Vertical Uplift Resistance of Two Interfering Horizontal Anchors in Clay

The vertical uplift resistance of two interfering rigid strip plate anchors embedded horizontally at the same level in clay has been examined. The lower and upper bound theorems of the limit analysis in combination with finite-elements and linear optimization have been employed to compute the failure load in a bound form. The analysis is meant for an undrained condition and it incorporates the increase of cohesion with depth. For different clear spacing (S) between the anchors, the magnitude of the efficiency factor (eta c gamma) resulting from the combined components of soil cohesion (c) and soil unit weight (gamma), has been computed for different values of embedment ratio (H/B), the rate of linear increase of cohesion with depth (m) and normalized unit weight (gamma H/c). The magnitude of eta c gamma has been found to reduce continuously with a decrease in the spacing between the anchors, and the uplift resistance becomes minimum for S/B=0. It has been noted that the critical spacing between the anchors required to eliminate the interference effect increases continuously with (1) an increase in H/B, and (2) a decrease in m.

Amide Functionalized Microporous Organic Polymer (Am-MOP) for Selective CO2 Sorption and Catalysis

We report the design and synthesis of an amide functionalized microporous organic polymer (Am-MOP) prepared from trimesic acid and p-phenylenediamine using thionyl chloride as a reagent. Polar amide (CONH) functional groups act as a linking unit between the node and spacer and constitute the pore wall of the continuous polymeric network. The strong covalent bonds between the building blocks (trimesic acid and p-phenylenediamine) through amide bond linkages provide high thermal and chemical stability to Am-MOP. The presence of a highly polar pore surface allows selective CO2 uptake at 195 K over other gases such as N-2, Ar, and O-2. The CO2 molecule interacts with amide functional groups via Lewis acid base type interactions as demonstrated through DFT calculations. Furthermore, for the first time Am-MOP with basic functional groups has been exploited for the Knoevenagel condensation reaction between aldehydes and active methylene compounds. Availability of a large number of catalytic sites per volume and confined microporosity gives enhanced catalytic efficiency and high selectivity for small substrate molecules.

SELECTIVE ALDEHYDE REDUCTION IN KETOALDEHYDES WITH NaBH4-Na2CO3-H2O AT ROOM TEMPERATURES

A variety of aliphatic and aromatic ketoaldehydes were reduced to the corresponding ketoalcohols with a mixture of sodium borohydride (1.2 equivalents) and sodium carbonate (sixfold molar excess) in water. Reactions were performed at room temperatures over (typically) 2 h, and yields of isolated products generally ranged from 70% to 85%. A biscarbonate-borane complex, (BH3)(2)CO2](2-) 2Na(+), possibly formed from the reagent mixture, is likely the active reductant. The moderated reactivity of this acylborane species would explain the chemoselectivity observed in the reactions. The readily available reagents and the mild aqueous conditions make for ease of operation and environmental compatibility, and make a useful addition to available methodology.

Zoledronic acid in combination with alfacalcidol has additive effects on trabecular microarchitecture and mechanical properties in osteopenic ovariectomized rats

