Structure Determination of Hydroxytrypargine: A New Tetrahydro‐β‐Carboline Toxin from the Venom of the Spider Parawixia bistriata

A new, highly active tetrahydro‐β‐carboline toxin from the spider Parawixia bistriata, the most‐common species of social spider occurring in Brazil, was isolated. The new toxin was identified as 1,2,3,4‐tetrahydro‐6‐hydroxy‐β‐carboline (=N‐[3‐(2,3,4,9‐tetrahydro‐6‐hydroxy‐1H‐pyrido[3,4‐b]indol‐1‐yl)propyl]guanidine; 3 ). This type of alkaloid, not common among spider toxins, was found to be the most‐potent constituent of the spider's chemical weaponry to kill prey. When P. bistriata catch arthropods in their web, they apparently attack their prey in groups of many individuals injecting their venoms. In vivo toxicity assays with 3 demonstrated a potent lethal effect to honeybees, giving rise to clear neurotoxic effects (paralysis) before death. The compound's toxicity (LD₅₀ value) was determined to be ca. 8 ng/g of honeybee. The investigation of the pharmacological properties and neurotoxic actions of 3 may be used in the future for the development of new drugs to be applied for pest control in agriculture.     

On a subvariety of semi-De Morgan algebras

A characterization of principal congruences of the subvariety C of semi-DeMorgan algebras is given. This characterization is applied to determine the subdirectly irreducible algebras of the variety C and to describe a poset such that the lattice of its order ideals is isomorphic to the lattice of subvarieties of C. This revised version was published online in June 2006 with corrections to the Cover Date.     

Enthalpic and entropic contributions of water molecules to the functional T → R transition of human hemoglobin in solution

Generalized solvent-mediated forces contribute to free energy at the functional T → R transition of human hemoglobin A (HbA). Their contribution is here sorted out quantitatively in both its enthalpic and entropic parts, along with the average number of water molecules involved. The latter (about 75 waters in average) must be considered together with HbA as one statistically defined functional unit for oxygen transport. Their configurations are expected to undergo frequent structural rearrangements. Lifetimes of statistically relevant configurations do not need to (although, of course, they may) exceed by more than a factor 5 the normal H-bond lifetimes of the pure solvent. Compared to the bare protein, the “functional unit” here evidenced for the first time involves a larger, higher dimensionality region of the phase space. The study allows a microscopic view of solvent-mediated generalized forces and evidences their qualitative and quantitative relevance to biomacromolecular function and stability.     

Dunaliella tertiolecta (Chlorophyta) Avoids Cell Death Under Ultraviolet Radiation By Triggering Alternative Photoprotective Mechanisms

The effect of different ultraviolet radiation (UVR) treatments combining PAR (P), UVA (A) and UVB (B) on the molecular physiology of Dunaliella tertiolecta was studied during 6 days to assess the response to chronic UVR exposure. UVR reduced cell growth but did not cause cell death, as shown by the absence of SYTOX Green labeling and cellular morphology. However, caspase‐like enzymatic activities (CLs), (regarded as cell death proteases), were active even though the cells were not dying. Maximal quantum yield of fluorescence (F_v/F_m) and photosynthetic electron transport rate (ETR) dropped. Decreased nonphotochemical quenching (NPQ) paralleled a drop in xanthophyll cycle de‐epoxidation under UVB. Reactive oxygen species (ROS) and D1 protein accumulation were inversely correlated. PAB exhibited elevated ROS production at earlier times. Once ROS decayed, D1 protein recovered two‐fold compared with P and PA at later stages. Therefore, PsbA gene was still transcribed, suggesting ROS involvement in D1 recovery by its direct effect on mRNA‐translation. We add evidence of an UVB‐induced positive effect on the cells when P is present, providing photoprotection and resilience, by means of D1 repair. This allowed cells to survive. The photoprotective mechanisms described here (which are counterintuitive in principle) conform to an important ecophysiological response regarding light stress acclimation.     

Recent developments in computer vision-based analytical chemistry: A tutorial review

Chemical analysis based on colour changes recorded with imaging devices is gaining increasing interest. This is due to its several significant advantages, such as simplicity of use, and the fact that it is easily combinable with portable and widely distributed imaging devices, resulting in friendly analytical procedures in many areas that demand out-of-lab applications for in situ and real-time monitoring. This tutorial review covers computer vision-based analytical (CVAC) procedures and systems from 2005 to 2015, a period of time when 87.5% of the papers on this topic were published. The background regarding colour spaces and recent analytical system architectures of interest in analytical chemistry is presented in the form of a tutorial. Moreover, issues regarding images, such as the influence of illuminants, and the most relevant techniques for processing and analysing digital images are addressed. Some of the most relevant applications are then detailed, highlighting their main characteristics. Finally, our opinion about future perspectives is discussed.     

Absolute intensity measurements of impurity emissions in a shock tunnel and their consequences for laser-induced fluorescence experiments

Absolute intensity measurements of impurity emissions in a shock tunnel nozzle flow are presented. The impurity emission intensities were measured with a photomultiplier and optical multichannel analyser and calibrated against an intensity standard. The various metallic contaminants were identified and their intensities measured in the spectral regions 290 to 330 nm and 375 to 385 nm. A comparison with calculated fluorescence intensities for predissociated laser-induced fluorescence signals is made. It is found that the emission background is negligible for most fluorescence experiments.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

On the use of fluorescent dyes for concentration measurements in water flows

An experiment was performed to evaluate the characteristics of various fluorescent dyes used as tracers for concentration measurements in water flows, by laser induced fluorescence. Three common fluorescent dyes (fluorescein, rhodamine B and rhodamine 6G) were used, to select the most suitable fluorescent dye and identify its range of linear response. The results showed that, in terms of the stability of the solution, fluorescein is inferior to either rhodamine B or rhodamine 6G and that for concentrations of rhodamine B less than 0.08 mg/1 the response of fluorescent to the incident light is linear.     

Structural-dynamical investigation of the ZnuA histidine-rich loop: involvement in zinc management and transport

Comparative homology modelling techniques have been used to model the protein ZnuA from Salmonella enterica serovar Typhimurium using the 3D structure of the homologous protein from Escherichia coli. These two-domain proteins bind one Zn²⁺ atom, with high affinity, in the inter-domain cleft and possess a histidine-rich loop in the N-terminal domain. Alternative structures of the ZnuA histidine-rich loop, never resolved by the X-ray diffraction method, have been modelled. A model of the apo form, one with the histidine-rich loop deleted and two alternative structures with a second zinc ion bound to the histidine-rich loop, have been generated. In all the modelled proteins, investigated through molecular dynamics simulation, the histidine-rich loop is highly mobile and its fluctuations are correlated to the ligand stability observed in the zinc sites. Based on the plasticity of the histidine-rich loop and its significant effects on protein mobility a possible role in the capture and/or transfer of the zinc ions has been suggested.