Diels-Alder reactions as an efficient route to high purity cyclic polymers

A simple and efficient route for the synthesis of cyclic polymer systems is presented. Linear furan protected α-maleimide-ω-cyclopentadienyl functionalized precursors (poly(methyl methacrylate) and poly(tert-butyl acrylate)) were synthesized via atom transfer radical polymerization (ATRP) and subsequent substitution of the bromine end-group with cyclopentadiene. Upon heating at high dilution, deprotection of the dieneophile occurs followed by an intramolecular Diels–Alder reaction yielding a high purity cyclic product.

Microwave curing of non-traditional polymer materials used in manufacture of injection moulds

Microwave heating technology is a cost-effective alternative way for heating and curing of used in polymer processing of various alternate materials. The work presented in this paper addresses the attempts made by the authors to study the glass transition temperature and curing of materials such as casting resins R2512, R2515 and laminating resin GPR 2516 in combination with two hardeners ADH 2403 and ADH 2409. The magnetron microwave generator used in this research is operating at a frequency of 2.45 GHz with a hollow rectangular waveguide. During this investigation it has been noted that microwave heated mould materials resulted with higher glass transition temperatures and better microstructure. It also noted that Microwave curing resulted in a shorter curing time to reach the maximum percentage cure. From this study it can be concluded that microwave technology can be efficiently and effectively used to cure new generation alternate polymer materials for manufacture of injection moulds in a rapid and efficient manner. Microwave curing resulted in a shorter curing time to reach the maximum percentage cure.

Response of partially grouted wider reinforced masonry walls to inplane cyclic shear

Partially grouted wider reinforced masonry wall, built predominantly using face shell bedded hollow concrete blocks, is an economical structural system and is popularly used in the cyclonic areas; its out-of-plane response to lateral loading is well understood, unfortunately its inplane shear behaviour is less well understood as to the effect of partial gouting in intervening the load paths within the wall. For rational analysis of the wall clarification is sought as to whether the wall acts as a composite of unreinforced panels and reinforced cores or as a continuum of masonry embedded with reinforced at wider spacing. This paper reports the results of four full scale walls tested under inplane cyclic shear loading to provide some insight into the effect of the grout cores in altering the load paths within the wall. The global lateral load - lateral deflection hysteric curves as well as local responses of some critical zones of the shear walls are presented.

Wider reinforced masonry shear walls subjected to cyclic lateral loading

Partially grouted wider reinforced masonry wall, built predominantly with the use of face shell bedded hollow concrete blocks, is adopted extensively in the cyclonic areas due to its economy. Its out-of-plane response to lateral pressure loading is well definied; however its in-plane shear behaviour is less well understood, in particular it is unclear how the grouted reinforced cores affect the load paths within the wall. For the rational design of the walls, clarification is sought as to whether the wall acts as a composite of unreinforced panels surrounded by the reinforced cores or simply as a continuum embedded with reinforcement at wider spacing. This paper reports four full scale walls tested under in-place cyclic shear loading to provide some insight into the effect of the grout cores in altering the load paths within the wall. The global lateral load - lateral deflection hysteretic curves as well as the local responses of some critical zones of the shear walls are presented. It is shown that the aspect ratio of the unreinforced masonry panels surrounded by the reinforced grouted cores within the shear walls have profound effect in ascertaining the behaviour of the shear walls.

Computational design of cyclic nitroxides as efficient redox mediators for dye-sensitized solar cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E° ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclic imides and an open-chain amide carboxylic acid from the facile reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with the isomeric monofluoroanilines

The structures of the cyclic imides cis-2-(2-fluorophenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, C14H14FNO2, (I), and cis-2-(4-fluorophenyl)-3a,4,5,6,7,7a-hexahydroisoindoline-1,3-dione, C14H14FNO2, (III), and the open-chain amide acid rac-cis-2-[(3-fluorophenyl)carbamoyl]cyclohexane-1-carboxylic acid, C14H16FNO3, (II), are reported. Cyclic imides (I) and (III) are conformationally similar, with comparable ring rotations about the imide N-Car bond [the dihedral angles between the benzene ring and the five-membered isoindole ring are 55.40 (8)° for (I) and 51.83 (7)° for (III)]. There are no formal intermolecular hydrogen bonds involved in the crystal packing of either (I) or (III). With the acid (II), in which the meta-related F-atom substituent is rotationally disordered (0.784:0.216), the amide group lies slightly out of the benzene plane [the interplanar dihedral angle is 39.7 (1)°]. Intermolecular amide-carboxyl N-HO hydrogen-bonding interactions between centrosymmetrically related molecules form stacks extending down b, and these are linked across c by carboxyl-amide O-HO hydrogen bonds, giving two-dimensional layered structures which lie in the (011) plane. The structures reported here represent examples of compounds analogous to the phthalimides or phthalanilic acids and have little precedence in the crystallographic literature.

