PCB-integrated optical waveguide sensors: An ammonia gas sensor

This paper presents a novel platform for the formation of cost-effective PCB-integrated optical waveguide sensors. The sensor design relies on the use of multimode polymer waveguides that can be formed directly on standard PCBs and commercially-available chemical dyes, enabling the integration of all essential sensor components (electronic, photonic, chemical) on low-cost substrates. Moreover, it enables the detection of multiple analytes from a single device by employing waveguide arrays functionalised with different chemical dyes. The devices can be manufactured with conventional methods of the PCB industry, such as solder-reflow processes and pick-and-place assembly techniques. As a proof of principle, a PCB-integrated ammonia gas sensor is fabricated on a FR4 substrate. The sensor operation relies on the change of the optical transmission characteristics of chemically functionalised optical waveguides in the presence of ammonia molecules. The fabrication and assembly of the sensor unit, as well as fundamental simulation and characterisation studies, are presented. The device achieves a sensitivity of approximately 30 ppm and a linear response up to 600 ppm at room temperature. Finally, the potential to detect multiple analytes from a single device is demonstrated using principal-component analysis. © 1983-2012 IEEE.

Treatment of nonlinear optical properties due to large amplitude anharmonic vibrational motions: umbrella motion in NH3

A general reduced dimensionality finite field nuclear relaxation method for calculating vibrational nonlinear optical properties of molecules with large contributions due to anharmonic motions is introduced. In an initial application to the umbrella (inversion) motion of NH3 it is found that difficulties associated with a conventional single well treatment are overcome and that the particular definition of the inversion coordinate is not important. Future applications are described

Anharmonic force constant calculations

The relationship of the anharmonic force constants in curvilinear internal coordinates to the observed vibration-rotation spectrum of a molecule is reviewed. A simplified method of setting up the required non-linear coordinate transformations is described: this makes use of an / tensor, which is a straightforward generalization of the / matrix used in the customary description of harmonic force constant calculations. General formulae for the / tensor elements, in terms of the familiar L matrix elements, are presented. The use of non-linear symmetry coordinates and redundancies are described. Sample calculations on the water and ammonia molecules are reported.

Mechanism of the formation and properties of antimony polyphosphate

Formation of antimony polyphosphate using Sb2O3 and/or (NH4)2HPO4 and NH4H 2PO4 as starting materials has been simulated by thermal analysis technique. The elimination of water and ammonia molecules induced by heating leads to the formation of intermediate ammonium polyphosphate, which subsequently reacts with Sb2O3. Morphologically, vitreous Sb(PO3)3 is composed of plaques having irregular shapes. Infrared spectra and NMR study is consistent with tetrametaphosphate anion arrangement. The compound is thermally unstable and may be recommended as a donor of -O-P-O- linkers in the preparation of special phosphate glasses. © 2005 Akadémiai Kiadó, Budapest.