We conducted the present study to investigate the therapeutic effects of the antiresorptive agent zoledronic acid (ZOL), alone and in combination with alfacalcidol (ALF), in a rat model of postmenopausal osteoporosis. Female Wistar rats were ovariectomized (OVX) or sham-operated at 3 months of age. Twelve weeks post surgery, rats were randomized into six groups: (1) sham + vehicle, (2) OVX + vehicle, (3) OVX + ZOL (100 mu g/kg, i.v. single dose), (4) OVX + ZOL (50 mu g/kg, i.v. single dose), (5) OVX + ALF (0.5 mu g/kg, oral gauge daily) and (6) OVX + ZOL (50 mu g/kg, i.v. single dose) + ALF (0.5 mu g/kg, oral gauge daily) for 12 weeks. After treatment, we evaluated the mechanical properties of the lumbar vertebra and femoral mid-shaft. Femurs were also tested for bone density, porosity and trabecular micro-architecture. Biochemical markers in serum and urine were also determined. With respect to improvement in the mechanical strength of the lumbar spine and the femoral mid-shaft, the combination treatment of ZOL and ALF was more effective than each administered as a monotherapy. Moreover, combination therapy using ZOL and ALF preserved the trabecular micro-architecture and cortical bone porosity. Furthermore, the combination treatment of ZOL and ALF corrected the decrease in serum calcium and increase in serum alkaline phosphatase and the tartarate-resistant acid phosphatase level better than single-drug therapy using ZOL or ALF in OVX rats. In addition, the combination treatment of ZOL and ALF corrected the increase in urine calcium, phosphorous and creatinine levels better than single-drug therapy using ZOL or ALF in OVX rats. These data suggest that the combination treatment of ZOL and ALF has a therapeutic advantage over each monotherapy for the treatment of osteoporosis.

A modeling study of the processes of surface salinity seasonal cycle in the Bay of Bengal

In response to the Indian Monsoon freshwater forcing, the Bay of Bengal exhibits a very strong seasonal cycle in sea surface salinity (SSS), especially near the mouths of the Ganges-Brahmaputra and along the east coast of India. In this paper, we use an eddy-permitting (similar to 25 km resolution) regional ocean general circulation model simulation to quantify the processes responsible for this SSS seasonal cycle. Despite the absence of relaxation toward observations, the model reproduces the main features of the observed SSS seasonal cycle, with freshest water in the northeastern Bay, particularly during and after the monsoon. The model also displays an intense and shallow freshening signal in a narrow (similar to 100 km wide) strip that hugs the east coast of India, from September to January, in good agreement with high-resolution measurements along two ships of opportunity lines. The mixed layer salt budget confirms that the strong freshening in the northern Bay during the monsoon results from the Ganges-Brahmaputra river discharge and from precipitation over the ocean. From September onward, the East India Coastal Current transports this freshwater southward along the east coast of India, reaching the southern tip of India in November. The surface freshening results in an enhanced vertical salinity gradient that increases salinity of the surface layer by vertical processes. Our results reveal that the erosion of the freshwater tongue along the east coast of India is not driven by northward horizontal advection, but by vertical processes that eventually overcome the freshening by southward advection and restore SSS to its premonsoon values. The salinity-stratified barrier layer hence only acts as a ``barrier'' for vertical heat fluxes, but is associated with intense vertical salt fluxes in the Bay of Bengal.

Improved Erlenmeyer Synthesis with 5-Thiazolone and Catalytic Mn(II) Acetate. Crystal Structure Confirmation of the Reaction Stereochemistry

2-Phenylthiazolin-5-one (5, a thioazlactone) condenses with various aldehydes in the presence of the mild base Mn(II) acetate as catalyst in CH2Cl2 solution. This leads to the corresponding Erlenmeyer reaction products (6) in excellent yields in the case of aromatic aldehydes and moderate yields in others. The mildness of the reaction conditions is apparently enabled by the aromaticity of the (putative) intermediate thiazolone anion. The structure and stereochemistry (Z) of the product derived from i-BuCHO was confirmed by single crystal X-ray diffraction. This study overcomes key limitations of the classical Erlenmeyer synthesis and also introduces the relatively nontoxic Mn(II) acetate as a reagent in heterocyclic chemistry.

Pullout capacity of inclined plate anchors embedded in sand

The pullout capacity of an inclined strip plate anchor embedded in sand has been determined by using the lower bound theorem of the limit analysis in combination with finite elements and linear optimization. The numerical results in the form of pullout factors have been presented by changing gradually the inclination of the plate from horizontal to vertical. The pullout resistance increases significantly with an increase in the horizontal inclination (theta) of the plate especially for theta > 30 degrees. The effect of the anchor plate-soil interface friction angle (delta) on the pullout resistance becomes extensive for a vertical anchor but remains insignificant for a horizontal anchor. The development of the failure zone around the anchor plates was also studied by varying theta and delta. The results from the analysis match well with the theoretical and experimental results reported in literature.

