Morphology of Palladium Thin Film Deposited on a Two-Dimensional Bilayer Aluminosilicate

Topics in Catalysis - The morphology of a thin palladium film deposited on bilayer Al0.35Si0.65O2/Ru(0001), previously proposed as a two-dimensional zeolite model, is investigated using a set of...     

Mixed bi-material electrodes based on LiMn2O4 and activated carbon for hybrid electrochemical energy storage devices

The performance of mixed bi-material electrodes composed of the battery material, LiMn₂O₄, and the electrochemical capacitor material, activated carbon, for hybrid electrochemical energy storage devices is investigated by galvanostatic charge/discharge and pulsed discharge experiments. Both, a high and a low conductivity lithium-containing electrolyte are used. The specific charge of the bi-material electrode is the linear combination of the specific charges of LiMn₂O₄ and activated carbon according to the electrode composition at low discharge rates. Thus, the specific charge of the bi-material electrode falls between the specific charge of the activated carbon electrode and the LiMn₂O₄ battery electrode. The bi-material electrodes have better rate capability than the LiMn₂O₄ battery electrode. For high current pulsed applications the bi-material electrodes typically outperform both the battery and the capacitor electrode.     

Pressure Sensitive Adhesives Based on Epoxidized Soybean Oil: Correlation Between Curing Conditions and Rheological Properties

Renewable resources, including vegetable oils, can be used as feedstock for the manufacture of pressure sensitive adhesives (PSA) that can compete with those derived from petrochemical sources, but with the environmental benefit of being sustainable. Completely bio‐based PSA with tunable viscoelastic properties were synthesized from mixtures of epoxidized soybean oil and sebacic acid by a solvent‐free one‐step reaction, in the absence of catalyst. Curing conditions and pot‐life were determined for formulations with stoichiometric acid/epoxy ratio. Curing time ranged from the gel point (t_gel) to t_gel + 30 min at the selected temperature (170 °C) to study the correlation between the reaction, rheological behavior, and potential adhesive performance. These renewable PSA can be tailored by controlling the curing parameters according to the desired application, since the rheological profile and gel content were greatly dependent on the curing conditions. In particular, the obtained adhesives cured at 170 °C between 65 and 75 min showed the best balance between tack and cohesion.     

Supramolecular Capsules Derived from Resorcin[4]arenes by H-Bonding and Metal Coordination: Synthesis,Characterization, and Single-Molecule Force Spectroscopy

Self-assembly by H-bonding and by metal-coordination of functionalized calix[4]arenes and cavitands to large supramolecular capsules is described. In addition, a new method of analyzing supramolecular recognition processes at the single molecule level is discussed. By measuring interaction forces in a hydrogen-bonded assembly using single-molecule force spectroscopy (SMFS), the dynamics of the self-assembly process can be evaluated. In the future, consequent application of this new technique will influence supramolecular design principles and the use of non-covalent interactions as construction elements in the field of nanotechnology.     

Bioluminescent Optogenetics: A Novel Experimental Therapy to Promote Axon Regeneration after Peripheral Nerve Injury

Functional recovery after peripheral nerve injury (PNI) is poor, mainly due to the slow and incomplete regeneration of injured axons. Experimental therapies that increase the excitability of the injured axons have proven remarkably successful in promoting regeneration, but their clinical applicability has been limited. Bioluminescent optogenetics (BL-OG) uses luminopsins, fusion proteins of light-generating luciferase and light-sensing ion channels that could be used to increase neuronal excitability if exposed to a suitable substrate. Excitatory luminopsins were expressed in motoneurons of transgenic mice and in wildtype mice transduced with adeno-associated viral vectors. Intraperitoneal administration of coelenterazine (CTZ), a known luciferase substrate, generated intense bioluminescence in peripheral axons. This bioluminescence increased motoneuron excitability. A single administration of CTZ immediately after sciatic nerve transection and repair markedly enhanced motor axon regeneration. Compound muscle action potentials were 3–4 times larger than controls by 4 weeks after injury. The results observed with transgenic mice were comparable to those of mice in which the luminopsin was expressed using viral vectors. Significantly more motoneurons had successfully reinnervated muscle targets four weeks after nerve injury in BL-OG treated mice than in controls. Bioluminescent optogenetics is a promising therapeutic approach to enhancing axon regeneration after PNI.     

