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.     

On the Position Representation of Pedram’s Higher Order GUP

In this paper we show that the position representation of the higher order generalized uncertainty principle (HGUP) is also well defined without approximation. We find the simpler form of this representation with a help of the signature of the discriminant of the cubic equation. Using this we discuss the HGUP derivative, HGUP exponential and HGUP trigonometric functions and HGUP-corrected Bohr atom model. Finally we discuss the D-dimensional HGUP algebra and compute the cosmological constant.

     

Effect of bulk resistivity,annealing temperature and illumination on oxygen sorption on CdSe surfaces

The bulk resistivity, annealing temperature and photo-illumination were found to have large effects on the oxygen sorption of the Cd (0001) surfaces of CdSe. For the higher resistivity surfaces, annealing at temperatures below ~ 400°C, no oxygen adsorption was detected. However, if the surfaces were annealed at temperatures above ~ 500°C, a significant amount of oxygen adsorption was subsequently detected at room temperature in darkness. This adsorbed oxygen could be partially desorbed by visible light and almost completely desorbed by UV light. On the other hand, surfaces of very low resistivities were so much more reactive to oxygen that appreciable oxygen adsorption in darkness was detected. This oxygen adsorption was always enhanced by illumination with UV or visible light. Annealing at ~ 550 °C had no significant effect on this photo-adsorptive behaviour. However, annealing at temperatures ~ 500–550°C decreased the diffraction intensity. Based on mass spectrometer analysis, the decrease in diffraction intensity was interpreted as due to diffusion of excess Cd to the surface. The oxygen sorption behaviours of all the surfaces investigated were adequately explained by the existing theories based on charge transfer between the surfaces and the adsorbed oxygen.     

Free-space Fresnel diffraction for the approximation of fractional Fourier transform

Fractional Fourier transformation of an object can be approximated by the object's free-space Fresnel diffraction pattern under some restricted conditions and plane wave illumination according to Hua's method. A better approximation is achieved under least-squared conditions developed in this paper. Simulation results verify that our theoretical development works for any fractional order a compared with the previous approach.     

Theranostic Iron@Gold Core–Shell Nanoparticles for Simultaneous Hyperthermia‐Chemotherapy upon Photo‐Stimulation

The challenges of nanoparticles, such as size‐dependent toxicity, nonbiocompatibility, or inability to undergo functionalization for drug conjugation, limit their biomedical application in more than one domain. Oval‐shaped iron@gold core–shell (oFe@Au) magnetic nanoparticles are engineered and their applications in magnetic resonance imaging (MRI), optical coherence tomography (OCT), and controlled drug release, are explored via photo stimulation‐generated hyperthermia. The oFe@Au nanoparticles have a size of 42.57 ± 5.99 nm and consist of 10.76 and 89.24 atomic % of Fe and Au, respectively. Upon photo‐stimulation for 10 and 15 minutes, the levels of cancer cell death induced by methotrexate‐conjugated oFe@Au nanoparticles are sixfold and fourfold higher, respectively, than oFe@Au nanoparticles alone. MRI and OCT confirm the application of these nanoparticles as a contrast agent. Finally, results of in vivo experiments reveal that the temperature is elevated by 13.2 °C, when oFe@Au nanoparticles are irradiated with a 167 mW cm^?2 808 nm laser, which results in a significant reduction in tumor volume and scab formation after 7 days, followed by complete disappearance after 14 days. The ability of these nanoparticles to generate heat upon photo‐stimulation also opens new doors for studying hyperthermia‐mediated controlled drug release for cancer therapy. Applications include biomedical engineering, cancer therapy, and theranostics fields.     

Efficient Krylov subspace methods for uncertainty quantification in large Bayesian linear inverse problems

Uncertainty quantification for linear inverse problems remains a challenging task, especially for problems with a very large number of unknown parameters (e.g., dynamic inverse problems) and for problems where computation of the square root and inverse of the prior covariance matrix are not feasible. This work exploits Krylov subspace methods to develop and analyze new techniques for large‐scale uncertainty quantification in inverse problems. In this work, we assume that generalized Golub‐Kahan‐based methods have been used to compute an estimate of the solution, and we describe efficient methods to explore the posterior distribution. In particular, we use the generalized Golub‐Kahan bidiagonalization to derive an approximation of the posterior covariance matrix, and we provide theoretical results that quantify the accuracy of the approximate posterior covariance matrix and of the resulting posterior distribution. Then, we describe efficient methods that use the approximation to compute measures of uncertainty, including the Kullback‐Liebler divergence. We present two methods that use the preconditioned Lanczos algorithm to efficiently generate samples from the posterior distribution. Numerical examples from dynamic photoacoustic tomography demonstrate the effectiveness of the described approaches.     

Broadband Light-Emitting Diodes with One-Dimensional Photonic Crystal Layer

In this article, a broadband gallium-nitride-based light-emitting diode with a one-dimensional photonic crystal layer is investigated. The broadband light-emitting diode using the proposed backside reflector has high reflectance (>95%) over a 270-nm bandwidth in visible light at an arbitrary incidence angle. A broadband light-emitting diode of high output power due to the high reflectivity is achieved. Also reported are the results for light-emitting diodes by the transistor outline can (TO-can) package. The proposed light-emitting diodes possess broadband high reflected spectra, high output power for light extraction, and a good view angle.     

Stability of a conditional Cauchy equation on a set of measure zero

In this paper, we prove the Hyers–Ulam stability theorem when \({f, g, h : \mathbb{R} \to \mathbb{R}}\) satisfy $$|f(x + y) - g(x) - h(y)| \leq \epsilon$$ in a set \({\Gamma \subset \mathbb{R}^{2}}\) of measure \({m(\Gamma) = 0}\) , which refines a previous result in Chung (Aequat Math 83:313–320, 2012) and gives an affirmative answer to the question in the paper. As a direct consequence we obtain that if \({f, g, h : \mathbb{R} \to \mathbb{R}}\) satisfy the Pexider equation $$f(x + y) - g(x) - h(y) = 0$$ in \({\Gamma}\) , then the equation holds for all \({x, y \in \mathbb{R}}\) . Using our method of construction of the set, we can find a set \({\Gamma \subset \mathbb{R}^{2n}}\) of 2n-dimensional measure 0 and obtain the above result for the functions \({f, g, h : \mathbb{R}^{n} \to \mathbb{C}}\) .     

An example of nonuniqueness of the cauchy problem for the heat equation

We give an example of non trivial solution of the homogeneous Cauchy problem of the heat equation, which is, for each t, bounded in the space variables.