Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylsulfonyl]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenyisulfonyI]propanamides Y-PhSO(2)CH(Me)C(O)N(OMe)Me (Y = OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by HF/6-31G(d,p) calculations of 3,, indicated the existence of two gauche conformers (g(1) and g(2)), the g, conformer being the most stable and the least polar one (in gas phase and in solution). Both conformers are present in solution of the non polar solvent (CCl(4)) for 1-5 and in solution of the more polar solvents (CHCl(3)) for 1. 4, 5 and (CH(2)Cl(2)) for 5, while only the g(1) conformer is present in solution of the most polar solvent (CH(3)CN) for 1-5. The g, and g2 conformers correspond to the enantiomeric pairs of diastereomers (diast(1) and diast(2)) whose relative configurations are [C(3)(R)N(R)]/[C(3)(s)N(s)] and [C(3)(R)N(s)]/[C(3)(s)N(R)], respectively. The computed carbonyl frequencies for g(1) (diast(1)) and g(2) (diast(2)) stereoisomers of3 match well the experimental values. The NBO analysis, for 3 shows the important role of the orbital interactions in conformer stabilization and the overall balance of these interactions corroborates that the g, conformer is more stable than the 92 one. The observed abnormal solvent effect on the relative intensities of the carbonyl doublet components is attributed to the molecular crowding in the g2 conformer which hinders its solvation in comparison to the g, conformer (diast(1)). X-ray single crystal analysis performed for 3 shows the existence Of two 92, and g(1b) conformers of diastereomers (diast2, and diast(1b)) whose absolute configurations are [C(3)(R)N(s)] and [C(3)(R)N(R)], respectively. The larger population and. thus, the larger stabilization of the g(2), conformer over the gib form in the crystals may be associated with a larger energy gain deriving from dipole moment coupling in the former conformer along with a series of C-H center dot center dot center dot O electrostatic and hydrogen bond interactions, (C) 2009 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylthio]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenylthio]propanamides Y-PhSCH(Me)C(O)N(OMe)Me (Y=OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by B3LYP/cc-pVDZ calculations of 3, indicated the existence of two gauche conformers (g(1) and g(2)), the g(1) conformer being the more stable and the less polar one (in gas phase and in solution). Both conformers are present in solution of the polar solvents (CH(2)Cl(2) and CH(3)CN) for 1-5 and in solution of the less polar solvent (CHCl(3)) for 1-4, while only the g(1) conformer is present in solution of non polar solvents (n-C(6)H(14) and CCl(4)) and in solution of CHCl(3) for 5. NBO analysis shows that both the sigma(C-S) -> pi*(C=O) (hyperconjugative) and the pi(C=O) -> sigma*(C-S) orbital interactions contribute almost to the same extent for the stabilization of g(1) and g(2) conformers. The pi*(C=O) -> sigma*(C-S), n(S) -> pi*(C=O) and the n(S) -> pi*(C=O) orbital interactions stabilize more the g(1) conformer than the g(2) one. Moreover, the suitable geometry of the g(1) conformer leads to its stabilization through the LP(O2) -> sigma*(C8-H11) orbital interaction (hydrogen bond) along with the strong O([CO])(delta-) center dot center dot center dot H([O-Ph])(delta+) electrostatic interaction. On the other hand, the appropriate geometry of the g(2) conformer leads to its stabilization by the LP(O22) -> sigma*(C9-H13) orbital interaction (hydrogen bond) along with the weak O([OMe])(delta-) center dot center dot center dot H([o`-Ph])(delta+) electrostatic static interaction. As for the 4`-nitro derivative 5 the ortho-phenyl hydrogen atom becomes more acidic, leading to a stronger O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) interaction and, thus, into a larger stabilization of the g(1) conformer in the whole series. This trend is responsible for the unique IR carbonyl band in CHCl(3) solution of 5. The larger occupancy of the pi*(C=O) orbital of the g(1) conformer relative to that of the g(2) conformer, along with the O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) electrostatic interaction (hydrogen bond) justifies the lower carbonyl frequency of the g(1) conformer with respect to the g(2) one, in gas phase and in solution. (C) 2008 Elsevier B.V. All rights reserved.

