QUANTIFICATION OF BINARY MIXTURES OF COCAINE AND ADULTERANTS USING DISPERSIVE RAMAN AND FT-IR SPECTROSCOPY AND PRINCIPAL COMPONENT REGRESSION

Current forensic methods for detecting and identifying cocaine and its adulterants are destructive, so evidence cannot be re-analyzed. Vibrational techniques [Raman and Fourier transform infrared (FT-IR) spectroscopy] allow rapid, economical, nondestructive analysis. This work compares these techniques as methods for quantifying mixtures of cocaine (in the crack presentation) and adulterants. The aim is to provide a method to determine the amount of cocaine in crack rocks and to identify and quantify possible adulterants. A sample of crack was adulterated with benzocaine, caffeine, sodium carbonate, and lidocaine to create binary mixtures of concentrations of 20%, 40%, 60%, and 80%; pure samples of each adulterant and of crack were also examined. All samples were observed using dispersive Raman and attenuated total reflectance FT-IR spectroscopy. Quantitative analysis was performed based on principal component regression (PCR) applied to simulated and real spectra. The PCR model revealed that the Raman spectra yielded only minor measurement errors and the highest correlations using the PC2 spectral vector, which presented spectral features of cocaine. Among the mixtures, the best and worst results were obtained for caffeine and sodium carbonate, respectively. Dispersive Raman spectroscopy outperformed FT-IR in the quantitative determination of binary mixtures of cocaine and adulterants.     

Crystal structure solution via precession electron diffraction data: the BEA algorithm

The statistical features of the amplitudes obtained via precession electron diffraction have been studied, with particular concern with their effects on direct phasing procedures. A new algorithm, denoted by BEA, is described: according to it, the average amplitude of the symmetry equivalent reflections is used in the Direct Methods step. Once an even imperfect structural model is available, the best amplitude among the equivalent reflections is used to improve the model. It is shown that BEA is able to provide more complete structural models, to make the phasing process more straightforward and to end with crystallographic residual much better than those usually obtained by electron diffraction.     

Electrical energy metering: Some challenges of the European Directive on Measuring Instruments (MID)

The introduction of static electric energy meter together with voltage and current distortions in the electric networks are revolutionizing the measurement of the electrical energy. Several questions and studies are proposed in the scientific literature concerning with metrological and reliability aspects of the actual electrical energy measurement. The European Directive on Measuring Instruments (MID) represents a different spin on setting the performance and safety requirements for those meters. The International Organization of Legal Metrology (OIML) has published the document D11 discussing recommendations for legislation to meet the MID. An OIML technical committee is drafting the recommendation (IR46) that would give regulatory bodies an easily-adoptable set of requirements and tests to meet the requirements of the MID. With the introduction of the MID directive, the actual discussion involves aspects as the metrological characterization of the meters. The paper proposes an analysis of the test settings imposed by the actual MID-harmonized standards, regarding the electric energy metering. The aim is to check the presence of degree of freedom in the test settings that could compromise both result reliability and the compliance/non-compliance of a given apparatus.     

A universal fluid cell for the imaging of biological specimens in the atomic force microscope

Recently, atomic force microscope (AFM) manufacturers have begun producing instruments specifically designed to image biological specimens. In most instances, they are integrated with an inverted optical microscope, which permits concurrent optical and AFM imaging. An important component of the set‐up is the imaging chamber, whose design determines the nature of the experiments that can be conducted. Many different imaging chamber designs are available, usually designed to optimize a single parameter, such as the dimensions of the substrate or the volume of fluid that can be used throughout the experiment. In this report, we present a universal fluid cell, which simultaneously optimizes all of the parameters that are important for the imaging of biological specimens in the AFM. This novel imaging chamber has been successfully tested using mammalian, plant, and microbial cells. Microsc. Res. Tech. 76:357–363, 2013. © 2013 Wiley Periodicals, Inc.     

Alumina/Zirconia Micro/Nanocomposites: A New Material for Biomedical Applications With Superior Sliding Wear Resistance

In the present investigation, the sliding wear behavior is described for Al₂O₃/ZrO₂ micro/nanocomposites and monolithic alumina of similar grain size under defined conditions of a constant sliding speed and different loads (20–150 N). Nano ZrO₂ particles (1.7 vol%) were observed uniformly distributing throughout the composites, and most of them were located within the matrix alumina grains. The wear rate of the alumina and the micro/nanocomposites increased as the contact load increased and a clear transition in friction and wear behavior was observed in both materials. However, the nanocomposite wear resistance at low contact loads was one order of magnitude higher than that of the alumina. In the severe regime, no difference was observed among the materials. The low wear rate (10⁻⁷ mm³·(N·m)⁻¹) along with low pullout indicates higher wear resistance of micro/nanocomposites in the mild regime compared with monolithic alumina. Based on the morphological observation of worn surfaces by scanning electron microscope and on residual stress analysis performed by neutron diffraction, some wear mechanisms of Al₂O₃–ZrO₂ micro/nanocomposites are proposed. The high wear resistance of the nanocomposites is discussed in terms of fracture resistance properties and residual stress. Improvements in mechanical and tribological properties of these composites make them promising candidates for biomedical applications.     

