The chemiluminescent peroxyoxalate system: state of the art almost 50 years from its discovery

Almost fifty years after the discovery of the peroxyoxalate reaction by E. A. Chandross in the early nineteen sixties, this review article intends to give a general overview on mechanistic aspects of this system and to describe the principles of its analytical application. After a short general introduction on the principles of chemiluminescence and the history of peroxyoxalate discovery, mechanistic aspects of high-energy intermediate formation, its structure and its reaction with an activator in the peroxyoxalate system are discussed. Finally, analytical applications of peroxyoxalate chemiluminescence are exemplified using representative recent examples, including oxalic acid detection in biological samples.

Discovery and redescription of type material of Nausithoe simplex (Kirkpatrick, 1890), comb. nov (Cnidaria: Scyphozoa: Coronatae: Nausithoidae) from the North Atlantic

With discovery and examination of type specimens in the Natural History Museum, London, UK, we reassign Stephanoscyphistoma simplex (Kirkpatrick, 1890) to the genus Nausithoe Kolliker, 1853, as Nausithoe simplex, comb. nov., and designate a lectotype for the species. Use of morphometric measurements is considered important in coronate systematics, but key features also include the unique whorl of internal cusps and the shape of these cusps. All previous records of N. simplex must be re-evaluated, taking into consideration the morphology of these internal cusps.

Dillapiole as Antileishmanial Agent: Discovery, Cytotoxic Activity and Preliminary SAR Studies of Dillapiole Analogues

In this paper, the isolation of dillapiole (1) from Piper aduncum was reported as well as the semi-synthesis of two phenylpropanoid derivatives [di-hydrodillapiole (2), isodillapiole (3)], via reduction and isomerization reactions. Also, the compounds' molecular properties (structural, electronic, hydrophobic, and steric) were calculated and investigated to establish some preliminary structureactivity relationships (SAR). Compounds were evaluated for in vitro antileishmanial activity and cytotoxic effects on fibroblast cells. Compound 1 presented inhibitory activity against Leishmania amazonensis (IC50?=?69.3 mu M) and Leishmania brasiliensis (IC50?=?59.4 mu M) and induced cytotoxic effects on fibroblast cells mainly in high concentrations. Compounds 2 (IC50?=?99.9 mu M for L. amazonensis and IC50?=?90.5 mu M for L. braziliensis) and 3 (IC50?=?122.9 mu M for L. amazonensis and IC50?=?109.8 mu M for L. brasiliensis) were less active than dillapiole (1). Regarding the molecular properties, the conformational arrangement of the side chain, electronic features, and the hydrophilic/hydrophobic balance seem to be relevant for explaining the antileishmanial activity of dillapiole and its analogues.

The discovery of male Potiicoara brasiliensis (Crustacea, Spelaeogriphacea) with notes on biology and distribution

The male of Potiicoara brasiliensis is reported for the first time with evidence of sexual dimorphism. Male diagnostic characters are described and compared with the other three species of Spelaeogriphidae. Males present differential morphology on both distal podomere articles of the antennula and antenna, an elongate and curved bare endopod on pleopod 2, a pair of short round penes on the sternum near the base of pereopod 7, and telson with dorsum almost smooth and apex straight. Material is sampled for the first time from karstic areas north of the species type-locality, Gruta Ricardo Franco near Corumba City, and Gruta do Curupira in the Araras Mountains. These new findings expand the distribution of the species over seven hundred kilometers. Comparisons between exemplars of both sexes are presented. A hypothesis on the distributional pattern of P. brasiliensis is introduced based on the geological history of Central-West Brazil.

