Self-Assembly of Molecular Prisms via Pt-3 Organometallic Acceptors and a Pt-2 Organometallic Clip

The design and two-component [2 + 3] self-assembly of a series of new organometallic molecular prisms (3a-d) are described. Assemblies 3a,b incorporate 4,4',4'-tris[ethynyl-trans-Pt(PEt3)(2)]triphenylamine (1a) containing a Pt-ethynyl functionality as tritopic planar acceptor and organic ``clips'' 2a and 2b, respectively [where 2a = 1,3-bis(3-pyridyl)isophthalic amide; 2b= 1,3-bis(ethynyl-3-pyridyl)benzene]. In a complementary approach all organic tritopic planar donor ligand 2c [2c 4,4',4'-tris(4-pyridylethynyl)triphenylamine] was assembled with all organometallic ``clip'', 1,8-bis[{trans-Pt(PEt3) (2)(NO3)}ethynyl]anthracene (1b), to obtain prism 3c. A organometallic carbon-centered acceptor, 1,1,1- tris[4-{trans-Pt(PEt3)(2)(NO3)}ethynylphenyl]ethane (1c), has been prepared, and its prism derivative (3d) using an organic `clip'' is prepared. Assemblies (3a-d) were characterized by multinuclear NMR spectroscopy, electrospray ionization mass spectroscopy, and elemental analysis. 3a-d showed fluorescence behavior in solution, and quenching of fluorescence intensity (3a,3c-d) was noticed upon addition of TNT (2,4,6-trinitrotoluene), a common constituent of many commercial explosives. A thin film of the assembly 3d made by spin coating of a solution of 3 x 10(-5) M in DMF on it 1 cm(2) quartz plate showed fluorescence response to the vapor of TNT.

Method for measurement of the angles of 90-, 45-, 45-deg and 60-, 30-, 90-deg prisms

A simple technique is devised to measure the angles of 90-, 45-, 45-deg and 60-, 30-, 90-deg prisms without using expensive spectrometers, autocollimators, and angle gauges. The method can be extended to unpolished and opaque prisms made of materials other then glass. (C) 1997 Society of Photo-Optical instrumentation Engineers.

Methods for making prisms with submultiple or half angles: applications to the measurement of the angles of Pechan and Pellin-Broca prisms

A simple technique is devised for making prisms with submultiple or half angles. As an application of these prisms, methods are suggested to measure the angles of the Pechan and Pellin-Broca prisms without using expensive spectrometers, autocollimators, and angle gauges. (C) 2002 Society of Photo-Optical Instrumentation Engineers.

Three-Component Self-Assembly of a Series of Triply Interlocked Pd12 Coordination Prisms and Their Non-Interlocked Pd6 Analogues

Template-assisted formation of multicomponent Pd6 coordination prisms and formation of their self-templated triply interlocked Pd12 analogues in the absence of an external template have been established in a single step through Pd?N/Pd?O coordination. Treatment of cis-[Pd(en)(NO3)2] with K3tma and linear pillar 4,4'-bpy (en=ethylenediamine, H3tma=benzene-1,3,5-tricarboxylic acid, 4,4'-bpy=4,4'-bipyridine) gave intercalated coordination cage [{Pd(en)}6(bpy)3(tma)2]2[NO3]12 (1) exclusively, whereas the same reaction in the presence of H3tma as an aromatic guest gave a H3tma-encapsulating non-interlocked discrete Pd6 molecular prism [{Pd(en)}6(bpy)3(tma)2(H3tma)2][NO3]6 (2). Though the same reaction using cis-[Pd(NO3)2(pn)] (pn=propane-1,2-diamine) instead of cis-[Pd(en)(NO3)2] gave triply interlocked coordination cage [{Pd(pn)}6(bpy)3(tma)2]2[NO3]12 (3) along with non-interlocked Pd6 analogue [{Pd(pn)}6(bpy)3(tma)2](NO3)6 (3'), and the presence of H3tma as a guest gave H3tma-encapsulating molecular prism [{Pd(pn)}6(bpy)3(tma)2(H3tma)2][NO3]6 (4) exclusively. In solution, the amount of 3' decreases as the temperature is decreased, and in the solid state 3 is the sole product. Notably, an analogous reaction using the relatively short pillar pz (pz=pyrazine) instead of 4,4'-bpy gave triply interlocked coordination cage [{Pd(pn)}6(pz)3(tma)2]2[NO3]12 (5) as the single product. Interestingly, the same reaction using slightly more bulky cis-[Pd(NO3)2(tmen)] (tmen=N,N,N',N'-tetramethylethylene diamine) instead of cis-[Pd(NO3)2(pn)] gave non-interlocked [{Pd(tmen)}6(pz)3(tma)2][NO3]6 (6) exclusively. Complexes 1, 3, and 5 represent the first examples of template-free triply interlocked molecular prisms obtained through multicomponent self-assembly. Formation of the complexes was supported by IR and multinuclear NMR (1H and 13C) spectroscopy. Formation of guest-encapsulating complexes (2 and 4) was confirmed by 2D DOSY and ROESY NMR spectroscopic analyses, whereas for complexes 1, 3, 5, and 6 single-crystal X-ray diffraction techniques unambiguously confirmed their formation. The gross geometries of H3tma-encapsulating complexes 2 and 4 were obtained by universal force field (UFF) simulations.

