Photophysics of Silicon Phthalocyanines in Aqueous Media

Phthalocyanines have been used as photodynamic therapy (PDT) agents because of their uniquely favorable optical properties and high photostability. They have been shown to be highly successful for the treatment of cancer through efficient singlet‐oxygen (¹O₂) production. However, due to their hydrophobic properties, the considerations of solubility and cellular location have made understanding their photophysics in vitro and in vivo difficult. Indeed, many quantitative assessments of PDT reagents are undertaken in purely organic solvents, presenting challenges for interpreting observations during practical application in vivo. With steady‐state and time‐resolved laser spectroscopy, we show that for axial ligated silicon phthalocyanines in aqueous media, both the water:lipophile ratio and the pH have drastic effects on their photophysics, and ultimately dictate their functionality as PDT drugs. We suggest that considering the presented photophysics for PDT drugs in aqueous solutions leads to guidelines for a next generation of even more potent PDT agents.     

Approximate reconstruction of torsional potential energy surface based on voronoi tessellation

Torsional modes within a complex molecule containing various functional groups are often strongly coupled so that the harmonic approximation and one-dimensional torsional treatment are inaccurate to evaluate their partition functions. A family of multi-structural approximation methods have been proposed and applied in recent years to deal with the torsional anharmonicity. However, these methods approximate the exact “almost periodic” potential energy as a summation of local periodic functions with symmetric barrier positions and heights. In the present theoretical study, we illustrated that the approximation is inaccurate when torsional modes present non-uniformly distributed local minima. Thereby, we proposed an improved method to reconstruct approximate potential to replace the periodic potential by using information of the local minima and their Voronoi tessellation. First, we established asymmetric barrier heights by introducing two periodicity parameters and assuming that the exact barrier positions are at the boundaries of Voronoi cells. Second, we used multiplicatively weighted Voronoi tessellation to refine the barrier heights and positions by defining a structure-related distance metric. The proposed method has been tested for a few higher-dimensional cases, all of which show promising improved accuracy.     

Self-adaptive gradient projection algorithms for variational inequalities involving non-Lipschitz continuous operators

Numerical Algorithms - In this paper, we introduce a self-adaptive inertial gradient projection algorithm for solving monotone or strongly pseudomonotone variational inequalities in real Hilbert...     

Strategies Towards Capturing Nitrogenase Substrates and Intermediates via Controlled Alteration of Electron Fluxes

Nitrogenase utilizes an ATP-dependent reductase to deliver electrons to its catalytic component to enable two important reactions: the reduction of N₂ to NH₄⁺, and the reduction of CO to hydrocarbons. The two nitrogenase-based reactions parallel the industrial Haber–Bosch and Fischer–Tropsch processes, yet they occur under ambient conditions. As such, understanding the enzymatic mechanism of nitrogenase is crucial for the future development of biomimetic strategies for energy-efficient production of valuable chemical commodities. Mechanistic investigations of nitrogenase has long been hampered by the difficulty to trap substrates and intermediates relevant to the nitrogenase reactions. Recently, we have successfully captured CO on the Azotobacter vinelandii V-nitrogenase via two approaches that alter the electron fluxes in a controlled manner: one approach utilizes an artificial electron donor to trap CO on the catalytic component of V-nitrogenase in the resting state; whereas the other employs a mismatched reductase component to reduce the electron flux through the system and consequently accumulate CO on the catalytic component of V-nitrogenase. Here we summarize the major outcome of these recent studies, which not only clarified the catalytic relevance of the one-CO (lo-CO) and multi-CO (hi-CO) bound states of nitrogenase, but also pointed to a potential competition between N₂ and CO for binding to the same pair of reactive Fe sites across the sulfur belt of the cofactor. Together, these results highlight the utility of these strategies in poising the cofactor at a well-defined state for substrate- or intermediate-trapping via controlled alteration of electron fluxes, which could prove beneficial for further elucidation of the mechanistic details of nitrogenase-catalyzed reactions.     