Discovery potential for supersymmetry at a high luminosity upgrade of LHC14

After completion of the LHC8 run in 2012, the plan is to upgrade the LHC for operation close to its design energy root s = 14 TeV, with a goal of collecting hundreds of fb(-1) of integrated luminosity. The time is propitious to begin thinking of what is gained by even further LHC upgrades. In this report, we compute an LHC14 reach for supersymmetry in the mSUGRA/CMSSM model with an anticipated high luminosity upgrade. We find that LHC14 with 300 (3000) fb(-1) has a reach for supersymmetry via gluino/squark searches of m((g) over tilde) similar to 3.2 TeV (3.6 TeV) for m((q) over tilde) similar to m((g) over tilde), and a reach of m((g) over tilde) similar to 1.8 TeV (2.3 TeV) for m((q) over tilde) >> m((g) over tilde). In the case where m((q) over tilde) >> m((g) over tilde), then the LHC14 reach for chargino-neutralino production with decay into the Wh + 6 is not an element of(T) final state reaches to m((g) over tilde) similar to 2.6 TeV for 3000 fb(-1).

Discovery and cross-section measurement of neutron-rich isotopes in the element range from neodymium to platinum with the FRS

Using the high-resolution performance of the fragment separator FRS at GSI we have discovered 60 new neutron-rich isotopes in the atomic number range of 60 <= Z <= 78. The new isotopes were unambiguously identified in reactions with a U-238 beam impinging on a Be target at 1 GeV/nucleon. The production cross-section for the new isotopes have been measured down to the pico-barn level and compared with predictions of different model calculations. For elements above hafnium fragmentation is the dominant reaction mechanism which creates the new isotopes, whereas fission plays a dominant role for the production of the new isotopes up to thulium. (C) 2012 Elsevier B.V. All rights reserved.

Identification of Leishmania infantum chagasi proteins in urine of patients with visceral leishmaniasis: a promising antigen discovery approach of vaccine candidates

Visceral leishmaniasis (VL) is a serious lethal parasitic disease caused by Leishmania donovani in Asia and by Leishmania infantum chagasi in southern Europe and South America. VL is endemic in 47 countries with an annual incidence estimated to be 500 000 cases. This high incidence is due in part to the lack of an efficacious vaccine. Here, we introduce an innovative approach to directly identify parasite vaccine candidate antigens that are abundantly produced in vivo in humans with VL. We combined RP-HPLC and mass spectrometry and categorized three L. infantum chagasi proteins, presumably produced in spleen, liver and bone marrow lesions and excreted in the patients urine. Specifically, these proteins were the following: Li-isd1 (XP_001467866.1), Li-txn1 (XP_001466642.1) and Li-ntf2 (XP_001463738.1). Initial vaccine validation studies were performed with the rLi-ntf2 protein produced in Escherichia coli mixed with the adjuvant BpMPLA-SE. This formulation stimulated potent Th1 response in BALB/c mice. Compared to control animals, mice immunized with Li-ntf2+ BpMPLA-SE had a marked parasite burden reduction in spleens at 40 days post-challenge with virulent L. infantum chagasi. These results strongly support the proposed antigen discovery strategy of vaccine candidates to VL and opens novel possibilities for vaccine development to other serious infectious diseases.

OXYGEN ABUNDANCES IN LOW- AND HIGH-alpha FIELD HALO STARS AND THE DISCOVERY OF TWO FIELD STARS BORN IN GLOBULAR CLUSTERS

Oxygen abundances of 67 dwarf stars in the metallicity range -1.6 < [Fe/H] < -0.4 are derived from a non-LTE analysis of the 777 nm O I triplet lines. These stars have precise atmospheric parameters measured by Nissen and Schuster, who find that they separate into three groups based on their kinematics and alpha-element (Mg, Si, Ca, Ti) abundances: thick disk, high-alpha halo, and low-alpha halo. We find the oxygen abundance trends of thick-disk and high-alpha halo stars very similar. The low-alpha stars show a larger star-to-star scatter in [O/Fe] at a given [Fe/H] and have systematically lower oxygen abundances compared to the other two groups. Thus, we find the behavior of oxygen abundances in these groups of stars similar to that of the a elements. We use previously published oxygen abundance data of disk and very metal-poor halo stars to present an overall view (-2.3 < [Fe/H] < +0.3) of oxygen abundance trends of stars in the solar neighborhood. Two field halo dwarf stars stand out in their O and Na abundances. Both G53-41 and G150-40 have very low oxygen and very high sodium abundances, which are key signatures of the abundance anomalies observed in globular cluster (GC) stars. Therefore, they are likely field halo stars born in GCs. If true, we estimate that at least 3% +/- 2% of the local field metal-poor star population was born in GCs.