Covalent assembly-disassembly of poly(ether imine) dendritic macromolecular monomers and megamers

Poly(ether imine) dendritic macromolecules were undertaken to study the reversible dendrimer monomer-megamer assembly-disassembly in aqueous solutions. Synthesis of thiol functionalized poly(ether imine) (PETIM) dendrimers and their covalent aggregation behavior in the aqueous solution of ethanol/water (2:1) is demonstrated. The dendritic megamers were characterized using microscopic techniques. Kinetics of the aggregation behavior was followed using turbidity measurements, light-scattering and atomic force microscopic techniques. Inherent luminescence behavior of PETIM dendrimer monomers was retained in the dendrimer megamers also, which allowed visualization of the megamers through confocal microscopy. Extent of thiol functionalities that remained after the megamer assembly was estimated through Ellman's assay. Subsequent to megamer assembly, disassembly of megamers to dendrimer monomers was conducted, using dithiothreitol reagent. Water-insoluble sudan I dye was encapsulated in dendrimer megamer and subsequent release profile was assessed during the disassembly in aqueous solutions. The studies were conducted using first, second and third generations, representing 4, 8 and 16 sulfhydryl groups at their peripheries of dendrimers, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

Riemann shock tube: 1D normal shocks in air, simulations and experiments

This paper presents numerical simulation of the evolution of one-dimensional normal shocks, their propagation, reflection and interaction in air using a single diaphragm Riemann shock tube and validate them using experimental results. Mathematical model is derived for one-dimensional compressible flow of viscous and conducting medium. Dimensionless form of the mathematical model is used to construct space-time finite element processes based on minimization of the space-time residual functional. The space-time local approximation functions for space-time p-version hierarchical finite elements are considered in higher order GRAPHICS] spaces that permit desired order of global differentiability of local approximations in space and time. The resulting algebraic systems from this approach yield unconditionally positive-definite coefficient matrices, hence ensure unique numerical solution. The evolution is computed for a space-time strip corresponding to a time increment Delta t and then time march to obtain the evolution up to any desired value of time. Numerical studies are designed using recently invented hand-driven shock tube (Reddy tube) parameters, high/low side density and pressure values, high- and low-pressure side shock tube lengths, so that numerically computed results can be compared with actual experimental measurements.

Seismic Bearing Capacity of Shallow Embedded Foundations on a Sloping Ground Surface

By using the lower-bound theorem of the limit analysis in conjunction with finite elements and nonlinear optimization, bearing-capacity factors, N-c and N-gamma q, with an inclusion of pseudostatic horizontal seismic body forces, have been determined for a shallow embedded horizontal strip footing placed on sloping ground surface. The variation of N-c and N-gamma q with changes in slope angle (beta) for different values of seismic acceleration coefficient (k(h)) has been obtained. The analysis reveals that irrespective of ground inclination and the embedment depth of the footing, the factors N-c and N-gamma q decrease quite considerably with an increase in k(h). As compared with N-c, the factor N-gamma q is affected more extensively with changes in k(h) and beta. Unlike most of the results reported in literature for the seismic case, the present computational results take into account the shear resistance of soil mass above the footing level. An increase in the depth of the embedment leads to an increase in the magnitudes of both N-c and N-gamma q. (C) 2014 American Society of Civil Engineers.

