Changes of Unit Cell Parameters in Lactose Saturated by Substances Technologically Processed by Dilution

Grain size effects on irradiated CeO2, ThO2, and UO2

The change in the orthorhombic structure of PbZrO3 was studied as a function of the La substitution for Pb and Ti substitution for Zr. Two types of changes can occur: (1) a change in the atom coordinates toward the positions for a perfect cubic perovskite lattice; and (2) a change of orthorhombic unit cell parameters so that ao, bo, and co exactly fit with the cubic cell parameter ac. Therefore, ao=ac√2, bo=ac.2√2, and co=ac.2, where ao, bo, and co are the orthorhombic cell parameters, and ac is the cubic cell parameter. Substitution of Pb by La in the orthorhombic PLZT leads to both a change in atom coordinates and a change in unit cell parameters toward the perfect cubic structure, especially for La≥4. Substitution of Zr by Ti in the orthorhombic PLZT leads to similar atom coordinate changes, but the unit cell parameters do not change. The composition 0/92.5/7.5 contains a major tetragonal phase and a minor orthorhombic phase. There are only small differences in the orthorhombic structure between the A and the B composition of PLZT. The A composition has a structure closer to the cubic structure than the B composition.

Hydroxylapatites are important biomaterials. Substitutions of Pb for Ca and As for P in hydroxylapatites are recently intensively studied due to their significance in the environmental immobilization of Pb and As (Lee et al. 2009; Chlebowska et al. 2015; Motyka et al. 2015) The general chemical formula of minerals in the apatite group is expressed by A 5 (XO 4 ) 3 Z, where A are bivalent cations (e.g., Ca 2+ or Pb 2+ , cations are distributed on two distinct crystallographic sites), XO 4 is a trivalent oxyanion (e.g., PO 4 3 - , AsO 4 3 - ), and Z is a monovalent anion (OH, F, Cl, or O). Positions Z and X may be partly filled with carbonate CO 3 2- . The structure of hydroxylapatite allows for unlimited substitutions of Pb 2+ for Ca 2+ and AsO 4 3- for PO 4 3- . The ability of lead and arsenic apatites to immobilize these toxic elements result from their high durability and low solubility at the conditions on the Earth surface. Various apatites possess different thermodynamic properties including different solubility in aqueous solutions but the systematic variation of these properties in solid solution series is poorly undertsood. The main objective of this research is determination of systematic variation in the solubilities of hydroxylapatites resulting from cationic substitutions of Pb 2+ for Ca 2+ and anionic substitutions of AsO 4 3- for PO 4 3- in their structure. Three solid solution series were synthesized: HPY hydroxypyromorphite Pb 5 (PO 4 ) 3 OH – HAP hydroxyapatite Ca 5 (PO 4 ) 3 OH HMi hydroxymimetite Pb 5 (AsO 4 ) 3 OH – JBM johnbaumite Ca 5 (AsO 4 ) 3 OH HAP hydroxyapatite Ca 5 (PO 4 ) 3 OH – JBM johnbaumite Ca 5 (AsO 4 ) 3 OH The phases were synthesized from aqueous solutions at high pH above 8, at ambient temperature, by dropwise mixing of chemical reagents. The products are white, fine, homogeneous crystalline powders. Chemical composition determined by SEM/EDS is close to theoretical. X-ray diffraction confirms their crystalline structure and systematic changes in unit cell parameters with ionic substitution. Dissolution experiments were run in thermostatic bath at 25°C. An aliquot of 0,5g of apatite was dissolved in 250 mL of 0,05M NH 4 NO 3 background solution at pH in the range of 3.5 – 5.0. Background solution was used to keep the ionic strength constant. The dissolution was carried out for 3 months. The bottles were manually stirred at least two times a week. The solution was syringe-sampled periodically and filtered through 0.2 μm polycarbonate filter to remove the suspended solids. The concentration of Pb and Ca was determined by atomic absorption spectroscopy. The concentration of dissolved phosphates and arsenates was determined by UV-vis colorimetry using a molybdenum blue method. The plateau on concentration evolution patterns from the dissolution experiments was observed to determine equilibrium in the suspensions. Dissolution of all the phases at the conditions of these experiments is incongruent. An increase in solution pH resulting from dissolution was observed in all cases. The system was considered in equilibrium when at least three consecutive samples showed identical concentration of Ca 2+ or AsO 4 3- . The equilibrium in HPY series was assumed by analogy. All the concentrations were recalculated to activities using PHREEQC model with Llnl database. The solubility K sp determined for the endmembers at 25°C conform with the literature data and equal to: HPY-K sp =10 -77,31 , HAP-K sp =10 -55,66 , HMi-K sp =10 -71,56 , and JBM K sp =10 -37,76 . This confirms that, despite the incongruency of dissolution, the experimental procedure and the calculation scheme provide with reliable approximation of the solubilities. The most soluble phase is johnbaumite Ca 5 (AsO 4 ) 3 OH. The solubility of all hydroxylapatites decreases linearly with the increase of Pb and P content. These trends do not correlate with the changes in Gibbs free energy of formation of the phases in question. This indicates that structural (e.g. the size of the ions) and the chemical factors (e.g. electronegativity) play the dominant role in the solubility of substituted hydroxylapatites.

