Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads: ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents

Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield Φ_T=60 %) was observed, with a triplet state lifetime (τ_T=436 μs) much longer than that accessed with the conventional heavy atom effect (τ_T=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the ¹CT/³LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC₅₀=75 nm ), with a negligible dark toxicity (EC₅₀=78.1 μm ) compared with the conventional heavy atom PSs (dark toxicity, EC₅₀=6.0 μm, light toxicity, EC₅₀=4.0 nm ). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.     

Cyanine-Flavonol Hybrids for Near-Infrared Light-Activated Delivery of Carbon Monoxide

Carbon monoxide (CO) is an endogenous signaling molecule that controls a number of physiological processes. To circumvent the inherent toxicity of CO, light-activated CO-releasing molecules (photoCORMs) have emerged as an alternative for its administration. However, their wider application requires photoactivation using biologically benign visible and near-infrared (NIR) light. In this work, a strategy to access such photoCORMs by fusing two CO-releasing flavonol moieties with a NIR-absorbing cyanine dye is presented. These hybrids liberate two molecules of CO in high chemical yields upon activation with NIR light up to 820 nm and exhibit excellent uncaging cross-sections, which surpass the state-of-the-art by two orders of magnitude. Furthermore, the biocompatibility and applicability of the system in vitro and in vivo are demonstrated, and a mechanism of CO release is proposed. It is hoped that this strategy will stimulate the discovery of new classes of photoCORMs and accelerate the translation of CO-based phototherapy into practice.     

Maximum norm stability of difference schemes for parabolic equations on overset nonmatching space-time grids

In this paper, theoretical results are described on the maximum norm stability and accuracy of finite difference discretizations of parabolic equations on overset nonmatching space-time grids. We consider parabolic equations containing a linear reaction term on a space-time domain which is decomposed into an overlapping collection of cylindrical subregions of the form , for . Each of the space-time domains are assumed to be independently grided (in parallel) according to the local geometry and space-time regularity of the solution, yielding space-time grids with mesh parameters and . In particular, the different space-time grids need not match on the regions of overlap, and the time steps can differ from one grid to the next. We discretize the parabolic equation on each local grid by employing an explicit or implicit -scheme in time and a finite difference scheme in space satisfying a discrete maximum principle. The local discretizations are coupled together, without the use of Lagrange multipliers, by requiring the boundary values on each space-time grid to match a suitable interpolation of the solution on adjacent grids. The resulting global discretization yields a large system of coupled equations which can be solved by a parallel Schwarz iterative procedure requiring some communication between adjacent subregions. Our analysis employs a contraction mapping argument.

Applications of the results are briefly indicated for reaction-diffusion equations with contractive terms and heterogeneous hyperbolic-parabolic approximations of parabolic equations.

     

Contractive projections and operator spaces

Parallel to the study of finite-dimensional Banach spaces, there is a growing interest in the corresponding local theory of operator spaces. We define a family of Hilbertian operator spaces , , generalizing the row and column Hilbert spaces and , and we show that an atomic subspace that is the range of a contractive projection on is isometrically completely contractive to an -sum of the and Cartan factors of types 1 to 4. In particular, for finite-dimensional , this answers a question posed by Oikhberg and Rosenthal. Explicit in the proof is a classification up to complete isometry of atomic w-closed -triples without an infinite-dimensional rank 1 w-closed ideal.

     

