Determination of total and speciated sulfur content in petrochemical samples using a pulsed flame photometric detector

The pulsed flame photometric detector (PFPD) has the advantage of being able to measure the concentration of individual sulfur compounds and total sulfur content in a petrochemical sample in a single gas chromatography run. Because it is an equimolar response detector, the PFPD's sulfur response is independent of a compound's molecular structure, and this feature allows quantitation of the total or speciated sulfur content in complex samples using a single calibrant. This paper is a survey describing a variety of applications using the PFPD for sulfur quantitation in petrochemical matrices. Several different approaches to quantitation are described, and simple techniques for circumventing the quenching of the sulfur signal by coeluting hydrocarbon peaks are discussed. Examples from a range of real-world samples are presented.     

Adsorption and desorption of binary mixtures in confined geometry: A pilot positron annihilation study

In confined (nanometer-scale) geometry, the effects of substrate forces and finite size produce a shift of the gas liquid phase boundary from that found in corresponding bulk. The pore transitions also show marked hysteresis. The phase behaviour of a binary gas mixture in confined geometry is likely to depend on the miscibility of the system and the interaction between the substrate and the individual fluid molecules/atoms. Here, we present the results of a pilot positronium annihilation study of the condensation and evaporation of argon-nitrogen mixtures confined in 4 nm diameter cylindrical pores in VYCOR glass.     

Characterization of AMA1-RON2L complex with native gel electrophoresis and capillary isoelectric focusing

Rhoptry neck protein 2 (RON2) binds to the hydrophobic groove of apical membrane antigen 1 (AMA1), an interaction essential for invasion of red blood cells (RBCs) by Plasmodium falciparum (Pf) parasites. Vaccination with AMA1 alone has been shown to be immunogenic, but unprotective even against homologous challenge in human trials. However, the AMA1-RON2L (L is referred to as the loop region of RON2 peptide) complex is a promising candidate, as preclinical studies with Freund's adjuvant have indicated complete protection against lethal challenge in mice and superior protection against virulent infection in Aotus monkeys. To prepare for clinical trials of the AMA1-RON2L complex, identity and integrity of the candidate vaccine must be assessed, and characterization methods must be carefully designed to not dissociate the delicate complex during evaluation. In this study, we developed a native Tris-glycine gel method to separate and identify the AMA1-RON2L complex, which was further identified and confirmed by Western blotting using anti-AMA1 monoclonal antibodies (mAbs 4G2 and 2C2) and anti-RON2L polyclonal Ab coupled with mass spectrometry. The formation of complex was also confirmed by Capillary Isoelectric Focusing (cIEF). A short-term (48 h and 72 h at 4°C) stability study of AMA1-RON2L complex was also performed. The results indicate that the complex was stable for 72 h at 4°C. Our research demonstrates that the native Tris-glycine gel separation/Western blotting coupled with mass spectrometry and cIEF can fully characterize the identity and integrity of the AMA1–RON2L complex and provide useful quality control data for the subsequent clinical trials.     

Beam action spectroscopy via inelastic scattering

In this article, a new technique we call Beam Action Spectroscopy via Inelastic Scattering (BASIS) is demonstrated. BASIS takes advantage of the sensitivity of rotational state distributions in a supersonic molecular beam to inelastic scattering within the beam. We exploit BASIS to achieve increased sensitivity in two very different types of experiments. In the first, the UV photodissociation spectrum of OClO is recovered by monitoring intensity changes in the pure rotational transition of a spectator molecule (OCS) downstream from the nozzle, revealing a new vibrational structure in the region between 30,000 and 36,000 cm(-1). In the second, the mid-IR vibrational spectrum of acetylene is recorded simply by monitoring a single pure rotational transition of OCS co-expanded with acetylene. The technique may prove particularly fruitful when an excitation process produces product dark states that are not easily probed by conventional spectroscopy.     

