Chemical abscess post vein of Galen aneurysmal malformation embolisation with ethylene vinyl alcohol copolymer.

Vein of Galen aneurysmal malformation (VGAM) is a rare congenital malformation characterised by arteriovenous fistulas between primitive choroidal arteries and the median prosencephalic vein, the embryonic precursor to the vein of Galen. Endovascular techniques have changed the management of these patients with improved prognosis. An eight-month-old with VGAM managed by endovascular embolisation using ethylene vinyl alcohol copolymer (EVOH) developed a chemical abscess - a rare complication. It was managed conservatively and showed promising clinical outcome. Contribution: Chemical abscesses following EVOH embolisation are scarce - with imaging differentials, which include brain abscess and onyx granuloma. Knowledge and successful identification of this entity are essential as its management as prognoses differ. Chemical abscess is managed conservatively and has a good prognosis.

Rational design and synthesis of novel triazole- and tetrazole-fused iminosugars as potential inhibitors of amyotrophic lateral sclerosis (ALS) linked SOD1 aggregation.

In this manuscript we report the first example of an iminosugar that inhibits superoxide dismutase fibrillation associated with the amyotrophic lateral sclerosis (ALS). The present work involves synthesis of novel triazole and tetrazole embedded iminosugars, synthesized in 11-13 high yielding steps starting from readily available tri-O-benzyl-D-glucal and proceeding through a concomitant azidation - thermal intramolecular [3 + 2] cycloaddition reaction as the key step. One of these pre-designed iminosugars was found to inhibit fibrillation of SOD1 and also has shown propensity to break pre-formed fibrils. Docking and MD simulation studies suggest that the most probable interaction of this compound is a hydrogen bonding with Arg69, a loop IV residue of SOD1, which has a crucial role in stabilizing the native conformation of SOD1.

An expeditious synthesis of novel DNA nucleobase mimics of (+)-anisomycin.

A glycal based expeditious synthesis of novel nucleoside analogues of (+)-anisomycin is reported. Readily available tri-O-benzyl-D-glucal was converted to a partially protected trihydroxypyrrolidine that is used as a common scaffold for the introduction of various nucleobases at the primary hydroxyl centre. Nucleoside analogues possessing all four DNA bases have been synthesized. Selective acetylation at C3 position was carried out with two of these unnatural nucleosides in order to mimic the structure of (+)-anisomycin. Cytotoxicity studies of some of these nucleosides showed that they display weaker activity on HeLa cells than Ara-C.

Effects of surface oxidation on the pH-dependent surface charge of oxidized aluminum gallium nitride.

HYPOTHESIS: The properties of the oxidized surface for common materials, such as silicon and titanium, are known to be markedly different from the reduced surface. We hypothesize that surface-oxidized aluminum gallium nitride ((oxidized-AlGaN)/GaN) surface charge behavior is different to unoxidized AlGaN (with ultrathin native oxide only), which can be validated via surfactant adsorption. Understanding these differences will explain why (oxidized-AlGaN)/GaN-based sensors are better performing than AlGaN ones, which has been previously demonstrated but not understood. EXPERIMENTS: The surface of an AlGaN/GaN structure was oxidized with hot piranha solution and oxygen plasma. AFM force measurements and imaging were performed to probe the charge properties of the surface in aqueous solutions of varying pH containing only an acid or base, or with an added ionic surfactant: cationic cetyltrimethylammonium bromide (CTAB) or anionic sodium dodecylsulfate (SDS). FINDINGS: The (oxidized-AlGaN)/GaN surface is positively charged at pH 4 and pH 5.5, although pH 5.5 should be close to the isoelectric point of the surface. The surface is negatively charged at pH 10 and pH 12, and sufficiently charged to attract cooperative adsorption of CTAB aggregates at pH 12. At pH 2, the evidence is inconclusive, but the surface is most likely positively charged. Compared to unoxidized AlGaN, the (oxidized-AlGaN)/GaN surface shows a wider range of surface charge magnitude over pH values between 2 and 12. This suggests that the (oxidized-AlGaN)/GaN surface has a higher surface hydroxyl group density than unoxidized AlGaN, which explains the higher sensitivity for pH sensors based on (oxidized-AlGaN)/GaN structures.

pH-Dependent surface charge at the interfaces between aluminum gallium nitride (AlGaN) and aqueous solution revealed by surfactant adsorption.