Influence of Joint Thickness and Mortar-Block Elastic Properties on the Strength and Stresses Developed in Soil-Cement Block Masonry

Soil-cement blocks are employed for load bearing masonry buildings. This paper deals with the study on the influence of bed joint thickness and elastic properties of the soil-cement blocks, and the mortar on the strength and behavior of soil-cement block masonry prisms. Influence of joint thickness on compressive strength has been examined through an experimental program. The nature of stresses developed and their distribution, in the block and the mortar of the soil-cement block masonry prism under compression, has been analyzed by an elastic analysis using FEM. Influence of various parameters like joint thickness, ratio of block to mortar modulus, and Poisson's ratio of the block and the mortar are considered in FEM analysis. Some of the major conclusions of the study are: (1) masonry compressive strength is sensitive to the ratio of modulus of block to that of the mortar (Eb/Em) and masonry compressive strength decreases as the mortar joint thickness is increased for the case where the ratio of block to mortar modulus is more than 1; (2) the lateral tensile stresses developed in the masonry unit are sensitive to the Eb/Em ratio and the Poisson's ratio of mortar and the masonry unit; and (3) lateral stresses developed in the masonry unit are more sensitive to the Poisson's ratio of the mortar than the Poisson's ratio of the masonry unit.

Comparative Study of Predictions of Flexural Strength of Steel Fiber Concrete

Several methods are available for predicting flexural strength of steel fiber concrete composites. In these methods, direct tensile strength, split cylinder strength, and cube strength are the basic engineering parameters that must be determined to predict the flexural strength of such composites. Various simplified forms of stress distribution are used in each method to formulate the prediction equations for flexural strength. In this paper, existing methods are reviewed and compared, and a modified empirical approach is developed to predict the flexural strength of fiber concrete composites. The direct tensile strength of the composite is used as the basic parameter in this approach. Stress distribution is established from the findings of flexural tests conducted as part of this investigation on fiber concrete prisms. A comparative study of the test values of an earlier investigation on fiber concrete slabs and the computed values from existing methods, including the one proposed, is presented.

Coordination-Driven Self-Assembly of M3L2 Trigonal Cages from Preorganized Metalloligands Incorporating Octahedral Metal Centers and Fluorescent Detection of Nitroaromatics

The design and preparation of novel M3L2 trigonal cages via the coordination-driven self-assembly of preorganized metalloligands containing octahedral aluminum(III), gallium(III), or ruthenium(II) centers is described. When tritopic or dinuclear linear metalloligands and appropriate complementary subunits are employed, M3L2 trigonal-bipyramidal and trigonal-prismatic cages are self-assembled under mild conditions. These three-dimensional cages were characterized with multinuclear NMR spectroscopy (H-1 and P-31) and high-resolution electrospray ionization mass spectrometry. The structure of one such trigonal-prismatic cage, self-assembled from an arene ruthenium metalloligand, was confirmed via single-crystal X-ray crystallography. The fluorescent nature of these prisms, due to the presence of their electron-rich ethynyl functionalities, prompted photophysical studies, which revealed that electron-deficient nitroaromatics are effective quenchers of the cages' emission. Excited-state charge transfer from the prisms to the nitroaromatic substrates can be used as the basis for the development of selective and discriminatory turn-off fluorescent sensors for nitroaromatics.

Photobehavior of crystalline 4-styrylcoumarin dimorphs: structure-reactivity correlations

4-Styrylcoumarin crystallizes from chloroform and hexane mixture in two morphologically different modifications. The monoclinic form (needles, P2(1)/c) undergoes stereospecific photodimerization producing anti head-to-tail dimer across pyrone double bond, whereas the triclinic modification (prisms, P ($) over bar 1) dimerizes yielding photodimer of the same configuration, but across styrenic double bond. Single crystal X-ray analyses of the dimorphs reveal the packing differences permitting rationalization of the regio- and stereochemistry of the photoproducts. The significantly low dimer yield from the prismatic crystals is rationalized.

Structural Behavior of Story-High Cement-Stabilized Rammed-Earth Walls under Compression

A rammed-earth wall is a monolithic construction made by compacting processed soil in progressive layers in a rigid formwork. There is a growing interest in using this low-embodied-carbon building material in buildings. The paper investigates the strength and structural behavior of story-high cement-stabilized rammed-earth (CSRE) walls, reviews literature on the strength of CSRE, and discusses results of the compressive strength of CSRE prisms, wallettes, and story-high walls. The strength of the story-high wall was compared with the strength of wallettes and prisms. There is a nearly 30% reduction in strength as the height-to-thickness ratio increases from about 5 to 20. The ultimate compressive strength of CSRE walls predicted using the tangent modulus theory is in close agreement with the experimental values. The shear failures noticed in the story-high walls resemble the shear failures of short-height prism and wallette specimens. The paper ends with a discussion of structural design and characteristic compressive strength of CSRE walls. DOI: 10.1061/(ASCE)MT.1943-5533.0000155. (C) 2011 American Society of Civil Engineers.

