Impact of 1,8-diiodooctane on the morphology of organic photovoltaic (OPV) devices – A Small Angle Neutron Scattering (SANS) study

The impact of the additive 1,8-diiodooctane on the morphology of bulk-heterojunction solar cells based on the systems P3HT:PC₇₁BM, PTB7:PC₇₁BM and PTB7-Th:PC₇₁BM is studied using a combination of Small Angle Neutron Scattering (SANS) and Atomic Force Microscopy (AFM). The results clearly show that while in the P3HT:PC₇₁BM system, the additive DIO promotes a slight coarsening of the phase domains (type I additive), in the systems PTB7:PC₇₁BM and PTB7-Th:PC₇₁BM, DIO promotes a large decrease in the size of the phase domains (type II additive). SANS is demonstrated as being particularly useful at detecting the minor morphological changes observed in the P3HT:PC₇₁BM system, which can be hardly seen in AFM. This work illustrates how SANS complements AFM and both techniques when used together provide a deeper insight into the nanoscale structure in thin organic photovoltaic (OPV) device films.     

Effect of Sol–Gel Encapsulation on Lipase Structure and Function: A Small Angle Neutron Scattering Study

The application of small angle neutron scattering (SANS) to the characterisation of sol–gel hosts containing biomolecules offers the opportunity to explore the relationship between gel structure and catalyst. A model system involving the immobilisation of Candida antarctica lipase B (CALB) was investigated.Gels were produced by fluoride-catalysed hydrolysis of fixed ratios of tetramethylorthosilicate (TMOS) and methyltrimethoxysilane (MTMS). Phase separation between the enzyme and the evolving sol–gel matrix was minimised by incorporating glycerol into the sol–gel precursor solution. The potential stabilising effect of the NaF catalyst upon the enzyme was also investigated. Scattering studies were conducted on both immobilised lipase, and lipase in free solution. Scattering studies on free enzyme provided evidence of multiple populations of enzyme aggregates and showed that choice of solvent affected the degree of aggregation. Both NaF and glycerol affected neutron scattering, indicating changes in lipase conformation. Increasing glycerol concentration increased the degree of aggregation and produced differences in solvent packing on the surface of protein molecules. Initial evidence from SANS data indicated that the presence of the enzyme during gel formation conferred structural changes on the gel matrix. Modelling the effect of sol–gel encapsulation on lipase requires comparison of data from free enzyme to the immobilised form. Removal of the enzyme from the sol–gel structure, post gelation, is necessary to better characterise the modified matrix. This methodological problem will be the subject of future investigations.     

Characteristics of AOT Microemulsion Structure: a Small Angle X-ray Scattering Study

The structure of micelles has attracted renewed attention during the past decade years due to the widespread use of microemulsions in technology1 and life science1,2. To obtain information of the micellar structure, using X-ray scattering (SAXS) whose wavelength is close to the size of the micellar aggregates is one of the most direct method3-5 and SAXS has been proved to be very sensitive for the change of micellar composition6,7. SAXS experiments have been carried out to compare the st…     

Small Angle X-ray Scattering Study of PS Conformation in Tetrahydrofuran Solvent with Gas Anti-solvent

Compressed gases or supercritical fluids (SCFs) are highly soluble in some liquid solvents, and thus reduces the solvent strength of the liquids1. As a result, precipitation of the dissolved solutes occurs, which is called as gas anti-solvent (GAS) process. Recently, this new technique has been used to produce fine particles of different compounds, such as polymers2. Effect of the dissolved gases on the conformation of polymer molecules is a very interesting topic. In this work, we report t…     

DOPE/DDAB Magneto‐Vesicles: Synthesis and Characterization

Biocompatible magneto‐vesicles (MVs) with multiple magnetic nanoparticles encapsulated inside were synthesized by the hydration‐sonication method in the presence of magnetic fluid with a mixture of two types of phospholipid molecules. The dimension and the size distribution of these MVs are in the same order as the vesicles synthesized in the similar method, indicating that the encapsulation does not change vesicles' properties dramatically. Releasing fluorophore molecules—carboxylfluorescein (CF) from MVs demonstrates that MVs with DOPE/DDAB layers can be a new type of magnetic carrier for biomedical applications.     