Reaktionen monovalenter Münzmetalle in flüssigem Ammoniak

Im Rahmen dieser Arbeit konnten erstmals eine Reihe von Ammoniakaten von Münzmetallhalogeniden (M(I)Hal) und Pseudohalogeniden aus flüssigem Ammoniak in einkristalliner Form isoliert und strukturell charakterisiert werden. Mit dem Ammoniakat des Gold(I)-iodids wurden Metathesen in flüssigem Ammoniak durchgeführt, die die Isolierung einiger sehr thermolabiler, teilweise explosiver Alkoholate des Golds ermöglichten. Die Bestimmung der Kristallstruktur eines Gold(I)-phenolates erlaubte erste Einblicke in deren Aufbau.rnIn der Reihe der Ammoniakate der M(I)Hal mit Ausnahme von Silberiodid, werden keine direkten Metall-Halogen-Kontakte ausgebildet. Die Ammoniakate der Chloride und Bromide des Kupfers und Silbers sowie des Kupferiodids besitzen isotype Strukturen. Sie liegen als Trisammoniakate [M(NH3)3]Hal vor. Im Ammoniakat von Silberiodid besitzen die Silberionen durchgängig die Koordinationszahl 4. Neben Ag•••NH3- findet man auch direkte Kationen-rnAnionen-Kontakte und sehr kurze Ag(I)-Ag(I)-Abstände. Das Goldkation im Ammoniakat von Goldiodid besitzt die Koordinationszahl 2 und wird ausschließlich durch Ammoniakmoleküle koordiniert. Die gebildeten H3N-NH3-Hanteln werden über aurophile Wechselwirkungen verknüpft.rn rnDie Ammoniakate der Cyanide von Silber und Gold, enthalten molekulare Baueinheiten des Typs:(H3N)nMCN [(n= 1 für M= Au und n= 2 für M= Ag].rnrnAnders als bei den solvatfreien Homologen wird eine Ausbildung von Polymerketten nicht beobachtet. Das linear aufgebaute Ammoniakat von Goldcyanid ermöglicht die Ausbildung von aurophilen Wechselwirkungen. Metallophile Wechselwirkungen zwischen dem als Dimer vorliegenden Ammoniakat von AgCN scheinen nicht ausgebildet zu werden.rnrnMetatheseversuche von Goldiodid mit einem Amid und diversen Alkanolaten lieferten teilweise explosive Produkte. Es ist davon auszugehen, dass mit zunehmender Basizität der eingesetzten Anionen, die an das Gold(I)-ion koordinierten Ammoniakmoleküle deprotoniert werden und explosives Goldamid gebildet wird. Der als zweites Produkt entstehende Alkohol kann ebenfalls ein Ammoniakat bilden. Im Fall von Li-Fencholat wird ein solches in Form sehr tiefschmelzender Einkristalle erhalten.rnrnDa die Deprotonierung der an Gold koordinierten Ammoniakmoleküle unweigerlich zu explosiven oder sehr instabilen Produkten führt, wurde die geringere Basizität der Phenolate ausgenutzt, um dies zu umgehen. Im Falle der Umsetzung von AuI mit Li-2,6-di-tert.-butylphenolat gelang tatsächlich die Isolierung eines kristallinen Gold(I)-phenolats.rn

Covariance analysis of the Coulomb explosion of ammonia induced by intense nanosecond laser at 532 nm

The Coulomb explosion of ammonia clusters induced by nanosecond laser at 532 not with an intensity of similar to 10(12) Wcm(-2) has been studied by time of flight mass spectrometry. The dominant multiply charged ions are N3+ and N2+ with kinetic energies of 110 and 50 eV respectively. The electrons generated from the multiphoton ionization are heated through inverse bremsstrahlung by the laser field when colliding with neutral or ionic particles. When their energies surpass the corresponding ionization potentials of the molecules or ions, the subsequent electron impact ionization may take place thus resulting in multi-charged nitrogen ions. Covariance analysis is made to study the possible pathways of the Coulomb explosion.

Determination of ammonia based on the electro-oxidation of hydroquinone in dimethylformamide or in the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The results detail a novel methodology for the electrochemical determination of ammonia based on its interaction with hydroquinone in DMF. It has been shown that ammonia reversibly removes protons from the hydroquinone molecules, thus facilitating the oxidative process with the emergence of a new wave at less positive potentials. The analytical utility of the proposed methodology has been examined with a linear range from 10 to 95 ppm and corresponding limit-of-detection of 4.2 ppm achievable. Finally, the response of hydroquinone in the presence of ammonia has been examined in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide, [EMIM][N(Tf)(2)]. Analogous voltammetric waveshapes to that observed in DMF were obtained, thereby confirming the viability of the method in either DMF or [EMIM][N(Tf)(2)] as solvent. (C) 2003 Elsevier B.V. All rights reserved.

Comparison of Model Chemistry and Density Functional Theory Thermochemical Predictions with Experiment for Formation of Ionic Clusters of the Ammonium Cation Complexed with Water and Ammonia; Atmospheric Implications

The G2, G3, CBS-QB3, and CBS-APNO model chemistry methods and the B3LYP, B3P86, mPW1PW, and PBE1PBE density functional theory (DFT) methods have been used to calculate ΔH° and ΔG° values for ionic clusters of the ammonium ion complexed with water and ammonia. Results for the clusters NH4+(NH3)n and NH4+(H2O)n, where n = 1−4, are reported in this paper and compared against experimental values. Agreement with the experimental values for ΔH° and ΔG° for formation of NH4+(NH3)n clusters is excellent. Comparison between experiment and theory for formation of the NH4+(H2O)n clusters is quite good considering the uncertainty in the experimental values. The four DFT methods yield excellent agreement with experiment and the model chemistry methods when the aug-cc-pVTZ basis set is used for energetic calculations and the 6-31G* basis set is used for geometries and frequencies. On the basis of these results, we predict that all ions in the lower troposphere will be saturated with at least one complete first hydration shell of water molecules.

