Nickel phosphonate MOF as efficient water splitting photocatalyst

A novel microporous two-dimensional(2D)Ni-based phosphonate metal-organic framework(MOF;denoted as IEF-13)has been successfully synthesized by a simple and green hydrothermal method and fully characterized using a combination of experimental and computational techniques.Structure resolution by single-crystal X-ray diffraction reveals that IEF-13 crystallizes in the triclinic space group Pi having bi-octahedra nickel nodes and a photo/electroactive tritopic phosphonate ligand.Remarkably,this material exhibits coordinatively unsaturated nickel(II)sites,free-P0₃H₂and-P0₃H acidic groups,a C0₂accessible microporosity,and an exceptional thermal and chemical stability.Further,its in-deep optoelectronic characterization evidences a photoresponse suitable for photocatalysis.In this sense,the photocatalytic activity for challenging H₂generation and overall water splitting in absence of any co-catalyst using UV-Vis irradiation and simulated sunlight has been evaluated,constituting the first report for a phosphonate-MOF photocatalyst.IEF-13 is able to produce up to 2,200 fimol of H₂per gram using methanol as sacrificial agent,exhibiting stability,maintaining its crystal structure and allowing its recycling.Even more,170μmol of H₂per gram were produced using IEF-13 as photocatalyst in the absence of any co-catalyst for the overall water splitting,being this reaction limited by the 0₂reduction.The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.     

Geopolymer assembly by emulsion templating: Emulsion stability and hardening mechanisms

This work investigates emulsion templating to synthesize hexadecane oil/geopolymer composites. In a system with hexadecane as the internal (dispersed) phase and an alkali activated continuous phase without added surfactant, adding aluminosilicate clay particles does not increase resistance against creaming or coalescence, while adding a surfactant (L35 or CTAB) stabilizes the solid-liquid interface. Infrared studies and rheological studies of the associated geopolymerization determined that the presence of the organic phase or surfactant has no significant effect on the geopolymerization kinetics, as determined by the change in time of the Si-O-T IR stretching frequency and the rheological moduli involved during the process. The stabilization of the organic template is reminiscent of Pickering emulsion even though we employ a much greater amount of inorganic material for geopolymer formation. Although the addition of surfactant has a significant effect on the behavior of the paste, the percolation of the network remains unmodified, highlighting the fact that the phenomenon is not dependent on viscosity. Finally, rheological measurements were used to obtain the mass fractal dimension of the as-made gel network, which is able to differentiate the interfacial effect between surfactant molecules with a slightly denser interphase when a cationic surfactant is used.     

Synthetic Peroxides Promote Apoptosis of Cancer Cells by Inhibiting P-Glycoprotein ABCB5

This article discloses a new horizon for the application of peroxides in medical chemistry. Stable cyclic peroxides are demonstrated to have cytotoxic activity against cancer cells; in addition a mechanism of cytotoxic action is proposed. Synthetic bridged 1,2,4,5-tetraoxanes and ozonides were effective against HepG2 cancer cells and some ozonides selectively targeted liver cancer cells (the selectivity indexes for compounds 11 b and 12 a are 8 and 5, respectively). In some cases, tetraoxanes and ozonides were more selective than paclitaxel, artemisinin, and artesunic acid. Annexin V flow-cytometry analysis revealed that the active ozonides 22 a and 23 a induced cell death of HepG2 by apoptosis. Further study showed that compounds 22 a and 23 a exhibited a strong inhibitory effect on P-glycoprotein (P-gp/ABCB5)-overexpressing HepG2 cancer cells. ABCB5 is a key player in the multidrug-resistant phenotype of liver cancer. Peroxides failed to demonstrate a direct correlation between oxidative potential and their biological activity. To our knowledge this is the first time that peroxide diastereoisomers have been found to show stereospecific antimalarial action against the chloroquine-sensitive 3D7 strain of Plasmodium falciparum. Stereoisomeric ozonide 12 b is 11 times more active than stereoisomeric ozonide 12 a (IC₅₀=5.81 vs 65.18 μm ). Current findings mean that ozonides merit further investigation as potential therapeutic agents for drug-resistant hepatocellular carcinoma.     

Making polyurethane foams from microemulsions

A remarkable correlation exists between the degree of expansion of polyurethane foams and the structure of the reacting premixes. Polyurethane foams obtained from reacting premixes containing microemulsions are highly expanded. The expansion rate is proportional to the volume fraction of microemulsion in the premix. The stability of premixes with and without microemulsion is completely different suggesting distinct creaming mechanisms. We apply this idea to synthesize polyurethane foams from microemulsions successfully. This approach can be used to rationalize the design of polyurethane formulations leading to highly expanded foams.     

Jitter in ATM networks and its impact on peak rate enforcement

Cells arriving to an ATM network experience random delays due to queueing in upstream multiplexing stages, notably in customer premises. This is the phenomenon of jitter and the aim of the present paper is to study its influence on peak rate enforcement. We first introduce some general characterizations of jitter and then, describe two models of jittered flows based on simple queueing systems. We discuss the objectives of peak rate enforcement and study the impact of jitter on the dimensioning of jumping window and leaky bucket mechanisms. A useful synthetic characterization of jitter appears to be a remote quantile of the cell delay distribution expressed in units of the initial inter-cell interval.     