Effect of calcium doping on La4(Ti2O8)O2 structure and conductivity

Ba[SnxZn(1–x)/3Nb2(1–x)/3]O3 (x = 0.0, 0.16, 0.226, 0.32, 0.4) solid solution ceramics were synthesized by the conventional solid-state reaction method. Crystal structures are studied by X-ray diffraction, and vibrational modes are obtained by Raman spectroscopy and Fourier transform far-infrared reflection spectroscopy. The correlation among dielectric properties, lattice vibrational modes, and crystal structures are discussed by analyses of vibrational modes. Spectroscopic and structural data show sensitivity of dielectric properties to structures of samples with Sn4+ concentration, and optimized dielectric properties of Ba[SnxZn(1–x)/3Nb2(1–x)/3]O3 are found where x = 0.32. The changes of unit cell parameters and the bulk densities of the samples with Sn4+ concentration are discussed. The changes of dielectric properties with the Raman modes and their full width at half-maximum are obtained. The frequencies of phonon modes are determined, and the widths of phonon modes are related to ionic radii for th...

The assignment of the 71 cm−1 band in the infrared spectrum of polyethylene to the B1u translational lattice vibration has been confirmed by dichroism studies on an a-axis oriented sample. This permits confident use of the Tasumi-Krimm calculations for the dependence of this frequency of unit-cell parameters. The results of these calculations have been applied to the analysis of the observed lattice frequency differences between odd and even n-paraffins, and it is shown that the frequency shifts are interpretable in terms of changes in unit cell parameters resulting from different methyl end-group packing. The variation of the lattice frequency with degree of branching observed in a series of low-density polyethylenes can be understood on the basis of incorporation of branches in the lattice. The dependence of the lattice frequency in high-density polyethylene on the physical state of the specimen can be correlated with different constraints imposed by the fold regions on the chain packing. These results indicate that the folds must be considered to be ``tight'' rather than ``loose.''

The transition-metal-incorporated nickel phosphate molecular sieves (TMI-VSB-5) have been hydrothermally synthesized at 453 K in weak basic conditions under microwave irradiation. By means of X-ray diffraction, inductively coupled plasma (ICP), ultraviolet-visible (UV-vis) diffuse reflectance, and Mössbauer spectroscopies, successful isomorphous (at least partial) substitution of transition-metal ions in the VSB-5 framework has been verified. Characterization results show that the framework structure of nanoporous VSB-5 can accommodate a substantial level of isomorphous substitution of transition-metal ions up to about 10, 5, and 3 atom % for Fe, Mn, and V, respectively, in both octahedral nickel sites (Mn and Fe) and tetrahedral phosphorus sites (V). The isomorphous substitution including the replacement mechanism was studied by not only the change of unit cell parameters but also spectroscopic analysis. The unit cell parameters of TMI-VSB-5 including a unit cell volume and a-axis length relied on the ionic radii difference between the incorporated ion and the original framework ions such as Ni or P (RTMI - RNi or RTMI - RP).

