5-(4-Chlorophenyl)-3-(2,4-dimethylthiazol-5-yl)-1,2,4-triazolo[3,4-a]isoquinoline

In the title molecule, C21H15ClN4S, the triazoloisoquinoline ring system is approximately planar, with an r.m.s. deviation of 0.054 (2) angstrom and a maximum deviation of 0.098 (2) angstrom from the mean plane for the triazole ring C atom that is bonded to the thiazole ring. The thiazole and benzene rings are twisted by 66.36 (7) and 56.32 (7)degrees respectively, with respect to the mean plane of the triazoloisoquinoline ring system. In the crystal structure, molecules are linked by intermolecular C-H center dot center dot center dot N interactions along the a axis. The molecular conformation is stabilized by a weak intramolecular pi-pi interaction involving the thiazole and benzene rings, with a centroid-centroid distance of 3.6546 (11) angstrom . In addition, two other intermolecular pi-pi stacking interactions are observed, between the triazole and benzene rings and between the dihydropyridine and benzene rings [centroid-centroid distances = 3.6489 (11) and 3.5967 (10) angstrom, respectively].

1-(3,5-Diethyl-1H-pyrazol-1-yl)-3-phenylisoquinoline

In the title molecule, C22H21N3, the isoquinoline ring is almost planar maximum deviation = 0.046 (1) A] and makes dihedral angles of 52.01 (4) and 14.61 (4)degrees with the pyrazole and phenyl rings, respectively. The phenyl ring and the pyrazole ring are twisted by 44.20 (6)degrees with respect to each other. The terminal C atoms of both of the ethyl groups attached to the pyrazole ring are disordered over two sites with occupancy ratios of 0.164 (7):0.836 (7) and 0.447 (16):0.553 (16). A weak intramolecular C-H...N contact may influence the molecular conformation. The crystal structure is stabilized by C-H...pi contacts involving the phenyl and pyrazole rings, and by pi-pi stacking interactions involving the pyridine and benzene rings centroid-centroid distance = 3.5972 (10) A].

3,12-dinitro-5,10,15,20-tetraphenylporphyrin- an example of a twisted intramolecular charge-transfer system

he porphyrin ring in the title compound, 10,19-dinitro-2,7,12,17-tetraphenyl-21,22,23,24-tetraazapenta-cyclo[16.2.1.1(3,6).1(8,11).1(13,16)]tetracosa-1,3,5,7,9,11(23),-12,14,16,18(21),19-undecaene 0.5-dichloromethane solvate, C44H28N6O4.0.5CH2Cl2, adopts a saddle conformation with neighbouring pyrrole rings tilted with respect to each other. The two nitro groups are situated on alternate pyrrole rings and have their planes angled away from those of the pyrrole rings, thereby indicating that interaction between the porphyrin and nitro groups is slight.

An Enantiospecific Approach to Tetraquinane Diterpenes Crinipellins: Synthesis of Norcrinipellins

An enantiospecific approach to the synthesis of tetraquinane diterpene crinipellins is described. The cyclopentane ring in campholenaldehyde was identified as the B ring. Two rhodium carbenoid CH insertion reactions for the construction of A and C rings and an intramolecular Michael addition reaction for the D ring of crinipellins were employed as key strategies for the enantiospecific synthesis of norcrinipellins.

Enantiospecific total synthesis of 15-hydroxy-5-(methoxymethoxy)crinipellin-9-one

Enantiospecific total synthesis of the crinipellin mentioned in the title was accomplished. In the present synthesis cyclopentane ring in campholenaldehyde was identified as the B-ring, two intramolecular rhodium carbenoid CH insertion reactions were employed for the construction of the A and C rings, and an intramolecular Michael addition reaction was utilized for the construction of the D-ring of crinipellin. (C) 2012 Elsevier Ltd. All rights reserved.

Crow instability in unitary Fermi gas

In this paper, we investigate the initiation and subsequent evolution of Crow instability in an inhomogeneous unitary Fermi gas using zero-temperature Galilei-invariant nonlinear Schrodinger equation. Considering a cigar-shaped unitary Fermi gas, we generate the vortex-antivortex pair either by phase-imprinting or by moving a Gaussian obstacle potential. We observe that the Crow instability in a unitary Fermi gas leads to the decay of the vortex-antivortex pair into multiple vortex rings and ultimately into sound waves.

