Urea-based constructs readily amplify and attenuate nonlinear optical activity in response to H-bonding and anion recognition

Urea-based molecular constructs are shown for the first time to be nonlinear optically (NLO) active in solution. We demonstrate self-assembly triggered large amplification and specific anion recognition driven attenuation of the NLO activity. This orthogonal modulation along with an excellent nonlinearity-transparency trade-off makes them attractive NLO probes for studies related to weak self-assembly and anion transportation by second harmonic microscopy.

Characterization and iodide adsorption behaviour of HDPY+ modified bentonite

Owing to its favourable physical, chemical and rheological properties, densely compacted bentonite or bentonite-sand mix is considered as a suitable buffer material in deep geological repositories to store high level nuclear waste. Iodine-129 is one of the significant nuclides in the high level waste owing to its long half life and poor sorption onto most geologic media. Bentonite by virtue of negatively charged surface has negligible affinity to retain iodide ions. As organo-bentonites are known to retain iodide ions, the present study characterizes hexadecylpyridinium chloride (HDPyCl.H2O) treated bentonite from Barmer India (referred as HDPy+B) for physico-chemical properties, engineering properties and the iodide adsorption behavior of the organo clay. Batch experiments revealed that HDPy+ ions are largely retained (94 % retention) via cation exchange; the ion-exchange process neutralizes the negative surface charge and bridges clay particles leading to reduction in Atterberg limits, clay content and sediment volume. The organo clay retains iodide by Coulombic attraction (at primary sites) and anion exchange (at secondary sites). The free-energy change (Delta G (o) = -25.5 kJ/mol) value indicated that iodide retention by organo clay is favored physical adsorption process. Iodide adsorption capacity of organo clay decreased significantly (85-100 %) on dilution with 50-80 % bentonite. On the other hand, dilution of bentonite with 50 % organo clay caused 58 % reduction in swell potential and 21 % reduction in swell pressure.

Clay mineral liner system for leachates containing organic contaminants

A conventional liner with a good performance against inorganic contaminants with a minimal hydraulic conductivity does not usually perform well for retention/removal of leachates containing organic contaminants. Organic modification of clay can render the naturally organophobic clay tobe organophilic. Incorporation of modified organo clay along with unmodified inorganic clay in liner systems can overcome the inherent incompatibility of conventional liners to organic contaminants and can increase organic sorption. The performance of commercially available organo clay and natural bentonite and mixtures of them in different pore fluids has been studied. It is found that the properties of mixtures improve with increase in organically modified clay particularly in non aqueous fluids from the considerations of liner application.

Bearing capacity of piles in soft clay underlaid by cohesive frictional soil

By using the axisymmetric quasi-lower bound finite-element limit analysis, the bearing capacity factors N-c(p) and N-gamma q(p) have been computed for axially loaded piles, with the shaft embedded in a fully cohesive soil medium and the tip placed over cohesive frictional soil strata. The results were obtained for various combinations of L/D, phi(l), and c(l)/c(u); the subscripts l and u refer to lower and upper soil strata, respectively. The factors N-c(p) and N-gamma q(p) increase continuously with increases in L/D and phi(l); the rate of increase of N-c(p) and N-gamma q(p) with L/D, however, decreases with an increase in L/D. For c(l)/c(u) > 100, the factor N-c(p) hardly depends on L/D.

Horizontal pullout capacity of a group of two vertical plate anchors in clay

The horizontal pullout capacity of a group of two vertical strip plate anchors, placed along the same vertical plane, in a fully cohesive soil has been computed by using the lower bound finite element limit analysis. The effect of spacing between the plate anchors on the magnitude of total group failure load (P-uT) has been evaluated. An increase of soil cohesion with depth has also been incorporated in the analysis. For a weightless medium, the total pullout resistance of the group becomes maximum corresponding to a certain optimum spacing between the anchor plates which has been found to vary generally between 0.5B and B; where B is the width of the anchor plate. As compared to a single plate anchor, the increase in the pullout resistance for a group of two anchors becomes greater at a higher embedment ratio. The effect of soil unit weight has also been analyzed. It is noted that the interference effect on the pullout resistance increases further with an increase in the unit weight of soil mass.

Numerical analysis of geocell reinforced ballast overlying soft clay subgrade

Geotextiles and geogrids have been in use for several decades in variety of geo-structure applications including foundation of embankments, retaining walls, pavements. Geocells is one such variant in geosynthetic reinforcement of recent years, which provides a three dimensional confinement to the infill material. Although extensive research has been carried on geocell reinforced sand, clay and layered soil subgrades, limited research has been reported on the aggregates/ballast reinforced with geocells. This paper presents the behavior of a railway sleeper subjected to monotonic loading on geocell reinforced aggregates, of size ranging from 20 to 75 mm, overlying soft clay subgrades. Series of tests were conducted in a steel test tank of dimensions 700 mm x 300 mm x 700 mm. In addition to the laboratory model tests, numerical simulations were performed using a finite difference code to predict the behavior of geocell reinforced ballast. The results from numerical simulations were compared with the experimental data. The numerical and experimental results manifested the importance that the geocell reinforcement has a significant effect on the ballast behaviour. The results depicted that the stiffness of underlying soft clay subgrade has a significant influence on the behavior of the geocell-aggregate composite material in redistributing the loading system.