Conformational and electronic interaction studies of some p-substituted alpha-methylsulfonyl-alpha-diethoxyphosphorylacetophenones

The analysis of the IR carbonyl band of the alpha-methylsulfonyl-alpha-diethoxyphosphoryl p-substituted acetophenones p-Y-Ph-C(O)CH(SO(2)Me)[P(O)(OEt)(2)] (Y = OMe 1, H 2, F 3, Cl 4, Br 5 and NO(2) 6) supported by HF/6-31G(d,p) ab initio calculations of the alpha-methylsulfonyl-alpha-diethoxyphosphoryl acetophenone 2, indicated the existence of a single stable cl conformer in gas phase and in solvents of increasing polarity, along with the presence of second less stable conformation in gas phase. The cl conformer present the (SO(2)Me) group and the [P(O)(OEt(2))] groups in a syn-clinal (gauche) geometry and is stabilised through of the 0(`60)... P(%), 01NO(owl Crco), ONO)... C(,C*.), 060)... S(`S`02.,) and 0(`S-02) q o) electronic interactions 08along with H(8S*o2M,). 0(660). HU(5C_H2)lP0Erl- 0(8so2m), H(6 +Ph)- - - (co) and H(8o+`-Ph). 0( `Po) intramolecular hydrogen bonds. The almost co nstant negative carbonyl frequency shifts (Av) for the title compounds 1-6 with respect to the parent acetophenones 7-14 corroborates the prevalence of the electronic interactions over the -l(y inductive effect of the ot-substituents for the title compounds and gives strong support for the existence of the crossed 0`(`C-O)... S`(1S+02m,) and 0(""S-02) C(`C+O) (charge transfer and electrostatic); 08-) (co P(`i o) and 01`M-OFt)l C(` o), (electrostatic) interactions. 0 2008 Elsevier B.V. All rights reserved.

Gas-Phase Acylium Ion Transfer Reactions Mediated by a Proton Shuttle Mechanism

The mechanism and the energy profile of the gas-phase reaction that mimics esterification under acidic conditions have been investigated at different levels of theory. These reactions are known to proceed with rate constants close to the collision limit in the gas-phase and questions have been raised as to whether the typical addition-elimination mechanism via a tetrahedral intermediate can explain the ease of these processes. Because these reactions are common to many organic and biochemical processes it is important to understand the intrinsic reactivity of these systems. Our calculations at different levels of theory reveal that a stepwise mechanism via a tetrahedral species is characterized by energy barriers that are inconsistent with the experimental results. For the thermoneutral exchange between protonated acetic acid and water and the exothermic reaction of protonated acetic acid and methanol our calculations show that these reactions proceed initially by a proton shuttle between the carbonyl oxygen and the hydroxy oxygen of acetic acid mediated by water, or methanol, followed by displacement at the acylium ion center. These findings suggest that the reactions in the gas-phase should be viewed as an acylium ion transfer reaction. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1596-1606, 2011

Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4 `-substituted)phenylsulfonyl]acetamides

The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4`-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

Conformational preferences for some 2-substituted N-methoxy-N-methylacetamides through spectroscopic and theoretical studies

The analysis of the IR carbonyl band of the 2-substituted N-methoxy-N-methylacetamides Y-CH(2)C(O)-N(OMe)Me (Y = F1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1-4, indicated the existence of cis-gauche conformers i.e. (c) and (g) for 1 and 3, (c(1), c(2)) and (g(1), g(2)) for 2, and (c) and (g(1), g(2)) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the (c(1) + c(2)) population prevails over the (g(1) + g(2)) one for 2, and the (g(1) + g(2)) conformer population is more abundant than (c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1-3. The occurrence of Fermi resonance in the nu(CO) region, in n-hexane, precludes the estimative of relative populations of the (c, g(1), g(2)) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the nu(CO) band component relative intensities for 1-3. NBO analysis showed that the n(N) -> pi.(CO), orbital interaction is the main factor which stabilizes the gauche (g, g(1), g(2)) conformers for 1-4 into a larger extent relative to the cis (c, c(1), c(2)) ones. The n(y) -> pi(.)(Co,) sigma(C-Y) -> pi.(CO,) pi(CO) -> sigma(C-Y) and 7co orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1-4 is responsible for the occurrence of Y(delta)-(4)center dot center dot center dot O(delta)-(9) and Y(delta)-(4)center dot center dot center dot N(delta)-(7) short contacts in the gauche (g, g(1), g(2)) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche (g, g(1), g(2)) and cis (c, c(1), c(2)) conformers, both in the gas phase and in the solution for 1-4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy-N-methyl acetamides 1-3, bearing in a first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N,N-dialkyl-acetamides. (C) 2010 Elsevier B.V. All rights reserved.

Anaerobic treatment of juice and fruit-processing effluents

Effluents from the juice and fruit processing industries have high organic matter content. Discharge of these effluents without appropriate treatment would therefore have a negative impact on the environment. High organic contents and low contamination levels make such effluents suitable for biological treatment, especially anaerobic digestion. In the latter process, significant amounts of digester gas can be produced, turning a waste stream into a source of renewable energy that can be used for electricity and heat production, leading to financial benefits.This paper investigates the feasibility of anaerobic digestion and the gas generation potential of five different effluents from the carrot-juice, orange-juice and sultana processing industries. Benefits are assessed in terms of digester gas production and organic matter reduction. The results show that the specific gas production ranges between 665 and 860 m3 per tonne of effluent treated (as organic dry matter). Furthermore, nearly 100% of the organic matter is converted into gas in the case of the carrot- and orange-juice processing residues, while a 84.5% reduction of the organic matter was found to be achievable in the case of the sultana wastes. While these results are promising, further testing will be required to validate them in a larger scale.