Bearing Capacity of Circular Footings on Reinforced Soils

A method is presented for determining the ultimate bearing capacity of a circular footing reinforced with a horizontal circular sheet of reinforcement placed over granular and cohesive-frictional soils. It was assumed that the reinforcement sheet could bear axial tension but not the bending moment. The analysis was performed based on the lower-bound theorem of the limit analysis in combination with finite elements and linear optimization. The present research is an extension of recent work with strip foundations reinforced with different layers of reinforcement. To incorporate the effect of the reinforcement, the efficiency factors eta(gamma) and eta(c), which need to be multiplied by the bearing capacity factors N-gamma and N-c, were established. Results were obtained for different values of the soil internal friction angle (phi). The optimal positions of the reinforcements, which would lead to a maximum improvement in the bearing capacity, were also determined. The variations of the axial tensile force in the reinforcement sheet at different radial distances from the center were also studied. The results of the analysis were compared with those available from literature. (C) 2014 American Society of Civil Engineers.

A delocalizable cationic headgroup together with an oligo-oxyethylene spacer in gemini cationic lipids improves their biological activity as vectors of plasmid DNA

Lipoplex nano-aggregates constituted of plasmid DNA (pDNA) pEGFP-C3 and mixed cationic liposomes, consisting of several percentages of a gemini cationic lipid (GCL) of the 1,2-bis(hexadecyl imidazolium) oxyethylene series, referred to as (C(16)Im)(2)(C2O)(n), with oxyethylene spacers (n = 1, 2 or 3) between the imidazolium cationic groups and the DOPE zwitterionic helper lipid, have been characterized by various biophysical and biological approaches carried out at several GCL compositions (alpha), and either the mass or the effective charge ratio of the lipoplex. The electrochemical study by zeta-potential confirms that the three GCLs yield a 10% lower effective charge than the nominal one, while compacted pDNA yields only a 25% effective negative charge. The SAXS study reveals, irrespective of the spacer length (n) and effective charge ratio (rho(eff)), the presence of two lamellar structures, i.e., one (L-alpha,L-main) in the whole GCL composition and another (L-alpha,L-DOPE,L-rich) with higher periodicity values that coexists with the previous one at low GCL composition (alpha = 0.2). The cryo-TEM analysis shows two types of multilamellar structures consisting of cationic lipidic bilayers with pDNA sandwiched between them: a cluster-type (C-type) at low alpha = 0.2 and a fingerprint-type (FP-type) at alpha >= 0.5, both with similar interlamellar spacing (d) in agreement with the L-alpha,L-main structure determined by SAXS. Transfection efficacies (TEs) of each lipid mixture were determined in four different cell lines (HEK293T, HeLa, Caco-2 and A549) at several alpha and rho(eff) values in the absence and presence of serum (FBS). The optimized formulations (alpha = 0.2 and rho(eff) = 2.0) substantially transfect cells much better than a commercial transfection reagent, Lipofectamine 2000 and previously studied efficient lipoplexes containing other cationic head groups or spacers both in the absence and presence of serum. The activity of optimized formulations may be attributed to the combination of several factors, such as: (a) the fusogenic character of DOPE which results in higher fluidity of the lipoplexes at alpha = 0.2, (b) the coexistence of two lamellar structures at alpha = 0.2 that synergizes the TE of these lipid vectors, and mainly (c) the higher biocompatibility of the GCLs reported in this work due to the presence of two imidazolium cationic groups together with an oligo-oxyethylene spacer. The length of the spacer in the GCL seems to have less impact, although (C(16)Im)(2)(C2O)(n)/DOPEpDNA lipoplexes with n = 1 and 3 show higher gene transfection than n = 2. All the optimum formulations reported herein are all highly efficient with negligible levels of toxicity, and thus, may be considered as very promising gene vectors for in vivo applications.

Design of an Automated Dispenser Unit

This paper presents our work on developing an automated micro positioner and a low cost disposable dispenser module having a disposable dispenser core. The dispenser core is made up of Polydimethylsiloxane (PDMS). Once the user specifies the dispensing location in the Graphical User Interface (GUI), the movement of the micropositioner is automatic. The design, fabrication and characterization results of the dispenser module are also presented. The dispensing experiments are performed with Di-Ethanol Amine as the working reagent. The minimum dispensed volume achieved is about 4 nL.