Liquefied Petroleum Gas Sensing of Polyaniline-Titanium Dioxide Nanocomposites

Polyaniline/titaniurn dioxide nanocomposites were prepared using alpha-dextrose as surfactant and ammonium persulphate as an oxidant. The PANI/TiO2 nanocomposite is characterized by FTIR, XRD and TEM. The FTIR spectra revel that the presence of characteristic peaks of benzenoid, qunoide rings and metal-oxygen stretching. The XRD studies show the monoclinic structure of the nanocomposites. The TEM study shows that the size of TiO2 is in the order of 9 nm where as the composite size is of the order of 13 nm and further it was observed that the TiO2 particles are intercalated to form a core shell of PANI. The maximum sensing response for LPG is found to be 90% for 30 wt.% of PANI/TiO2 nanocomposites at 400 ppm whereas for Benzene and Toluene it is negligibly small (<= 20%) and for the cyclohexane sensing response it is around 30% for different wt.%.

Variable field ion traps

This paper presents a technique to vary the electric field within a cylindrical ion trap (CIT) mass spectrometer while it is in operation. In this technique, the electrodes of the CIT are split into number of mini-electrodes and different voltages are applied to these split-electrodes to achieve the desired field. In our study we have investigated two geometries of the split-electrode CIT. In the first, we retain the flat endcap electrodes of the CIT but split the ring electrode into five mini-rings. In the second configuration, we split the ring electrode of the CIT into three mini-rings and also divide the endcaps into two mini-discs. By applying different potentials to the mini-rings and mini-discs of these geometries we have shown that the field within the trap can be optimized to desired values. In our study, two different types of fields were targeted. In the first, potentials were adjusted to obtain a linear electric field and, in the second, a controlled higher order even multipole field was obtained by adjusting the potential. We have shown that the different potentials required can be derived from a single RF generator by connecting appropriate capacitor terminations to split electrodes. The field within the trap can be modified by changing the values of the external capacitors. (C) 2013 Elsevier B.V. All rights reserved.

Numerical analysis of segmented-electrode Orbitraps

Simple geometries which are possible alternatives for the Orbitrap are studied in this paper. We have taken up for numerical investigation two segmented-electrode structures, ORB1 and ORB2, to mimic the electric field of the Orbitrap. In the ORB1, the inner spindle-like electrode and the outer barrel-like electrode of the Orbitrap have been replaced by 35 rings and 35 discs of fixed radii, respectively. In this structure two segmented end cap electrodes have been added. In this geometry, different potentials are applied to the different electrodes keeping top-bottom symmetry intact. In the second geometry, ORB2, the inner and outer electrodes of the Orbitrap were replaced by an approximate step structure which follows the profile of the Orbitrap electrodes. In the present study 45 steps have been used. In the ORB2, like the Orbitrap, the inner electrode is held at a negative potential and the outer electrode is at ground potential. For the purpose of comparing the performance of ORB1 and ORB2 with that of the Orbitrap, the following studies have been undertaken: (1) variation of electric potential, (2) computation of ion trajectories, (3) simulation of image currents. These studies have been carried out using both 2D and 3D Boundary Element Method (BEM), the 3D BEM was developed specifically for this study. It has been seen in these investigations that ORB1 and ORB2 have performance similar to that of the Orbitrap, with the performance of the ORB1 being seen to be marginally superior to that of the ORB2. It has been shown that with proper optimization, geometries containing far fewer electrodes can be used as mass analyzers. A novel technique of optimization of the electric field has been proposed with the objective of minimizing the dependence of axial frequency of ion motion on the initial position of an ion. The results on the optimization of 9 and 15 segmented-electrode traps having the same design as ORB1 show that it can provide accurate mass analysis. (C) 2015 Elsevier B.V. All rights reserved.

Numerical analysis of segmented-electrode Orbitraps

Simple geometries which are possible alternatives for the Orbitrap are studied in this paper. We have taken up for numerical investigation two segmented-electrode structures, ORB1 and ORB2, to mimic the electric field of the Orbitrap. In the ORB1, the inner spindle-like electrode and the outer barrel-like electrode of the Orbitrap have been replaced by 35 rings and 35 discs of fixed radii, respectively. In this structure two segmented end cap electrodes have been added. In this geometry, different potentials are applied to the different electrodes keeping top-bottom symmetry intact. In the second geometry, ORB2, the inner and outer electrodes of the Orbitrap were replaced by an approximate step structure which follows the profile of the Orbitrap electrodes. In the present study 45 steps have been used. In the ORB2, like the Orbitrap, the inner electrode is held at a negative potential and the outer electrode is at ground potential. For the purpose of comparing the performance of ORB1 and ORB2 with that of the Orbitrap, the following studies have been undertaken: (1) variation of electric potential, (2) computation of ion trajectories, (3) simulation of image currents. These studies have been carried out using both 2D and 3D Boundary Element Method (BEM), the 3D BEM was developed specifically for this study. It has been seen in these investigations that ORB1 and ORB2 have performance similar to that of the Orbitrap, with the performance of the ORB1 being seen to be marginally superior to that of the ORB2. It has been shown that with proper optimization, geometries containing far fewer electrodes can be used as mass analyzers. A novel technique of optimization of the electric field has been proposed with the objective of minimizing the dependence of axial frequency of ion motion on the initial position of an ion. The results on the optimization of 9 and 15 segmented-electrode traps having the same design as ORB1 show that it can provide accurate mass analysis. (C) 2015 Elsevier B.V. All rights reserved.