The visible and ultraviolet organic light-emitting diodes with germanium dioxide as facile solution-processed anode buffer layer

Germanium dioxide (GeO₂) aqueous solutions are facilely prepared and the corresponding anode buffer layers (ABLs) with solution process are demonstrated. Atomic force microscopy, X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy measurements show that solution-processed GeO₂ behaves superior film morphology and enhanced work function. Using GeO₂ as ABL of organic light-emitting diodes (OLEDs), the visible device with tris(8-hydroxy-quinolinato)aluminium as emitter gives maximum luminous efficiency of 6.5 cd/A and power efficiency of 3.5 lm/W, the ultraviolet device with 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole as emitter exhibits short-wavelength emission with peak of 376 nm, full-width at half-maximum of 42 nm, maximum radiance of 3.36 mW/cm² and external quantum efficiency of 1.5%. The performances are almost comparable to the counterparts with poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) as ABL. The current, impedance, phase and capacitance as a function of voltage characteristics elucidate that the GeO₂ ABL formed from appropriate concentration of GeO₂ aqueous solution favors hole injection enhancement and accordingly promoting device performance.     

Double dehydrogenation of carbocyclic β-dicarbonyl compounds:Koser's reagent can do what iodine(V) reagents can

Koser's reagent is found to be effective in the oxidative double dehydrogenation of various carbocyclic β-dicarbonyl compounds,which constitutes the first example on dehydrogenation reactivity of hypervalent iodine(Ⅲ) reagents for carbocyclic carbonyl compounds. DFT calculations reveal that the rate-determining step is the electrophilic addition of PhI+OH onto enolate of monodehydrogenated product.     

Fabrication of Pre-tilted Vertical Alignment Layers for High-Speed Liquid Crystal Display Using Bi-functional Photoreactive Monomers

Abstract

To enable recent 3D and moving picture applications, liquid crystal displays (LCD) must exhibit fast response and wide viewing angle characteristics. Pre-tilted vertical alignment layers for high-speed LCD were fabricated using bi-functional photoreactive monomers. The monomers can be confined to the polyimide layer and photo-polymerized by UV exposure under voltage. Response characteristics of photo-controlled alignment films according to the structure were investigated. Vertical alignment properties were evaluated using a polarizing optical microscope, and electro-optical characteristics were compared through the voltage-transmittance curve and response time measurement. Faster response speed could be obtained by using photoreactive monomers having a long alkyl chain.     

Existence of multi-solitary waves with logarithmic relative distances for the NLS equation

We construct 2-solitary wave solutions with logarithmic distance to the nonlinear Schrödinger equation,

$\mathrm{i}{?}_{t}u+\mathrm{\Delta }u+|u{|}^{p?1}u=0,t\in \mathbb{R},x\in {\mathbb{R}}^d,$

in mass-subcritical cases $1<p<1+\frac{4}{d}$ and mass-supercritical cases $1+\frac{4}{d}<p<\frac{d+2}{d?2}$, i.e. solutions $u(t)$ satisfying

${6u(t)?{\mathrm{e}}^{\mathrm{i}\gamma (t)}\sum _{k=1}^{2}Q(??x_k(t))6}_{H^1}\to 0$

and

$|x_1(t)?x_2(t)|～2\log ?t,\text{as}t\to +\infty ,$

where Q is the ground state. The logarithmic distance is related to strong interactions between solitary waves.In the integrable case ($d=1$ and $p=3$), the existence of such solutions is known by inverse scattering (E. Olmedilla, Multiple pole solutions of the nonlinear Schrödinger equation, Physica D 25 (1987) 330–346; T. Zakharov, A.B. Shabat, Exact theory of two-dimensional self-focusing and one-dimensional self-modulation of waves in nonlinear media, Sov. Phys. JETP 34 (1972) 62–69). The mass-critical case $p=1+\frac{4}{d}$ exhibits a specific behavior related to blow-up, previously studied in Y. Martel, P. Raphaël (Strongly interacting blow up bubbles for the mass critical NLS, Ann. Sci. Éc. Norm. Supér. 51 (2018) 701–737).     

On periodic subsolutions to steady second-order systems and applications

Bostan and Namah (Remarks on bounded solutions of steady Hamilton–Jacobi equations, C. R. Acad. Sci. Paris, Ser. I 347(15–16) (2009) 873–878) proved that constant functions are the only bounded solutions to $H(Du)=H(0)$ when H is superlinear and strictly convex. In this short note, we present a proof other than that of Bostan and Namah for equations that can be easily applied to some types of possibly degenerate parabolic systems. Our proof applies for periodic subsolutions instead of bounded solutions like that of Bostan and Namah; however, we need periodic subsolutions, which is quite restrictive. We do not consider Hopf–Lax's formula in our proof, so we can relax some restrictions on H. We also present an application to the large-time behavior of solutions to degenerate parabolic systems.