Neutral loss fragmentation pattern based screening for arginine-rich natural products in xenorhabdus and photorhabdus

Although sharing a certain degree of structural uniformity, natural product classes exhibit variable functionalities such as different amino acid or acyl residues. During collision induced dissociation, some natural products exhibit a conserved fragmentation pattern close to the precursor ion. The observed fragments result from a shared set of neutral losses, creating a unique fragmentation pattern, which can be used as a fingerprint for members of these natural product classes. The culture supernatants of 69 strains of the entomopathogenic bacteria Photorhabdus and Xenorhabdus were analyzed by MALDI-MS(2), and a database comprising MS(2) data from each strain was established. This database was scanned for concordant fragmentation patterns of different compounds using a customized software, focusing on relative mass differences of the fragment ions to their precursor ion. A novel group of related natural products comprising 25 different arginine-rich peptides from 16 different strains was identified due to its characteristic neutral loss fragmentation pattern, and the structures of eight compounds were elucidated. Two biosynthesis gene clusters encoding nonribosomal peptide synthetases were identified, emphasizing the possibility to identify a group of structurally and biosynthetically related natural products based on their neutral loss fragmentation pattern.     

Angular velocity estimation from measurement vectors of star tracker

In most spacecraft, there is a need to know the craft's angular rate. Approaches with least squares and an adaptive Kalman filter are proposed for estimating the angular rate directly from the star tracker measurements. In these approaches, only knowledge of the vector measurements and sampling interval is required. The designed adaptive Kalman filter can filter out noise without information of the dynamic model and inertia dyadic. To verify the proposed estimation approaches, simulations based on the orbit data of the challenging minisatellite payload (CHAMP) satellite and experimental tests with night-sky observation are performed. Both the simulations and experimental testing results have demonstrated that the proposed approach performs well in terms of accuracy, robustness, and performance.     

Color fringe-projected technique for measuring dynamic objects based on bidimensional empirical mode decomposition

A triple-frequency color fringe-projected technique is presented to measure dynamic objects. Three fringe patterns with a carrier frequency ratio of 1:3:9 are encoded in red, green, and blue channels of a color fringe pattern and projected onto an object's surface. Bidimensional empirical mode decomposition is used for decoupling the cross talk among color channels and for extracting the fundamental frequency components of the three fringe patterns. The unwrapped phase distribution of the high-frequency fringe is retrieved by a three-step phase unwrapping strategy to recover the object's height distribution. Owing to its use of only a single snapshot, the technique is suitable for measuring dynamically changing objects with large discontinuity or spatially isolated surfaces.     

Peptide biosensors for the electrochemical measurement of protein kinase activity

The kinase activities are elucidated using the novel redox-active cosubstrate adenosine 5'-[gamma-ferrocene] triphosphate (Fc-ATP), which enables the kinase-catalyzed transfer of a redox active gamma-phosphate-Fc to a hydroxyamino acid. In this report, a versatile electrochemical biosensor is developed for monitoring the activity and inhibition of a serine/threonine kinase, casein kinase 2 (CK2), and protein tyrosine kinases, Abl1-T315I and HER2, in buffered solutions and in cell lysates. The method is based on the labeling of a specific phosphorylation event with Fc, followed by electrochemical detection. The electrochemical response obtained from the "ferrocenylated" peptides enables monitoring the activity of the kinase and its substrate, as well as the inhibition of small molecule inhibitors on protein phosphorylation. Kinetic information was extracted from the electrochemical measurements for the determination of K(m) and V(m) values, which were in agreement with those previously reported. Kinase reactions were also performed in the presence of well-defined inhibitors of CK2, 4,5,6,7-tetrabromo-2-azabenzimidazole, 2-dimethylamino-4,5,6,7-tetrabromo-1H-benzimidazole, and E-3-(2,3,4,5-tetrabromophenyl)acrylic acid as well as the nonspecific kinase inhibitors, staurosporine and N-benzoylstaurosporine. On the basis of the dependency of the Fc signal on inhibitor concentration, K(i) of the inhibitors was estimated, which were also in agreement with the literature values. The performance of the biosensor was optimized including the kinase reaction, incubation with Fc-ATP, and the small molecule inhibitors. Peptide modified electrochemical biosensors are promising candidates for cost-effective in vitro kinase activity and inhibitor screening assays.     

