A Post‐Synthetically Modified MOF for Selective and Sensitive Aqueous‐Phase Detection of Highly Toxic Cyanide Ions

Selective and sensitive detection of toxic cyanide (CN^?) by a post‐synthetically altered metal–organic framework (MOF) has been achieved. A post‐synthetic modification was employed in the MOF to incorporate the specific recognition site with the CN^? ion over all other anions, such as Cl^?, Br^?, and SCN^?. The aqueous‐phase sensing and very low detection limit, the essential prerequisites for an effective sensory material, have been fulfilled by the MOF. Moreover, the present detection level meets the standard set by the World Health Organization (WHO) for the permissible limit of cyanide concentration in drinking water. The utilization of MOF‐based materials as the fluorometric probes for selective and sensitive detection of CN^? ions has not been explored till now.     

Coordination polymers of La(III) as bunched infinite nanotubes and their conversion into an open-framework structure

Pyridine-2,6-dicarboxylic acid (pdcH2) reacts with LaCl3 x 7H2O under hydrothermal conditions followed by evaporation at room temperature to give a metal-organic framework structure of the empirical formula, [La(pdc)(H2O)4] x Cl (1), in the form of infinitely long bunched nanotubes. The chloride ions and water molecules occupy the tubular as well as the inter-tubular spaces. When La(NO3)3 x 7H2O is used in place of LaCl3 x 6H2O, a similar structure is formed with the empirical formula, [La(pdc)(H2O)4] x NO3 (2), where water molecules and the nitrate anions occupy the voids as in the case of 1. When an aqueous solution of AgNO3 is added to an aqueous solution of 1, the Cl- ions are replaced completely by NO3- ions to form 2; thus, the tubular structure is conserved. However, when AgBF4 is used in place of AgNO3, the tubular structure breaks down, and a new 3-D MOF structure, [La(pdc)(pdcH)(H2O)2] x 4H2O (3), is formed where the cavities are occupied by hexameric and dimeric water clusters. Structure 3 is also formed as the sole product when La(OAc)3 x xH2O is treated with pyridine-2,6-dicarboxylic acid following the method adopted for 1 and 2. Formation of the tubular structure depends on the molar ratio of the ligand and the metal. When higher than 1 equiv of the metal is taken, a linear coordination polymer, [La2(pdc)3(H2O)6] x 2H2O (4), is formed. This study provides the first nanotubular structure of a pure lanthanide metal.     

White-beam X-ray diffraction and radiography studies on high-boron-containing borosilicate glass at high pressures

ABSTRACT

Multi-angle energy-dispersive X-ray diffraction studies and white-beam X-ray radiography were conducted with a cylindrically shaped (1?mm diameter and 0.7?mm high) high-boron-content borosilicate glass sample (17.6% B₂O₃) to a pressure of 13.7?GPa using a Paris-Edinburgh (PE) press at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The measured structure factor S(q) to large q?=?19 Å^?1 is used to determine information about the internuclear bond distances between various species of atoms within the glass sample. Sample pressure was determined with gold as a pressure standard. The sample height as measured by radiography showed an overall uniaxial compression of 22.5% at 13.7?GPa with 10.6% permanent compaction after decompression to ambient conditions. The reduced pair distribution function G(r) was extracted and Si–O, O–O and Si–Si bond distances were measured as a function of pressure. Raman spectroscopy of the pressure recovered sample as compared to starting material showed blue-shift and changes in intensity and widths of Raman bands associated with silicate and four-coordinated boron.     

X-Ray Analysis of N'-Acetyl-4-formyl-N'-phenylbenzohydrazide

Crystallography Reports - This communication is devoted to the X-ray diffraction study of a single crystal of the compound N '-acetyl-4-formyl-N '-phenylbenzohydrazide. The...     

Bivariate Entropy Analysis of Electrocardiographic RR–QT Time Series

QT interval variability (QTV) and heart rate variability (HRV) are both accepted biomarkers for cardiovascular events. QTV characterizes the variations in ventricular depolarization and repolarization. It is a predominant element of HRV. However, QTV is also believed to accept direct inputs from upstream control system. How QTV varies along with HRV is yet to be elucidated. We studied the dynamic relationship of QTV and HRV during different physiological conditions from resting, to cycling, and to recovering. We applied several entropy-based measures to examine their bivariate relationships, including cross sample entropy (XSampEn), cross fuzzy entropy (XFuzzyEn), cross conditional entropy (XCE), and joint distribution entropy (JDistEn). Results showed no statistically significant differences in XSampEn, XFuzzyEn, and XCE across different physiological states. Interestingly, JDistEn demonstrated significant decreases during cycling as compared with that during the resting state. Besides, JDistEn also showed a progressively recovering trend from cycling to the first 3 min during recovering, and further to the second 3 min during recovering. It appeared to be fully recovered to its level in the resting state during the second 3 min during the recovering phase. The results suggest that there is certain nonlinear temporal relationship between QTV and HRV, and that the JDistEn could help unravel this nuanced property.     

Synthesis,Characterization, and Crystal Structure of (E)-4-(2-(4-Cyanobenzylidene)hydrazinyl)benzonitrile Dimethyl Sulfoxide Hemisolvate

Crystallography Reports - (E)-4-(2-(4-Cyanobenzylidene)hydrazinyl)benzonitrile dimethyl sulfoxide hemisolvate, C15H10N4 ⋅ 0.5C2H6OS is synthesized following a green protocol and its crystal...     