HYPOTHESIS: The net surface charge of AlGaN/GaN structures, where AlGaN is in contact with the solution, is controlled by the pH-dependent protonation and deprotonation of the surface hydroxyl groups and possibly the electron-deficient surface electronic states. We hypothesize that atomic force microscopy (AFM) force measurements of ionic surfactant adsorption can reveal how the AlGaN surface properties vary with pH. EXPERIMENTS: AFM force curves and images were used to probe the AlGaN/solution interface in water as a function of pH, and with added cationic surfactant cetyltrimethylammonium bromide (CTAB) or anionic surfactant sodium dodecylsulfate (SDS). FINDINGS: The AlGaN/solution interface is negatively charged at pH 12, has an isoelectric point near pH 5.5, and is positively charged at pH values less than 5.5. Surfactant adsorption data suggests AlGaN surface is somewhat hydrophobic at acidic pH. Compared to gallium nitride (GaN), at pH 2, AlGaN has a lower charge density and hydrophobicity, but at other values of pH, the surface properties of AlGaN and GaN are similar.

Supramolecular Architecture through Self-Organization of Janus-Faced Homoazanucleosides.

Design of Janus-faced or double-headed homoazanucleosides with the possibility to undergo self-organization through base pairing has been conceptualized and accomplished. The synthetic strategy demonstrates the unique ability to introduce two similar or complementary nucleobases on opposite arms of a chiral polyhydroxypyrrolidine while also ensuring that their faces are anti to each other to allow only intermolecular interactions between the nucleobases, an essential requisite for self-assembly. Single-crystal X-ray structures were determined for all three types of homoazanucleosides, one possessing two adenine molecules, the other with two thymine moieties, and the third containing both adenine and thymine. The crystal structures of all three display noncovalent interactions, including Watson-Crick base pairing, Hoogsteen H-bonding, and π-π stacking, resulting in unusual supramolecular patterns. The most striking supramolecular motif among them, which emerged from the crystal structure of the homoazanucleoside containing both adenine and thymine, is a left-handed helix formed through Watson-Crick pairing between nucleobases. The present study thus forms a prelude to the design of Janus-faced building blocks to establish helical pillars as well as lateral branches that together define a three-dimensional (3D) lattice. The ready accessibility of these molecules is expected to spur the next generation of discoveries in the design of functional nanomaterials.

A glycal based approach to the synthesis of (+)-bulgecinine, 3-hydroxy-2,5-dihydroxymethylpyrrolidine and 2-oxapyrrolizidin-3-one.

A glycal based synthesis of (+)-bulgecinine, 3-hydroxy-2,5-dihydroxymethylpyrrolidine and 2-oxapyrrolizidin-3-ones proceeding through a common intermediate is reported. The key step in the work presented here is a two-step conversion of 4,6-di-O-benzyl-d-glucal to 2,3-dideoxy-2-tosylamido-d-glucose. This manuscript reports the first carbohydrate based approach to the synthesis of (+)-bulgecinine and the whole sequence has been accomplished with complete stereochemical integrity without the formation of mixture of products in any of these steps.

Compliant Micron-Sized Patterned InGaN Pseudo-Substrates Utilizing Porous GaN.

