Dynamics of capillary spreading along hydrophilic microstripes

We have studied the capillary spreading of a Newtonian liquid along hydrophilic microstripes that are chemically defined on a hydrophobic substrate. The front of the spreading film advances in time according to a power law x=Bt1/2. This exponent of 1/2 is much larger than the value 1/10 observed in the axisymmetric spreading of a wetting droplet. It is identical to the exponent found for wicking in open or closed microchannels. Even though no wicking occurs in our system, the influence of surface curvature induced by the lateral confinement of the liquid stripe also leads to an exponent of 1/2 but with a strongly modified prefactor B. We obtain excellent experimental agreement with the predicted time dependence of the front location and the dependence of the front speed on the stripe width. Additional experiments and simulations reveal the influence of the reservoir volume, liquid material parameters, edge roughness, and nonwetting defects. These results are relevant to liquid dosing applications or microfluidic delivery systems based on free-surface flow

Evidence of Program Quality and Youth Outcomes in the DYCD Out-of-School Time Initiative: Report on the Initiative's First Three Years

Examines New York City's progress in improving out-of-school-time program quality and serving more children and youth, participants' and parents' overall satisfaction with quality and accessibility, and links between programming, quality, and benefits

Evaluation of the Beacon Community Centers Middle School Initiative: Report on the First Year

Evaluates the first year of an initiative to provide structured after-school and summer programs for fifth- through eighth-graders. Examines the centers' adaptation to the new focus, enrollment and participation levels, and implementation of core goals

R. Rawson Wilson, In Palamedes’ Shadow : Explorations in Play, Game and Narrative Theory

In Palamedes’ Shadow : Explorations in Play, Game and Narrative Theory

Proton reduction by molecular catalysts in water under demanding atmospheres.

The electrocatalytic proton reduction activity of a Ni bis(diphosphine) (NiP) and a cobaloxime (CoP) catalyst has been studied in water in the presence of the gaseous inhibitors O2 and CO. CoP shows an appreciable tolerance towards O2, but its activity suffers severely in the presence of CO. In contrast, NiP is strongly inhibited by O2, but produces H2 under high CO concentrations.Financial support from the EPSRC (EP/H00338X/2), the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and National Foundation for Research, Technology and Development), and the OMV Group is gratefully acknowledged.Originally published by The Royal Society of Chemistry, Chem. Commun., 2014, 50, 15995, http://dx.doi.org/10.1039/C4CC06159

Diffusion mechanisms of localised knots along a polymer

We consider the diffusive motion of a localized knot along a linear polymer chain. In particular, we derive the mean diffusion time of the knot before it escapes from the chain once it gets close to one of the chain ends. Self-reptation of the entire chain between either end and the knot position, during which the knot is provided with free volume, leads to an L^3 scaling of diffusion time; for sufficiently long chains, subdiffusion will enhance this time even more. Conversely, we propose local ``breathing'', i.e., local conformational rearrangement inside the knot region (KR) and its immediate neighbourhood, as additional mechanism. The contribution of KR-breathing to the diffusion time scales only quadratically, L^2, speeding up the knot escape considerably and guaranteeing finite knot mobility even for very long chains.Comment: 7 pages, 2 figures. Accepted to Europhys. Let

The Evolution of Library Instruction Delivery in the Chemistry Curriculum Informed by Mixed Assessment Methods

As information continues to evolve over time, the information literacy expectations for chemistry students also change. This article examines transformations to an undergraduate chemistry course that focuses on chemical literature and information literacy and is co-taught by a chemistry professor and a chemistry librarian. This article also describes results from assessment of both content knowledge and student perception, and discusses how the assessment was used to inform changes to the course. This type of student assessment and evaluation has not previously been examined in the delivery of required undergraduate chemistry information courses. Since this course has used in-person, online, and blended delivery methods, the article describes what students can learn from online modules, and where they need more intensive classroom instruction.Publisher allows immediate open acces

[NiFeSe]-hydrogenase chemistry.