Experimental investigation and numerical simulation of heat transfer in quenching fluidised beds

Fluidisation characteristics at different surfaces of a work-piece of complex geometry are conducted in a fluidised bed at various conditions including fluidising number, bed temperature and fluidising medium. The quenching of the work-piece is performed experimentally. In particular, the major frequency and energy of the pressure fluctuations are measured as a function of either fluidising velocity or heat transfer position and the results are used to develop a mathematic model. A computational model is developed to simulate gas dynamics and heat transfer between the fluidised bed and the work-piece surface, as well as simulating the temperature within the work-piece. The predicted cooling curves are in good agreement with the experimental results. Based on the simulation results, the flow characteristics of the gas and the temperature of the dense gas-solid phase near the work-piece surface are analysed to understand the heat transfer mechanism in the fluidised bed.

The TRIPS agreement and developing countries: a discussion of the paragraph 6 of the Doha declaration on public health

The Paragraph 6 solution arrived on 30th August 2003 to facilitate export of drugs to the countries which were not able to manufacture said drugs shows the total marginalization of developing countries in international treaty negotiations. A simple proposal by developing counties to use Article 30 of the TRIPS Agreement for such manufacture and export to non-manufacturing countries in order to avoid expensive litigations with the pharmaceutical multinationals took an ugly turn where not only the said proposal was totally rejected but export was added as one of the patenting rights in the TRIPS Agreement with payment of remuneration to patent holders. This introduction of export as one of the patenting rights was surrounded by a thicket of rules on the plea that such products would be diverted to ensure that the needing countries never acquire the requisite drugs. This article analyses the events leading to the establishment of the TRIPS Agreement, the elimination of developing countries from such negotiations through the use of suitably placed officials in the negotiating forums, the role of CEOs of the multinationals and the business NGOs such as International Intellectual Property Alliance and IPC (Intellectual Property Committee), epistemic community consisting of individuals such as Jacques Gorlin and Eric Smith and the subsequent development leading to the finalization of Para 6 Solution, which was an exact replication of events during the TRIPS negotiations. The analysis suggests that developing countries do not have any say in international negotiations and their agreements to such negotiations are essentially to legitimize their colonized existence.

Improvement of adhesion of conductive polypyrrole coating on wool and polyester fabrics using atmospheric plasma treatment

In this paper wool and polyester fabrics were pretreated with atmospheric plasma glow discharge (APGD) to improve the ability of the substrate to bond with anthraquinone-2-sulfonic acid doped conducting polypyrrole coating. A range of APGD gas mixtures and treatment times were investigated. APGD treated fabrics were tested for surface contact angle, wettability and surface energy change. Effect of the plasma treatment on the binding strength was analyzed by studying abrasion resistance, surface resistivity and reflectance. Investigations showed that treated fabrics exhibited better hydrophilicity and increased surface energy. Surface treatment by an APGD gas mixture of 95% helium/5% nitrogen yielded the best results with respect to coating uniformity, abrasion resistance and conductivity.

Photodegradation, interaction with iron oxides and bioavailability of dissolved organic matter from forested floodplain sources

Photochemical degradation of dissolved organic matter (DOM) can influence food webs by altering the availability of carbon to microbial communities, and may be particularly important following periods of high DOM input (e.g. flooding of forested floodplains). Iron oxides can facilitate these reactions, but their influence on subsequent organic products is poorly understood. Degradation experiments with billabong (= oxbow lake) water and river red gum (Eucalyptus camaldulensis) leaf leachate were conducted to assess the importance of these reactions in floodplain systems. Photochemical degradation of DOM in sunlight-irradiated quartz tubes (with and without amorphous iron oxide) was studied using gas chromatography and UV-visible spectroscopy. Photochemical reactions generated gaseous products and small organic acids. Bioavailability of billabong DOM increased following irradiation, whereas that of leaf leachate was not significantly altered. Fluorescence excitation-emission spectra suggested that the humic component of billabong organic matter was particularly susceptible to degradation, and the source of DOM influenced the changes observed. The addition of amorphous iron oxide increased rates of photochemical degradation of leachate and billabong DOM. The importance of photochemical reactions to aquatic systems will depend on the source of the DOM and its starting bioavailability, whereas inputs of freshly formed iron oxides will accelerate the processes.