Thermal expansion of the nanocrystalline titanium diboride

Background 
             Drugs at ultra high dilution (UHD) have been used in homeopathy for a couple of centuries. The central theme in homeopathic Materia Medica is that each drug has its own distinctive features which need to be matched with the symptoms of a patient for eliciting therapeutic response. However, UHD’s very often (above 12 cH) cross the Avogadro number, and are, therefore, devoid of original drug molecules. How do they maintain their individual identity ? This study aims to address this pertinent question.
  
 Objective :
             The medium of UHD’s is ethanol water. It is thought that water structures in a UHD carry the identity of the drug and its rank of dilution. The objective is to decipher the exact nature of water structure in UHD’s of different drugs by laser Raman spectroscopy.
  
 Method :
             Six homeopathic drugs and their control ethanol, all in 90% ethanol v/v, were used in the study. For Sulphur and Natrum mur, potencies used were 30 cH, 200 cH and 1000 cH, and for Calcarea carb and Sepia the potencies were 8 cH, 202 cH and 1002 cH. In addition to the four drugs we also used X-ray and Magnetis poli ambo which did not originate from any substance by exposure of ethanol water to X radiation and strong magnetic field.For this we could use their mother tinctures as well as ultrahigh dilutions(potencies) like 8cH, 14cH and 32cH. The potencies used for ethanol control were 8 cH, 14cH, 32cH and 20 cH. Raman spectra of all the potencies of 6 drugs, ethanol control and pure water were taken in the wave number region of 2400-4200 cm-1. All the samples were reduced to 25% ethanol by adding appropriate volume of water to each of them before taking the spectra. The mother tinctures MT of X-ray and Magnetis were studied.
 The intensity ratio of vibration frequencies between 3200 cm-1 and 3420 cm-1 (R1) and that between 3620 cm-1 and 3420 cm-1 (R2) were calculated for each UHD of the samples.
  
 Results :
 All the UHD’s of the drugs and the control tested show difference in intensities in the stretching vibrations of CH and OH groups. The three UHD’s from low to high ranks of both Natrum mur and Sulphur show negative relationship with respect to R1 values, and positive one concerning  R2 values. R1 values for 3 UHD’s of Calcarea carb and Sepia show negative and positive relationships, respectively. In case of R2 values the relationship in 3 UHD’s is 81002 for Calcarea carb, and 8>202

Until few years, the so-called implausible science, homeopathy, was on the verge of being rejected on conventional physicochemical grounds. The mere selection of ultrahigh dilutions (UHD) (homeopathic potencies) for experimentation by mainstream scientists seemed impossible, but the curiosity to explore the science behind homeopathy kept igniting intellectual alma mater who subjected homeopathy to laboratories and test tubes, to know beyond its clinical application.
 Still, there exist a huge gap and a challenge to convince a conventional scientist to go beyond his domains and look for something which is apparently invisible (beyond Avogadro). But gradually we are overcoming this dogma and exploring the finer aspects and applications of UHDs. Much research has been undertaken, at least, to protect the identity of UHDs, and we are now verge of proving the plausibility of homeopathy from every aspect. 
 This issue of International Journal of High Dilution Research features two interesting articles on nature of UHDs and their unconventional application.
 The first article by NC Sukul et al aimed to decipher the nature of the water structure of UHDs of two commonly used homeopathic drugs Natrum muriaticum and Sulphur by Laser Raman Spectroscopy. This work is in the series undertaken by the group, who earlier experimented using Nuclear Magnetic Resonance; Electronic, Vibrational and Raman spectroscopy to shown differences in UHDs of various drugs. The present experiment could differentiate the intensities (potencies) of Nat-m and Sulph when compared to their controls, on the basis of hydrogen bond strength and free OH groups. 
 The second article by Nandy et al proposes a new dimension to the application of UHD. In an interesting manner, the author used UHDs of Ferrum metallicum and Zincum oxidatum to improve the electrical properties of the electroactive Poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP). The PVDF-HFP composite films were synthesized in their usual way, but an incorporation of Ferrum and Zinc-o could make the film as homeo-PVDF-composite. This enhancement of the electrical properties and are possibly due to the presence of nanoparticle, as hypothesized by the group. 
 The nature and application of UHDs are promising but challenging areas, which can only be validated through extensive research and validation. The realm of UHDs is expanding, and the day is not far when plausibility of homeopathy would be proved from every aspect, but at the same time we should also keep the momentum of research at pace in clinical research too!