Synergistic Lewis base and anion-binding catalysis for the enantioselective vinylogous addition of deconjugated butenolides to allenoates

An enantioselective vinylogous umpolung addition of deconjugated butenolides to allenoates has been developed for the first time with the help of synergistic combination of an achiral phosphine and a chiral squaramide, and represents the first example of a catalytic enantioselective C gamma-C gamma bond formation between two different carbonyl partners.

Triarylborane-dipyrromethane conjugates bearing dual receptor sites: the synthesis and evaluation of the anion binding site preference

The synthesis and optical properties of four new triarylborane-dipyrromethane (TAB-DPM) conjugates (3a-d) containing dual binding sites (hydrogen bond donor and Lewis acid) have been reported. The new compounds exhibit a selective fluorogenic response towards the F-ion. The NMR titrations show that the anions bind to the TAB-DPM conjugates via the Lewis acidic triarylborane centre in preference to the hydrogen bond donor (dipyrromethane) units.

Response of vertically loaded pile in clay: a probabilistic study

This study presents the response of a vertically loaded pile in undrained clay considering spatially distributed undrained shear strength. The probabilistic study is performed considering undrained shear strength as random variable and the analysis is conducted using random field theory. The inherent soil variability is considered as source of variability and the field is modeled as two dimensional non-Gaussian homogeneous random field. Random field is simulated using Cholesky decomposition technique within the finite difference program and Monte Carlo simulation approach is considered for the probabilistic analysis. The influence of variance and spatial correlation of undrained shear strength on the ultimate capacity as summation of ultimate skin friction and end bearing resistance of pile are examined. It is observed that the coefficient of variation and spatial correlation distance are the most important parameters that affect the pile ultimate capacity.

Triarylborane-Appended New Triad and Tetrad: Chromogenic and Fluorogenic Anion Recognition

Facile synthesis of triad 3 and tetrad 4 incorporating -B(Mes)(2) (Mes = mesityl (2,4,6-trimethylphenyl)), boron dipyrromethene (BODIPY), and triphenylamine is reported. Introduction of two dissimilar acceptors (triarylborane and BODIPY) on a single donor resulted in two distinct intramolecular charge transfer processes (amine-to-borane and amine-to-BODIPY). The absorption and emission properties of the new triad and tetrad are highly dependent on individual building units. The nature of electronic communication among the individual fluorophore units has been comprehensively investigated and compared with building units. Compounds 3 and 4 showed chromogenic and fluorogenic responses for small anions such as fluoride and cyanide.

Going beyond Red with a Tri- and Tetracoordinate Boron Conjugate: Intriguing Near-IR Optical Properties and Applications in Anion Sensing

The design and synthesis of a new tri- and tetracoordinate boron conjugate is reported. The conjugate shows broad near-IR emission (similar to 625-850 nm) and is found to be a selective colorimetric and ratiometric sensor for fluoride ions.

Dual Binding Site Assisted Chromogenic and Fluorogenic Recognition and Discrimination of Fluoride and Cyanide by a Peripherally Borylated Metalloporphyrin: Overcoming Anion Interference in Organoboron Based Sensors

Peripherally triarylborane decorated porphyrin (2) and its Zn(II) complex (3) have been synthesized. Compound 3 contains of two different Lewis acidic binding sites (Zn(II) and boron center). Unlike all previously known triarylborane based sensors, the optical responses of 3 toward fluoride and cyanide are distinctively different, thus enabling the discrimination of these two interfering anions. Metalloporphyrin 3 shows a multiple channel fluorogenic response toward fluoride and cyanide and also a selective visual colorimetric response toward cyanide. By comparison with model systems and from detailed photophysical studies on 2 and 3, we conclude that the preferential binding of fluoride occurs at the peripheral borane moieties resulting in the cessation of the EET (electronic energy transfer) process from borane to porphyrin core and with negligible negetive cooperative effects. On the other hand, cyanide binding occurs at the Zn(II) core leading to drastic changes in its absorption behavior which can be followed by the naked eye. Such changes are not observed when the boryl substituent is absent (e.g., Zn-TPP and TPP). Compounds 2 and 3 were also found to be capable of extracting fluoride from aqueous medium.

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.

Iodide Retention by Modified Kaolinite in the Context of Safe Disposal of High Level Nuclear Waste

Bentonite clay is identified as potential buffer in deep geological repositories (DGR) that store high level radioactive wastes (HLW) as the expansive clay satisfies the expected mechanical and physicochemical functions of the buffer material. In the deep geological disposal of HLW, iodine-129 is one of the significant nuclides, attributable to its long half-life (half life 1⁄4 1:7 × 107 years). However, the negative charge on the basal surface of bentonite particles precludes retention of iodide anions. To render the bentonite effective in retaining hazardous iodide species in DGR, improvement of the anion retention capacity of bentonite becomes imperative. The iodide retention capac-ity of bentonite is improved by admixing 10 and 20% Ag-kaolinite (Ag-K) with bentonite (B) on a dry mass basis. The present study produced Ag-kaolinite by heating silver nitrate-kaolinite mixes at 400°C. Marginal release of iodide retained by Ag-kaolinite occurred under extreme acidic (pH 1⁄4 2:5) and alkaline (pH 1⁄4 12:5) conditions. The swell pressure and iodide etention results of the B-Ag-K specimens bring out that mixing Ag-K with bentonite does not chemically modify the expansive clay; the mixing is physical in nature and Ag-K presence only contributes to iodide retention of the admixture. DOI: 10.1061/(ASCE)HZ.2153-5515.0000121. © 2012 American Society of Civil Engineers.