LHC discovery potential for supersymmetry with root s=7 TeV and 5-30 fb(-1)

We extend our earlier results delineating the supersymmetry reach of the CERN Large Hadron Collider operating at a center-of-mass energy root s = 7 TeV to integrated luminosities in the range 5-30 fb(-1). Our results are presented within the paradigm minimal supergravity model or constrained minimal supersymmetric standard model. Using a six-dimensional grid of cuts for the optimization of signal to background ratio-including missing E-T-we find for m((g) over tilde) similar to m((q) over tilde) an LHC 5 sigma supersymmetry discovery reach of m((g) over tilde) similar to 1:3, 1.4, 1.5, and 1.6 TeV for 5, 10, 20, and 30 fb(-1), respectively. For m((q) over tilde) >> m((g) over tilde), the corresponding reach is instead m((g) over tilde) similar to 0: 8, 0.9, 1.0, and 1.05 TeV, for the same integrated luminosities.

THE GEMINI NICI PLANET-FINDING CAMPAIGN: DISCOVERY OF A MULTIPLE SYSTEM ORBITING THE YOUNG A STAR HD 1160

We report the discovery of two low-mass companions to the young A0V star HD 1160 at projected separations of 81 +/- 5 AU (HD 1160 B) and 533 +/- 25 AU (HD 1160 C) by the Gemini NICI Planet-Finding Campaign. Very Large Telescope images of the system taken over a decade for the purpose of using HD 1160 A as a photometric calibrator confirm that both companions are physically associated. By comparing the system to members of young moving groups and open clusters with well-established ages, we estimate an age of 50(-40)(+50) Myr for HD 1160 ABC. While the UVW motion of the system does not match any known moving group, the small magnitude of the space velocity is consistent with youth. Near-IR spectroscopy shows HD 1160 C to be an M3.5 +/- 0.5 star with an estimated mass of 0.22(-0.04)(+0.03) M-circle dot, while NIR photometry of HD 1160 B suggests a brown dwarf with a mass of 33(-9)(+12) M-Jup. The very small mass ratio (0.014) between the A and B components of the system is rare for A star binaries, and would represent a planetary-mass companion were HD 1160 A to be slightly less massive than the Sun.

Discovery of the Persistent Luminescence Mechanism of CdSiO3:Tb3+

The persistent luminescence of CdSiO3:Tb3+ was investigated with photoluminescence, thermoluminescence (TL), synchrotron radiation X-ray absorption (XANES and EXAFS) and UV-VUV spectroscopies. Only the typical intraconfigurational 4f(8)-4f(8) transitions of the Tb3+ ion were observed with no traces of band emission in either the conventional UV excited or persistent luminescence spectra. The trap structure from TL with three traps from 0.65 to 0.85 eV is ideal for room-temperature persistent luminescence similar to, e.g., Sr2MgSi2O7:Eu2+,R3+. Despite the rather low band gap energy, 5.28 eV, the persistent luminescence from Tb3+ is produced only under UV irradiation due to the inauspicious position of the F-7(6) ground level deep in the band gap of CdSiO3. This confirms the role of electrons as the charge carriers in the mechanism of Tb3+ persistent luminescence. The XANES spectra indicated the presence of only the trivalent Tb3+ species, thus excluding the direct Tb3+ -> Tb-IV oxidation during the charging process of persistent luminescence. Eventually, a unique persistent luminescence mechanism for Tb3+ in CdSiO3 was constructed based on the comprehensive experimental data.

