representing diverse issues. Also, there is no theory for facilitating sensitivity to socio-political elements. A synthesis of the two called ‘Holon Dynamics' is proposed. After an SSM intervention, a second stage continues the socio-political analysis and also operates within a new perspective which values dynamic coherence of the mental construct - the holon - which is capable of expressing the proposed changes. A model of this holon is constructed using SD and the changes are thus rendered `systemically desirable' in the additional sense that dynamic consistency has been confirmed. The paper closes with reflections on the proposal and the need for theoretical consistency when mixing tools is emphasised.

Solvothermal synthesis of one-dimensional chalcogenides containing group 13 elements

The solvothermal synthesis and characterisation of [C6H16N2][GaS2]2 (1), [C6H16N2][Ga2Se3(Se2)] (2), and mixed-metal phases with composition [C6H16N2][Ga2–xInxSe3(Se2)] (0 < x < 2)(3–5), is described. These materials have been characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis and UV/Vis diffuse reflectance spectroscopy. The materials contain one-dimensional anionic chains. In 1, these chains consist of edge-linked GaS4 tetrahedra, whilst in 2–5, the chains contain perselenide (Se2)2– units and comprise alternating four-membered [M2Se2] and five-membered [M2Se3] rings (where M = Ga, In). Compounds 3–5 represent the first examples of ternary mixed-metal [M2Se3(Se2)]2– chains.