Direct electrochemistry of laccase immobilized on au nanoparticles encapsulated-dendrimer bonded conducting polymer: application for a catechin sensor

The direct electrochemistry of laccase was promoted by Au nanoparticle (AuNP)-encapsulated dendrimers (Den), which was applied for the detection of catechin. To increase the electrical properties, AuNPs were captured in the interiors of the dendrimer (Den-AuNPs) as opposed to attachment at the periphery of dendrimer. To prepare Den-AuNPs, the Au(III) ions were first coordinated in the interior of dendrimer with nitrogen ligands and then reduced to form AuNPs. The size of AuNPs encapsulated within the interior of the dendrimer was determined to be 1.7 +/- 0.4 nm. AuNPs-encapsulated dendrimers were then used to covalently immobilize laccase (PDATT/ Den(AuNPs)/laccase) through the formation of amide bonds between carboxylic acid groups of the dendrimer and the amine groups of laccase. Each layer of the PDATT/Den(AuNPs)/laccase probe was characterized using CV, EIS, QCM, XPS, SEM, and TEM. The PDATT/Den(AuNPs)/laccase probe displayed a well-defined direct electron-transfer (DET) process of laccase. The quasi-reversible redox peak of the Cu redox center of the laccase molecule was observed at -0.03/+0.13 V vs Ag/AgCl, and the electron-transfer rate constant was determined to be 1.28 s (-1). A catechin biosensor based on the electrocatalytic process by direct electrochemistry of laccase was developed. The linear range and the detection limit in the catechin analysis were determined to be 0.1-10 and 0.05 +/- 0.003 microM, respectively. Interference effects from various phenolic and polyphenolic compounds were also studied, and the general applicability of the biosensor was evaluated by selective analysis of real samples of catechin.     

Effect of non-lattice oxygen on ZrO2-based resistive switching memory

ABSTRACT: ZrO2-based resistive switching memory has attracted much attention according to its possible application in the next-generation nonvolatile memory. The Al/ZrO2/Pt resistive switching memory with bipolar resistive switching behavior is revealed in this work. The thickness of the ZrO2 film is only 20 nm. The device yield improved by the non-lattice oxygen existing in the ZrO2 film deposited at room temperature is firstly proposed. The stable resistive switching behavior and the long retention time with a large current ratio are also observed. Furthermore, it is demonstrated that the resistive switching mechanism agrees with the formation and rupture of a conductive filament in the ZrO2 film. In addition, the Al/ZrO2/Pt resistive switching memory is also possible for application in flexible electronic equipment because it can be fully fabricated at room temperature.     

Synthesis of micro-sized SnO2@carbon hollow spheres with enhanced lithium storage properties

Uniform and stable micro-sized SnO(2) hollow spheres are prepared by templating against polystyrene microspheres. After being coated with a thin layer of amorphous carbon, the as-obtained SnO(2)@carbon hollow microspheres are shown to exhibit improved lithium storage properties, delivering a reversible capacity of 570 mA h g(-1) after 50 cycles at a high current density of 400 mA g(-1).     

Biomimetic graphene films and their properties

Biomimetic fabrication has long been considered a short cut to the rational design and production of artificial materials or devices that possess fascinating properties, just like natural creatures. Considering the fact that graphene exhibits a lot of exceptional properties in a wide range of scientific fields, biomimetic fabrication of graphene multiscale structures, denoted as biomimetic graphene, is of great interest in both fundamental research and industrial applications. Especially, the combination of graphene with biomimetic structures would realize structural and functional integrity, and thus bring a new opportunity of developing novel graphene-based devices with remarkable performance. In this feature article, we highlight the recent advances in biomimetic graphene films and their structure-defined properties. Functionalized graphene films with multiscale structures inspired from a wide range of biomaterials including rose petals, butterfly wings, nacre and honeycomb have been collected and presented. Moreover, both current challenges and future perspectives of biomimetic graphene are discussed. Although research of the so-called "biomimetic graphene" is still at an early stage, it might become a "hot topic" in the near future.     

UV radiation induces genome-mediated, site-specific cleavage in viral proteins

Much research has been dedicated to understanding the molecular basis of UV damage to biomolecules, yet many questions remain regarding the specific pathways involved. Here we describe a genome-mediated mechanism that causes site-specific virus protein cleavage upon UV irradiation. Bacteriophage MS2 was disinfected with 254 nm UV, and protein damage was characterized with ESI- and MALDI-based FT-ICR, Orbitrap, and TOF mass spectroscopy. Top-down mass spectrometry of the products identified the backbone cleavage site as Cys46-Ser47 in the virus capsid protein, a location of viral genome-protein interaction. The presence of viral RNA was essential to inducing backbone cleavage. The similar bacteriophage GA did not exhibit site-specific protein cleavage. Based on the major protein fragments identified by accurate mass analysis, a cleavage mechanism is proposed by radical formation. The mechanism involves initial oxidation of the Cys46 side chain followed by hydrogen atom abstraction from Ser47 C(α). Computational protein QM/MM studies confirmed the initial steps of the radical mechanism. Collectively, this study describes a rare incidence of genome-induced protein cleavage without the addition of sensitizers.