Assessing utility of handheld laser induced breakdown spectroscopy as a means of Dalbergia speciation.

Many species of Dalbergia are prized hardwoods, generally referred to as 'Rosewood,' and used in high-end products due to their distinctive hue and scent. Despite more than 58 species of Dalbergia being listed as endangered in Appendix 1 of The Convention on International Trade in Endangered Species of Fauna and Flora (CITES), the illegal logging and trade of this timber is ongoing. In this work, a handheld laser induced breakdown spectrometer (LIBS) was used to analyze seven Dalbergia species and two other exotic hardwood species to evaluate the ability of handheld LIBS for rapid classification of Dalbergia in the field. The KNN model of the classification presented 80% to 90% sensitivity for discriminating between Dalbergia species in the training set. PLS-DA models were based on a binary decision tree structure. Cumulatively, the PLS-DA decision tree model showed greater than 97% sensitivity and 99% selectivity for prediction of Dalbergia species included in the training set. The data presented in the following study are promising for the use of handheld LIBS devices and both KNN and PLS-DA models for applications in customs screenings at the port of entry of hard woods, among others.

Distinguishing wild from cultivated agarwood (Aquilaria spp.) using direct analysis in real time and time of-flight mass spectrometry.

RATIONALE: It is important for the enforcement of the CITES treaty to determine whether agarwood (a resinous wood produced in Aquilaria and Gyrinops species) seen in trade is from a plantation that was cultivated for sustainable production or was harvested from natural forests which is usually done illegally. METHODS: We analyzed wood directly using Direct Analysis in Real Time (DART™) ionization coupled with Time-of-Flight Mass Spectrometry (TOFMS). Agarwood was obtained from five countries, and the collection contained over 150 samples. The spectra contained ions from agarwood-specific 5,6,7,8-tetrahydro-2-(2-phenylethyl)chromones as well as many other ions. The data was analyzed using either kernel discriminant analysis or kernel principal component analysis. Probability estimates of origin (wild vs cultivated) were assigned to unknown agarwood samples. RESULTS: Analysis of the DART-TOFMS data shows that many of the chromones found in cultivated and wild agarwood samples are similar; however, there is a significant difference in particular chromones that can be used for differentiation. In certain instances, the analysis of these chromones also allows inferences to be made as to the country of origin. Mass Mountaineer™ software provides an estimate of the accuracy of the discriminate model, and an unknown sample can be classified as cultivated or wild. Eleven of the thirteen validation samples (85%) were correctly assigned to either cultivated or wild harvested for their respective geographic provenance. The accuracy of each classification can be estimated by probabilities based on Z scores. CONCLUSIONS: The direct analysis of wood for the diagnostic chromones using DART-TOFMS followed by discriminant analysis is sufficiently robust to differentiate wild from cultivated agarwood and provides strong inference for the origin of the agarwood.

A portrait of Staphylococcus aureus from the other side of the Mediterranean Sea: molecular characteristics of isolates from Western Algeria.

Algerian hospitals have experienced a dramatic increase in methicillin-resistant Staphylococcus aureus (MRSA) prevalence in recent years. To investigate this phenomenon, we have determined molecular characteristics of 61 methicillin-resistant or -susceptible strains isolated between 2003 and 2007 in Oran Hospital. Susceptible isolates were related to diverse genetic backgrounds, of which clone with sequence type (ST) 8 accounted for most of the samples. Resistance to methicillin was almost limited to two international spreading clones; the most frequent, ST80, contained isolates producing Panton-Valentine leukocidine, with SCCmec type IV. The increase of MRSA prevalence observed in Western Algeria, in outpatients as well as in hospitalized patients, is linked to dissemination of ST80 strains usually considered as community-acquired MRSA.

Composition controlled spin polarization in Co(1-x)Fe(x)S(2) alloys.

