Retinoblastoma (Rb) is the most common primary intraocular tumor in children. Local treatment of disease usually effective if diagnosed early; however advanced Rb can metastasize through routes that involve invasion choroid, sclera and optic nerve or more broadly via ocular vasculature. Metastatic patients have very high mortality rates. While current therapy for directed toward blocking cell division growth, there are no specific treatments targeted to block metastasis. Two such targets...

NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as site of catalytic activity but differ with respect to relevant redox state. A combination hybrid periodic density functional theory calculations spectroelectrochemical experiments elucidate electronic structure thermodynamics Ni-only mixed thin-film...

Protons venture into the inverted region One of most counterintuitive features electron transfer kinetics is region. As Marcus theory predicts and experiments have borne out, slows down once driving force for it becomes especially favorable. Parada et al. now offer evidence such behavior in proton-coupled (see Perspective by Dempsey). Specifically, they examined a series compounds with phenol bridging anthracene (electron acceptor) pyridine (proton derivatives. Time-resolved spectroscopy...

The selective reduction of O2, typically with the goal forming H2O, represents a long-standing challenge in field catalysis. Macrocyclic transition-metal complexes, and cobalt porphyrins particular, have been focus extensive study as catalysts for this reaction. Here, we show that mononuclear Co-tetraarylporphyrin complex, Co(porOMe) (porOMe = meso-tetra(4-methoxyphenyl)porphyrin), catalyzes either 2e-/2H+ or 4e-/4H+ O2 high selectivity simply by changing identity Brønsted acid...

A soluble, bis-ketiminate-ligated Co complex [Co(N2O2)] was recently shown to catalyze selective reduction of O2 H2O2 with an overpotential as low 90 mV. Here we report experimental and computational mechanistic studies the Co(N2O2)-catalyzed reaction (ORR) decamethylferrocene (Fc*) reductant in presence AcOH MeOH. Analysis Co/O2 binding stoichiometry kinetic support pathway involving a mononuclear cobalt species. The catalytic rate exhibits first-order dependence on [AcOH], but no [Fc*] or...

<italic>Ab initio</italic> molecular dynamics of an aqueous electrode interface reveal the electrostatic, structural, and dynamic effects quantifiable voltage biases on water.

Electric fields control chemical reactivity in a wide range of systems, including enzymes and electrochemical interfaces. Characterizing the electric at electrode–solution interfaces is critical for understanding heterogeneous catalysis associated energy conversion processes. To address this challenge, recent experiments have probed response nitrile stretching frequency 4-mercaptobenzonitrile (4-MBN) attached to gold electrode changes solvent applied potential. Herein, system modeled with...

The first step of the hydrogen evolution reaction, an important reaction for storage renewable energy, is formation a surface-adsorbed atom through proton discharge to electrode surface, commonly known as Volmer reaction. Herein theoretical description presented. In this formulation, electronic states are represented in framework empirical valence bond theory, and solvent interactions treated using dielectric continuum model linear response regime. nuclear quantum effects transferring...

The newly purified extracellular polysaccharides (exopolysaccharides) from Parachlorella kessleri (PCEPS) were evaluated on their antitumor and immunomodulatory effects in cell culture mouse colon carcinoma peritoneal dissemination model. In two-dimensional culture, the PCEPS treatment inhibited growth of both murine human cells a dose- time-dependent manner. contrast, splenocytes (SPLs) bone marrow (BMCs) stimulated by with PCEPS. also increased specific subpopulations BMCs: antigen...

The discharge of protons on electrode surfaces, known as the Volmer reaction, is a ubiquitous reaction in heterogeneous electrocatalysis and plays an important role renewable energy technologies. Recent experiments with triethylammonium (TEAH+) donating proton to gold acetonitrile demonstrate significantly different Tafel slopes for TEAH+ its deuterated counterpart, TEAD+. As result, kinetic isotope effect (KIE) hydrogen evolution changes considerably function applied potential. Herein...

The electrical double layer (EDL) at metal oxide-electrolyte interfaces critically affects fundamental processes in water splitting, batteries, and corrosion. However, limitations the microscopic-level understanding of EDL have been a major bottleneck controlling these interfacial processes. Herein, we use ab initio-based machine learning potential simulations incorporating long-range electrostatics to unravel molecular-scale picture prototypical anatase TiO2-electrolyte interface under...

