Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides

Two shape-persistent covalent cages (CC1(r) and CC2(r)) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1(r) and CC2(r) are 2+3] and 8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1(r) and Pd@CC2(r) have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as similar to 1.8 nm PdNPs could be stabilized inside the CC1(r), while larger CC2(r) could stabilize similar to 3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.

Archean tectonics and crustal evolution of the Biligiri Rangan Block, southern India

The Southern Granulite Terrain in India is a collage of crustal blocks ranging in age from Archean to Neoproterozoic. This study investigate the tectonic evolution of one of the northernmost block- the Biligiri Block (BRB) through a multidisciplinary approach involving field investigation, petrographic studies, LA-ICPMS zircon U-Pb geochronology, Hf isotopic analyses, metamorphic P-T phase diagram computations, and crustal thickness modeling. The garnet bearing quartzofeldspathic gneiss from the central BRB preserve Mesoarchean magmatic zircons with ages between 3207 and 2806 Ma and positive epsilon Hf value (+2.7) which possibly indicates vestiges of a Mesoarchean primitive continental crust. The occurrence of quartzite-iron formation intercalation as well as ultramafic lenses along the western boundary of the BRB is interpreted to indicate that the Kollegal structural lineament is a possible paleo-suture. Phase diagram computation of a metagabbro from the southwestern periphery of the Kollegal suture zone reveals high-pressure (similar to 18.5 kbar) and medium-temperature (similar to 840 degrees C) metamorphism, likely during eastward subduction of the Western Dharwar oceanic crust beneath the Mesoarchean BRB. In the model presented here, slab subduction, melting and underplating processes generated arc magmatism and subsequent charnockitization within the BRB between ca. 2650 Ma and ca. 2498 Ma. These results thus reveal Meso- to Neoarchean tectonic evolution of the BRB. The spatial variation of crustal thickness, derived from flexure inversion technique, provides additional constraints on the tectonic linkage of the BRB with its surrounding terrains. In conjunction with published data, the Moyar and the Kollegal suture zones are considered to mark the trace of ocean closure along which the Nilgiri and Biligiri Rangan Blocks accreted on to the Western Dharwar Craton. (C) 2016 Elsevier B.V. All rights reserved.

An Amino Acid Substitution Matrix for Protein Conformation Identification

Amino acid substitution matrices play an essential role in protein sequence alignment, a fundamental task in bioinformatics. Most widely used matrices, such as PAM matrices derived from homologous sequences and BLOSUM matrices derived from aligned segments of PROSITE, did not integrate conformation information in their construction. There are a few structure-based matrices, which are derived from limited data of structure alignment. Using databases PDB_SELECT and DSSP, we create a database of sequence-conformation blocks which explicitly represent sequence-structure relationship. Members in a block are identical in conformation and are highly similar in sequence. From this block database, we derive a conformation-specific amino acid substitution matrix CBSM60. The matrix shows an improved performance in conformational segment search and homolog detection.

Effect of Rock Mass Structure and Block Size on the Slope Stability-Physical Modeling and Discrete Element Simulation

This paper studies the stability of jointed rock slopes by using our improved three-dimensional discrete element methods (DEM) and physical modeling. Results show that the DEM can simulate all failure modes of rock slopes with different joint configurations. The stress in each rock block is not homogeneous and blocks rotate in failure development. Failure modes depend on the configuration of joints. Toppling failure is observed for the slope with straight joints and sliding failure is observed for the slope with staged joints. The DEM results are also compared with those of limit equilibrium method (LEM). Without considering the joints in rock masses, the LEM predicts much higher factor of safety than physical modeling and DEM. The failure mode and factor of safety predicted by the DEM are in good agreement with laboratory tests for any jointed rock slope.

Microstructure and Evolution of Mechanically-Induced Ultrafine Grain in Surface Layer of Al-Alloy Subjected to USSP

Experiments were conducted to investigate the ultrafine-grained (UFG) microstructures in the surface layer of an aluminum alloy 7075 heavily worked by ultrasonic shot peening. Conventional and high-resolution electron microscopy was performed at various depths of the deformed layer. Results showed that UFG structures were introdued into the surface layer of 62 μm thick. With increasing strain, the various microstructural features, e.g., the dislocation emission source, elongated microbands, dislocation cells, dislocation cell blocks, equiaxed submicro-, and nano-crystal grains etc., were successively produced. The grain subdivision into the subgrains was found to be the main mechanism responsible for grain refinement. The simultaneous evolution of high boundary misorientations was ascribed to the subgrain boundary rotation for accommodating further strains. Formed microstructures were highly nonequilibratory.  2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Electronic structure of the ferroelectric layered perovskite SrBi2Ta2O9

The band structure of the layered perovskite SrBi2Ta2O9 (SBT) was calculated by tight binding and the valence band density of states was measured by x-ray photoemission spectroscopy. We find both the valence and conduction band edges to consist of states primarily derived from the Bi-O layer rather than the perovskite Sr-Ta-O blocks. The valence band maximum arises from O p and some Bi s states, while the conduction band minimum consists of Bi p states, with a wide band gap of 5.1 eV. It is argued that the Bi-O layers largely control the electronic response whereas the ferroelectric response originates mainly from the perovskite Sr-Ta-O block. Bi and Ta centered traps are calculated to be shallow, which may account in part for its excellent fatigue properties. © 1996 American Institute of Physics.