The transition metal (TM) chalcogenides of the form TMX(2) (X = S or Se) have been studied for decades due to their interesting electronic and magnetic properties such as metamagnetism and metal-insulator transitions. In particular, the Co(1-x)Fe(x)S(2) alloys were the subject of investigation in the 1970s due to general interest in itinerant ferromagnetism. In recent years (2000-present) it has been shown, both by electronic structure calculations and detailed experimental investigations, that Co(1-x)Fe(x)S(2) is a model system for the investigation of highly spin polarized ferromagnetism. The radically different electronic properties of the two endpoint compounds (CoS(2) is a narrow bandwidth ferromagnetic metal, while FeS(2) is a diamagnetic semiconductor), in a system forming a substitutional solid solution allows for composition control of the Fermi level relative to the spin split bands, and therefore composition-controlled conduction electron spin polarization. In essence, the recent work has shown that the concept of 'band engineering' can be applied to half-metallic ferromagnets and that high spin polarization can be deliberately engineered. Experiments reveal tunability in both sign and magnitude of the spin polarization at the Fermi level, with maximum values obtained to date of 85% at low temperatures. In this paper we review the properties of Co(1-x)Fe(x)S(2) alloys, with an emphasis on properties of relevance to half-metallicity. Crystal structure, electronic structure, synthesis, magnetic properties, transport properties, direct probes of the spin polarization, and measurements of the total density of states at the Fermi level are all discussed. We conclude with a discussion of the factors that influence, or even limit, the spin polarization, along with a discussion of opportunities and problems for future investigation, particularly with regard to fundamental studies of spintronic devices.

Smectic-Calpha*-smectic-C* phase transition and critical point in binary mixtures.

We have investigated the smectic-Calpha*-smectic-C* (SmCalpha*-SmC*) transition in a series of binary mixtures with resonant x-ray diffraction, differential optical reflectivity, and heat capacity measurements. Results show that the phases are separated by a first-order transition that ends at a critical point. We report the observation of such a critical point. We have proposed the appropriate order parameter and obtained values of two critical exponents associated with this transition. The values of the critical exponents suggest that long-range interactions are present in the SmCalpha*-SmC* critical region.

Prolactin, vasoactive intestinal peptide, and peptide histidine methionine elicit selective increases in REM sleep in rabbits.

The purpose of these experiments was to determine whether (1) vasoactive intestinal peptide (VIP) produces effects on rabbit sleep similar to those reported for rats and cats; (2) peptide histidine methionine (PHM), a peptide closely related to VIP, mimics the sleep effects of VIP; and (3) pituitary prolactin (PRL), a pituitary hormone that has a sleep-related secretory pattern and for which VIP and PHM act as releasing factors, has similar effects on sleep. VIP or PHM (0.01, 0.1 and 1.0 nmol/kg) was intracerebroventricularly (i.c.v.) injected; PRL (ovine PRL, 45 and 200 IU/kg) was subcutaneously (s.c.) administered. Sleep-wake activity and brain temperature were recorded for 6 h. For controls, rabbits received artificial cerebrospinal fluid i.c.v. or PRL-vehicle s.c. VIP and PHM promoted rapid eye movement sleep (REMS), although these effects were not dose-dependent. In addition, the high dose of VIP and PHM transiently increased wakefulness. Increases in REMS occurred only during hours 2-6 after i.c.v. injection of VIP and peptide histidine leucine (PHI). After s.c. injection of PRL, REMS started to increase in postinjection hour 3. The effect of the high dose was significantly more pronounced than that of the small dose. Each substance enhanced the frequency of REMS episodes, and the high dose of PRL also increased the duration of REMS bouts. These results are consistent with the hypothesis that VIP is involved in physiological regulation of REMS, and that the VIP- and PHM-induced increases in REMS may be mediated via release of PRL.

Interleukin-6 is pyrogenic but not somnogenic.

Interleukin-6 (IL6) induces acute phase protein production and is hypothesized to mediate systemic and central effects of IL1. To determine whether IL6 possesses somnogenic properties, rabbits were injected intracerebroventricularly with IL6; sleep-wake activity was determined and brain temperatures recorded for 6 hr. IL6 induced fever in a dose-related manner with no effect on sleep-wake activity. IL6, therefore, is the first cytokine reported to elicit fever without promoting sleep. We conclude that the somnogenic action of IL1 is not mediated through IL6.

