Isomerization of α-pinene over dealuminated ferrierite-type zeolites

Isomerization of α-pinene was performed on a series of dealuminated ferrierite (FER)-type zeolites in liquid phase at 363 K using a batch reactor. The course of zeolite dealumination was followed in detail using ²⁹Si, ²⁷Al, ¹H MAS NMR, XRD, FTIR, and sorption of nitrogen. The ammonium form of FER was dealuminated with aqueous solutions of HCl. While retaining the crystallinity of the zeolite particles, the treatments removed up to 53% of the tetrahedrally coordinated aluminum atoms from the FER framework. According to ²⁹Si MAS NMR studies, the framework aluminum atoms located at the 10-membered rings in the main channels of FER (T_B sites) were depleted preferentially from their positions. Even relatively mild dealumination of FER led to an active catalyst containing both Brønsted and Lewis centers, yielding up to 97% conversion of α-pinene at 363 K, in contrast to the 72% observed for the parent hydrogen form. Such catalytic behavior was discussed in terms of the conversion of a reactant inside micropores of the zeolite catalyst, on Brønsted acid centers with enhanced strength located probably in the vicinity of Lewis sites. The selectivity toward camphene and limonene changed smoothly with the dealumination level; thus, a higher selectivity toward limonene was observed at the expense of camphene formation with increasing the n_Si/n_Al ratio of the catalysts. The selectivity toward camphene and limonene was close to 85% for all of the materials studied. The initial rates of α-pinene transformations over FER-type materials exceeded those observed for other catalytic systems, heteropoly acid/SiO₂ and H₂SO₄/ZrO₂. This study demonstrates the successful application of a medium-pore zeolite for the catalytic transformation of α-pinene in liquid phase.     

Nitroalkenes and Sesquiterpene Hydrocarbons from the Frontal Gland of Three Prorhinotermes Termite Species

Frontal gland contents of soldiers of three Prorhinotermes species, Prorhinotermes canalifrons, Prorhinotermes inopinatus, and Prorhinotermes simplex, consisted of two groups of compounds: nitroalkenes and sesquiterpene hydrocarbons. Analysis by gas chromatography-mass spectrometry revealed (E)-1-nitropentadec-1-ene as the major component of the glands with mean values of 152, 207, and 293 μg/individual for P. canalifrons, P. inopinatus, and P. simplex, respectively. Four other 1-nitroalkenes (C13, C14, C16, and C17), and two nitrodienes (C15 and C17) were also detected in the three species. The C17:1 nitroalkene was identified as (E)-1-nitroheptadec-1-ene. The sesquiterpene composition of the gland was species-specific: P. simplex contained (3Z,6E)-α-farnesene (mean of 39 μg/individual), while P. canalifrons and P. inopinatus contained the same compound (means of 0.5 and 1.5 μg/individual, respectively) as well as the (3E,6E) isomer (means of 1.8 and 0.7 μg/individual, respectively). Two other sesquiterpenes, trans-β-bergamotene and (Z)-γ-bisabolene, were also found in low quantities in the frontal gland of P. canalifrons.     

Tagged Benzoxazin-4-Ones as Novel Activity-Based Probes for Serine Proteases

Activity-based probes (ABPs) are valuable chemical tools for profiling enzymes. They have been particularly useful in the study of proteases. ABPs rely on electrophilic scaffolds that covalently modify the target enzymes. Ideally, they can be made in a fast and uncomplicated manner. Here, we explore alkyne-substituted benzoxazin-4-ones as ABPs for serine proteases, because they inhibitserine proteases covalently and their synthesis is very straightforward. We show that alkyne-tagged benzoxazin-4-ones can be used in two-step bioorthogonal tandem labeling procedures or pre-functionalized with a biotin or fluorophore. We demonstrate that these reagents can be used to label and identify various serine proteases. Therefore, we expect that tagged benzoxazin-4-ones will offer easily synthesizable tools for profiling of serine proteases.     

