An amperometric sensor based on hemin adsorbed on silica gel modified with titanium oxide for electrocatalytic reduction and quantification of artemisinin

The present work describes the development of an amperometric sensor based on hemin immobilized on a titanium oxide modified silica toward detection of artemisinin (ARN) in neutral medium at an applied potential of −0.5 V vs. Ag/AgCl. The sensor presented its best performance in 0.1 mol L⁻¹ phosphate buffer solution, at pH 7.0. After optimizing the operational conditions, the sensor provided a linear response range for ARN reduction from 50 nmol L⁻¹ to 1000 nmol L⁻¹ with a sensitivity, detection and quantification limits of 24.66 A L mol⁻¹, 15 nmol L⁻¹ and 52 nmol L⁻¹, respectively. The proposed sensor showed a stable response for at least 80 successive determinations. The repeatability of the measurements with the sensor and the preparation of a series of electrodes, evaluated in terms of relative standard deviation, were 4.1% and 5.0%, respectively, for n = 10. The developed sensor was applied for the determination of ARN in the crude extracts of A. vulgaris L and the average recovery for these samples is 101.4 (± 3.1)%.     

Tumor Carbohydrate Associated Antigen Analogs as Potential Binders for Siglec-7

We investigated two recently synthesized and characterized sialyl derivatives, bearing the Neu5Ac-α-(2-6)-Gal epitope, as promising binders for Siglec-7, an inhibitory Siglec mainly found on natural killer cells. A variety of sialoglycan structures can be recognized by Siglec-7 with implications in the modulation of immune responses. Notably, overexpression of sialylated glycans recognized by Siglec-7 can be associated with the progression of several tumors, including melanoma and renal cell carcinoma. NOE-based NMR techniques, including Saturation Transfer Difference and transferred-NOESY NMR, together with molecular docking and dynamic simulations were combined to shed light on the molecular basis of Siglec-7 recognition of two conformationally constrained Sialyl-Tn antigen analogs. We, therefore, identify the ligands epitope mapping and their conformational features and propose 3D models accurately describing the protein-ligand complexes. We found that the binding site of Siglec-7 can accommodate both synthetic analogs, with the sialic acid mainly involved in the interaction. Moreover, the flexibility of Siglec-7 loops allows a preferred accommodation of the more rigid compound bearing a biphenyl moiety at position 9 of the sialic acid that contributed to the interaction to a large extent. Our findings provided insights for developing potential novel high affinity ligands for Siglec-7 to hinder tumor evasion.     

Heart rate variability analysis by chaotic global techniques in children with attention deficit hyperactivity disorder

Attention deficit hyperactivity disorder (ADHD) is characterized by decreased attention span, impulsiveness, and hyperactivity. Autonomic nervous system imbalance was previously described in this population. We aim to compare the autonomic function of children with ADHD and controls by analyzing heart rate variability (HRV). Children with ADHD (22 boys, mean age 9.964 years) and 28 controls (15 boys, mean age 9.857 years) rested in supine position with spontaneous breathing for 20 min. Heart rate was recorded beat by beat. HRV analysis was performed by use of chaotic global techniques. ADHD promoted an increase in the chaotic forward parameter. The algorithm which applied all three chaotic global parameters was only the second optimum statistically measured by Kruskal–Wallis (P < 0.0001) and low standard deviations. It was also highly influential by principal component analysis with almost all variation covered by the first two components. The third algorithm which lacked the (high spectral Detrended Fluctuation Analysis) parameter performed best statistically. However, we chose the algorithm which applied all three chaotic globals due to previous studies mentioned in the text—forward and inverse problems. Comparison of the autonomic function by analyzing HRV with chaotic global techniques suggests an increase in chaotic activity in children with ADHD in relation to the control group. © 2015 Wiley Periodicals, Inc. Complexity 21: 412–419, 2016     

Structural study of the stability of the captopril drug regarding the formation of its captopril disulphide dimer