Molecular orientation arrangements in the smectic-C* variant liquid-crystal phases.

Recent experiments have identified three-layer and four-layer distorted helical structures in the smectic liquid-crystal phases Sm C*(FI1) and Sm C*(FI2), respectively. However, no theories have explained the existence of all these phases. A discrete phenomenological model of the free-energy is analyzed and found to predict the stability of distorted three-layer and four-layer structures, as well as simple helical solutions in smectic liquid crystals. A simple physical picture is provided to explain the stability of the phases exhibiting distorted helical structures.

Surface structures and transitions in the smectic-C* phase of one chiral liquid crystal compound.

Three optical probes have been employed on free-standing films to study surface structure and transitions of the SmC* phase of one liquid crystal compound. While the interior layers show the SmC* structure, the tilt in adjacent surface layers is found to be anticlinic. The number of anticlinic surface layers grows rapidly as the transition to the SmC*(FI2) phase is approached.

Detailed optical studies of several banana-shaped compounds in liquid crystal B2 phase.

Null-transmission ellipsometry has been performed on free-standing films of one compound in the liquid crystal B2 phase. We have studied films of thickness from 1 to 121 layers. One of the compounds used has an unusually wide 59 K window for the B2 phase. The tilt angle was investigated as a function of temperature and found to be constant over this temperature range to within our resolution of 1 degrees. The one-layer films studied exhibit the same structure as the thicker films, and have helped us to refine the optical model for the B2 phase. For thin films we find that modeling a single smectic layer as two uniaxial layers is a better description of the data than a single biaxial layer, but that for thick films the model used does not effect the simulated result appreciably. Preliminary results also find that the surface layers are less tilted than the interior layers, in contrast to rodlike liquid crystals, which show an enhanced surface tilt.

Optical studies of the smectic-C(*)(alpha) phase layer structure in free-standing films.

The layer structure of the smectic-C(*)(alpha) phase of one liquid-crystal compound has been acquired from both differential optical reflectivity and ellipsometry measurements in the free-standing film geometry. The data from both techniques display characteristic oscillations as a function of temperature, which can be described by a model for the film consisting of surface anticlinic layers and an interior short-pitched azimuthal helix. These results are consistent with those found previously for another compound. Depolarized reflected light microscopy is used to study the films when the unique features of the aforementioned oscillations occur.

Dramatic effect of an additional CH2 group on the temperature variation of the Sm-C(*)(alpha) short helical pitch.

High-resolution differential optical reflectivity was used to study the temperature evolution of the short helical pitch in the Sm-C(*)(alpha) phase of successive members from two liquid-crystal homologous series. With the addition of one CH2 group, the magnitude and temperature evolution of the pitch change dramatically, and the molecular arrangements between consecutive surface layers found in free-standing films change from being anticlinic to synclinic.

Optical investigations on the biaxial smectic- A phase of a bent-core compound.

Several unique optical properties have been obtained from freestanding films of a bent-core compound. Our experimental results indicate the existence of the antiferroelectric biaxial smectic-A (Sm A) phase. The critical exponent associated with the biaxiality through the uniaxial-antiferroelectric biaxial Sm A transition has been measured to be 0.82+/-0.04 , which is in good agreement with our theoretical calculation. Our theoretical advances further demonstrate that the critical behavior of the optical biaxiality with the order parameter being a vector is described by the secondary-order parameter of the three-dimensional XY model. We also observe a remarkable even-odd layering effect exhibited by the surface layers of freestanding films under an applied electric field (approximately 20 V/cm) in the film plane.

Experimental investigations of one liquid-crystal compound exhibiting the no-layer-shrinkage effect near the Sm-A-Sm- C(*) transition.

