Highly Efficient Ir(III)-Coumarin Photo-Redox Catalyst for Synergetic Multi-Mode Cancer Photo-Therapy

Four photo-catalysts of the general formula [Ir(CO6/ppy)₂(L)]Cl where CO6=coumarin 6 ( Ir1 – Ir3 ), ppy=2-phenylpyridine ( Ir4 ), L=4′-(3,5-di-tert-butylphenyl)-2,2′ : 6′,2′′-terpyridine ( Ir1 ), 4′-(3,5-bis(trifluoromethyl)phenyl)-2,2′ : 6′,2′′-terpyridine ( Ir2 and Ir4 ), and 4-([2,2′ : 6′,2′′-terpyridin]-4′-yl)-N,N-dimethylaniline ( Ir3 ) were synthesized and characterized. These photostable photo-catalysts ( Ir1 – Ir3 ) showed strong visible light absorption between 400–550 nm. Upon light irradiation (465 and 525 nm), Ir1 – Ir3 generated singlet oxygen and induced rapidly photo-catalytic oxidation of cellular coenzymes NAD(P)H. Ir1 – Ir3 showed time-dependent cellular uptake with excellent intracellular retention efficiency. Upon green light irradiation (525 nm), Ir2 provided a much higher photo-index (PI=793) than the clinically used photosensitizer, 5-aminolevulinicacid (5-ALA, PI>30) against HeLa cancer cells. The observed necro-apoptotic anticancer activity of Ir2 was due to the Ir2 triggered photo-induced intracellular redox imbalance (by NAD(P)H oxidation and ROS generation) and change in the mitochondrial membrane potential. Remarkably, Ir2 showed in vivo photo-induced catalytic anticancer activity in mouse models.     

The enumeration of extreme rigid honeycombs

Journal of Algebraic Combinatorics - Rigid honeycombs were introduced by Knutson et al. (J Am Math Soc 17:19–48, 2004), and they were shown in Bercovici et al. (J Funct Anal...     

Photosensitized [4+2]- and [2+2]-Cycloaddition Reactions of N-Sulfonylimines

The synthesis of polycyclic compounds is of high interest due to the prevalence of these motifs in drugs and natural products. Herein, we report on the stereoselective construction of 3D bicyclic scaffolds and azetidine derivatives by modulation of N-sulfonylimines to achieve either [4+2]- or [2+2]-cycloaddition reactions. The utility of the method was established by further modulation of the product. Mechanistic studies are also included, which support reaction via Dexter energy transfer.     

Heteroleptic Square Planar Cobalt(I/II) Complexes

Reduction of the cobalt(II) chloride complex, Ph₂B(^tBuIm)₂Co(THF)Cl ( 1 ) in the presence of ^tBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph₂B(^tBuIm)₂Co(C≡N^tBu)₂ ( 2 ). This is a rare example of a 16-electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of 2 , as calculated by DFT, reveals that the HOMO is largely d_z² in character. Complex 2 is readily oxidized to its cobalt(II) congener [Ph₂B(^tBuIm)₂Co(C=N^tBu)₂]BPh₄ ( 3 -BPh₄), whose EPR spectral parameters are characteristic of low-spin d⁷ with an unpaired electron in an orbital of d_z² parentage. This is also consistent with the results of DFT calculations. Despite its 16-electron configuration and the d_z² parentage of the HOMO, the only tractable reactions of 2 involve one electron oxidation to afford 3 .     

A Central Limit Theorem for Non-stationary Strongly Mixing Random Fields

In this paper we extend a central limit theorem of Peligrad for uniformly strong mixing random fields satisfying the Lindeberg condition in the absence of stationarity property. More precisely, we study the asymptotic normality of the partial sums of uniformly \(\alpha \)-mixing non-stationary random fields satisfying the Lindeberg condition, in the presence of an extra dependence assumption involving maximal correlations.     

Time Discrete Approximation of Weak Solutions to Stochastic Equations of Geophysical Fluid Dynamics and Applications

As a first step towards the numerical analysis of the stochastic primitive equations of the atmosphere and the oceans,the time discretization of these equations by an implicit Euler scheme is studied.From the deterministic point of view,the 3D primitive equations are studied in their full form on a general domain and with physically realistic boundary conditions.From the probabilistic viewpoint,this paper deals with a wide class of nonlinear,state dependent,white noise forcings which may be interpreted in either the It6 or the Stratonovich sense.The proof of convergence of the Euler scheme,which is carried out within an abstract framework,covers the equations for the oceans,the atmosphere,the coupled oceanic-atmospheric system as well as other related geophysical equations.The authors obtain the existence of solutions which are weak in both the PDE and probabilistic sense,a result which is new by itself to the best of our knowledge.     

Dimension Reduction for the Landau-de Gennes Model on Curved Nematic Thin Films

We use the method of \(\Gamma \)-convergence to study the behavior of the Landau-de Gennes model for a nematic liquid crystalline film attached to a general fixed surface in the limit of vanishing thickness. This paper generalizes the approach in Golovaty et al. (J Nonlinear Sci 25(6):1431–1451, 2015) where we considered a similar problem for a planar surface. Since the anchoring energy dominates when the thickness of the film is small, it is essential to understand its influence on the structure of the minimizers of the limiting energy. In particular, the anchoring energy dictates the class of admissible competitors and the structure of the limiting problem. We assume general weak anchoring conditions on the top and the bottom surfaces of the film and strong Dirichlet boundary conditions on the lateral boundary of the film when the surface is not closed. We establish a general convergence result to an energy defined on the surface that involves a somewhat surprising remnant of the normal component of the tensor gradient. Then we exhibit one effect of curvature through an analysis of the behavior of minimizers to the limiting problem when the substrate is a frustum.     

Half Inverse Riordan Arrays and Their Related Vertical Recurrence Relation

We discuss two different procedures to study the half Riordan arrays and their inverses. One of the procedures shows that every Riordan array is the half Riordan array of a unique Riordan array. It is well known that every Riordan array has its half Riordan array. Therefore, this paper answers the converse question: Is every Riordan array the half Riordan array of some Riordan arrays? In addition, this paper shows that the vertical recurrence relation of the column entries of the half Riordan array is equivalent to the horizontal recurrence relation of the original Riordan array''s row entries.     

Strong convergence to global solutions for multidimensional flows of compressible,viscous fluids with polytropic equations of state and discontinuous initial data

We extend to general polytropic pressures P() = K, > 1, the existence theory of [8] for isothermal (= 1) flows of Navier-Stokes fluids in two and three space dimensions, with fairly general initial data. Specifically, we require that the initial density be close to a constant in L ² and L , and that the initial velocity be small in L ² and bounded in L ^{2 n} (in two dimensions the L ² norms must be weighted slightly). Solutions are obtained as limits of approximate solutions corresponding to mollified initial data. The key point is that the approximate densities are shown to converge strongly, so that nonlinear pressures can be accommodated, even in the absence of any uniform regularity information for the approximate densities.