Hierarchical mechanochemical switches in angiostatin

We wish to propose a novel mechanism by which the triggering of a biochemical signal can be controlled by the hierarchical coupling between a protein redox equilibrium and an external mechanical force. We have characterized this mechanochemical mechanism in angiostatin, and we have evidence that it can switch the access to partially unfolded structures of this protein. We have identified a metastable intermediate that is specifically accessible under thioredoxin-rich reducing conditions, like those met by angiostatin on the surface of a tumor cell. The structure of the same intermediate accounts for the unexplained antiangiogenic activity of angiostatin. These findings demonstrate a new link between redox biology and mechanically regulated processes.     

Torque‐rheometry investigation of model transreactions involving condensation polymers. I. Polyesters

The chemical transformations taking place when poly(ethylene terephthalate) (PET) or poly(ethylene naphthalate) (PEN) are blended in the melt with different low molar mass substances containing hydroxyl, carboxyl, or amine functional groups have been investigated as models of the transreactions, undergone by the polyesters in reactive blending operations. The polyester molecular weight changes caused by the alcoholysis, acidolysis, aminolysis, and esterolysis reactions have been monitored by torque‐rheometry, using a Brabender Plasticorder static mixer. The degradation of the polyesters by hydrolysis was also studied, under similar conditions, by the addition of a water‐releasing substance (wet polyamide‐6), and was shown to occur quite rapidly, although most of the added water was lost by flash vaporization caused by the high temperature of the polyester melt. It has been shown that the rate constants of the reactions leading to breakage of the inner ester bonds of the polyester macromolecules decrease in the following order: aminolysis (with aliphatic amines, either primary and secondary) > alcoholysis (with aliphatic alcohols) ≈ hydrolysis > acidolysis (with aromatic acids) ≥ acidolysis (with aliphatic acids) ? aminolysis (with aromatic amines) > alcoholysis (with phenols) ? esterolysis. POLYM. ENG. SCI. 46:139–152, 2006. © 2005 Society of Plastics Engineers     

Chemiotropic behavior of female olive fly (Bactrocera oleae GMEL.) onOlea europaea L

An interpretation is given of a number of observations on the chemiotropic behavior ofBactrocera oleae in connection with olive maceration water and the fly's return to the olive groves after the first summer rains. To this end, the headspace of both maceration water and leaf leaching water, simulating rainfall, were examined. In both cases, the presence of ammonia, which is generally known to attract fruit flies (Diptera, Tephritidae), was detected and, for the first time, in addition to other compounds that are inert for the fly, the presence of styrene was also detected. This aromatic hydrocarbon was found to be a strong attractant. It is shown that both ammonia and styrene are products of the metabolism of microbial flora present on the olive and leaf surface.     

Self-nucleation of isotactic poly(1-butene) in the trigonal modification

Isotactic poly(1-butene) (i-PBu) is a polyolefin of industrial relevance which exhibits an interesting polymorphism. Upon cooling from the relaxed melt at atmospheric pressure, a tetragonal phase (Form II) develops. However, being metastable, this structure slowly evolves upon aging in the stable trigonal modification (Form I). Another trigonal modification, denoted Form I′, can also crystallize directly from the melt if proper conditions are met, e.g., high pressure, low tacticity, ultrathin samples etc. In this work, we aim to verify whether, by acting on the nucleation stage via a proper thermal history, the direct formation of the trigonal polymorph from the melt in a bulk sample is possible. Nucleation of i-PBu has been tailored by means of the self-nucleation technique, imposed on previously aged samples (Form I). DSC and temperature-resolved WAXS show that different crystallization pathways can be observed, depending on the residual concentration of Form I self-nuclei. With decreasing self-nucleation temperature we first encounter “cross-nucleation” of the tetragonal crystal on trigonal nuclei, followed by concomitant crystallization of Form II and Form I′ and eventually the sole formation of the trigonal modification (Form I′).