Derivations on Real and Complex JB*-Triples

At the regional conference held at the University of California,Irvine, in 1985 [24], Harald Upmeier posed three basic questionsregarding derivations on JB*-triples: (1) Are derivations automatically bounded? (2) When are all bounded derivations inner? (3) Can bounded derivations be approximated by inner derivations? These three questions had all been answered in the binary cases.Question 1 was answered affirmatively by Sakai [17] for C*-algebrasand by Upmeier [23] for JB-algebras. Question 2 was answeredby Sakai [18] and Kadison [12] for von Neumann algebras andby Upmeier [23] for JW-algebras. Question 3 was answered byUpmeier [23] for JB-algebras, and it follows trivially fromthe Kadison–Sakai answer to question 2 in the case ofC*-algebras. In the ternary case, both question 1 and question 3 were answeredby Barton and Friedman in [3] for complex JB*-triples. In thispaper, we consider question 2 for real and complex JBW*-triplesand question 1 and question 3 for real JB*-triples. A real orcomplex JB*-triple is said to have the inner derivation propertyif every derivation on it is inner. By pure algebra, every finite-dimensionalJB*-triple has the inner derivation property. Our main results,Theorems 2, 3 and 4 and Corollaries 2 and 3 determine whichof the infinite-dimensional real or complex Cartan factors havethe inner derivation property.     

The connectivity of a graph on uniform points on [0,1]

A random graph G_n(x) is constructed on independent random points U₁,…,U_n distributed uniformly on [0,1]^d, d1, in which two distinct such points are joined by an edge if the l_∞-distance between them is at most some prescribed value 0<x<1. The connectivity distance c_n, the smallest x for which G_n(x) is connected, is shown to satisfy

(1)

For d2, the random graph G_n(x) behaves like a d-dimensional version of the random graphs of Erdös and Rényi, despite the fact that its edges are not independent: c_n/d_n→1, a.s., as n→∞, where d_n is the largest nearest-neighbor link, the smallest x for which G_n(x) has no isolated vertices.     

Modelling self-ordering behaviour on Ag covered Pt vicinal surfaces

We use computer simulation to explore the formation process of a monolayer of Ag on a stepped Pt(111) substrate and the formation of 3D Pt nanostructures on an Ag covered (111) and (100) Pt substrate. We show that broken lines of Pt nanostructures are preferred at the step edges on the (111) substrate while continuous lines of Pt nanowires are preferred at the step edge on the (100) substrate. This different behaviour is due to the exposed front facet of the nanostructures running along the step, specifically for the (100) stepped substrate a nanowire grown on the step edge has a stable (111) exposed front facet, whereas a nanowire grown on the (111) substrate would have an unstable (100) front facet (depending on the direction of the step). For the Pt nanowires grown on the (100) substrate we show how arriving Pt dimers (and monomers) preferentially move up off the Ag substrate onto the nanowire's (111) facet where they undergo fast diffusion. We also show that these Pt dimers (and monomers) move up and down the nanowire's facet until a vacancy or defect is encountered.     

Quantum Monte Carlo calculations of the potential energy curve of the helium dimer

We report results of two quantum Monte Carlo methods -- variational Monte Carlo and diffusion Monte Carlo -- on the potential energy curve of the helium dimer. In contrast to previous quantum Monte Carlo calculations on this system, we have employed trial wave functions of the Slater-Jastrow form and used the fixed node approximation for the fermion nodal surface. We find both methods to be in excellent agreement with the best theoretical results at short range. In addition, the diffusion Monte Carlo results give very good agreement across the whole potential energy curve, while the Slater-Jastrow wave function fails to bind the dimer at all.     

Secondary Metabolites,including a New 5,6-Dihydropyran-2-One,Produced by the Fungus Diplodia corticola. Aphicidal Activity of the Main Metabolite,Sphaeropsidin A

An undescribed 5,6-dihydropyran-2-one, namely diplopyrone C, was isolated and characterized from the cultures of an isolate of the fungus Diplodia corticola recovered from Quercus suber in Algeria. The structure and relative stereostructure of (5S,6S,7Z,9S,10S)-5-hydroxy-6-(2-(3-methyloxiran-2-yl)vinyl)-5,6-dihydro-2H-pyran-2-one were assigned essentially based on NMR and MS data. Furthermore, ten known compounds were isolated and identified in the same cultures. The most abundant product, the tetracyclic pimarane diterpene sphaeropsidin A, was tested for insecticidal effects against the model sucking aphid, Acyrthosiphon pisum. Results showed a toxic dose-dependent oral activity of sphaeropsidin A, with an LC₅₀ of 9.64 mM.