Ability of the PM3 Quantum Mechanical Method to Model Intermolecular Hydrogen Bonding between Neutral Molecules

The PM3 semiempirical quantum-mechanical method was found to systematically describe intermolecular hydrogen bonding in small polar molecules. PM3 shows charge transfer from the donor to acceptor molecules on the order of 0.02-0.06 units of charge when strong hydrogen bonds are formed. The PM3 method is predictive; calculated hydrogen bond energies with an absolute magnitude greater than 2 kcal mol-' suggest that the global minimum is a hydrogen bonded complex; absolute energies less than 2 kcal mol-' imply that other van der Waals complexes are more stable. The geometries of the PM3 hydrogen bonded complexes agree with high-resolution spectroscopic observations, gas electron diffraction data, and high-level ab initio calculations. The main limitations in the PM3 method are the underestimation of hydrogen bond lengths by 0.1-0.2 for some systems and the underestimation of reliable experimental hydrogen bond energies by approximately 1-2 kcal mol-l. The PM3 method predicts that ammonia is a good hydrogen bond acceptor and a poor hydrogen donor when interacting with neutral molecules. Electronegativity differences between F, N, and 0 predict that donor strength follows the order F > 0 > N and acceptor strength follows the order N > 0 > F. In the calculations presented in this article, the PM3 method mirrors these electronegativity differences, predicting the F-H- - -N bond to be the strongest and the N-H- - -F bond the weakest. It appears that the PM3 Hamiltonian is able to model hydrogen bonding because of the reduction of two-center repulsive forces brought about by the parameterization of the Gaussian core-core interactions. The ability of the PM3 method to model intermolecular hydrogen bonding means reasonably accurate quantum-mechanical calculations can be applied to small biologic systems.

Ammonia effects on proton conductivity properties of coordination polymers

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Positive correlation of male and female Bactrocera tryoni (Froggatt) (Diptera: Tephritidae) catches in orange-ammonia traps

Populations of the Queensland fruit fly, Bactrocera tryoni, are routinely monitored using cue-lure, a male-only attractant. Such monitoring provides no information about females and there is little information available to show if male and female B. tryoni numbers are correlated in the field. Using a data set of 1 148 weekly clearances of orange-ammonia baited traps, which catch both males and females, the correlation between male and female numbers was tested for 48 weeks of the year (four weeks each month) and for the combined data set. Weekly male and female trap catches were almost entirely highly correlated, regardless of mean population size or time of year. For the whole year, the correlation between male and female numbers was r = 0.722, significant at p<0.001. Results suggest that changes in the number if male B. tryoni, as detected through cue-lure sampling, will reflect changes in numbers of female B. tryoni.

Manipulating double-decker molecules at the liquid-solid interface

We have used a scanning tunneling microscope to manipulate heteroleptic phthalocyaninato, naphthalocyaninato, porphyrinato double-decker molecules at the liquid/solid interface between 1-phenyloctane solvent and graphite. We employed nano-grafting of phthalocyanines with eight octyl chains to place these molecules into a matrix of heteroleptic double-decker molecules; the overlayer structure is epitaxial on graphite. We have also used nano-grafting to place double-decker molecules in matrices of single-layer phthalocyanines with octyl chains. Rectangular scans with a scanning tunneling microscope at low bias voltage resulted in the removal of the adsorbed doubledecker molecular layer and substituted the double-decker molecules with bilayer-stacked phthalocyanines from phenyloctane solution. Single heteroleptic double-decker molecules with lutetium sandwiched between naphthalocyanine and octaethylporphyrin were decomposed with voltage pulses from the probe tip; the top octaethylporphyrin ligand was removed and the bottom naphthalocyanine ligand remained on the surface. A domain of decomposed molecules was formed within the double-decker molecular domain, and the boundary of the decomposed molecular domain self-cured to become rectangular. We demonstrated a molecular “sliding block puzzle” with cascades of double-decker molecules on the graphite surface.