Discovery of hearing impairment by the family: seeing an idealized future collapse

OBJECTIVE: To portray the family experience when the discovery of hearing impairment in their child. METHODS: Qualitative research with Symbolic Interactionism and Grounded Theory as theoretical and methodological frameworks. Data collection instrument: semi-structured interview. The study included nine families (32 participants). RESULTS: The theme, "Seeing an idealized future collapse", shows that for the family, discovered the possibility of having a child with hearing loss is a moment that involves many negative feelings. CONCLUSION: Discover the hearing loss has a meaning of the expected loss of the perfect child, frustrated expectations and uncertain future. The family has been inadequately approached and the diagnosis has been made late, which requires immediate changes to the practices of professionals.

Web Scale Discovery Systems – How to assess the best solution

The University of São Paulo has been experiencing the increase in contents in electronic and digital formats, distributed by different suppliers and hosted remotely or in clouds, and is faced with the also increasing difficulties related to facilitating access to this digital collection by its users besides coexisting with the traditional world of physical collections. A possible solution was identified in the new generation of systems called Web Scale Discovery, which allow better management, data integration and agility of search. Aiming to identify if and how such a system would meet the USP demand and expectation and, in case it does, to identify what the analysis criteria of such a tool would be, an analytical study with an essentially documental base was structured, as from a revision of the literature and from data available in official websites and of libraries using this kind of resources. The conceptual base of the study was defined after the identification of software assessment methods already available, generating a standard with 40 analysis criteria, from details on the unique access interface to information contents, web 2.0 characteristics, intuitive interface, facet navigation, among others. The details of the studies conducted into four of the major systems currently available in this software category are presented, providing subsidies for the decision-making of other libraries interested in such systems.

CID: an efficient complexity-invariant distance for time series

The ubiquity of time series data across almost all human endeavors has produced a great interest in time series data mining in the last decade. While dozens of classification algorithms have been applied to time series, recent empirical evidence strongly suggests that simple nearest neighbor classification is exceptionally difficult to beat. The choice of distance measure used by the nearest neighbor algorithm is important, and depends on the invariances required by the domain. For example, motion capture data typically requires invariance to warping, and cardiology data requires invariance to the baseline (the mean value). Similarly, recent work suggests that for time series clustering, the choice of clustering algorithm is much less important than the choice of distance measure used.In this work we make a somewhat surprising claim. There is an invariance that the community seems to have missed, complexity invariance. Intuitively, the problem is that in many domains the different classes may have different complexities, and pairs of complex objects, even those which subjectively may seem very similar to the human eye, tend to be further apart under current distance measures than pairs of simple objects. This fact introduces errors in nearest neighbor classification, where some complex objects may be incorrectly assigned to a simpler class. Similarly, for clustering this effect can introduce errors by “suggesting” to the clustering algorithm that subjectively similar, but complex objects belong in a sparser and larger diameter cluster than is truly warranted.We introduce the first complexity-invariant distance measure for time series, and show that it generally produces significant improvements in classification and clustering accuracy. We further show that this improvement does not compromise efficiency, since we can lower bound the measure and use a modification of triangular inequality, thus making use of most existing indexing and data mining algorithms. We evaluate our ideas with the largest and most comprehensive set of time series mining experiments ever attempted in a single work, and show that complexity-invariant distance measures can produce improvements in classification and clustering in the vast majority of cases.

Pharmacokinetic properties and in silico ADME modeling in drug discovery

The discovery and development of a new drug are time-consuming, difficult and expensive. This complex process has evolved from classical methods into an integration of modern technologies and innovative strategies addressed to the design of new chemical entities to treat a variety of diseases. The development of new drug candidates is often limited by initial compounds lacking reasonable chemical and biological properties for further lead optimization. Huge libraries of compounds are frequently selected for biological screening using a variety of techniques and standard models to assess potency, affinity and selectivity. In this context, it is very important to study the pharmacokinetic profile of the compounds under investigation. Recent advances have been made in the collection of data and the development of models to assess and predict pharmacokinetic properties (ADME - absorption, distribution, metabolism and excretion) of bioactive compounds in the early stages of drug discovery projects. This paper provides a brief perspective on the evolution of in silico ADME tools, addressing challenges, limitations, and opportunities in medicinal chemistry.