Captopril disulphide is obtained under hydrothermal conditions. The IR and Raman spectra data are in agreement with the X-ray diffraction results. The disappearance of the band at 2566 cm^–1 (ν(SH)) in both spectra of captopril disulphide is consistent with the formation of the S–S bond. The degradation of the captopril drug is investigated by Raman spectroscopy and the results indicate that after 6 weeks of air exposure, a band at 512 cm^–1, assigned as ν(SS), is observed, suggesting the formation of captopril disulphide. DFT calculations in the solid state are performed for captopril and captopril disulphide. The results indicate that captopril disulphide is approximately 30 kcal?mol^–1 more stable than captopril. The analysis of the total density of states (DOS) reveals that the captopril valence band contains a significant contribution from the S atom, whereas for captopril disulphide, the O atom is the most important for the valence band.     

Electrochemical Detection Using an Engraved Microchip – Capillary Electrophoresis Platform

The present study describes a simple strategy to integrate electrochemical detection with an assembled microchip‐capillary electrophoresis platform. The electrochemical cell was integrated with a microfluidic device consisting of five plastic squares interconnected with fused silica capillaries, forming a four‐way injection cross between the separation channel and three side‐arms (each of 15 mm in length) acting as buffer/sample reservoirs. The performance of the system was evaluated using electrodes made with either carbon ink, carbon nanotubes, or gold and under different experimental conditions of pH, capillary length, and injection time. Using this system it was possible to separate the neurotransmitters dopamine and cathecol and to quantify phenol from a real sample using a linear calibration curve with a calculated LOD of 0.7 µM. A similar concept was applied to determine glucose, by including a pre‐reactor filled with beads modified with glucose oxidase (GOx). The latter system was used to determine glucose in a commercial sample, with a recovery of 95.2 %. Overall, the presented approach represents a simple, inexpensive, and versatile approach to integrate electrochemical detection with CE separations without requiring access to microfabrication facilities.     

Precise mass measurement of a double-stranded 500 base-pair (309 kDa) polymerase chain reaction product by negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd.     

A precise measurement of the partial decay width ratio {R_{\mathrm{b}}}^0 = \Gamma_{\mathrm{b\bar{b}}}/\Gamma_{\mathrm{had}}

The partial decay width of the Z to quark pairs has been measured by the DELPHI detector at LEP using data taken in the years 1992 to 1995. Decays of b-hadrons were tagged by several methods using tracks with large impact parameters and/or reconstructed secondary vertices, complemented by event shape variables. Combining these methods in a multivariate analysis the value was obtained, where the production fraction was fixed to its Standard Model value. Received: 18 December 1998 / Revised version: 26 April 1999 / Published online: 3 August 1999     

Measurement of the strange quark forward-backward asymmetry around the Z^{0} peak

A precise measurement of the strange quark forward-backward asymmetry used 3.2M multihadronic events around the Z peak collected by the DELPHI experiment from 1992 to 1995. The ring imaging Cherenkov detectors in the barrel and end-cap regions identify high energy charged kaons which tag the s quark. The s quark asymmetry was measured at different centre-of-mass energies; in particular at the Z pole taking the expected d and u quark asymmetries from the Standard Model. The quark flavour fractions are assumed from the Standard Model and the fragmentation process is modelled by JETSET. From the s quark pole asymmetry the electroweak mixing angle was determined: The parity violating coupling of the s quark to the Z was determined to be: Received: 8 October 1999 / Revised version: 23 February 2000 / Published online: 18 May 2000     

Identified charged particles in quark and gluon jets

A sample of 2.2 million hadronic Z decays, selected from the data recorded by the Delphi detector at Lep during 1994–1995 was used for an improved measurement of inclusive distributions of and p and their antiparticles in gluon and quark jets. The production spectra of the individual identified particles were found to be softer in gluon jets compared to quark jets, with a higher multiplicity in gluon jets as observed for inclusive charged particles. A significant proton enhancement in gluon jets is observed indicating that baryon production proceeds directly from colour objects. The maxima, , of the -distributions for kaons in gluon and quark jets are observed to be different. Received: 24 January 2000 / Revised version: 15 May 2000 / Published online: 8 September 2000