Tetraphenylethene-Based Conjugated Fluoranthene: A Potential Fluorescent Probe for Detection of Nitroaromatic Compounds

This study reports the synthesis and photophysical properties of a star-shaped, novel, fluoranthene-tetraphenylethene (TFPE) conjugated luminogen, which exhibits aggregation-induced blue-shifted emission (AIBSE). The bulky fluoranthene units at the periphery prevent intramolecular rotation (IMR) of phenyl rings and induces a blueshift with enhanced emission. The AIBSE phenomenon was investigated by solvatochromic and temperature-dependent emission studies. Nanoaggregates of TFPE, formed by varying the water/THF ratio, were investigated by SEM and TEM and correlated with optical properties. The TFPE conjugate was found to be a promising fluorescent probe towards the detection of nitroaromatic compounds (NACs), especially for 2,4,6-trinitrophenol (PA) with high sensitivity and a high Stern-Volmer quenching constant. The study reveals that nanoaggregates of TFPE formed at 30 and 70% water in THF showed unprecedented sensitivity with detection limits of 0.8 and 0.5ppb, respectively. The nanoaggregates formed at water fractions of 30 and 70% exhibit high Stern-Volmer constants (K-sv=79998 and 51120m(-1), respectively) towards PA. Fluorescence quenching is ascribed to photoinduced electron transfer between TFPE and NACs with a static quenching mechanism. Test strips coated with TFPE luminogen demonstrate fast and ultra-low-level detection of PA for real-time field analysis.

Johann Heinrich von Thünen: Leben und Werk des Namenspatrons des neuen Bundesforschungsinstituts für Ländliche Räume, Wald und Fischerei

A new concept for resource oriented federal research within the competence of the German Ministry of Food, Agriculture and Consumer Protection was implemented in 2008. The Johann Heinrich von Thünen-Institute, Federal Research Institute for Rural Areas, Forestry and Fisheries is one of 4 newly established large scale federal research institutions. It comprises the former Federal Research Centre for Fisheries, the Federal Research Centre for Forestry and Forest Products and large parts of the Federal Agricultural Research Centre. The institute is named after Johann Heinrich von Thünen, a famous national economist and social reformer of the 19th century. He developed the first serious treatment of spatial economics (the so-called Thünen rings) and the basics of the theory of the natural pay.

A dynamical systems analysis of vortex pinch-off

Vortex rings constitute the main structure in the wakes of a wide class of swimming and flying animals, as well as in cardiac flows and in the jets generated by some moss and fungi. However, there is a physical limit, determined by an energy maximization principle called the Kelvin-Benjamin principle, to the size that axisymmetric vortex rings can achieve. The existence of this limit is known to lead to the separation of a growing vortex ring from the shear layer feeding it, a process known as `vortex pinch-off', and characterized by the dimensionless vortex formation number. The goal of this thesis is to improve our understanding of vortex pinch-off as it relates to biological propulsion, and to provide future researchers with tools to assist in identifying and predicting pinch-off in biological flows.

To this end, we introduce a method for identifying pinch-off in starting jets using the Lagrangian coherent structures in the flow, and apply this criterion to an experimentally generated starting jet. Since most naturally occurring vortex rings are not circular, we extend the definition of the vortex formation number to include non-axisymmetric vortex rings, and find that the formation number for moderately non-axisymmetric vortices is similar to that of circular vortex rings. This suggests that naturally occurring vortex rings may be modeled as axisymmetric vortex rings. Therefore, we consider the perturbation response of the Norbury family of axisymmetric vortex rings. This family is chosen to model vortex rings of increasing thickness and circulation, and their response to prolate shape perturbations is simulated using contour dynamics. Finally, the response of more realistic models for vortex rings, constructed from experimental data using nested contours, to perturbations which resemble those encountered by forming vortices more closely, is simulated using contour dynamics. In both families of models, a change in response analogous to pinch-off is found as members of the family with progressively thicker cores are considered. We posit that this analogy may be exploited to understand and predict pinch-off in complex biological flows, where current methods are not applicable in practice, and criteria based on the properties of vortex rings alone are necessary.