We design, develop, and experimentally validate a complete integrated software/hardware platform for airborne cognitive networking in both indoor outdoor environments. first present the concept of all-spectrum describe distributed algorithm maximizing network spectral efficiency by jointly optimizing channel access code-waveforms routes multi-hop network. then discuss system design parameters implementation details setting up software-defined radio (SDR) testbed that enables...

Developing new strategies to activate and cleave C–H bonds is important for a broad range of applications. Recently approach bond activation using multi-site concerted proton-coupled electron transfer (PCET) involving intermolecular an oxidant coupled intramolecular proton was reported. For series oxidants reacting with 2-(9H-fluoren-9-yl)benzoate, experimental studies revealed atypical Brønsted α, defined as the slope logarithm PCET rate constant versus equilibrium or scaled driving force....

The electrical double layer (EDL) at aqueous solution-metal oxide interfaces critically affects many fundamental processes in electrochemistry, geology and biology, yet understanding its microscopic structure is challenging for both theory experiments. Here we employ ab initio-based machine learning potentials including long-range electrostatics large-scale atomistic simulations of the EDL TiO2-electrolyte interface. Our provide a molecular-scale picture that demonstrates limitations...

Previous electrophysiological investigation shows that combinations of compounds classified by humans as umami-tasting, such glutamate salts and 5′-ribonucleotides, elicit synergistic responses in neurons throughout the rodent taste system produce a pattern resembles to sweet compounds.The current study tested hypothesis mixture monopotassium (MPG) inositol monophosphate (IMP) possesses perceptual similarity sucrose mice.We estimated behavioral among these tastants individual umami using...

Photoinduced proton-coupled electron transfer (PCET) plays a key role in wide range of energy conversion processes, and understanding how to design systems control the PCET rate constant is significant challenge. Herein theoretical formulation utilized identify conditions under which photoinduced may exhibit inverted region behavior. In region, decreases as driving force increases even though reaction becomes more thermodynamically favorable. will behavior when following criteria are...

Neurodegenerative diseases often have a devastating impact on those affected. Retinal ganglion cell (RGC) loss is implicated in an array of diseases, including diabetic retinopathy and glaucoma, addition to normal aging. Despite their importance, RGCs been extremely difficult study until now due part the fact that they comprise only small percentage wide variety cells retina. In addition, current isolation methods use intracellular markers identify RGCs, which produce non-viable cells. These...

The nature of electron transfer across metal oxide–water interfaces depends significantly on the band gap oxide and its edge energies relative to potentials relevant aqueous redox couples. Here we focus water interface with MgO, a prototypical wide whose conduction is close in energy that water. We investigate behavior an excess at out equilibrium near using ab initio molecular dynamics based hybrid density functional theory. Our simulations show under conditions (donated by Al impurity MgO)...

Hole states at the surface of hematite (α-Fe2O3) are highly influential in material's performance as a photoanode for oxygen evolution reaction. Zn-doping is known to both lower overpotential and introduce hole carriers near surface. In this work, aqueous interface (0001) were characterized using density functional theory-based ab initio molecular dynamics (AIMD) together with hybrid theory (DFT) calculations electronic structure. PBE0 12% exact exchange Zn-doped slabs vacuum revealed state...

Purpose: Vitreous seeding remains the primary reason for treatment failure in eyes with retinoblastoma (Rb). Systemic and intra-arterial chemotherapy, each its own inherent set of complications, have improved salvage rates advanced disease, but location biology vitreous seeds present a fundamental challenge developing treatments minimal toxicity risk. The aim this study was to target platelet-derived growth factor (PDGF)– PDGF-receptor β (PDGFRβ) signaling pathway investigate role Rb seeds,...

Neurodegenerative diseases often have a devastating impact on those affected.Retinal ganglion cell (RGC) loss is implicated in an array of diseases, including diabetic retinopathy and glaucoma, addition to normal aging.Despite their importance, RGCs been extremely difficult study until now due part the fact that they comprise only small percentage wide variety cells retina.In addition, current isolation methods use intracellular markers identify RGCs, which produce non-viable cells.These...

Abstract Natural products obtained from various resources are often found to be new sources of effective drugs for disease including cancer. The novel extracellular polysaccharides (exopolysaccharides) purified Parachlorella kessleri (PCEPS), a generous gift by Panac ADVANCE Co. Ltd. (Tokyo, Japan), were evaluated on their antitumor and immunomodulatory effects in cell culture mouse colon carcinoma peritoneal dissemination model. In two-dimensional culture, the PCEPS treatment inhibited...