On the limit of proton-coupled electronic doping in a Ti(iv)-containing MOF

Ti^IV-containing metal–organic frameworks are known to accumulate electrons in their conduction bands, accompanied by protons, when irradiated in the presence of alcohols. The archetypal system, MIL-125, was recently shown to reach a limit of 2e⁻ per Ti₈ octomeric node. However, the origin of this limit and the broader applicability of this unique chemistry relies not only on the presence of Ti^IV, but also access to inorganic inner-sphere Lewis basic anions in the MOF nodes. Here, we study the loading of protons and electrons in MIL-125, and assess the thermodynamic limit of doping these materials. We find that the limit is determined by the reduction potential of protons: in high charging regimes the MOF exceeds the H⁺/H₂ potential. Generally, we offer the design principle that inorganic anions in MOF nodes can host adatomic protons, which may stabilize meta-stable low valent transition metals. This approach highlights the unique chemistry afforded by MOFs built from inorganic clusters, and provides one avenue to developing novel catalytic scaffolds for hydrogen evolution and transfer hydrogenation.

Photo-promoted doping of MIL-125 is limited by the potential of MOF-bound protons exceeding the hydrogen evolution reaction.     

Viscoelastic analysis of single-component and composite PEG and alginate hydrogels简

Hydrogels, three-dimensional hydrophilic polymer networks, are appealing candidate materials for study- ing the cellular microenvironment as their substantial water content helps to better mimic soft tissue. However, hydrogels can lack mechanical stiffness, strength, and tough- ness. Composite hydrogel systems have been shown to improve upon mechanical properties compared to their single- component counterparts. Poly （ethylene glycol） dimethacrylate （PEGDMA） and alginate are polymers that have been used to form hydrogels for biological applications. Single- component and composite PEGDMA and alginate systems were fabricated with a range of total polymer concentrations. Bulk gels were mechanically characterized using spherical indentation testing and a viscoelastic analysis framework. An increase in shear modulus with increasing polymer con- centration was demonstrated for all systems. Alginate hydro- gels were shown to have a smaller viscoelastic ratio than the PEGDMA gels, indicating more extensive relaxation over time. Composite alginate and PEGDMA hydrogels exhib- ited a combination of the mechanical properties of the con- stituents, as well as a qualitative increase in toughness. Additionally, multiple hydrogel systems were produced that had similar shear moduli, but different viscoelastic behaviors. Accurate measurement of the mechanical properties of hydrogels is necessary in order to determine what parameters are key in modeling the cellular microenvironment.     

Prevention of iron- and copper-mediated DNA damage by catecholamine and amino acid neurotransmitters, L-DOPA, and curcumin: metal binding as a general antioxidant mechanism

Concentrations of labile iron and copper are elevated in patients with neurological disorders, causing interest in metal-neurotransmitter interactions. Catecholamine (dopamine, epinephrine, and norepinephrine) and amino acid (glycine, glutamate, and 4-aminobutyrate) neurotransmitters are antioxidants also known to bind metal ions. To investigate the role of metal binding as an antioxidant mechanism for these neurotransmitters, L-dihydroxyphenylalanine (L-DOPA), and curcumin, their abilities to prevent iron- and copper-mediated DNA damage were quantified, cyclic voltammetry was used to determine the relationship between their redox potentials and DNA damage prevention, and UV-vis studies were conducted to determine iron and copper binding as well as iron oxidation rates. In contrast to amino acid neurotransmitters, catecholamine neurotransmitters, L-DOPA, and curcumin prevent significant iron-mediated DNA damage (IC(50) values of 3.2 to 18 μM) and are electrochemically active. However, glycine and glutamate are more effective at preventing copper-mediated DNA damage (IC(50) values of 35 and 12.9 μM, respectively) than L-DOPA, the only catecholamine to prevent this damage (IC(50) = 73 μM). This metal-mediated DNA damage prevention is directly related to the metal-binding behaviour of these compounds. When bound to iron or copper, the catecholamines, amino acids, and curcumin significantly shift iron oxidation potentials and stabilize Fe(3+) over Fe(2+) and Cu(2+) over Cu(+), a factor that may prevent metal redox cycling in vivo. These results highlight the disparate antioxidant activities of neurotransmitters, drugs, and supplements and highlight the importance of considering metal binding when identifying antioxidants to treat and prevent neurodegenerative disorders.     

