Synthesis, Crystal Structure and Magnetic Properties of the Linear-Chain Cobalt Oxide Sr5Pb3CoO12

The novel spin-chain cobalt oxide Sr5Pb3CoO12 [P-62m, a = 10.1093(2) A and c = 3.562 51(9) A at 295 K] is reported. Polycrystalline sample of the compound was studied by neutron diffraction (at 6 and 295 K) and magnetic susceptibility measurements (5 to 390 K). The cobalt oxide was found to be analogous to the copper oxide Sr5Pb3CoO12, which is comprised of magnetic-linear chains at inter-chain distance of 10 A. Although the cobalt oxide chains (mu_eff of 3.64 mu_B per Co) are substantially antiferromagnetic (theta_W = -38.8 K), neither low-dimensional magnetism nor long-range ordering has been found; a local-structure disorder in the chains might impact on the magnetism. This compound is highly electrically insulating.Comment: To be published in J. Solid State Che

Strategies for the Diversity-Oriented Synthesis of Macrocycles.

Macrocycles have long been recognized as useful chemical entities for medicine, with naturally occurring and synthetic macrocycles clinically approved for use as prescription drugs. Despite this promise, the synthesis of collections of macrocycles has been historically challenging due to difficulties in the formation of large rings. Diversity-Oriented Synthesis (DOS) emerged in the early 2000s as a powerful strategic solution to the construction of diverse molecular libraries. This review details the various strategies developed within the field of DOS for the synthesis of macrocycle libraries, utilizing modern synthetic methodology to deliver structurally diverse collections of macrocyclic molecules, and the exploration of their therapeutic potential. Section 1 of this work details the use of algorithmic strategies and is divided into Build/Couple/Pair, Advanced Build/Couple/Pair, Initiate/Propagate/Terminate, Fragment-Based Domain Shuffling, Two-Directional Synthesis, and Successive Ring Expansion. Section 2 covers strategies based on ring distortion reactions, including Sequential Cycloaddition/Fragmentation, Ring Expansions, and Miscellaneous

Photolabile Linkers for Solid-Phase Synthesis

Photolabile linkers are the subjects of intense research because they allow the release of the target molecule simply by irradiation. Photochemical release of synthesis products is often facilitated without additional reagents under mild reaction conditions, which may even be environmentally friendly and appealing in the context of greener chemistry. The mild conditions also allow for applications of released material in subsequent biological screening experiments, where contamination with cleavage reagents would be detrimental. This Review pays attention to the increasing number of photolabile linkers developed for solid-phase synthesis and release and covers: (i) o-nitrobenzyloxy linkers, (ii) o-nitrobenzylamino linkers, (iii) α-substituted o-nitrobenzyl linkers, (iv) o-nitroveratryl linkers, (v) phenacyl linkers, (vi) p-alkoxyphenacyl linkers, (vii) benzoin linkers, (viii) pivaloyl linkers, and (ix) other photolabile linkers

Effective electro-optical modulation with high extinction ratio by a graphene-silicon microring resonator

Graphene opens up for novel optoelectronic applications thanks to its high carrier mobility, ultra-large absorption bandwidth, and extremely fast material response. In particular, the opportunity to control optoelectronic properties through tuning of Fermi level enables electro-optical modulation, optical-optical switching, and other optoelectronics applications. However, achieving a high modulation depth remains a challenge because of the modest graphene-light interaction in the graphene-silicon devices, typically, utilizing only a monolayer or few layers of graphene. Here, we comprehensively study the interaction between graphene and a microring resonator, and its influence on the optical modulation depth. We demonstrate graphene-silicon microring devices showing a high modulation depth of 12.5 dB with a relatively low bias voltage of 8.8 V. On-off electro-optical switching with an extinction ratio of 3.8 dB is successfully demonstrated by applying a square-waveform with a 4 V peak-to-peak voltage.Comment: 12 pages, including 7 figure