High quality assembly of phase-only liquid crystal on silicon ((LCOS) devices

Liquid crystal on silicon (LCOS) for phase-only holography is ideally made to better optical tolerance than that for conventional amplitude modulating applications. Die-level assembly is suited to custom devices and pre-production prototypes because of its flexibility and efficiency in conserving the silicon backplane. Combined with automated assembly, it will allow high reproducibility and fast turnaround time, paving the way for pre-production testing and customer sampling before mass production. Pre-assembly optical testing is the key element in the process. By taking into account the flatness of both the backplane and the front glass plate, we have assembled high quality LCOS devices. We have reached our aim of less than one quarter wavelength phase distortion across the active area. © 2011 IEEE.

Uplift resistance of buried pipelines in blocky clay backfill

This paper presents the results from 10 minidrum centrifuge tests conducted at the Schofield Centre, compiled with 4 additional test results from Thusyanthan et al., 2008. All these tests were designed to measure the uplift resistance of a pipeline installed into stiff clay by trenching and backfilling, then uplifted approximately 3 months after installation. All tests were conducted at 1:30 scale using soil obtained from offshore clay samples. Experimental results show that clay blocks remained intact after 3 prototype months of consolidation, and were lifted rather than sheared during pipe pullout. The uplift resistance therefore depends on the weight of the soil cover and the shearing resistance mobilised at the softening contact points between the intact blocks and within the interstitial slurry. Slow drained pullout led to lower resistance than fast pullout, indicating that the drained response is critical for design. The varying scatter shows that peak uplift resistance is very sensitive to the arrangement of the backfill blocks when the cover and pipe diameter are comparable to the block size. Copyright © 2009 by The International Society of Offshore and Polar Engineers (ISOPE).

Significant Residue Features Revealed By Eigenvalue Decomposition Analysis Of Blosum Matrices

Here we attempt to characterize protein evolution by residue features which dominate residue substitution in homologous proteins. Evolutionary information contained in residue substitution matrix is abstracted with the method of eigenvalue decomposition. Top eigenvectors in the eigenvalue spectrums are analyzed as function of the level of similarity, i.e. sequence identity (SI) between homologous proteins. It is found that hydrophobicity and volume are two significant residue features conserved in protein evolution. There is a transition point at SI approximate to 45%. Residue hydrophobicity is a feature governing residue substitution as SI >= 45%. Whereas below this SI level, residue volume is a dominant feature. (C) 2007 Elsevier B.V. All rights reserved.

Evaluación de técnicas de defensa y de la densidad en el cultivo de una nueva hortaliza : Cucúrbita pepo var. vegetable spaghetti

El zapallo Spaghetti, cultivo vigoroso de clima templado, constituye una alternativa productiva interesante y novedosa para nuestro país. El objetivo de este estudio fue evaluar el efecto del mulching y de la densidad sobre el rendimiento total, el peso medio y el calibre de los frutos. El estudio se llevó a cabo en Azul sobre un suelo Argiudol típico en camellones de 0,80 m de ancho con diferentes densidades de siembra. Se realizó una fertilización profunda en bandas de 0,80 m con fosfato diamónico, controlando las malezas en forma química, manual y mecánicamente, y las plagas haciendo aplicaciones preventivas de insecticidas y fungicidas. La siembra manual se efectuó el 2 de noviembre y los tratamientos fueron: densidades de siembra de 20, 15, 10 y 5 mil pl/ha (D1, D2, D3 y D4), con y sin mulching. Se trabajó con 32 parcelas y cada una tenía tres surcos de seis metros de longitud separados entre si por 2m. Se realizaron cuatro cosechas al llegar a la madurez completa (15/2, 29/2, 7/3 y 3/4). Los calibres evaluados fueron: (1) 2,2 kg, (2) 1,7 kg; (3) 1,3 kg y (4) 0,8 kg / fruto. Para el análisis de los datos se utilizó un modelo de bloques completamente aleatorizados con parcelas sub-divididas. En la parcela principal se evaluó el efecto del mulching, en la subparcela la densidad y la interacción de mulching por densidad, y en la subsubparcelas las diferentes cosechas. La cosecha total mostró diferencias significativas para el efecto del mulching, obteniéndose 71,90 t/ha (a) (con mulching) y 62,02 t/ha (b) (sin mulching); para cada densidad se detectaron diferencias significativas para el efecto mulching: D1: 84,45 t/ha (a), D2: 76,47 t/ha (ab); D3: 65,14 t/ha (b) y D4: 61,55 t/ha (b). Se observaron diferencias significativas en el número de frutos cosechados: con mulching (51.667 frutos/ha) y sin mulching (44.167 frutos/ha), y para las diferentes densidades: D1: 54.167 (a); D2: 50.000 (ab); D3: 47.700 (ab) y D4: 40.833 (b) t/ha. La composición de calibres de frutos cosechados fue el mismo para todos los tratamientos y cosechas.