Surface chemistry of SnO2 nanowires on Ag-catalyst-covered Si substrate studied using XPS and TDS methods

In this paper we investigate the surface chemistry, including surface contaminations, of SnO₂ nanowires deposited on Ag-covered Si substrate by vapor phase deposition (VPD), thanks to x-ray photoelectron spectroscopy (XPS) in combination with thermal desorption spectroscopy (TDS). Air-exposed SnO₂ nanowires are slightly non-stoichiometric, and a huge amount of C contaminations is observed at their surface. After the thermal physical desorption (TPD) process, SnO₂ nanowires become almost stoichiometric without any surface C contaminations. This is probably related to the fact that C contaminations, as well as residual gases from air, are weakly bounded to the crystalline SnO₂ nanowires and can be easily removed from their surface. The obtained results gave us insight on the interpretation of the aging effect of SnO₂ nanowires that is of great importance for their potential application in the development of novel chemical nanosensor devices.     

Genes and Pathways Involved in Adult Onset Disorders Featuring Muscle Mitochondrial DNA Instability

Replication and maintenance of mtDNA entirely relies on a set of proteins encoded by the nuclear genome, which include members of the core replicative machinery, proteins involved in the homeostasis of mitochondrial dNTPs pools or deputed to the control of mitochondrial dynamics and morphology. Mutations in their coding genes have been observed in familial and sporadic forms of pediatric and adult-onset clinical phenotypes featuring mtDNA instability. The list of defects involved in these disorders has recently expanded, including mutations in the exo-/endo-nuclease flap-processing proteins MGME1 and DNA2, supporting the notion that an enzymatic DNA repair system actively takes place in mitochondria. The results obtained in the last few years acknowledge the contribution of next-generation sequencing methods in the identification of new disease loci in small groups of patients and even single probands. Although heterogeneous, these genes can be conveniently classified according to the pathway to which they belong. The definition of the molecular and biochemical features of these pathways might be helpful for fundamental knowledge of these disorders, to accelerate genetic diagnosis of patients and the development of rational therapies. In this review, we discuss the molecular findings disclosed in adult patients with muscle pathology hallmarked by mtDNA instability.     

Random and block copolymers based on 4-methyl-1-pentene and 1-pentene

The zirconium acetamidinate catalyst {Cp*Zr(Me)₂[N(Et)C(Me)N(tBu)]} (Cp* = ?⁵-C₅Me₅) was used to synthesize both random and block copolymers based on 4-methyl-1-pentene (4M1P) and 1-pentene. The polymers have been characterized by NMR spectroscopy, SEC, DSC, high temperature HPLC and CRYSTAF. Unexpectedly, the yields and molecular weights decreased with increasing amounts of 1-pentene. The reason for this behavior is that 1-pentene occasionally undergoes 2,1-misinsertions trapping the catalyst in a dormant state. These 2,1-misinsertions do not seem to occur with the bulky 4M1P (branched α-olefin). Adding a small amount of ethylene reactivates the catalyst. Unlike most semi-crystalline polymers, the density of the crystalline phase of isotactic P4M1P can be lower than of the amorphous phase, when crystallized under very high pressures. To characterize this peculiar behavior of 4M1P-based polymers, various samples have been subjected to Pressure-Volume-Temperature (PVT) measurements. While the P4M1P homopolymers and block copolymers show the expected decrease in specific volume upon crystallization, the 4M1P-rich random copolymers proved not to vary in specific volume under the same conditions.     

Submicron machining and biomolecule immobilization on porous silicon by electron beam

Three-dimensional submicrometric structures and biomolecular patterns have been fabricated on a porous silicon film by an electron beam-based functionalization method. The immobilized proteins act as a passivation layer against material corrosion in aqueous solutions. The effects'' dependence on the main parameters of the process (i.e., the electron beam dose, the biomolecule concentration, and the incubation time) has been demonstrated.     

Confocal ultrafast pump-probe spectroscopy: a new technique to explore nanoscale composites

This article is devoted to the exploration of the benefits of a new ultrafast confocal pump-probe technique, able to study the photophysics of different structured materials with nanoscale resolution. This tool offers many advantages over standard stationary microscopy techniques because it directly interrogates excited state dynamics in molecules, providing access to both radiative and non-radiative deactivation processes at a local scale. In this paper we present a few different examples of its application to organic semiconductor systems. The first two are focussed on the study of the photophysics of phase-separated polymer blends: (i) a blue-emitting polyfluorene (PFO) in an inert matrix of PMMA and (ii) an electron donor polythiophene (P3HT) mixed with an electron acceptor fullerene derivative (PCBM). The experimental results on these samples demonstrate the capability of the technique to unveil peculiar interfacial dynamics at the border region between phase-segregated domains, which would be otherwise averaged out using conventional pump-probe spectroscopy. The third example is the study of the photophysics of isolated mesoscopic crystals of the PCBM molecule. Our ultrafast microscope could evidence the presence of two distinctive regions within the crystals. In particular, we could pinpoint for the first time areas within the crystals showing photobleaching/stimulated emission signals from a charge-transfer state.