Itaconimides as Novel Quorum Sensing Inhibitors of Pseudomonas aeroginosa

Pseudomonas aeruginosa is known as an opportunistic pathogen that often causes persistent infections associated with high level of antibiotic-resistance and biofilms formation. Chemical interference with bacterial cell-to-cell communication, termed quorum sensing (QS), has been recognized as an attractive approach to control infections and address the drug resistance problems currently observed worldwide. Instead of imposing direct selective pressure on bacterial growth, the right bioactive compounds can preferentially block QS-based communication and attenuate cascades of bacterial gene expression and production of virulence factors, thus leading to reduced pathogenicity. Herein, we report on the potential of itaconimides as quorum sensing inhibitors (QSI) of P. aeruginosa. An initial hit was discovered in a screening program of an in-house compound collection, and subsequent structure-activity relationship (SAR) studies provided analogs that could reduce expression of central QS-regulated virulence factors (elastase, rhamnolipid, and pyocyanin), and also successfully lead to the eradication of P. aeruginosa biofilms in combination with tobramycin. Further studies on the cytotoxicity of compounds using murine macrophages indicated no toxicity at common working concentrations, thereby pointing to the potential of these small molecules as promising entities for antimicrobial drug development.NRF (Natl Research Foundation, S’pore)MOE (Min. of Education, S’pore)Published versio

Oxidative Modification of Tryptophan-Containing Peptides

We herein present a broadly useful method for the chemoselective modification of a wide range of tryptophan-containing peptides. Exposing a tryptophan-containing peptide to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) resulted in a selective cyclodehydration between the peptide backbone and the indole side chain of tryptophan to form a fully conjugated indolyl-oxazole moiety. The modified peptides show a characteristic and significant emission maximum at 425 nm, thus making the method a useful strategy for fluorescence labeling

Structure of nanoparticles embedded in micellar polycrystals

We investigate by scattering techniques the structure of water-based soft composite materials comprising a crystal made of Pluronic block-copolymer micelles arranged in a face-centered cubic lattice and a small amount (at most 2% by volume) of silica nanoparticles, of size comparable to that of the micelles. The copolymer is thermosensitive: it is hydrophilic and fully dissolved in water at low temperature (T ~ 0{\deg}C), and self-assembles into micelles at room temperature, where the block-copolymer is amphiphilic. We use contrast matching small-angle neuron scattering experiments to probe independently the structure of the nanoparticles and that of the polymer. We find that the nanoparticles do not perturb the crystalline order. In addition, a structure peak is measured for the silica nanoparticles dispersed in the polycrystalline samples. This implies that the samples are spatially heterogeneous and comprise, without macroscopic phase separation, silica-poor and silica-rich regions. We show that the nanoparticle concentration in the silica-rich regions is about tenfold the average concentration. These regions are grain boundaries between crystallites, where nanoparticles concentrate, as shown by static light scattering and by light microscopy imaging of the samples. We show that the temperature rate at which the sample is prepared strongly influence the segregation of the nanoparticles in the grain-boundaries.Comment: accepted for publication in Langmui

Increased sinusoidal flow is not the primary stimulus to liver regeneration

Background: Hemodynamic changes in the liver remnant following partial hepatectomy (PHx) have been suggested to be a primary stimulus in triggering liver regeneration. We hypothesized that it is the increased sinusoidal flow per se and hence the shear-stress stimulus on the endothelial surface within the liver remnant which is the main stimulus to regeneration. In order to test this hypothesis we wanted to increase the sinusoidal flow without performing a concomitant liver resection. Accordingly, we constructed an aorto-portal shunt to the left portal vein branch creating a standardized four-fold increase in flow to segments II, III and IV. The impact of this manipulation was studied in both an acute model (6 animals, 9 hours) using a global porcine cDNA microarray chip and in a chronic model observing weight and histological changes (7 animals, 3 weeks). Results: Gene expression profiling from the shunted segments does not suggest that increased sinusoidal flow per se results in activation of genes promoting mitosis. Hyperperfusion over three weeks results in the whole liver gaining a supranormal weight of 3.9% of the total body weight (versus the normal 2.5%). Contrary to our hypothesis, the weight gain was observed on the non-shunted side without an increase in sinusoidal flow. Conclusions: An isolated increase in sinusoidal flow does not have the same genetic, microscopic or macroscopic impact on the liver as that seen in the liver remnant after partial hepatectomy, indicating that increased sinusoidal flow may not be a sufficient stimulus in itself for the initiation of liver regeneration