Numerical study on rainfall infiltration in rock-soil slop

A mathematical model for the rain infiltration in the rock-soil slop has been established and solved by using the finite element method. The unsteady water infiltrating process has been simulated to get water content both in the homogeneous and heterogeneous media. The simulated results show that the rock blocks in the rock-soil slop can cause the wetting front moving fast. If the rain intensity is increased, the saturated region will be formed quickly while other conditions are the same. If the rain intensity keeps a constant, it is possible to accelerate the generation of the saturated region by properly increasing the vertical filtration rate of the rock-soil slop. However, if the vertical filtration rate is so far greater than the rain intensity, it will be difficult to form the saturated region in the rock-soil slop. The numerical method was verified by comparing the calculation results with the field test data.

Analysis of critical excavation depth for a jointed rock slope using a face-to-face discrete element method

The critical excavation depth of a jointed rock slope is an important problem in rock engineering. This paper studies the critical excavation depth for two idealized jointed rock slopes by employing a face-to-face discrete element method (DEM). The DEM is based on the discontinuity analysis which can consider anisotropic and discontinuous deformations due to joints and their orientations. It uses four lump-points at each surface of rock blocks to describe their interactions. The relationship between the critical excavation depth D-s and the natural slope angle alpha, the joint inclination angle theta as well as the strength parameters of the joints c(r) ,phi(r) is analyzed, and the critical excavation depth obtained with this DEM and the limit equilibrium method (LEM) is compared. Furthermore, effects of joints on the failure modes are compared between DEM simulations and experimental observations. It is found that the DEM predicts a lower critical excavation depth than the LEM if the joint structures in the rock mass are not ignored.

[R_SanMillan_Yuso] Documentación geométrica de las excavaciones arqueológicas realizadas en el Monasterio de Yuso (San Millán de la Cogolla, La Rioja)

[ES] El seguimiento arqueológico se realiza sobre las capillas del la nave Norte de la iglesia más la capilla “de las reliquias”, en total 9 capillas de unos 10 x 10 metros cada una. Los elementos a documentar son las unidades estratigráficas exhumadas que, en gran medida corresponden a enterramientos (fosas y los propios esqueletos).

[G_Oñati_Arantzazu] Documentación fotográfica del Apostolado y la Piedad del exterior del Monasterio de Arantzazu (Oñati, Gipuzkoa)

[ES] Conjunto de figuras en piedra de gran porte (unos 4 metros de altura cada una), lo componen 14 figuras en la zona baja del apostolado y un conjunto de 2 personajes más formando la Piedad en la parte superior. Se trata de formas esquemáticas de perfil redondeado que corresponden artísticamente a una de las corrientes más destacadas del siglo XX.

Numerical Analyses of Transonic Fluid/Structure interaction in Aircraft Engineering

Through the coupling between aerodynamic and structural governing equations, a fully implicit multiblock aeroelastic solver was developed for transonic fluid/stricture interaction. The Navier-Stokes fluid equations are solved based on LU-SGS (lower-upper symmetric Gauss-Seidel) Time-marching subiteration scheme and HLLEW (Harten-Lax-van Leer-Einfeldt-Wada) spacing discretization scheme and the same subiteration formulation is applied directly to the structural equations of motion in generalized coordinates. Transfinite interpolation (TFI) is used for the grid deformation of blocks neighboring the flexible surfaces. The infinite plate spline (IPS) and the principal of virtual work are utilized for the data transformation between fluid and structure. The developed code was fort validated through the comparison of experimental and computational results for the AGARD 445.6 standard aeroelastic wing. In the subsonic and transonic range, the calculated flutter speeds and frequencies agree well with experimental data, however, in the supersonic range, the present calculation overpredicts the experimental flutter points similar to other computations. Then the flutter character of a complete aircraft configuration is analyzed through the calculation of the change of structural stiffness. Finally, the phenomenon of aileron buzz is simulated for the weakened model of a supersonic transport wing/body model at Mach numbers of 0.98 and l.05. The calculated unsteady flow shows, on the upper surface, the shock wave becomes stronger as the aileron deflects downward, and the flow behaves just contrary on the lower surface of the wing. Corresponding to general theoretical analysis, the flow instability referred to as aileron buzz is induced by a stronger shock alternately moving on the upper and lower surfaces of wing. For the rigid structural model, the flow is stable at all calculated Mach numbers as observed in experiment