Physicochemical characterization of particulate emissions from a compression ignition engine employing two injection technologies and three fuels

Alternative fuels and injection technologies are a necessary component of particulate emission reduction strategies for compression ignition engines. Consequently, this study undertakes a physicochemical characterization of diesel particulate matter (DPM) for engines equipped with alternative injection technologies (direct injection and common rail) and alternative fuels (ultra low sulfur diesel, a 20% biodiesel blend, and a synthetic diesel). Particle physical properties were addressed by measuring particle number size distributions, and particle chemical properties were addressed by measuring polycyclic aromatic hydrocarbons (PAHs) and reactive oxygen species (ROS). Particle volatility was determined by passing the polydisperse size distribution through a thermodenuder set to 300 °C. The results from this study, conducted over a four point test cycle, showed that both fuel type and injection technology have an impact on particle emissions, but injection technology was the more important factor. Significant particle number emission (54%–84%) reductions were achieved at half load operation (1% increase–43% decrease at full load) with the common rail injection system; however, the particles had a significantly higher PAH fraction (by a factor of 2 to 4) and ROS concentrations (by a factor of 6 to 16) both expressed on a test-cycle averaged basis. The results of this study have significant implications for the health effects of DPM emissions from both direct injection and common rail engines utilizing various alternative fuels.

Hydrogen-bonding in cyclic imides and amide carboxylic acid derivatives from the facile reaction of cis-cyclohexane-1,2-carboxylic anhydride with o- and p-anisidine and m- and p-aminobenzoic acids

The structures of the open chain amide carboxylic acid rac-cis-[2-(2-methoxyphenyl)carbamoyl]cyclohexane-1-carboxylic acid, C15H19NO4, (I) and the cyclic imides rac-cis-2-(4-methoxyphenyl)-3a,4,5,6,7,7-hexahydroisoindole-1,3-dione,C15H17NO3, (II), chiral cis-2-(3-carboxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, C15H15NO4,(III) and rac-cis-2-(4-carboxyphenyl)- 3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione monohydrate, C15H15NO4. H2O) (IV), are reported. In the amide acid (I), the phenylcarbamoyl group is essentially planar [maximum deviation from the least-squares plane = 0.060(1)Ang. for the amide O atom], the molecules form discrete centrosymmetric dimers through intermolecular cyclic carboxy-carboxy O-H...O hydrogen-bonding interactions [graph set notation R2/2(8)]. The cyclic imides (II)--(IV) are conformationally similar, with comparable phenyl ring rotations about the imide N-C(aromatic) bond [dihedral angles between the benzene and isoindole rings = 51.55(7)deg. in (II), 59.22(12)deg. in (III) and 51.99(14)deg. in (IV). Unlike (II) in which only weak intermolecular C-H...O(imide) hydrogen bonding is present, the crystal packing of imides (III) and (IV) shows strong intermolecular carboxylic acid O-H...O hydrogen-bonding associations. With (III), these involve imide O-atom acceptors, giving one-dimensional zigzag chains [graph set C(9)], while with the monohydrate (IV), the hydrogen bond involves the partially disordered water molecule which also bridges molecules through both imide and carboxyl O-atom acceptors in a cyclic R4/4(12) association, giving a two-dimensional sheet structure. The structures reported here expand the structural data base for compounds of this series formed from the facile reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with substituted anilines, in which there is a much larger incidence of cyclic imides compared to amide carboxylic acids.

Cyclic Imide and Open-Chain Amide Carboxylic Acid Derivatives from the Facile Reaction of cis-Cyclohexane-1,2-dicarboxylic Anhydride with Three Substituted Anilines

The structures of the compounds from the reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with 4-chloroaniline [rac-N-(4-chlorophenyl)-2-carboxycycloclohexane-1-carboxamide] (1), 4-bromoaniline [2-(4-bromophenyl)-perhydroisoindolyl-1,3-dione] (2) and 3-hydroxy-4-carboxyaniline (5-aminosalicylic acid) [2-(3-hydroxy-4-carboxyphenyl)-perhydroisoindolyl-1,3-dione] (3) have been determined at 200 K. Crystals of the open-chain amide carboxylic acid 1 are orthorhombic, space group Pbcn, with unit cell dimensions a = 20.1753(10), b = 8.6267(4), c = 15.9940(9) Å, and Z = 8. Compounds 2 and 3 are cyclic imides, with 1 monoclinic having space group P21 and cell dimensions a = 11.5321(3), b = 6.7095(2), c = 17.2040(5) Å, β = 102.527(3)o. Compound 3 is orthorhombic with cell dimensions a = 6.4642(3), b = 12.8196(5), c = 16.4197(7) Å. Molecules of 1 form hydrogen-bonded cyclic dimers which are extended into a two-dimensional layered structure through amide-group associations: 3 forms into one-dimensional zigzag chains through carboxylic acid…imide O-atom hydrogen bonds, while compound 2 is essentially unassociated. With both cyclic imides 2 and 3, disorder is found which involves the presence of partial enantiomeric replacement of the cis-cyclohexane-1,2-substituted ring systems.