Structural Features of <Emphasis Type="Italic">Ortho</Emphasis>-hydroxy Bis-phenols and Their Comparison with <Emphasis Type="Italic">Para</Emphasis>-hydroxy Bis-phenols

Abstract The crystal structures of four bis-phenols are reported to substantiate the fact that the weak interactions play a major role in the crystal packing of bis-phenols. The reaction of 2,4-dimethylphenol with aldehydes such as 2-naphthaldehyde, terephthaldehyde in the presence of trifluoracetic acid gave 2-[bis(2-hydroxy 3,5-dimethylphenyl)methyl]naphthalene (1) and 4-[bis(2-hydroxy 3,5-dimethylphenyl) methyl]benzaldehyde (2), respectively. The 2-[bis-(2-hydroxy 3,5-dimethylphenyl)-methyl]naphthalene (1) crystallizes in orthorhombic, Pbca, a = 11.905(3) ?, b = 18.788(5) ?, c = 18.894(5) ?, 4-[bis(2-hydroxy 3,5-dimethylphenyl)methyl] benzaldehyde (2) in monoclinic, Cc, a = 8.880(3) ?, b = 16.394(7) ?, c = 13.700(5) ?, γ = 104.542(2)°. The reaction of 2-nitrobenzaldehyde with 2,4-dimethylphenol gave 2-benzo[c] isoxazo-3-yl 4,6-dimethylphenol (3) and its crystal parameters are orthorhombic, P2₁2₁2₁, a = 7.737(6) ?, b = 11.885(9) ?, c = 13.336(8) ?. The reaction of 2,6-dimethylphenol with 4-nitrobenzaldehyde and 2-chlorobenzaldehyde gave bis(4-hydroxy 3,5-dimethylphenyl)(4-nitrophenyl)methane (4) and bis(4-hydroxy 3,5-dimethylphenyl)(2-chlorophenyl)methane (5), respectively. The bis(4-hydroxy 3,5dimethylphenyl)(4-nitrophenyl)methane (4) crystallizes in monoclinic, C2/c, a = 25.921(1) ?, b = 12.202(4) ?, c = 15.6084(7) ?, β = 122.172(4)°, and bis(4-hydroxy 3,5-dimethylphenyl) (2-chlorophenyl)methane crystallizes as acetonitrile solvate (5) in triclinic, P-1, a = 12.314(3) ?, b = 14.111(3) ?, c = 15.078(5) ?, α = 98.268(2)°, β = 111.268(2)°, γ = 114.304(1)˚. The unit cell of 5 contains two pairs of crystallographically unsymmetric molecules of bis-phenols. Index abstract The crystal structures of four bis-phenols are reported to substantiate the fact that the weak interactions plays a major role in crystal packing and can induce symmetry non-equivalence among bis-phenols in unit cell of bis-phenols.      

Analysis of urinary stone constituents using powder X-ray diffraction and FT-IR

Constituents of urinary stones obtained from various patients from western part of India, which is a highly urinary stone disease-prone area, have been analysed. Eight stones from four patients were collected through urologists and have been analysed using powder X-ray diffraction and FT-IR. Thermogravimetric analysis (TGA) and scanning electron microscopic (SEM) image of selected samples were also carried out. The analysis revealed that calcium oxalate monohydrate, which is also known as whewellite, is the common constituent of all of the stones, particularly at the initial stage of stone formation. However, multi phases viz. whewellite phase, and hydroxyl and carbonate apatite phases are also detected in the case of third and fourth patients, from where multiple stones were obtained. Interestingly, in these mixed phase stones the concentration of whewellite decreases with increasing the concentration of apatite phases. Thermal behaviour of the whewellite phase was studied by TGA and variable temperature XRD analysis. Morphology of the whewellite and apatite phases, examined by SEM image, has also been reported.     

Experimental validation of computational fluid dynamics modeling for narrow tillage tool draft

Energy requirement of a tillage tool, mostly represented by tool draft, is a function of different soil–tool interaction components like soil parameters, tool parameters and system parameters. Soil–tool interaction modeling was conducted using computational fluid dynamics (CFD) approach considering soil as a Bingham material. Soil bin tests were conducted to validate tool draft predictions obtained from this numerical modeling. Numerical predictions and soil bin experiments for the tool draft were observed with 40 mm wide vertical tool operating at four different depths of 40, 80, 120, and 160 mm. The tool was operated at four different operating speeds of 1, 8, 16 and 24 km h⁻¹ in clay loam soil with two moisture contents of 14% and 20%. Thus, the experimental design consisted in a (2 × 4 × 4) complete randomized factorial with two replications for each test. Simulation results over-predicted tool draft in comparison to the experimental values. The difference between the predicted and measured draft were not consistent and ranged from 1% to 42%, with an average of 24% and 22% for moisture contents of 14% and 20%, respectively. The agreement of simulation data with experimental values was higher at shallow depth of operation and lower tool operating speed. The correlation coefficient between the simulation and experimental draft were found to vary from 0.9275 to 0.9914.