Directed evolution of terpene synthases for non-natural substrates

Terpenes represent about half of known natural products, with terpene synthases catalyzing reactions to increase the complexity of substrates and generate cyclizations of the linear diphosphate substrates, therefore forming rings and stereocenters. With their diverse functionality, terpene synthases may be highly evolvable, with the ability to accept a wide range of non-natural compounds and with high product selectivity. Our hypothesis is that directed evolution of terpene synthases can be used to increase selectivity of the synthase on a specific substrate. In the first part of the work presented herein, three natural terpene synthases, Cop2, BcBOT2, and SSCG_02150, were tested for activity against the natural substrate and a non-natural substrate, called Surrogate 1, and the relative activities on both the natural and non-natural substrates were compared. In the second part of this work, a terpene synthase variant of BcBOT2 that has been evolved for thermostability, was used for directed evolution for increased activity and selectivity on the non-natural substrate referred to as Surrogate 2. Mutations for this evolution were introduced using random mutagenesis, with error prone polymerase chain reactions, and using site-specific saturation mutagenesis, in which an NNK library is designed with a specific active site amino acid targeted for mutation. The mutant enzymes were then screened and selected for enhancement of the desired functionality. Two neutral mutants, 19B7 W367F and 19B7 W118Q, were found to maintain activity on Surrogate 2, as measured by the screen.

Dinâmica de crescimento de Cedrela odorata L. (Meliaceae) na Floresta Atlântica do Estado do Rio de Janeiro: fenologia, atividade cambial e dendrocronologia

Ao longo do século XX, poucos estudos de dendrocronologia foram desenvolvidos com espécies de ambientes tropicais, em função da crença de que as condições climáticas nessas regiões não apresentavam variações suficientemente marcantes e regulares para induzir um ritmo anual de crescimento radial. A realização de trabalhos sobre esse tema nas últimas décadas revelou que a formação de anéis de crescimento anuais nos trópicos pode estar associada a fatores diversos, como: existência de estação seca bem definida, ocorrência de inundações sazonais, respostas ao comportamento fenológico, respostas ao fotoperíodo e a ritmos endógenos. O presente estudo tem por objetivo compreender a dinâmica de crescimento radial de uma espécie da Mata Atlântica se desenvolvendo em ambiente natural. Para tanto, propôs-se: i) investigar a periodicidade da atividade cambial e dos fatores que a influenciam; ii) estimar a idade e taxa de crescimento diamétrico e iii) correlacionar os fatores ambientais com os anéis de crescimento, em indivíduos de Cedrela odorata L. Para o estudo da atividade cambial, foram obtidas amostras de caule a 1,30 m do solo, contendo periderme, faixa cambial e xilema e floema secundários, por métodos não destrutivos. A fenologia vegetativa e a frutificação dos indivíduos amostrados foram acompanhadas durante todo o período do experimento. O material coletado foi processado segundo técnicas usuais em Anatomia Vegetal e analisado sob microscopia óptica e de fluorescência. Os dados de fotoperíodo, precipitação, temperatura e fenologia vegetativa foram correlacionados à atividade cambial. Para o estudo dos anéis de crescimento, as coletas também foram realizadas a 1,30 m do solo, por meio de sonda de Pressler. As amostras obtidas foram polidas e analisadas sob microscópio estereoscópio, para demarcação e aferição do número de anéis de crescimento, e a largura dos anéis foi mensurada para a determinação das taxas de crescimento radial. A série histórica de temperatura e precipitação foi correlacionada à cronologia dos anéis de crescimento. Os resultados indicaram que a atividade cambial segue um ritmo anual de crescimento, correlacionado à sazonalidade do fotoperíodo, da precipitação e da fenologia vegetativa. A análise dos anéis de crescimento permitiu estimar a idade dos indivíduos e determinar a taxa média de incremento e as taxas de incremento diamétrico acumulado e incremento médio anual para a espécie no sítio de estudo. Os dados de incremento radial evidenciaram a ausência de relação entre a idade e o diâmetro das árvores. A análise da variação na largura dos anéis não apresentou correlações significativas com os fatores climáticos analisados.