The compliant behavior of densely packed 10 × 10 µm2 square patterned InGaN layers on top of porous GaN is demonstrated. The elastic relaxation of the InGaN layers is enabled by the low stiffness of the porous GaN under layer. High resolution X-ray diffraction measurements show that upon InGaN re-growths on these InGaN-on-porous GaN pseudo-substrates, not only was the regrown layer partially relaxed, but the degree of relaxation of the InGaN pseudo-substrate layer on top of the porous GaN also showed an increase in the a-lattice constant. Furthermore, methods to improve the surface morphology of the InGaN layers grown by metal-organic chemical vapor deposition (MOCVD) were explored in order to fabricate InGaN pseudo-substrates for future optoelectronic and electronic devices. The largest a-lattice constant demonstrated in this study using this improved method was 3.209 Å, corresponding to a fully relaxed InGaN film with an indium composition of 0.056.

pH-dependent surface properties of the gallium nitride - Solution interface mapped by surfactant adsorption.

HYPOTHESIS: The surface charge of gallium nitride (GaN) in contact with solution is controlled by pH via surface protonation and deprotonation, similar to silica. Ionic surfactants adsorb on surfaces via electrostatic and hydrophobic interactions and can be utilized to reflect the surface charge of GaN. EXPERIMENTS: The surface charge properties of Ga-polar GaN in solution were probed as a function of pH using atomic force microscopy (AFM). AFM soft-contact images and force curves were used to study the pH-dependent adsorption of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and anionic surfactant sodium dodecylsulfate (SDS) on GaN surfaces. To further confirm the AFM results, GaN/AlGaN/GaN heterostructure-based ion sensing devices were used to measure the surfactant adsorption over the same pH range. FINDINGS: SDS aggregates adsorb on GaN below pH 2.75 while CTAB aggregates adsorb above pH 10. This shows that the GaN surface carries substantial net positive charge at low pH, and negative charge at high pH. There is no clear SDS or CTAB adsorption on the GaN surface between pH 3 and 9.75, which indicates the surface is weakly charged. GaN/AlGaN/GaN heterostructure-based devices confirm these results, and demonstrate the utility of these devices for measuring surfactant adsorption.

Ca2+ detection utilising AlGaN/GaN transistors with ion-selective polymer membranes.

We demonstrate highly selective and sensitive potentiometric ion sensors for calcium ion detection, operated without the use of a reference electrode. The sensors consist of AlGaN/GaN heterostructure-based transistor devices with chemical functionalisation of the gate area using poly (vinylchloride)-based (PVC) membranes having high selectivity towards calcium ions, Ca2+. The sensors exhibited stable and rapid responses when introduced to various concentrations of Ca2+. In both 0.01 M KCl and 0.01 M NaCl ionic strength buffer solutions, the sensors exhibited near Nernstian responses with detection limits of less than 10-7 M, and a linear response range between 10-7-10-2 M. Also, detection limits of less than 10-6 M were achieved for the sensors in both 0.01 M MgCl2 and 0.01 M LiCl buffer solutions. AlGaN/GaN-based devices for Ca2+ detection demonstrate excellent selectivity and response range for a wide variety of applications. This work represents an important step towards multi-ion sensing using arrays of ion-selective field effect transistor (ISFET) devices.

Origin of defect-insensitive emission probability in In-containing (Al,In,Ga)N alloy semiconductors.

Group-III-nitride semiconductors have shown enormous potential as light sources for full-colour displays, optical storage and solid-state lighting. Remarkably, InGaN blue- and green-light-emitting diodes (LEDs) emit brilliant light although the threading dislocation density generated due to lattice mismatch is six orders of magnitude higher than that in conventional LEDs. Here we explain why In-containing (Al,In,Ga)N bulk films exhibit a defect-insensitive emission probability. From the extremely short positron diffusion lengths (<4 nm) and short radiative lifetimes of excitonic emissions, we conclude that localizing valence states associated with atomic condensates of In-N preferentially capture holes, which have a positive charge similar to positrons. The holes form localized excitons to emit the light, although some of the excitons recombine at non-radiative centres. The enterprising use of atomically inhomogeneous crystals is proposed for future innovation in light emitters even when using defective crystals.