Structural Characteristics of Xyloglucan – Congo Red Aggregates as Observed by Small Angle X-ray Scattering

Xyloglucan is a type of hemicellulose with a cellulose backbone containing (1→6)-α-xylose or (1→2)-β-galactoxylose as a side chain. It is soluble in water. Its aqueous solution forms a gel or gel-like precipitate by addition of Congo red. Xyloglucan gel structures with various concentrations of Congo red were observed by small angle X-ray scattering (SAXS) at the nano-level. SAXS results indicated that the xyloglucan chains interacted with Congo red, and that an increase of concentration of Congo red induced a characteristic cross-linking domain, which consisted of a flat structure containing stacked xyloglucan chain assemblies. The Congo red molecules are inserted between the xyloglucan chains.     

Synthesis and Crystallographic Study of1,6‐bis‐(N‐phenothiazinyl)‐2,4‐hexadiyne

1,6‐bis‐(N‐phenothiazinyl)‐2,4‐hexadiyne (I) was synthesized in high yield by oxidative coupling of N‐propargyl phenothiazine. Grown from methylene chloride‐hexane solution, I is a monoclinic crystal, space group C2/c a=14.9500(18) Å; b=13.5512(15) Å; c=12.0116(10) Å; β=102.628(9)° Å; V=2374.6(4) ų. The intermolecular distances and arrangement of I in the unit cell preclude the usual diacetylene reactivity. Nevertheless, heating of I at 145°C results in decomposition of I to phenothiazine and a dark brown solid. In addition, cation‐radicals of I were prepared by oxidation with nitrosonium tetrafluoroborate and iodine to give stable ion‐radical salts.     

Scattering Factor of C_(60) Molecule

ThisprojectwassupportedbytheYouthScienceFoundationoftheUniveristyofScienceandTechnologyofChinainspiredconsiderableinterestinthephysicalandchemicalpropertiesofthisnewformofcarbon.TheC6omoleculeisproposedtohaveatomsdistributedonthesurfaceofaspherewithalternatingfiveandsixmemberringsasinthepatternofseamsonasoc-cerballt3'4i.Atroomtemperature,single-crystalX-raydiffractionshowsthatthemoleculesarecenteredonsitesofaface-centered-cubic(fcc)Bravaislattice,a=1.4l7nm,withahighdegreeofrotationaldisord…     

After‐Rinsing Hair Growth Promotions of Hinokitiol‐Containing Vesicles and Emulsions

Two kinds of topical dosage forms of hinokitiol (HKL), namely vesicles and oil‐in‐water (O/W) emulsions, were prepared. Behenyl trimethylammonium chloride (BTMAC) and fatty acids were used as bilayer‐forming materials of the vesicles, and oils were employed as oil phases of the emulsions. The substantivity of HKL in the preparations was evaluated in vitro using hairless mouse skins. After applying the preparations onto the skin and rinsing it, the amount of HKL left on the skin was determined using high performance liquid chromatography (HPLC). It was higher when HKL was encapsulated in cationic vesicles rather than in nonionic vehicles, emulsions. An ionic interaction between the cationic vehicle and negatively charged skin is likely to account for the high substantivity. Among the emulsion preparations, an emulsion having octyl salicylate as oil phase exhibited the highest substantivity of HKL. This is probably because that the oil is a good solvent for HKL and it is skin‐retentive. In vivo hair growth‐promotion effect of each dosage form was investigated, where the sample application onto the clipped backs of female mice (C57BL6) and the subsequent rinsing of the backs were done once a day for 30 days. Only HKL in the cationic vesicles had hair growth promotion effect, possibly due to the significant substantivity.     