A low-cost intelligent gas sensing device for military applications

The field of electronic noses and gas sensing has been developing rapidly since the introduction of the silicon based sensors. There are numerous systems that can detect and indicate the level of a specific gas. We introduce here a system that is low power, small and cheap enough to be used in mobile robotic platforms while still being accurate and reliable enough for confident use. The design is based around a small circuit board mounted in a plastic case with holes to allow the sensors to protrude through the top and allow the natural flow of gas evenly across them. The main control board consists of a microcontroller PCB with surface mount components for low cost and power consumption. The firmware of the device is based on an algorithm that uses an Artificial Neural Network (ANN) which receives input from an array of gas sensors. The various sensors feeding the ANN allow the microcontroller to determine the gas type and quantity. The Testing of the device involves the training of the ANN with a number of different target gases to determine the weightings for the ANN. Accuracy and reliability of the ANN is validated through testing in a specific gas filled environment.

UnitingCare West Outreach Services and the Good Lives Model of offender rehabiliation

UnitingCare West is a not-for-profit community services organisation committed to achieving justice, hope and opportunity for all, and works to support and empower in particular those most in need in the WA community. Through its program Outreach Services, it delivers a specialist re-entry service for sex offenders and men serving life and indeterminate sentences. The program has recently been reviewed by Dr Andrew Day from the Centre for Offender Reintegration, Deakin University with input from Dr Tony Ward, University of Victoria, Wellington, New Zealand. In this paper we describe the aims of the review, the process and findings and our ongoing work in developing a rationale for the service that is underpinned by the Good Lives Model (GLM) of offender rehabilitation. More generally, the presentation will seek to understand the needs of offenders who re-enter the community following long-term imprisonment in relation to those areas of need identified in the GLM.

Dynamic characteristics and efficiency of a fluidized bed heat treatment process

The dynamic characteristics of gas bubbles in fluidized beds are important to determine the heat and mass transfer rates at component surfaces and the treated profiles of components. They also have great impact on the components’ structural, mechanical and physical properties. However, it has been very difficult to monitor those characteristics dynamically. In this paper, a specifically designed fluidized bed was introduced to facilitate the capturing of its dynamic characteristics and a new video image processing and analysis algorithm was developed. The algorithm is robust and adaptive in terms of locating both bubbles and components in beds with a single or multiple components. It has many advantages in dynamic characterization of gas bubbles and monitoring component treatment. By using this algorithm, the properties of gas bubbles over any period of time can be accurately obtained. This technology will provide a potential on-line dynamic monitoring and quality control system for the chemical heat treatment processes with fluidized beds.

Exposure to fumes and gases during welding operations

The exposure to fumes and gases is one of the hazards associated with welding operations. Apart from research conducted on the mechanism of fume and gas formation and the relationship between fume formation rates and common welding parameters, little is known about the exposure process during welding. This research project aimed to identify the factors that influence exposure, develop an understanding of their role in the exposure process and through this understanding formulate strategies for the effective control of exposure during welding. To address these aims a literature review and an experimental program was conducted The literature review surveyed epidemiological, toxicological and exposure data. The experimental program involved three approaches, the first, an evaluation of the factors that influence exposure by assessing a metal inert gas/mild steel welding process in a workshop setting. The second approach involved the study of exposure in a controlled environment provided by a wind tunnel and simulated welding process. The final approach was to investigate workplace conditions through an assessment of exposure and control strategies in industry. The exposure to fumes and gases during welding is highly variable and frequently in excess of the health based exposure standards. Exposure is influenced by a number of a factors including the welding process, base material, arc time, electrode, arc current, arc voltage, arc length, electrode polarity, shield gas, wire-to-metal-work distance (metal inert gas), metal transfer mode, intensity of the UV radiation (ozone), the frequency of arc ignitions (ozone), thermal buoyancy generated by the arc process, ventilation (natural and mechanical), the welding environment, the position of the welder, the welders stance, helmet type, and helmet position. Exposure occurs as a result of three processes: the formation of contaminants at or around the arc region; their transport from the arc region, as influenced by the entry and thermal expansion of shield gases, the vigorous production of contaminants, thermal air currents produced by the heat of the arc process, and ventilation; and finally the entry of contaminants into the breathing zone of the welder, as influenced by the position of the welder, the welders stance, helmet type, and the helmet position. The control of exposure during welding can be achieved by several means: through the selection of welding parameters that generate low contaminant formation rates; through the limitation of arc time; and by isolating the breathing zone of the welder from the contaminant plume through the use of ventilation, welder position or the welding helmet as a physical barrier. Effective control is achieved by careful examination of the workplace, the selection of the most appropriate control option, and motivation of the workforce.