Structure and conformation of the calcium complex of cyclo(Ala-Leu-Pro-Gly)2 in two crystal forms

Crystal structures of two different forms of the calcium perchlorate complex of cyclo(Ala-Leu-Pro-Gly)2 have been determined and refined using X-ray crystallographic techniques. Orthorhombic form: C32H52N8O8.Ca(ClO4)2.7H2O.2CH3OH, space group C222(1), a = 14.366, b = 18.653, c = 19.824 A, Z = 4, R = 0.068 for 2208 observed reflections. Monoclinic form: C32H52N8O8.Ca(ClO4)2.4H2O, space group C2, a = 21.096, b = 10.182, c = 11.256 A, beta = 103.33 degrees, Z = 2, R = 0.075 for 2165 observed reflections. The cyclic peptide molecule in both the structures has the form of a twofold symmetric, slightly elongated bowl. Type II' beta-turns, involving Gly and Ala at the corners, exist at the two ends of the molecule. The interior of the molecule is substantially hydrophilic, and the external surface of the bowl is largely hydrophobic. The calcium ion is located at the centre of the mouth of the bowl-like molecule. In both crystal forms, four peptide carbonyl oxygens from the cyclic peptide and two solvent oxygens coordinate to the metal ion. The mode of complexation may be described as incomplete encapsulation as, for example, in the case of metal complexes of antamanide. In the crystal structures the complex ions are held together by hydrogen bonds involving perchlorate ions and water molecules. The molecular structure observed in the crystals is entirely consistent with the results of solution studies, which also indicate the conformation of the cyclic peptide in the complex to be similar to that of the uncomplexed molecule.

Cement stabilised rammed earth. Part A: compaction characteristics and physical properties of compacted cement stabilised soils

Rammed earth is used for load bearing walls of buildings and there is growing interest in this low carbon building material. This paper is focused on understanding the compaction characteristics and physical properties of compacted cement stabilised soil mixtures and cement stabilised rammed earth (CSRE). This experimental study addresses (a) influence of soil composition, cement content, time lag on compaction characteristics of stabilised soils and CSRE and (b) effect of moulding water content and density on compressive strength and water absorption of compacted cement stabilised soil mixes. Salient conclusions of the study are (a) compaction characteristics of soils are not affected by the addition of cement, (b) there is 50% fall in strength of CSRE for 10 h time lag, (c) compressive strength of compacted cement stabilised soil increases with increase in density irrespective of moulding moisture content and cement content, and (d) compressive strength increases with the increase in moulding water content and compaction of CSRE on the wet side of OMC is beneficial in terms of strength.

Cement stabilised rammed earth. Part B: compressive strength and stress-strain characteristics

Strength and behaviour of cement stabilised rammed earth (CSRE) is a scantily explored area. The present study is focused on the strength and elastic properties of CSRE. Characteristics of CSRE are influenced by soil composition, density of rammed earth, cement and moisture content. The study is focused on examining (a) role of clay content of the soil on strength of CSRE and arriving at optimum clay fraction of the soil mix, (b) influence of moisture content, cement content and density on strength and (c) stress-strain relationships and elastic properties for CSRE. Major conclusions are (a) there is considerable difference between dry and wet compressive strength of CSRE and the wet to dry strength ratio depends upon the clay fraction of soil mix and cement content, (b) optimum clay fraction yielding maximum compressive strength for CSRE is about 16%, (c) strength of CSRE is highly sensitive to density and for a 20% increase in density the strength increases by 300-500% and (d) in dry state the ultimate strain at failure for CSRE is as high as 1.5%, which is unusual for brittle materials.

An electron-spin-resonance study of MN2+ doped calcium hydrazine carboxylate monohydrate

Single crystals of calcium hydrazine carboxylate, monohydrate have been studied by ESR of Mn2+ doped in the calcium sites. X-band ESR indicated a large crystal field splitting necessitating experiments at Q band. The analysis shows two magnetically inequivalent (but chemically equivalent) sites with g(xx) = 2.0042+/-0.0038, g(yy) = 2.0076 +/-00029, g(zz) =2.0314+/-0.001, A(zz) = 0.0099+/-0.0002 cm(-1), A(xx) = 0.0099+/-0.0002 cm(-1), A(yy) = 0.0082+/-0.0002cm(-1), D = 3/2D(zz) = 0.0558+/-0.0006cm(-1), and E = 1/2(D-xx-D-yy) = 0.0127+/-0.0002 cm(-1).One of the principal components of the crystal field, (D-zz), is found to be along the Ca<->Ca direction in the structure and a second one, (D-xx), along the perpendicular to the plane of the triangle formed by three neighbouring calciums. The A tensor is found to have an orientation different from that of the g and D tensors reflecting the low symmetry of the Ca2+ sites.