Valence orbital response to pseudorotation of tetrahydrofuran: a snapshot using dual space analysis

The pseudorotation of tetrahydrofuran (THF) (C(4)H(8)O) has been studied using density functional theory, with respect to the valence orbital responses to the ionization potentials and to orbital electron and momentum distributions. Three conformations of THF, the global minimum structure C(s), local minimum structure C(2), and a transition state structure C(1), which are characteristic configurations on the potential energy surface, are examined using the SAOP/et-pVQZ//B3LYP/6-311++G** models with the aforementioned dual space analysis. It is noted in the ionization energy spectra that the minimum structures C(s) and C(2) are not directly connected by pseudorotation, but through the transition state structure C(1). As a result, some orbitals of the C(s) conformer are able to "correlate" to orbitals of the C(2) conformer without a strict symmetry constraint, i.e., orbital 7a' of the C(s) conformer is correlated to orbital 5b of the C(2) conformer. It is also noted that although the valence orbital ionization potentials are not significantly altered by the pseudorotation of THF, their spectra (mainly due to excitation) are quite different indeed. Detailed orbital analysis based on dual space analysis is given. The valence orbital behavior of the conformations is orbital dependent. It can be approximately divided into three groups: the "signature group" is associated with orbitals experiencing significant changes. The frontier orbitals are in this group. The "nearly identical group" includes orbitals without apparent changes across the conformations. Most of the orbitals showing a certain degree of distortion during the pseudorotation process belong to the third group. The present study demonstrates that a comprehensive understanding of the pseudorotation of THF and its dynamics requires multidimensional information and that the information gained from momentum space is complementary to that from the more familiar coordinate space.     

Electrochemical Immunosensors for Food Analysis: A Review of Recent Developments

Electrochemical immunosensors have the potential to transform analytical procedures within the food industry by providing highly specific, rapid, and inexpensive determination of pathogens. In this paper, recent advances in this area are outlined. In particular, attention is paid to new methods that have been developed for the modification of working electrode surfaces. Many advances have been related to the use of novel nanomaterials such as carbon nanotubes, graphene, and metallic nanoparticles, often used in conjunction with each other or polymers. The use of these materials has generally provided superior sensor sensitivity. The application of immunosensors to the detection of a range of pathogens in real samples is then investigated to establish whether they provide solutions in practical applications.     

Low Noise mm-Wave Amplifier Design Methodology

A design methodology for mm-wave LNAs is presented. The optimum bias point selection is outlined. The stabilisation strategy is described, and the impact of packaging requirements on the amplifier design is discussed. A bond wire compensation technique is detailed. The tradeoff between input match and noise figure is presented, and a design with a suitable tradeoff is¹ developed. A very simple inter-stage match requirement is a novel outcome of this design approach. An effective means of achieving a broadband response is also outlined. A four stage 30 – 50 GHz LNA design was fabricated and characterised in a customised package. A maximum MMIC gain of 28 dB at 32 GHz was achieved, and the gain exceeded 20 dB over the frequency range 26 – 44 GHz. A noise figure of 4.5 dB and a P1dB of +11 dBm were also obtained. It is the authors' opinion that the methodology presented in this paper will be of significant interest to other mm-wave LNA designers.     

Preliminary Structure–Activity Relationship Study of the MMV Pathogen Box Compound MMV675968 (2,4-Diaminoquinazoline) Unveils Novel Inhibitors of Trypanosoma brucei brucei

New drugs are urgently needed for the treatment of human African trypanosomiasis (HAT). In line with our quest for novel inhibitors of trypanosomes, a small library of analogs of the antitrypanosomal hit (MMV675968) available at MMV as solid materials was screened for antitrypanosomal activity. In silico exploration of two potent antitrypanosomal structural analogs (7-MMV1578647 and 10-MMV1578445) as inhibitors of dihydrofolate reductase (DHFR) was achieved, together with elucidation of other antitrypanosomal modes of action. In addition, they were assessed in vitro for tentative inhibition of DHFR in a crude trypanosome extract. Their ADMET properties were also predicted using dedicated software. Overall, the two diaminoquinazoline analogs displayed approximately 40-fold and 60-fold more potency and selectivity in vitro than the parent hit, respectively (MMV1578445 (10): IC₅₀ = 0.045 µM, SI = 1737; MMV1578467 (7): IC₅₀ = 0.06 µM; SI = 412). Analogs 7 and 10 were also strong binders of the DHFR enzyme in silico, in all their accessible protonation states, and interacted with key DHFR ligand recognition residues Val32, Asp54, and Ile160. They also exhibited significant activity against trypanosome protein isolate. MMV1578445 (10) portrayed fast and irreversible trypanosome growth arrest between 4–72 h at IC₉₉. Analogs 7 and 10 induced in vitro ferric iron reduction and DNA fragmentation or apoptosis induction, respectively. The two potent analogs endowed with predicted suitable physicochemical and ADMET properties are good candidates for further deciphering their potential as starting points for new drug development for HAT.