Objective: To confirm that free water molecules and hydrogen bond strength of OH groups underlie difference between two homeopathic drugs at ultrahigh dilution (UHD).
 Method: FTIR and Laser Raman spectra of UHDs of X-ray and Magnetis Poli Ambo were obtained in the wave number regions of 2400-4000 cm-1 and 2400-4200 cm-1, respectively. Mother tincture (MT) were prepared by exposing ethanol water to X-radiation for X-ray and magnetic field for Magnetis. Spectra of the reference water and the three UHDs of Ethanol were also taken. All the samples were in water-ethanol solution in which the ethanol content was 25%. For FTIR the difference spectrum (absorbance of a UHD minus absorbance of reference water) was obtained after normalization of the spectrum at 3410 cm-1. For Raman spectra the intensity ratio at vibration frequencies between 3200 and 3420 cm-1 (R1), and that between 3620 and 3420 cm-1 (R2), were calculated for each UHD. The intensity at 3600 cm-1 in the difference spectra (FTIR) represents the number of free water molecules in UHDs. R2 values in Raman scattering suggest the same thing.
 Results: The data in both cases follow almost a similar pattern of difference among the UHDs studied here. For example, X-ray: FTIR 14

Schiff base complexes of ruthenium were encapsulated within the zeolite cages by the technique of flexible ligand method. Zeolite encapsulated Ru(III) complexes of the Schiff bases were characterized by various techniques. The percentages of carbon, hydrogen and nitrogen indicate the encapsulation of complexes in the zeolite cages . The retention of the zeolite structure is indicated by the same Si/Al ratio and similarity in diffraction patterns. The characterization by diffraction technique provides valuable information on crystallinity and changes in unit cell parameters occurring during encapsulation. Similarity in diffraction patterns of RuY and encapsulated complexes suggests that the reduction in surface area is not due to the breakage of crystalline structure of the zeolite but due to encapsulation of complexes within the super cages of the zeolite. The lowering of surface area and pore volume values of encapsulated complexes when compared to the metal exchanged zeolite suggests encapsulation. The thermal stability of heterogeneous complexes as obtained from the TG data is found to be greater than the analogous homogeneous ones. The spectral data of the encapsulated complexes confirms the formation of complexes inside the zeolite cages. The ligand SSC coordinate through the nitrogen atom of the azomethine group, the oxygen of the phenolic hydroxyl group and oxygen of the carbonyl group. The electronic spectra indicate the presence of a paramagnetically active Ru(III) ion. Based on the spectral studies, it was proposed that the complex possess an octahedral geometry.

