Enhanced C?O Functionality on Carbon Papers Ensures Lowering Nucleation Delay of ALD for Ru towards Unprecedented Alkaline HER Activity

The success in lowering the nucleation delay for Atomic Layer Deposition (ALD) of Ru on carbon surfaces is mitigated by constructive pretreatments resulting enhancement of C O functionality. Treatment of the carbon papers (CP) allowed Ru species deposition for minimum number of ALD cycles (25 cycles) with good conformality. The development of electrocatalysts from single atoms to nanoparticles (NPs) on conductive supports with low metal loadings, thus improving performance, is essential in electrocatalysis. For alkaline hydrogen evolution reaction, ALD decorated CPs with Ru exhibit low onset potentials of ≈4.7 mV versus reversable hydrogen electrode (RHE) (at 10 mA cm⁻²) and a high turnover frequency of 1.92 H₂ s⁻¹ at 30 mV versus RHE. The Ru decorated CPs show comparable to higher catalytic activity than of Platinum (Pt) decorated CP also developed by ALD. The current representation of unfamiliar catalytic activities of Ru active centers developed by ALD, pave a bright and sustainable path for energy conversion reactions.     

On Darwinian Networks

We suggest Darwinian Networks (DNs) as a simplification of working with Bayesian networks (BNs). DNs adapt a handful of well‐known concepts in biology into a single framework that is surprisingly simple yet remarkably robust. With respect to modeling, on one hand, DNs not only represent BNs but also faithfully represent the testing of independencies in a more straightforward fashion. On the other hand, with respect to three exact inference algorithms in BNs, DNs simplify each of them while unifying all of them. DNs can determine good elimination orderings using the same platform as used for modeling and inference. Finally, we demonstrate how DNs can represent two additional frameworks. Practical benefits of DNs include faster algorithms for inference and modeling.     

Kinetics and Mechanisms of Homogeneous Catalytic Reactions. Part 11. Regioselective Hydrogenation of Quinoline Catalyzed by Rhodium Systems Containing 1,2-Bis(diphenylphosphino)ethane

Abstract  

The system prepared in situ by addition of two equivalents of 1,2-bis(diphenylphosphino)ethane (dppe) to Rh₂Cl₂(COE)₄ (COE = cyclooctene) showed to be an efficient and regioselective precatalyst for the hydrogenation of quinoline (Q). This reaction showed to be independent of the Q concentration and of fractional order on H₂ and catalyst concentrations (1.5 and 0.6, respectively). The fractional order on catalyst concentration indicates that several catalytic species with different activities are present in the reaction medium; however, the cationic species [Rh (dppe)₂]⁺ was the only phosphorous-containing compound detected by ³¹P{¹H} NMR. For the acac salt of this cationic bis(dppe) complex, a kinetic study led to the rate law r = {K₁k₂/(1 + K₁[H₂])}[M][H₂]²; [M(Q)(κ²-dppe)(κ¹-dppe)]⁺ was proposed as the catalytically active species (CAS) of the cycle. The general mechanism involves a reversible oxidative addition of H₂ to generate a dihydrido complex, which transfers the hydride ligands to the coordinated Q to yield species containing a 1,2-dihydroquinoline (DHQ) ligand, followed by a second oxidative addition of H₂, considered as the rate-determining step of the cycle; hydrogen transfer toward the DHQ ligand yields THQ, regenerates the CAS and restarts the catalytic cycle.     

The Rationale for “Laser-Induced Thermal Therapy (LITT) and Intratumoral Cisplatin” Approach for Cancer Treatment

Cisplatin is one of the most widely used anticancer drugs in the treatment of various types of solid human cancers, as well as germ cell tumors, sarcomas, and lymphomas. Strong evidence from research has demonstrated higher efficacy of a combination of cisplatin and derivatives, together with hyperthermia and light, in overcoming drug resistance and improving tumoricidal efficacy. It is well known that the antioncogenic potential of CDDP is markedly enhanced by hyperthermia compared to drug treatment alone. However, more recently, accelerators of high energy particles, such as synchrotrons, have been used to produce powerful and monochromatizable radiation to induce an Auger electron cascade in cis-platinum molecules. This is the concept that makes photoactivation of cis-platinum theoretically possible. Both heat and light increase cisplatin anticancer activity via multiple mechanisms, generating DNA lesions by interacting with purine bases in DNA followed by activation of several signal transduction pathways which finally lead to apoptosis. For the past twenty-seven years, our group has developed infrared photo-thermal activation of cisplatin for cancer treatment from bench to bedside. The future development of photoactivatable prodrugs of platinum-based agents injected intratumorally will increase selectivity, lower toxicity and increase efficacy of this important class of antitumor drugs, particularly when treating tumors accessible to laser-based fiber-optic devices, as in head and neck cancer. In this article, the mechanistic rationale of combined intratumor injections of cisplatin and laser-induced thermal therapy (CDDP–LITT) and the clinical application of such minimally invasive treatment for cancer are reviewed.     

On a simple method for testing independencies in Bayesian networks

Testing independencies is a fundamental task in reasoning with Bayesian networks (BNs). In practice, d‐separation is often used for this task, since it has linear‐time complexity. However, many have had difficulties understanding d‐separation in BNs. An equivalent method that is easier to understand, called m‐separation, transforms the problem from directed separation in BNs into classical separation in undirected graphs. Two main steps of this transformation are pruning the BN and adding undirected edges. In this paper, we propose u‐separation as an even simpler method for testing independencies in a BN. Our approach also converts the problem into classical separation in an undirected graph. However, our method is based upon the novel concepts of inaugural variables and rationalization. Thereby, the primary advantage of u‐separation over m‐separation is that m‐separation can prune unnecessarily and add superfluous edges. Our experiment results show that u‐separation performs 73% fewer modifications on average than m‐separation.     

Vitamins as Active Agents for Highly Emissive and Stable Nanostructured Halide Perovskite Inks and 3D Composites Fabricated by Additive Manufacturing

The use of non-toxic and low-cost vitamins like α-tocopherol (α-TCP, vitamin E) to improve the photophysical properties and stability of perovskite nanocrystals (PNCs), through post-synthetic ligand surface passivation, is demonstrated for the first time. Especially interesting is its effect on CsPbI₃ the most unstable inorganic PNC. Adding α-TCP produces that the photoluminescence quantum yield (PLQY) of freshly prepared and aged PNCs achieves values of ≈98% and 100%, respectively. After storing 2 months under ambient air and 60% relative humidity, PLQY is maintained at 85% and 67%, respectively. α-TCP restores the PL features of aged CsPbI₃ PNCs, and mediates the radiative recombination channels by reducing surface defects. In addition, the combination of α-TCP and PNCs facilitates the chemical formulation to prepare PNCs-acrylic polymer composites processable by additive manufacturing. This enables the development of complex shaped parts with improved luminescent features and long-term stability for 4 months, which is not possible for non-modified PNCs. A PLQY ≈92% is reached in the 3D printed polymer/PNC composite, the highest value obtained for a red-emitting composite solid until now as far as it is known. The passivation shell provided by α-TCP makes that PNCs inks do not suffer any degradation process avoiding the contact with the environment and preserve their properties after reacting with polar monomers during composite polymerization.