Dielectric Spectroscopy Study on Vesicles of CTAB/SDBS System

IntroductionWhen the cationic and anionic surfactants in which the total carbon number is equal to or greater than 20 are mixed, then the vesicles can form spontaneously due to the strong interactions or by sonication1. Vesicle is of bilayer structure containing a closed aqueous room, resembling the structure of a real cell. So it seems to be imperative to study the membrane mimicry system like vesicle in order to understand the structure and functions of real cells further. In addition, it ca…     

Synthesis of (E)‐ and (Z)‐5‐(Bromomethylene)furan‐2(5H)‐one by Bromodecarboxylation of (E)‐2‐(5‐Oxofuran‐2(5H)‐ylidene)acetic Acid

(E)‐ and (Z)‐5‐(bromomethylene)furan‐2(5H)‐one have been prepared starting from the commercially available adduct between furan and maleic anhydride. A bromodecarboxylation reaction is a key step in the synthesis. The reaction gives the (E)‐ or (Z)‐5‐(bromomethylene)furan‐2(5H)‐one as the major product, dependent on the method used in the bromodecarboxylation.     

Synthesis of (±)‐ar‐Macrocarpene

An efficient first synthesis of the sesquiterpene ar‐macrocarpene, an irregular sesquiterpene isolated from Cupressus macrocarpa foliage, starting from 3‐methylcyclohexenone has been described, which confirmed the structures of macrocarpenes.     

A Conformational Study on the Interaction of Saporin-S6 with Phospholipid Vesicles

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Kinetic Study of Complex Formation of by 2‐Nitroso‐1‐naphthol with Cobalt (II) Ion in Presence of Cetyltrimethylammonium Bromide Surfactant

The kinetic complex formation of 0.001 M 2‐nitroso‐1‐naphthol (NAPH)with 0.01 M cobalt (II) ion (Co²⁺) in aqueous in presence of 0.02 M NaOH at 30°C in aqueous and/or in and 0.002 M cetyltrimethylammonium bromide (CTAB) have been studied using spectrophotometer at 430 nm. The present data showed that the reaction is first‐order with respect to [Co²⁺]_T and NAPH. Also, k _obs have constant values within concentration 0.015–0.05 M of NaOH and decreases with increase of concentration of CTAB to 0.002 M, then, k _obs have constant values up to 0.005 M. The rate of the reaction in the presence of micelles has been explained with the pseudo‐phase model of the kinetics. Association constants of Co²⁺ and NAPH to CTAB micelle have been calculated. The activation parameters ΔH* and ΔS* have been obtained. The increase of reaction rate with sodium benzoate (C₇H₅O₂Na) also has been discussed.     

How the Aggregates Determine Bound Rubber Models in Silicone Rubber? A Contrast Matching Neutron Scattering Study

The correlation between aggregates and bound rubber structures in silicone rubbers(S(phr)) with various silica fractions(ΦSi) has been investigated by contrast matching small-angle neutron scattering(SANS), swelling kinetics, and low-field nuclear magnetic resonance(NMR).Mixed solvents with deuterated cyclohexane fractions of 4.9% and 53.7% were chosen to match the scattering length densities of the matrix(SMP(phr)) and the filler(SMS(phr)), respectively. All the data consistently suggest that:(i) There is a critical threshold ΦSic between 10 and 30 phr;below ΦSic, the isolated aggregates are dominant, while beyond ΦSic, some rubber fraction is trapped among the agglomerate;(ii) ΦSiindependent thicknesses around 7.5 nm(NMR) and 8.6 nm(SANS) suggest that the bound rubber formation is determined by inherent properties of the components, and the power-law around 4.2 suggests an exponential changed gradient density of the bound rubber;(iii) SMS(80) presents a bicontinuous bound rubber with three characteristic lengths of 41, 100, and 234 nm. The expanded correlation length, a 20 nm smaller aggregate sizes suggest that such existent bicontinuous network in dry samples with less ΦSi is kind of impacted by swelling. With the obtained bound rubber models, the reinforcing mechanism of filled silicone rubber is elucidated.     