Co-liposomes of redox-active alkyl-ferrocene modified low MW branched PEI and DOPE for efficacious gene delivery in serum

Herein, we present six new lipopolymers based on low molecular weight, branched polyethylenimine (BPEI 800 Da) which are hydrophobically modified using ferrocene terminated alkyl tails of variable lengths. The effects of degree of grafting, spacer length and the redox state of ferrocene in the lipopolymers on the self assembly properties were investigated in detail by TEM, AFM, DLS and zeta potential measurements. The assemblies displayed an oxidation induced increase in the size of the aggregates. The co-liposomes comprising the lipopolymer and a helper lipid, 1,2-dioleoyl phosphatidyl ethanolamine (DOPE), showed excellent gene (pDNA) delivery capability in a serum containing environment in two cancer cell lines (HeLa and U251 cells). Optimized formulations showed remarkably higher transfection activity than BPEI (25 kDa) and were also significantly better than a commercial transfection reagent, Lipofectamine 2000 as evidenced from both the luciferase activity and GFP expression analysis. Oxidation of ferrocene in the lipopolymers led to drastically reduced levels of gene transfection which was substantiated by reduced cellular internalization of fluorescently labelled pDNA as detected using confocal microscopy and flow cytometry. Moreover, the transfection inactive oxidized lipopolyplexes could be turned transfection active by exposure to ascorbic acid (AA) in cell culture medium during transfection. Endocytosis inhibition experiments showed that gene expression mediated by reduced formulations involved both clathrin and caveolae mediated pathways while the oxidized formulations were routed via the caveolae. Cytotoxicity assays revealed no obvious toxicity for the lipopolyplexes in the range of optimized transfection levels in both the cell lines studied. Overall, we have exploited the redox activity of ferrocene in branched PEI-based efficient polymeric gene carriers whose differential transfection activities could be harnessed for spatial or temporal cellular transfections.

Efficacious redox-responsive gene delivery in serum by ferrocenylated monomeric and dimeric cationic cholesterols

Herein, we present the design and synthesis of new redox-active monomeric and dimeric (gemini) cationic lipids based on ferrocenylated cholesterol derivatives for gene delivery. The cationic cholesterols are shown to be transfection efficient after being formulated with the neutral helper lipid DOPE in the presence of serum (FBS). The redox activity of the resulting co-liposomes and their lipoplexes could be regulated using the alkanyl ferrocene moiety attached to the ammonium head groups of the cationic cholesterols. Atomic force microscopy (AFM), dynamic light scattering (DLS) and zeta potential measurements were performed to characterize the co-liposomal aggregates and their complexes with pDNA. The transfection efficiency of lipoplexes could be tuned by changing the oxidation state of the ferrocene moiety. The gene transfection capability was assayed in terms of green fluorescence protein (GFP) expression using pEGFP-C3 plasmid DNA in three cell lines of different origins, namely Caco-2, HEK293T and HeLa, in the presence of serum. The vesicles possessing ferrocene in the reduced state induced an efficient transfection, even better than a commercial reagent Lipofectamine 2000 (Lipo 2000) as evidenced by flow cytometry and fluorescence microscopy. All the co-liposomes containing the oxidized ferrocene displayed diminished levels of gene expression. Gene transfection events from the oxidized co-liposomes were further potentiated by introducing ascorbic acid (AA) as a reducing agent during lipoplex incubation with cells, leading to the resumption of transfection activity. Assessment of transfection capability of both reduced and oxidized co-liposomes was also undertaken following cellular internalization of labelled pDNA using confocal microscopy and flow cytometry. Overall, we demonstrate here controlled gene transfection activities using redox-driven, transfection efficient cationic monomeric and dimeric cholesterol lipids. Such systems could be used in gene delivery applications where transfection needs to be performed spatially or temporally.