Calcium ionophore, A23187 and its amino acid complexes: spectroscopic and molecular modeling studies.

The circular dichroism, fluorescence, Nuclear Magnetic Resonance and BLM conductance studies indicate that A23187 forms a stable complex with amino acids at low ionophore concentrations (<10(-4)M). However, A23187 prefers to be in a dimeric structure with no significant binding to amino acids, at concentrations higher than 10(-4)M. It was also observed that at lower concentrations, at which the amino acids bind to the ionophore, the affinity for calcium ions was several orders of magnitude lower than that at higher ionophore concentrations. We have also conducted molecular modeling studies to examine the structure of the A23187 dimer and its amino acid complexes. The results of these modeling studies strongly support our experimental results and validate the formation of a hydrogen bonded and energetically stable A23187 dimer and its amino acid complexes.

Intracellular free calcium level and its response to cAMP stimulation in developing Dictyostelium cells transformed with jellyfish apoaequorin CDNA

A new method is described for measuring intracellular free calcium concentrations, [(Ca2+)(i)], in the cells of Dictyostelium discoideum transformed with apoaequorin cDNA of the jellyfish, Aequorea victoria. Aequorin, a calcium-specific indicator, was regenerated in vivo from apoaequorin produced in the cells by incubation with coelenterazine. The results showed that [(Ca2+)(i)] in developing cells markedly increases at the aggregation stage and again at the culmination stage after a temporary drop at the migration stage. Except for the vegetative stage, the cells al all stages of development exhibit a sharp transient increase in [(Ca2+)(i)] upon stimulation with a cAMP (50 nM) pulse, high responses being observed at the migration and culmination stages. Separated prestalk cells of migrating slugs contain more than twice as much [(Ca2+)(i)] and show three times as large a response to cAMP stimulation as prespore cells.

Proportioning of fly-ash cement concrete mixes

The accumulation of fly ash throughout the world is several million tons per day. The main problem with the usage of fly ash is the slow rate of strength gain, primarily due to slow pozzolanic reactions. Existing methods of proportioning fly ash concrete are lacking. These methods are involved and do not directly take into account the properties of the constituent materials. The Generalized Approach for Mix Proportioning developed at the Indian Institute of Science, Bangalore, is the basis for the development of the proposed method, which takes into account the characteristics of cement, fly ash, and aggregates. Based on the basic trial mix data obtained by using the American Concrete Institute (ACI 211.1-81) method, the proportions of fly-ash concrete mixes were arrived at using the Generalized Approach for Mix Proportioning. The method proposed was applied to and found applicable for fly-ash concretes using fly ashes from two different sources.

Calcium/Calmodulin Dependent Protein Kinase II Bound to NMDA Receptor 2B Subunit Exhibits Increased ATP Affinity and Attenuated Dephosphorylation

Calcium/calmodulin dependent protein kinase II (CaMKII) is implicated to play a key role in learning and memory. NR2B subunit of N-methyl-D-aspartate receptor (NMDAR) is a high affinity binding partner of CaMKII at the postsynaptic membrane. NR2B binds to the T-site of CaMKII and modulates its catalysis. By direct measurement using isothermal titration calorimetry (ITC), we show that NR2B binding causes about 11 fold increase in the affinity of CaMKII for ATP gamma S, an analogue of ATP. ITC data is also consistent with an ordered binding mechanism for CaMKII with ATP binding the catalytic site first followed by peptide substrate. We also show that dephosphorylation of phospho-Thr(286)-alpha-CaMKII is attenuated when NR2B is bound to CaMKII. This favors the persistence of Thr(286) autophosphorylated state of CaMKII in a CaMKII/phosphatase conjugate system in vitro. Overall our data indicate that the NR2B- bound state of CaMKII attains unique biochemical properties which could help in the efficient functioning of the proposed molecular switch supporting synaptic memory.