Asymmetric Synthesis of (2S)‐1‐(3,4‐Dihydroxyphenoxy)‐3‐(3,′4′‐Dimethoxyphenoxy) Ethylamino‐2‐propanol hydrochloride (RO363)

Enantiomerically pure (S)‐RO363 was synthesized by using (R,R) Salen Co(III) complex for the resolution of terminal epoxide. The hydrolytic kinetic resolution process was carried out at room temperature in excellent enantioselectivity. The method can be applied for large‐scale preparation of (S) RO363.     

Efficient Synthesis of 2‐(N‐Substituted)‐2‐imidazolines and 2‐(N‐Substituted)‐1,4,5,6‐tetrahydropyrimidines

A general method for the preparation of 2‐(N‐Substituted)‐2‐imidazolines and 2‐(N‐Substituted)‐1,4,5,6‐tetrahydropyrimidines is described. These heterocycles can be synthesized from their respective anilines with 2‐chloro‐2‐imidazoline or 2‐chloro‐1,4,5,6‐tetrahydropyrimidine, generated in situ from imidazolidin‐2‐one and tetrahydropyrimidin‐2(1H)‐one activated by dimethyl chlorophosphate, in good to excellent yields.     

Efficient Preparation of ((3‐Chloro‐2‐fluoro‐phenyl)‐[7‐methoxy‐8‐(3‐morpholin‐4‐yl‐propoxy)‐10,11‐dihydro‐5‐oxa‐2,4,11‐triaza‐dibenzo(a,d)cyclohepten‐1‐yl]‐amine) for In‐Vivo Study

An improved route for the preparation of highly functionalized 5,6‐dihydro‐pyrimido[4,5‐b][1,4]oxazepine 1a in multigram quantities was developed. This new methodology was highlighted by the proper methoxy disposition via a regioselective methylation of 2,4,5‐trihydroxy‐benzaldehyde followed by a magnesium sulfate–promoted cyclization.     

Application of Sulfinyl bis(2,4‐dihydroxythiobenzoyl) in the Synthesis of N‐Substituted 2‐Amino‐5‐(2,4‐dihydroxyphenyl)‐1,3,4‐thiadiazoles

One‐stage synthesis of N‐substituted 2‐amino‐5‐(2,4‐dihydroxyphenyl)‐1,3,4‐thiadiazoles is described. The compounds were prepared by the reaction of the sulfinyl bis(2,4‐dihydroxythiobenzoyl) (STB) with 4‐substituted 3‐thiosemicarbazides. STB was obtained from 2,4‐dihydroxybenzenecarbodithioic acid and thionyl dichloride. The structure of compounds was confirmed by IR, ¹H NMR, ¹³C NMR, and EI‐MS data.     

Synthesis,Characterization and Photocrosslinking Properties of Poly(1‐(4‐Methacrylamidophenyl)‐1‐(4‐nitrophenyl)prop‐1‐en‐3‐one)

The phenylmethacrylamide monomer, 1‐(4‐methacrylamidophenyl)‐1‐(4‐nitrophenyl)prop‐1‐en‐3‐one (MPNP) containing a photosensitive group was synthesized by reacting 4‐nitrocinnamoylaniline with methacryloyl chloride in the presence of triethylamine at 0–5°C. The functional monomer, MPNP was polymerized in ethyl methyl ketone (EMK) under nitrogen atmosphere at 70°C using benzoyl peroxide (BPO) as the initiator. The synthesized polymer was characterized by UV, IR, ¹H‐NMR and ¹³C‐NMR spectroscopy. The molecular weight data of the polymer as obtained from gel permeation chromatography suggests a higher tendency for chain termination by radical recombination than disproportionation. The thermal studies of the polymer were obtained from thermogravimetric analysis. The glass transition temperature of the polymer was determined by differential scanning calorimetry. The solubility of the polymer was tested in various organic solvents at room temperature. The photosensitivity of the polymer was investigated in various solvents in the presence and absence of triplet photosensitizers. The effect of the different solvents nature and concentration on the rate of photocrosslinking of the polymer were also examined for using the polymer as negative photoresist materials.