Uniqueness of highly representative surface embeddings

Let Σ be a (connected) surface of “complexity” κ; that is, Σ may be obtained from a sphere by adding either ½κ handles or κ crosscaps. Let ρ ≥ 0 be an integer, and let Γ be a “ρ-representative drawing” in Σ; that is, a drawing of a graph in Σ so that every simple closed curve in Σ that meets the drawing in < ρ points bounds a disc in Σ. Now let Γ′ be another drawing, in another surface Σ′ of complexity κ′, so that Γ and Γ′ are isomorphic as abstract graphs. We prove that. (i) If ρ ≥ 100 log κ/ log log κ (or ρ ≥ 100 if κ ≤ 2) then κ′ ≥ κ, and if κ′ = κ and Γ is simple and 3-connected there is a homeomorphism from Σ to Σ′ taking Γ to Γ′, and. (ii) if Γ is simple and 3-connected and Γ′ is 3-representative, and ρ ≥ min (320, 5 log κ), then either there is a homeomorphism from Σ to Σ′ taking Γ to Γ′, or κ′ ≥ κ + 10^-4 ρ². © 1996 John Wiley & Sons, Inc.     

Enhanced Electrocatalytic Activity of a Zinc Porphyrin for CO2 Reduction: Cooperative Effects of Triazole Units in the Second Coordination Sphere

The control of the second coordination sphere in a coordination complex plays an important role in improving catalytic efficiency. Herein, we report a zinc porphyrin complex ZnPor8T with multiple flexible triazole units comprising the second coordination sphere, as an electrocatalyst for the highly selective electrochemical reduction of carbon dioxide (CO₂) to carbon monoxide (CO). This electrocatalyst converted CO₂ to CO with a Faradaic efficiency of 99 % and a current density of −6.2 mA cm⁻² at −2.4 V vs. Fc/Fc⁺ in N,N-dimethylformamide using water as the proton source. Structure-function relationship studies were carried out on ZnPor8T analogs containing different numbers of triazole units and distinct triazole geometries; these unveiled that the triazole units function cooperatively to stabilize the CO₂-catalyst adduct in order to facilitate intramolecular proton transfer. Our findings demonstrate that incorporating triazole units that function in a cooperative manner is a versatile strategy to enhance the activity of electrocatalytic CO₂ conversion.     

Audio and sound archives as a resource for voice science: A preliminary review

Archives of voice recordings could provide a source of information for voice scientists and clinicians interested in voice analysis and in cultural and historical changes of vocal styles and qualities. Large collections of sound recordings exist that could be used as databases for such inquiries, although no comprehensive list of such collections currently exists. A preliminary survey of major collections is presented. Voice scientists and voice archivists have many common areas of interest in the recording, reproduction, copying, and analysis of sound. The Recording and Research Center, as part of its ongoing research in establishment of standards for voice analysis, has begun an archive of laboratory recordings. A protocol for recording trained, normal, abnormal, and neurologically impaired voices is in development. This survey of sound archives will continue as well.     

Traces and determinants of linear operators

A general theory of tracestr _D A and determinantsdet _D (I+A) in normed algebrasD of operators acting in Banach spacesB is proposed. In this approach trace and determinant are defined as continuous extensions of the corresponding functionals from finite dimensional operators. We characterize the algebras for which such extensions exist and describe sets of possible values of traces and determinants for the same operator in different algebras. In spite of the fact that the extended traces and determinants may differ in different algebrasD, operatorI+A (withA D) is invertible inB if and only ifdet _D (I+A) does not vanish. Cramer's rule and formulas for the resolvent are obtained and they are expressed in different algebras by the same formulas viadet _D (I+A) andtr _D (A). A large set of examples and illustrations are also presented.     

Formation constants at high ionic strength-II. The ionic strength correction of formation constants using a simplified pitzer equation

A simplified approach to the correction of equilibrium constants from one ionic strength and/or medium to another is developed. A computer program capable of performing these calculations is presented together with results of its application to the NH (3)H (+), CH (3)COO (-)H (+), CH (3)CH (2)COO (-)H (+), - OOCCH (2)COO (-)H (+) and HOOCCH (2)COO (-)H (+) systems.     

Sonochemical reactions at 640 kHz using an efficient reactor. Oxidation of potassium iodide

Ultrasound can be used to oxidize aqueous pollutants. However, due to economic reasons higher oxidation/destruction rates and higher energy efficiency are needed. Recent studies suggest that the higher ultrasound frequencies provide better oxidation rates than the conventional 20 kHz. Another area for improvement is reactor configuration. We have tested two new reactor configurations with proper focusing and reflection of ultrasound for maximum utilization. Reactor configuration plays an important role in the overall efficiency. In the new reactors, transducers and reaction mixture are separated by a polymer acoustic window which allows efficient transfer of ultrasound energy and not the heat from the transducer to the reaction mixture. One reactor at 640 kHz provides a 100% enhancement over the best reported rate for the oxidation of potassium iodide, on a per-Watt basis. Experiments conducted at varying initial KI concentrations show interesting behavior. Increasing the KI concentration by over eight fold merely increases the iodine production rate by two fold. This suggests that in the oxidation region surrounding the bubble, the KI concentration is much different than in the bulk. It is proposed that the hydrophobic bubble region has lower and near saturation KI concentration.