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.

The level of sequestered calcium in vegetative amoebae of Dictyostelium discoideum can predict post-aggregative cell fate

When freshly starved amoebae of Dictyostelium discoideum are stained with chlortetracycline (CTC), a cell type-specific fluorescent probe for membrane-associated calcium (Ca2+) the resulting fluorescence distribution falls into two functional classes. Fluorescence-activated cell sorting shows that highly fluorescing amoebae tend to enter the prestalk pathway while those with low fluorescence tend to become prespores. In the light of previous findings, these results indicate that in addition to cell cycle phase at starvation, phenotypic variation in the level of sequestered calcium is an early correlate of cell fate.

Rice-Husk-Ash Cement - A Review

The use of silica from rice-husk for the production of various materials, including rice-husk ash-lime binder, has gained significance. In this context, the decomposition of husk, the properties of the silica ash, including its crystallization and the ash-lime reaction, are reviewed. The mechanism of ash-lime reaction is controlled mostly by the development of osmotic pressure. For lime-deficient ash-lime mixtures the reaction is complete in the initial few days and therefore no strength development is observed for such mortars in the later ages. The use of optimum ash/lime ratio is recommended for obtaining consistently good performance for the mortar. A method for the determination of this ratio is also discussed.

Spatial gradients of calcium in the slug of Dictyostelium discoideum

Starved amoebae of D. discoideum aggregate and give rise to a long and thin multicellular structure called the slug. The cells within the slug eventually differentiate according to a simple anterior/posterior dichotomy. This motivates a search for gradients of putative morphogens along its axis. Calcium may be one such morphogen. On the basis of observations made by using the calcium-sensitive fluorescent dyes fura-2 and chlortetracyline, we report that there are spatial gradients in cytoplasmic and sequestered calcium in the slug. Anteriorly located and genetically defined prestalk cells (ecmA/pstA, ecmB/pstAB) contain significantly higher levels of calcium than the prespore cells in the posterior. However, the proportion of 'calcium-rich' cells in the slug is greater than that of the subset of prestalk cells defined by the expression of the ecmA or ecmB genes.

Strontium and calcium zirconyl citrates as precursors for the low-temperature synthesis of SrZrO3 and CaZrO3 fine powders

Synthesis and the thermal decomposition behavior of new molecular precursors, strontium, and calcium zirconyl citrates are presented. The pathway to the metazirconate formation has been found to proceed through a multistep process. The precursors yield SrZrO3 and CaZrO3 fine powders at temperatures as low as 650 degrees C. Physico-chemical, spectroscopic, thermoanalytical, and microscopic techniques have enabled the identification of the sequence of events leading to the perovskite formation and proposition of a thermolysis scheme. Retention of the molecular level mixing of the metal ions during the course of the precursor decomposition is supported by these techniques. Prior to the formation of MZrO3 (M = Sr and Ca) an ionic oxycarbonate, M2Zr2O5CO3 (M = SI. and Ca), intermediate is produced by the thermal decomposition of the citrate precursors.

Structures of the catalytic site mutants D99A and H48Q and the calcium-loop mutant D49E of phospholipase A(2)

Crystal structures of the active-site mutants D99A and H48Q and the calcium-loop mutant D49E of bovine phospholipase A(2) have been determined at around 1.9 Angstrom resolution. The D99A mutant is isomorphous to the orthorhombic recombinant enzyme, space group P2(1)2(1)2(1), The H48Q and the calcium-loop mutant D49E are isomorphous to the trigonal recombinant enzyme, space group P3(1)21, The two active-site mutants show no major structural perturbations. The structural water is absent in D99A and, therefore, the hydrogen-bonding scheme is changed. In H48Q, the catalytic water is present and hydrogen bonded to Gln48 N, but the second water found in native His48 is absent. In the calcium-loop mutant D49E, the two water molecules forming the pentagonal bipyramid around calcium are absent and only one O atom of the Glu49 carboxylate group is coordinated to calcium, resulting in only four ligands.