Three experimental probes have been employed to investigate the nature of the smectic- A -smectic- C ( Sm-A-Sm- C(*) ) phase transition of one liquid-crystal compound showing almost no layer-shrinkage effect through the transition. Results from both x-ray diffraction and optical studies indicate that the compound exhibits a crossover behavior of different molecular packing arrangements within the bulk Sm-A phase window. The calorimetry results show a significant critical anomaly near the Sm-A-Sm- C(*) transition, although it was found to be weakly first order.

Optical studies of the liquid crystal B2 phase formed by banana-shaped molecules.

Null-transmission ellipsometry and depolarized light microscopy have been performed on free-standing films of three achiral banana-shaped compounds in the B2 phase. Our results support a two-layer unit cell previously proposed to explain the observed antiferroelectricity in thin films and bulk samples. We have studied thicker films than previously reported and have found no deviations in the film structure from the earlier findings. Moreover, we can determine the layer spacing, the molecular tilt from the layer normal, and the three principal indices of refraction in the molecular reference frame.

Effect of enantiomeric excess on surface structures and phase sequences in free-standing liquid-crystal films.

We present differential optical reflectivity and null transmission ellipsometry data from several mixtures of MHPBC enantiomers. From this data, we have determined the chiral smectic phase sequence as a function of enantiomeric excess. The data suggest a change in the structure of the smectic-C(*)(alpha) phase and the surface tilt state as the enantiomeric excess is reduced. The results also show that the intermediate phases, smectic C(*)(FI2), smectic C(*)(FI1), and smectic C(*)(alpha), disappear sequentially on reducing the net chirality.

Nonplanar structure of molecular tilt planes in the surface layers of smectic-A free-standing liquid crystal films.

We present ellipsometric results from thin free-standing films of one chiral liquid crystal compound. In the bulk SmA range with surface-induced molecular tilt, a nonplanar arrangement of the molecular orientations of the tilted surface layers is found under a small applied electric field.

Optical studies on free-standing films of an achiral smectic liquid crystal.

Employing null transmission ellipsometry and depolarized reflected light microscopy, we have studied two smectic phases, Sm-C1 and Sm-C2, of one achiral mesogen. Our results show that Sm-C1 and Sm-C2 are the synclinic Sm-C and anticlinic Sm-C(A) phases, respectively. We find no evidence to support recent claims that the Sm-C1 is chiral and ferroelectric [R. Stannarius et al., Phys. Rev. Lett. 90, 025502 (2003)].

Unusual behavior of the surface-induced tilted layers in free-standing films of a non-layer-shrinkage liquid crystal compound.

Null-transmission ellipsometry has been conducted to study the molecular arrangements in free-standing films of one chiral compound above the bulk smectic-A-smectic-C* transition temperature. Upon cooling under a proper electric field, a nonplanar-anticlinic-synclinic or a nonplanar-synclinic transition has been observed. The nonplanar structure continuously evolves into the anticlinic or synclinic structures. Increasing electric field can induce a rare transition from a synclinic to an anticlinic structure.

Interlayer structures of the chiral smectic liquid crystal phases revealed by resonant X-ray scattering.

The structures of the liquid crystalline chiral subphases exhibited by several materials containing either a selenium or sulphur atom have been investigated using a resonant x-ray scattering technique. This technique provides a unique structural probe for the ferroelectric, ferrielectric, antiferroelectric, and SmC(*)(alpha) phases. An analysis of the scattering features allows the structural models of the different subphases to be distinguished, in addition to providing a measurement of the helical pitch. This paper reports resonant scattering features in the antiferroelectric hexatic phase, the three- and four-layer intermediate phases, the antiferroelectric and ferroelectric phases and the SmC(*)(alpha) phase. The helicoidal pitch has been measured from the scattering peaks in the four-layer intermediate phase as well as in the antiferroelectric and ferroelectric phases. In the SmC(*)(alpha) phase, an investigation into the helical structure has revealed a pitch ranging from 5 to 54 layers in different materials. Further, a strong resonant scattering signal has been observed in mixtures of a selenium containing material with as much as 90% nonresonant material.