Electron-donating properties of p-phenylene phosphine imides: an electrochemical and spectroscopic investigation

[reaction: see text] Electronic properties of phosphine imide based organic electron donors have been investigated. N,N'-p-Phenylenebis(triphenyl)phosphine imide (Ph(3)P=NC(6)H(4)N=PPh(3), 1) has two reversible single-electron oxidations (0.04 and 0.53 V vs SCE). Spectroscopic investigations of poly(p-phenylene phosphine imide)s (2) are similar to those of polymer model compounds, suggesting formation of localized radical cations on the polymer chains and electronically insulating phosphorus atoms.     

A survey on inborn errors of metabolism in 323 neonates from the state of Rio de Janeiro, Brazil

Inborn errors of metabolism (IEM) are a relevant cause of morbidity and death among children, and neonates in particular. However, little is known about the prevalence of these disorders in Brazilian newborns. Our laboratory of IEM (LABEIM) at the Department of Biochemistry, Institute of Chemistry, Federal University of Rio de Janeiro (UFRJ), has been working on the diagnosis of IEM since 1988. Out of 3,300 patients (90% children), screened and evaluated from 1989 to 2,000 because of a high clinical suspicion of having an IEM, 323 (9.8%) were neonates. Patients came from different regions of the state of Rio de Janeiro, in which lives approximately 8.5% of the total Brazilian population. Chemical tests, various chromatographic techniques and enzyme assays were performed in urine, plasma and in some cases, cerebrospinal fluid (CSF). This study describes our laboratory and the experience with the 323 investigated neonates, among which 28 cases (8.7%) of IEM were identified and 18 (5.6%), strongly suspected. All these cases were related mainly to the metabolism of amino acids, organic acids, lysosomal enzymes and carbohydrates. Furthermore, data on population, community and health services are presented.     

Application of transmission diffusing wave spectroscopy to the study of gelation of milk by acidification and rennet

Transmission diffusing wave spectroscopy has been used to study and compare three milk gelling systems (acid gelation of heated and unheated milks and rennet coagulation of unheated milk). In all cases, DWS was able to demonstrate the point of gelation as indicated by a rapid increase in particle size, as well as the small decreases in casein micelle radius attributed to the collapse or removal of the hairy kappa-casein layer. More importantly, the photon transport mean free path (l(*)) was measured. This parameter is unique to transmission DWS and can potentially give information about developing microstructures and the mechanical properties between different types of gels. The values of l(*) changed during the gelation processes, and these changes were manifested earlier than any change in particle aggregation or rheology of the systems. All three different gelling systems showed different changes in l(*) with time, showing the development of different interactions as the acidification or renneting reactions proceeded. Although a full analysis of the l(*) parameter and its changes cannot be made, it is concluded that they can provide important information on the pre-gelation states of aggregating systems.     

EXCITATION OF CHLOROPHYLL DURING THE PEROXIDASE-CATALYZED OXIDATION OF ETHYL α-FORMYLPHENYLACETATE

Abstract When micelle-solubilyzed chlorophyll is present during the horseradish peroxidase catalyzed aerobic oxidation of ethyl α-formylphenylacetate its fluorescence is observed. The excitation of chlorophyll may occur via energy transfer from the enzyme-generated triplet ethyl benzoylformate. These results imply that excited states may be generated in the roots of Datura innoxia .     

Optimum phase-behavior formulation of surfactant/oil/water systems for the determination of chromium in heavy crude oil and in bitumen-in-water emulsion

An “oil in water” formulation was optimized to determine chromium in heavy crude oil (HCO) and bitumen-in-water emulsion (Orimulsion-400®) samples by transversally heated electrothermal atomic absorption spectrometry (TH-ET AAS) using Zeeman effect background correction. The optimum proportion of the oil-water mixture ratio was 7:3 v/v (70 ml of oil as the internal phase) with a non-ionic surfactant concentration (Intan-100) in the emulsion of 0.2% w/w. Chromium was determined in different crude oil samples after dilution of the emulsions 1:9 v/v with a 0.2% w/w solution of surfactant in order to further reduce the viscosity from 100 to 1.6 cP and at the same time to bring the concentration of chromium within the working range of the ET AAS technique. The calibration graph was linear from 1.7 to 100 μg Cr l⁻¹. The sensitivity was of 0.0069 s l μg⁻¹, the characteristic mass (m_o) was of 5.7 pg per 0.0044 s and the detection limit (3σ) was of 0.52 μg l⁻¹. The relative standard deviation of the method, evaluated by replicate analyses of three crude oil samples varied in all cases between 1.5 and 2.6%. Recovery studies were performed on four Venezuelan crude oils, and the average chromium recovery values varied between 95.9-104.8, 90.6-107.6, 95.6-104.0 and 98.8-103.9% for the Cerro Negro, Crudo Hamaca and Boscán crude oils and for the Orimulsión®-400, respectively. The results obtained in this work for the Cerro Negro, Crudo Hamaca and Boscán crude oils and for the Orimulsión®-400 following the proposed procedure were of 0.448±0.008, 0.338±0.004 0.524±0.021 and 0.174±0.008 mg Cr l⁻¹, respectively, which were in good agreement with the values obtained by a tedious recommended standard procedure (respectively: 0.470±0.05, 0.335±0.080, 0.570±0.021 and 0.173±0.009 mg Cr l⁻¹).     