Shear mode coupling and tilted grain growth of A1N thin films in BAW resonators.

Polycrystalline A1N thin films were deposited by RF reactive magnetron sputtering on Pt(111)/Ti electrode films. The substrates were tilted by an angle ranging from 40 degrees to 70 degrees with respect to the target normal. A low deposition temperature and a high sputter gas pressure were found ideal for tilted growth. The resulting grain tilt angle amounts to about half the substrate tilt angle. For coupling evaluation, 5 GHz solidly mounted resonator structures have been realized. The tilted grain A1N films exhibited a permittivity in the 9.5-10.5 range and loss tangent of 0.3%. Two shear modes as well as the longitudinal mode could be clearly identified. The coupling coefficient k2(eff) of the fundamental thickness shear mode (TS0) was found to be about 0.5%, which is compatible with a c-axis tilt of about 6 degrees.     

Fabrication of a biocompatible flexible electroosmosis micropump

In in-vivo microsystems, one of the components is a biocompatible micropump in order to produce the necessary force to deliver the fluid from the inlet to the outlet. In this contribution, a flexible micropump is fabricated which is aimed to be suitable in drug delivery applications. It provides high degree of biocompatibility, since the only employed materials are implantation grade polydimethylsiloxane elastomer and gold for the electrical interconnects. The working principle of the micropump is based on transverse DC electroosmosis which is a new variant of conventionally applied high voltage DC electroosmosis. This new technique is based on topography irregularities introduced in the channel resulting in a non-uniform charge distribution. The advantage is to drive the micropump using a relatively low DC voltage of 10 V while getting an effective flow speed of 60 μm/s. In order to characterize the flow speed, dyed 3 μm beads are dispersed in the working fluid and their speed is measured by the line scanning technique using a confocal microscope. It is also observed that the flow has a helical profile which is an attractive feature for an efficient micro-mixer in active microfluidics and μ-TAS applications.     

P2Y11 Agonism Prevents Hypoxia/Reoxygenation- and Angiotensin II-Induced Vascular Dysfunction and Intimal Hyperplasia Development

Vascular dysfunction in cardiovascular diseases includes vasomotor response impairments, endothelial cells (ECs) activation, and smooth muscle cells (SMCs) proliferation and migration to the intima. This results in intimal hyperplasia and vessel failure. We previously reported that activation of the P2Y11 receptor (P2Y11R) in human dendritic cells, cardiofibroblasts and cardiomyocytes was protective against hypoxia/reoxygenation (HR) lesions. In this study, we investigated the role of P2Y11R signaling in vascular dysfunction. P2Y11R activity was modulated using its pharmacological agonist NF546 and antagonist NF340. Rat aortic rings were exposed to angiotensin II (AngII) and evaluated for their vasomotor response. The P2Y11R agonist NF546 reduced AngII-induced vascular dysfunction by promoting EC-dependent vasorelaxation, through an increased nitric oxide (NO) bioavailability and reduced AngII-induced H₂O₂ release; these effects were prevented by the use of the P2Y11R antagonist NF340. Human vascular SMCs and ECs were subjected to AngII or H/R simulation in vitro. P2Y11R agonist modulated vasoactive factors in human ECs, that is, endothelial nitric oxide synthase (eNOS) and endothelin-1, reduced SMC proliferation and prevented the switch towards a synthetic phenotype. H/R and AngII increased ECs secretome-induced SMC proliferation, an effect prevented by P2Y11R activation. Thus, our data suggest that P2Y11R activation may protect blood vessels from HR-/AngII-induced injury and reduce vascular dysfunctions. These results open the way for new vasculoprotective interventions.     

Peer to peer trade in HTM5 meta model for agent oriented cloud robotic systems

Cloud computing is a methodology and not a technology. Adaptation of cloud computing services for robotic applications is relatively straightforward while adaptation of underlying ideas will require a new design attitude. Cloud computing is a cost-effective and dynamic business model. Currently cloud robotics is understood as a client server methodology which enables robots utilize resources and services placed at centralized servers. These cloud servers treat robots as any other client computer offering them platform, infrastructure, process or algorithm as a service. HTM5 is an OMG MDA based multi-view meta-model for agent oriented development of cloud robotic systems. HTM5 encourages design of peer-to-peer service ecosystems based on an open registry and matchmaking mechanism. In peer-to-peer cloud robotics, a robot can trade its hardware, software and functional resources as a service to other robots in the ecosystem. The peer-to-peer trade in such systems may be driven by contracts and relationships between its member agents. This article discusses trade-view model of HTM5 methodology and its use in developing a cloud robotic ecosystem that implements peer-to-peer, contract based economy. The article also presents a case study with experiments that implement distributed artificial intelligence and peer-to-peer service oriented trade on simulated and real robot colonies.