Flexural bond strength of masonry using various blocks and mortars

This paper deals with an experimental study on flexural bond strength of masonry using various blocks in combination with different mortars. Flexural bond strength of masonry has been determined by testing stack-bonded prisms using a modified bond wrench test set-up. The effect of mortar composition and strength on the masonry's. flexural bond strength using three types of masonry units (stabilized mud blocks, stabilized soil-sand blocks and burnt brick) has been examined. The effect of the masonry unit's moisture content on flexural bond strength has also been studied. Increases in mortar strength lead to increased flexural bond strength for cement mortar, irrespective of the type of masonry unit. It has been found that combination mortars, such as soil-cement mortar and cement-lime mortar, lead to better bond strength compared to cement mortars. The moisture content of the masonry unit at the time of casting has displayed significant influence on the flexural bond strength of the masonry. It has been found that for each type of masonry unit, an optimum moisture content exists, beyond which the flexural bond strength falls off quickly.

Method for measurement of the angles of an equilateral (60-deg) prism

A simple technique is devised io measure the angles of equilateral (60-deg) prisms, without using the expensive spectrometers, autocollimators, and angle gauges. The method can be extended to unpolished and opaque prisms made out of materials other than glass. (C) 1997 Society of Photo-Optical Instrumentation Engineers.

Spectrographic technique for determining refractive indices

A new experimental technique is proposed to determine refractive indices of liquids and isotropic solids at different wavelengths. A Pellin-Broca hollow prism filled with a liquid sample produces the spectrum (of the liquid prism) on the photographic plate of the camera. A plane reflector, mounted at a small angle to the normal of the exit face of the prism, also forms a direct image of the collimator slit in the plane of the same photographic plate. All the necessary information for determining the refractive indices (for different wavelengths) is extracted directly from the spectrogram without using any goniometric system. Experiments are conducted with the liquid prisms of isopropyl alcohol, water, and benzene. The results of the experiments are compared with those obtained by a Pulfrich refractometer (critical angle method). The proposed new technique gives the refractive indices for visible and invisible spectral lines to an accuracy of 2x10(-5). (C) 1997 Society of Photo-Optical Instrumentation Engineers.

Strength characteristics of stone masonry

This paper deals with an experimental investigation on the strength of stone and stone masonry. Granitoid-gneiss is commonly used for masonry construction in India. The compressive strength of stone has been determined through 80 mm size cubes. It has been found that the compressive strength of granitoid-gneiss is greater when the load is parallel to the mineral bands. The compressive strength of stone masonry was studied through masonry prisms using 1:4 and 1:8 cement mortars. These tests have revealed that masonry strength is higher when the load applied is parallel to the mineral bands. The flexural bond strength of stone masonry walls was studied through full-scale tests. Flexural bond strength appears to play a major role in the failure of stone masonry walls.

Role of clay content and moisture on characteristics of cement stabilised rammed earth

Rammed earth is an energy efficient and low carbon emission alternative for load bearing walls. This paper attempts to examine the influence of clay content and moisture content on the compressive strength of cement stabilised rammed earth (CSRE) through experimental investigations. Compressive strength of CSRE prisms was monitored both in dry and wet (saturated) conditions. Major conclusions of the study are:(a) Optimum clay content for maximum compressive strength is about 16%, (b) the strength of CSRE is sensitive to the moisture content at the time of testing, (c) Strength in saturated condition is less than half of the dry strength and (d) Water absorption (saturated water content) increases as the clay content of the soil mix increases and it is in the range of 12 to 16% for the CRSE prisms with 8% cement.

Measurement of Stress-Strain Response of A Rammed Earth Prism In Compression Using Fiber Bragg Grating Sensors

A comparative study of strain response and mechanical properties of rammed earth prisms, has been made using Fiber Bragg Grating (FBG) sensors (optical) and clip-on extensometer (electro-mechanical). The aim of this study is to address the merits and demerits of traditional extensometer vis-à-vis FBG sensor; a uni-axial compression test has been performed on a rammed earth prism to validate its structural properties from the stress - strain curves obtained by two different methods of measurement. An array of FBG sensors on a single fiber with varying Bragg wavelengths (..B), has been used to spatially resolve the strains along the height of the specimen. It is interesting to note from the obtained stress-strain curves that the initial tangent modulus obtained using the FBG sensor is lower compared to that obtained using clip-on extensometer. The results also indicate that the strains measured by both FBG and extensometer sensor follow the same trend and both the sensors register the maximum strain value at the same time.