A Direct OnFlow Assay to Monitor the Activity of Purine Nucleoside Phosphorylase from Mycobacterium tuberculosis

Purine nucleoside phosphorylase (PNP) catalyzes the phosphorolysis of N-ribosidic bonds of purine nucleosides and deoxynucleosides to the corresponding purine bases and (deoxy)ribosyl-1-phosphate. PNP plays a central role in purine recycling and salvage pathway and has been considered an attractive chemotherapeutic target for several diseases. In this work, PNP from Mycobacterium tuberculosis (MtPNP) was covalently immobilized into fused-silica capillaries. The activity of the produced immobilized enzyme reactor (MtPNP-IMER) was monitored onflow in a multidimensional liquid chromatography system containing the MtPNP-IMER in the first dimension. A C18 analytical column inserted in the second dimension furnished the rapid chromatographic separation of the substrate (inosine) and product (hypoxanthine) from the MtPNP catalyzed reaction, allowing monitoring MtPNP-IMER activity through the direct quantification of hypoxanthine formed. Kinetic studies showed that the K_M values (59.19 μmol L^?1) for substrates using the immobilized enzyme were consistent with those reported for the free enzyme in solution (40 μmol L^?1). To validate the use of the proposed methodology for screening purposes, a fourth-generation immucillin derivative (DI4G), known as a PNP inhibitor, was used as a standard inhibitor. The studies revealed that the immobilized enzyme retained the ability to recognize enzyme inhibitors and the onflow assay allowed the characterization of the inhibitor by determining the IC₅₀ (29.85?±?1.02 nmol L^?1), inhibition mechanism and constant (K_i?=?34.8?±?0.2 nmol L^?1). The results revealed that the immobilized MtPNP retained its catalytic activity (up to 60%) and the ability to recognize ligands with high stability for up to 10 days. The proposed model has as advantages the automation and the possibility of reusing the same amount of enzyme in several assays.

     

Isolation and characterization of chlorophylls and xanthophylls in grass by high-speed countercurrent chromatography

To isolate chlorophyll from grass extract by means of high-speed countercurrent chromatography, a solvent system composed of n-hexane–dichloromethane–ethanol–water 4:2:6:2 (v/v/v/v) was applied. The isolation of chlorophylls a, b, and pheophytins a, b was successfully performed from grass when dichloromethane was part of the solvent system. Comparatively, when chloroform is part of the stationary phase instead of dichloromethane, the xanthophyll separation showed better resolution compared to chlorophylls. Through the solvent system, we could demonstrate the meaningful difference of polarity between dichloromethane, a polar aprotic solvent, and chloroform, a non-polar solvent. Therefore, n-hexane–dichloromethane–ethanol–water 4:2:6:2 (v/v/v/v) is adequate for chlorophylls separation because it changes the system to yield more polarity. This hypothesis supports the fact that the elution mode length was 10?hr and the extrusion mode 2?hr, whereas with chloroform the elution mode length was 7?hr and the extrusion mode 4?hr. Online high-performance liquid chromatography in conjunction with atmospheric pressure chemical ionization mass spectrometry (HPLC/APCI-MS) was suitable to identify xanthophylls and chlorophylls fractions by means of mass spectra in positive (+) mode. Structure elucidation of chlorophylls and pheophytins was done by nuclear magnetic resonance (NMR) 1D/2D-NMR experiments.     

Strategies for efficient virtual microscopy in pathological samples using JPEG2000

This paper describes the design, implementation and validation of a new strategy for efficiently browsing large microscopical images (mega-images). A mega-image is constructed by registering a sequential set of microscopic fields of view, compressed and stored in hard disk using the JPEG2000 standard (J2K). Navigation is accelerated by fully exploiting J2K properties through the introduction of a cache strategy and an optimal delivering of quality information. Cache is introduced at the level of the spatial and resolution dimensions while optimal delivering is implemented on the organisation of minimal information units. Navigation with the conventional use of J2K results in extraction times of about 500 ms. We show that these strategies can improve navigation velocities up to a 30%, while we can efficiently represent high-quality and high-resolution colour images of microscopic specimens.     

Force free projective motions of the sphere

Suppose that the sphere Sⁿ$S^n$ has initially a homogeneous distribution of mass and let G$G$ be the Lie group of orientation preserving projective diffeomorphisms of Sⁿ$S^n$. A projective motion of the sphere, that is, a smooth curve in G$G$, is called force free if it is a critical point of the kinetic energy functional. We find explicit examples of force free projective motions of Sⁿ$S^n$ and, more generally, examples of subgroups H$H$ of G$G$ such that a force free motion initially tangent to H$H$ remains in H$H$ for all time (in contrast with the previously studied case for conformal motions, this property does not hold for H=S_On+1$H=S{O}_{n+1}$). The main tool is a Riemannian metric on G$G$, which turns out to be not complete (in particular not invariant, as happens with non-rigid motions), given by the kinetic energy.     

Serine sublimes with spontaneous chiral amplification

Sublimation of near-racemic samples of serine yields a sublimate which is highly enriched in the major enantiomer; this simple one-step process occurs under relatively mild conditions, and represents a possible mechanism for the chiral amplification step in homochirogenesis.