An investigation of gaseous and particulate emissions from compression ignition engines operated with alternative fuels, injection technologies, and combustion strategies

Whilst the compression ignition (CI) engine exhibits many design advantages relative to its spark ignition engine counterpart; such as: high thermal efficiency, fuel economy and low carbon monoxide and hydrocarbon emissions, the issue of Diesel Particulate Matter (DPM) emissions continues to be an unresolved problem for the CI engine. Primarily, this thesis investigates a range of DPM mitigation strategies such as alternative fuels, injection technologies and combustion strategies conducted with a view to determine their impact on the physico-chemical properties of DPM emissions, and consequently to shed light on their likely human health impacts. Regulated gaseous emissions, Nitric oxide (NO), Carbon monoxide (CO), and Hydrocarbons (HCs), were measured in all experimental campaigns, although the major focus in this research program was on particulate emissions...

Analysis of indirect message injection for MAC generation using stream ciphers

This paper presents a model for generating a MAC tag with a stream cipher using the input message indirectly. Several recent proposals represent instances of this model with slightly different options. We investigate the security of this model for different options, and identify cases which permit forgery attacks. Based on this, we present a new forgery attack on version 1.4 of 128-EIA3. Design recommendations to enhance the security of proposals following this general model are given.

A general model for MAC generation using direct injection

This paper presents a model for generating a MAC tag by injecting the input message directly into the internal state of a nonlinear filter generator. This model generalises a similar model for unkeyed hash functions proposed by Nakano et al. We develop a matrix representation for the accumulation phase of our model and use it to analyse the security of the model against man-in-the-middle forgery attacks based on collisions in the final register contents. The results of this analysis show that some conclusions of Nakano et al regarding the security of their model are incorrect. We also use our results to comment on several recent MAC proposals which can be considered as instances of our model and specify choices of options within the model which should prevent the type of forgery discussed here. In particular, suitable initialisation of the register and active use of a secure nonlinear filter will prevent an attacker from finding a collision in the final register contents which could result in a forged MAC.

The influence of fatty acid methyl ester profiles on inter-cycle variability in a heavy duty compression ignition engine

With the advent of alternative fuels, such as biodiesels and related blends, it is important to develop an understanding of their effects on inter-cycle variability which, in turn, influences engine performance as well as its emission. Using four methanol trans-esterified biomass fuels of differing carbon chain length and degree of unsaturation, this paper provides insight into the effect that alternative fuels have on inter-cycle variability. The experiments were conducted with a heavy-duty Cummins, turbo-charged, common-rail compression ignition engine. Combustion performance is reported in terms of the following key in-cylinder parameters: indicated mean effective pressure (IMEP), net heat release rate (NHRR), standard deviation of variability (StDev), coefficient of variation (CoV), peak pressure, peak pressure timing and maximum rate of pressure rise. A link is also established between the cyclic variability and oxygen ratio, which is a good indicator of stoichiometry. The results show that the fatty acid structures did not have a significant effect on injection timing, injection duration, injection pressure, StDev of IMEP, or the timing of peak motoring and combustion pressures. However, a significant effect was noted on the premixed and diffusion combustion proportions, combustion peak pressure and maximum rate of pressure rise. Additionally, the boost pressure, IMEP and combustion peak pressure were found to be directly correlated to the oxygen ratio. The emission of particles positively correlates with oxygen content in the fuel as well as in the air-fuel mixture resulting in a higher total number of particles per unit of mass.

Cyclic pull-out strength of steel roof and wall cladding systems

When crest-fixed thin steel roof cladding systems are subjected to wind uplift, local pull-through or pull-out failures occur prematurely at their screwed connections. During high wind events such as storms and cyclones these localised failures then lead to severe damage to buildings and their contents. In recent times, the use of thin steel battens/purlins has increased considerably. This has made the pull-out failures more critical in the design of steel cladding systems. Recent research has developed a design formula for the static pull-out strength of steel cladding systems. However, the effects of fluctuating wind uplift loading that occurs during high wind events are not known. Therefore a series of constant amplitude cyclic tests has been undertaken on connections between steel battens made of different thicknesses and steel grades, and screw fasteners with varying diameter and pitch. This paper presents the details of these cyclic tests and the results.