Samples of Gd2O3:Tb(3 mol%) phosphor were obtained by sol-gel method followed by annealing at 800oC and 1200oC in air. At high annealing temperature, the intensities of the main emission bands 484 and 541 nm increase, but the ratio of the intensities of these emission bands to their satellites 493 and 549 nm respectively decreases. Based on the analysis of X-ray diffractometry, radiation spectra, far-infrared and Raman spectroscopy, as well as diffuse reflectance spectroscopy, we established: the increase in the crystallinity of the samples with a significant reduction of the lattice strain stress at elevated annealing temperatures, changes in the structure of the bandgap with degenerated acceptor and donor zones of impurities Tb4+ and Tb3+ respectively. The diffuse reflection spectra of the sample after annealing at 800oC under optical excitation showed a direct charge transition through the bandgap with Eg = 2.56 eV. After elevated annealing temperature the concentration of Tb4+ ions decreases due to reduction to Tb3+. As a result, at low excitation energies the degeneracy of the acceptor zone is still preserved and there is a direct transition of charges through the bandgap with Eg = 2.55 eV. At high excitation energies the degeneracy of the acceptor zone is removed and there is a direct transition through the bandgap with Eg = 3.39 eV. These effects are accompanied by a relatively large increase in the emission intensity of the satellites, especially at the 549 nm.

Samples of Gd2O3 : Tb(3 mol%) phosphor were obtained by sol-gel method followed by annealing at 800oC and 1200oC in air. At high annealing temperature, the intensities of the main emission bands 484 and 541 nm increase, but the ratio of the intensities of these emission bands to their satellites 493 and 549 nm respectively decreases. Based on the analysis of X-ray diffractometry, emission spectra, far-infrared and Raman spectroscopy, as well as diffuse reflectance spectroscopy, we established: the increase in the crystallinity of the samples with a significant reduction of the lattice strain stress at elevated annealing temperatures, changes in the structure of the bandgap with degenerated acceptor and donor zones of impurities Tb4+ and Tb3+ respectively. The diffuse reflection spectra of the sample after annealing at 800oC under optical excitation showed a direct charge transition through the bandgap with Eg=2.56 eV. After elevated annealing temperature the concentration of Tb4+ ions decreases due to reduction to Tb3+. As a result, at low excitation energies the degeneracy of the acceptor zone is still preserved and there is a direct transition of charges through the bandgap with Eg=2.55 eV. At high excitation energies the degeneracy of the acceptor zone is removed and there is a direct transition through the bandgap with Eg=3.39 eV. These effects are accompanied by a relatively large increase in the emission intensity of the satellites, especially at the 549 nm. Keywords: Gd oxide, Tb3++ photoluminescence spectra, far infrared and Raman spectroscopy spectra, structure of the bandgape, distribution of Tb3+ and Tb4+ in cation sublattice.

Objective: To decipher the nature of water structure in two ultrahigh diluted (UHD) homeopathic drugs by Laser Raman Spectroscopy.
 Method: Two homeopathic drugs Calcarea carbonica (Calc.) and Sepia officinalis (Sep.) in 8cH, 202cH, and 1002cH and their diluent medium 90% ethanol in 8cH and 202cH were used in the present study. Laser Raman spectra of all the samples were obtained in the wave number region of 2400 – 4200 cm-1. The intensity ratio at vibration frequencies between 3200 and 3420 (R1) and that between 3620 and 3420 (R2) were calculated for each UHD of the samples. 
 Results: The spectra show a marked difference in intensities in the stretching vibrations of CH and OH groups of all the samples. R1 values for three UHDs of Calc. and Sep. show negative and positive relationships, respectively. In the case of R2 values, the relationship in three UHDs is 81002 for Calc., and 8> 202 < 1002 for Sep. In the case of control (ethanol UHDs) both R1 and R2 show a negative relationship.
 Conclusion: R1 denotes a relative number of OH groups with strong and weak hydrogen bonds. R2 indicates the relative number of OH groups with broken and weak H-bonds. Therefore, the UHDs of the two drugs and the control are different from each other with respect to hydrogen bond strength of OH groups and the number of free OH groups or non-hydrogen bonded water molecules.