Biomarkers of Angiogenesis and Neuroplasticity as Promising Clinical Tools for Stroke Recovery Evaluation

Several key issues impact the clinical practice of stroke rehabilitation including a patient’s medical history, stroke experience, the potential for recovery, and the selection of the most effective type of therapy. Until clinicians have answers to these concerns, the treatment and rehabilitation are rather intuitive, with standard procedures carried out based on subjective estimations using clinical scales. Therefore, there is a need to find biomarkers that could predict brain recovery potential in stroke patients. This review aims to present the current state-of-the-art stroke recovery biomarkers that could be used in clinical practice. The revision of biochemical biomarkers has been developed based on stroke recovery processes: angiogenesis and neuroplasticity. This paper provides an overview of the biomarkers that are considered to be ready-to-use in clinical practice and others, considered as future tools. Furthermore, this review shows the utility of biomarkers in the development of the concept of personalized medicine. Enhancing brain neuroplasticity and rehabilitation facilitation are crucial concerns not only after stroke, but in all central nervous system diseases.     

Electronic Circular Dichroism of the Cas9 Protein and gRNA:Cas9 Ribonucleoprotein Complex

The Streptococcus pyogenes Cas9 protein (SpCas9), a component of CRISPR-based immune system in microbes, has become commonly utilized for genome editing. This nuclease forms a ribonucleoprotein (RNP) complex with guide RNA (gRNA) which induces Cas9 structural changes and triggers its cleavage activity. Here, electronic circular dichroism (ECD) spectroscopy was used to confirm the RNP formation and to determine its individual components. The ECD spectra had characteristic features differentiating Cas9 and gRNA, the former showed a negative/positive profile with maxima located at 221, 209 and 196 nm, while the latter revealed positive/negative/positive/negative pattern with bands observed at 266, 242, 222 and 209 nm, respectively. For the first time, the experimental ECD spectrum of the gRNA:Cas9 RNP complex is presented. It exhibits a bisignate positive/negative ECD couplet with maxima at 273 and 235 nm, and it differs significantly from individual spectrum of each RNP components. Additionally, the Cas9 protein and RNP complex retained biological activity after ECD measurements and they were able to bind and cleave DNA in vitro. Hence, we conclude that ECD spectroscopy can be considered as a quick and non-destructive method of monitoring conformational changes of the Cas9 protein as a result of Cas9 and gRNA interaction, and identification of the gRNA:Cas9 RNP complex.     

Conventional and back-side focused ion beam milling for off-axis electron holography of electrostatic potentials in transistors

Off-axis electron holography is used to characterize a linear array of transistors, which was prepared for examination in cross-sectional geometry in the transmission electron microscope (TEM) using focused ion beam (FIB) milling from the substrate side of the semiconductor device. The measured electrostatic potential is compared with results obtained from TEM specimens prepared using the more conventional 'trench' FIB geometry. The use of carbon coating to remove specimen charging effects, which result in electrostatic fringing fields outside 'trench' specimens, is demonstrated. Such fringing fields are not observed after milling from the substrate side of the device. Analysis of the measured holographic phase images suggests that the electrically inactive layer on the surface of each FIB-milled specimen typically has a thickness of 100 nm.     

Object-based facilitation and inhibition from visual orienting in the human split-brain.

Object-based attention was examined in 2 split-brain patients. A precued object could move within a visual field or cross the midline to the opposite field. Normal individuals show an inhibition in detecting signals in the cued object whether it moves within or between fields. Both patients showed this effect when the cued object moved within a visual field. When it crossed the midline into the opposite visual field, however, detection was faster in the cued box. These results reveal both facilitatory and inhibitory effects on attention that are object based and may last for several hundred milliseconds. However, the inhibition requires an intact corpus callosum for interhemispheric transfer, whereas the facilitation is transferred subcortically. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

High temperature CoSb3-Cu junctions

The subject of this work is to develop contact joints between a CoSb₃ thermoelectric material and a copper electrode. The CoSb₃-Cu junctions were produced by the resistance brazing (RB) technique in the atmosphere of protective gases (90% Ar + 10% H₂), with the application of Ag-Cu metal fillers. The diffusion barriers (Ni, Mo, Cr₈₀Si₂₀) on the TE segments made of the polycrystalline CoSb₃ were prepared by the magnetron sputtering method.The microstructure and the chemical composition of the joints were examined using a scanning microscope (SEM) with an X-ray energy dispersion analysis (EDX). The examinations of the electrical parameters of the joints such as: the Seebeck coefficient, resistivity, and current-voltage characteristics were performed by a scanning thermoelectric microprobe (STM).