The development of technology for the inexpensive generation of the renewable energy vector H2 through water splitting is of immediate economic, ecological, and humanitarian interest. Recent interest in hydrogenases has been fueled by their exceptionally high catalytic rates for H2 production at a marginal overpotential, which is presently only matched by the nonscalable noble metal platinum. The mechanistic understanding of hydrogenase function guides the design of synthetic catalysts, and selection of a suitable hydrogenase enables direct applications in electro- and photocatalysis. [FeFe]-hydrogenases display excellent H2 evolution activity, but they are irreversibly damaged upon exposure to O2, which currently prevents their use in full water splitting systems. O2-tolerant [NiFe]-hydrogenases are known, but they are typically strongly biased toward H2 oxidation, while H2 production by [NiFe]-hydrogenases is often product (H2) inhibited. [NiFeSe]-hydrogenases are a subclass of [NiFe]-hydrogenases with a selenocysteine residue coordinated to the active site nickel center in place of a cysteine. They exhibit a combination of unique properties that are highly advantageous for applications in water splitting compared with other hydrogenases. They display a high H2 evolution rate with marginal inhibition by H2 and tolerance to O2. [NiFeSe]-hydrogenases are therefore one of the most active molecular H2 evolution catalysts applicable in water splitting. Herein, we summarize our recent progress in exploring the unique chemistry of [NiFeSe]-hydrogenases through biomimetic model chemistry and the chemistry with [NiFeSe]-hydrogenases in semiartificial photosynthetic systems. We gain perspective from the structural, spectroscopic, and electrochemical properties of the [NiFeSe]-hydrogenases and compare them with the chemistry of synthetic models of this hydrogenase active site. Our synthetic models give insight into the effects on the electronic properties and reactivity of the active site upon the introduction of selenium. We have utilized the exceptional properties of the [NiFeSe]-hydrogenase from Desulfomicrobium baculatum in a number of photocatalytic H2 production schemes, which are benchmark systems in terms of single site activity, tolerance toward O2, and in vitro water splitting with biological molecules. Each system comprises a light-harvesting component, which allows for light-driven electron transfer to the hydrogenase in order for it to catalyze H2 production. A system with [NiFeSe]-hydrogenase on a dye-sensitized TiO2 nanoparticle gives an enzyme-semiconductor hybrid for visible light-driven generation of H2 with an enzyme-based turnover frequency of 50 s(-1). A stable and inexpensive polymeric carbon nitride as a photosensitizer in combination with the [NiFeSe]-hydrogenase shows good activity for more than 2 days. Light-driven H2 evolution with the enzyme and an organic dye under high O2 levels demonstrates the excellent robustness and feasibility of water splitting with a hydrogenase-based scheme. This has led, most recently, to the development of a light-driven full water splitting system with a [NiFeSe]-hydrogenase wired to the water oxidation enzyme photosystem II in a photoelectrochemical cell. In contrast to the other systems, this photoelectrochemical system does not rely on a sacrificial electron donor and allowed us to establish the long sought after light-driven water splitting with an isolated hydrogenase.We acknowledge support by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and National Foundation for Research, Technology and Development), the OMV Group, the EPSRC (EP/H00338X/2) and a Marie Curie fellowship to C.C. (GAN 624997).This is the accepted manuscript. It is currently embargoed pending publication

Solar hydrogen production using carbon quantum dots and a molecular nickel catalyst.

Carbon quantum dots (CQDs) are established as excellent photosensitizers in combination with a molecular catalyst for solar light driven hydrogen production in aqueous solution. The inexpensive CQDs can be prepared by straightforward thermolysis of citric acid in a simple one-pot, multigram synthesis and are therefore scalable. The CQDs produced reducing equivalents under solar irradiation in a homogeneous photocatalytic system with a Ni-bis(diphosphine) catalyst, giving an activity of 398 μmolH2 (gCQD)(-1) h(-1) and a "per Ni catalyst" turnover frequency of 41 h(-1). The CQDs displayed activity in the visible region beyond λ > 455 nm and maintained their full photocatalytic activity for at least 1 day under full solar spectrum irradiation. A high quantum efficiency of 1.4% was recorded for the noble- and toxic-metal free photocatalytic system. Thus, CQDs are shown to be a highly sustainable light-absorbing material for photocatalytic schemes, which are not limited by cost, toxicity, or lack of scalability. The photocatalytic hybrid system was limited by the lifetime of the molecular catalyst, and intriguingly, no photocatalytic activity was observed using the CQDs and 3d transition metal salts or platinum precursors. This observation highlights the advantage of using a molecular catalyst over commonly used heterogeneous catalysts in this photocatalytic system.This work was supported by an Oppenheimer PhD scholarship (to B.C.M.M.), a Poynton PhD scholarship (to G.A.M.H.), a Marie Curie postdoctoral fellowship (GAN 624997 to C.C.), an EPSRC Career Acceleration Fellowship (EP/H00338X/2 to E.R.), the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research, and Economy and the National Foundation for Research, Technology and Development), and the OMV Group.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/jacs.5b01650

A Tool to Recover Scalar Time-Delay Systems from Experimental Time Series

We propose a method that is able to analyze chaotic time series, gained from exp erimental data. The method allows to identify scalar time-delay systems. If the dynamics of the system under investigation is governed by a scalar time-delay differential equation of the form $dy(t)/dt = h(y(t),y(t-\tau_0))$, the delay time $\tau_0$ and the functi on $h$ can be recovered. There are no restrictions to the dimensionality of the chaotic attractor. The method turns out to be insensitive to noise. We successfully apply the method to various time series taken from a computer experiment and two different electronic oscillators