Light-driven horseradish peroxidase cycle by using photo-activated methylene blue as the reducing agent

In this work, the regeneration of native horseradish peroxidase (HRP), following the consecutive reduction of oxo-ferryl pi-cation (compound I) and oxo-ferryl (compound II) forms, was observed by UV-visible spectrometry and electron paramagnetic resonance (EPR) in the presence of methylene (MB+), in the dark and under irradiation. In the dark, MB+ did not affect the rate of HRP compound I and II reduction, compatible with hydrogen peroxide as the solely reducing species. Under irradiation, the dye promoted a significant increase in the native HRP regeneration rate in a pH-dependent manner. Flash photolysis measurements revealed significant redshift of the MB+ triplet absorbance spectrum in the presence of native HRP. This result is compatible with the dye binding on the enzyme structure leading to the increase in the photogenerated MB* yield. In the presence of HRP compound II, the lifetime of the dye at 520 nm decreased approximately 75% relative to the presence of native HRP that suggests MB* as the heme iron photochemical reducing agent. In argon and in air-saturated media, photoactivated MB+ led to native HRP regeneration in a time- and concentration-dependent manner. The apparent rate constant for photoactivated MB+-promoted native HRP regeneration, in argon and in air-saturated medium and measured as a function of MB+ concentration, exhibited saturation that is suggestive of dye binding on the HRP structure. The dissociation constant (KMB) observed for the binding of dye to HRP was 5.4+/-0.6 microM and 0.57+/-0.05 microM in argon and air-saturated media, respectively. In argon-saturated medium, the rate of the conversion of HRP compound II to native HRP was significantly higher, k2argon=(2.1+/-0.1)x10(-2) s(-1), than that obtained in air-equilibrated medium, k2air=(0.73+/-0.02)x10(-2) s(-1). Under these conditions the efficiency of photoactivated MB(+)-promoted native HRP regeneration was determined in argon and air-equilibrated media as being, respectively: k2/KMB=3.9x10(3) and 12.8x10(3) M(-1) s(-1).     

Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Hooker’s ‘lapachol peroxide’ revisited

The structure of ‘lapachol peroxide’ was published by Hooker in 1936; however, we recently discovered a mistake in the originally proposed structure; the correct structure, according to X-ray spectroscopy, is given here.     

Electronic temperature measurement in a Rb ultracold plasma

In this paper, we report electronic temperature measurement in a Rb ultracold plasma formed in a magneto-optical trap. We used the ion evaporation rate and the model presented by Comparat et al. [Mon. Not. R. Astron. Soc. 361, 1227 (2005)] to extract the electronic temperature in the plasma as a function of the energy difference between the laser photon and the ionization threshold. The obtained results are similar to those obtained in Cs; however, they do not seem to show any saturation. Comparison with other models may lead to improvements in the experiments and the theoretical models.     

On the Singular Effects in the Relativistic Landau Levels in Graphene with a Disclination

The effect of a pseudo Aharonov-Bohm (AB) magnetic field generated by a disclination on a two-dimensional electron gas in graphene is addressed in the continuum limit within the geometric approach. The influence of the coupling between the spinor fields and the singular conical curvature is investigated, which shows that singularities have pronounced impact in the Hall conductivity. Moreover, the degeneracy related to the Dirac valleys is broken for negative values of the angular momentum quantum numbers, l, includingl ≡ 0. In this case, a Hall plateau develops at the null filling factor. Obtaining the Hall conductivity by summing over the positive and the negative l's, the null Landau level is recovered and the plateau at the null filling factor disappears. In any case, the standard plateaus, which are seen in a flat graphene are not obtained with these curvature and singular effects.     

Introduction to Topological Phases and Electronic Interactions in (2+1) Dimensions

A brief introduction to topological phases is provided, considering several two-band Hamiltonians in one and two dimensions. Relevant concepts of the topological insulator theory, such as: Berry phase, Chern number, and the quantum adiabatic theorem, are reviewed in a basic framework, which is meant to be accessible to non-specialists. We discuss the Kitaev chain, SSH, and BHZ models. The role of the electromagnetic interaction in the topological insulator theory is addressed in the light of the pseudo-quantum electrodynamics (PQED). The well-known parity anomaly for massless Dirac particle is reviewed in terms of the Chern number. Within the continuum limit, a half-quantized Hall conductivity is obtained. Thereafter, by considering the lattice regularization of the Dirac theory, we show how one may obtain the well-known quantum Hall conductivity for a single Dirac cone. The renormalization of the electron energy spectrum, for both small and large coupling regime, is derived. In particular, it is shown that massless Dirac particles may, only in the strong correlated limit, break either chiral or parity symmetries. For graphene, this implies the generation of Landau-like energy levels and the quantum valley Hall effect.     

Chemical Physical Characterization and Profile of Fruit Volatile Compounds from Different Accesses of Myrciaria floribunda (H. West Ex Wild.) O. Berg through Polyacrylate Fiber

Among the many species of native fruit of Brazil that have been little explored, there is Myrciaria floribunda (also known as rumberry, cambuizeiro, or guavaberry), a species with significant variability, which has fruits of different colors (orange, red, and purple) when ripe. The physical-chemical characteristics evaluated were fruit weight (FW), seed weight (SW), pulp weight (PW), number of seeds (NS), longitudinal diameter (LD), transverse diameter (TD), format (LD/TD), hydrogen potential (pH), soluble solids (SS), titratable acidity (TA), and ratio (SS/TA); further, the volatile organic compounds (VOCs) of nine accesses of rumberry orchards were identified. The averages of the variables FW, SW, PW, NS, LD, TD, shape, and firmness were 0.76 g, 0.22 g, 0.54 g, 1.45, 10.06 mm, 9.90 mm, 1.02, 2.96 N, respectively. LD/TD data showed that the fruits have a slightly rounded shape (LD/TD = 1). The averages for pH, SS, TA, and SS/TA were 3.74, 17.58 Brix, 4.31% citric acid, and 4.31, respectively. The evaluated parameters indicated that the fruits can be consumed both in natura and industrialized, with the red-colored fruits presenting a good balance of SS/TA, standards demanded by the processing industries. Thirty-six VOCs were identified, with emphasis on the sesquiterpenes. Caryophyllene (21.6% to 49.3%) and γ-selinene (11.3% to 16.3%) were the most predominant compounds in rumberry fruits.