Characterization of thermo-oxidative stability of polymer optical fibers using chemiluminescence technique

The thermo-oxidative stability of commercially available polymer optical fibers (POFs) and their components (cores and claddings) was investigated. All the bare POFs (core and cladding only) studied here were based on poly(methyl methacrylate) (PMMA) core. The fibers were exposed to 100 °C/low humidity for about 4200 h. Chemiluminescence (CL) technique was applied to investigate the thermo-oxidative stability and for measuring the transmission loss during exposure a prototype device called multiplexer was used. POFs exhibited variation in thermo-oxidative stability although they possessed identical core material PMMA. This was due to difference in the chemical compositions of claddings. Claddings were more susceptible to the thermo-oxidative degradation compared to cores. The thermo-oxidative degradation of both the cladding and the core was found in POFs as a result of climatic exposure. POFs showed an early drop-off followed by a slow decline of transmission. The early drop-off of transmission was attributed to physical changes like thermal expansion and the slow decline of transmission to chemical changes like oxidative degradation of POFs. A good linear relationship between optical transmission stability and thermo-oxidative stability of POFs was established from these studies.     

The Dynamic Behaviour and NMR Solution structures of complexes of the type (Bisphosphine)(cycloocta-1,5-diene)iridium(I) and the X-ray crystal structure of (cycloocta-1,5-diene)((−)-norphos)iridium(I) hexafluorophosphate

A square-planar coordination geometry was found for the complex [Ir(cod){(?)-norphos}][PF₆] ( 1b [PF₆]; cod = cylcoocta-1,5-diene and (?)-norphos = [(2R,3R)-8-9-10-trinorborn-5-ene-2,3-diyl]bis(diphenylphosphine)) in the solid state by X-ray diffraction. Crystal data: monoclinic, space group P2₁, a = 10.751 (6), b = 18.669(14), c = 12.037(8) Å, β = 114.82(5)°, Z = 2. A total structural assignment including the configurational and conformational aspects of this and the related compounds [Ir(bishosphine)(cod)]X (bisphosphine = (?)-chiraphos = (2S,3S)-2,3-bis(diphenylphosphino)butane and (?)-norphos, X = Cl, CF₃SO₃, or PF₆) was carried out in solution by one- and two-dimensional NMR spectroscopy. The complexes containing the CF₃SO₃^? and PF₆^? anions are four-coordinate cations with square-planar geometry, whereas the chlorides are five-coordinate neutral compounds showing solvent-dependent dynamic behaviour. In toluene, two diastereoisomers of [IrCl(cod){(?)-norphos}] ( 2b ) exist and interconvert slowly at room temperature. This interchange is fast in CDCl₃ solution, and it is likely to involve Cl dissociation and the formation of the cation [Ir(cod){(?)-norphos}]⁺ as an intermediate.     

Preferred dimerization of tetra-tolyl- and tetra-tosylurea derivatives of flexible and rigidified calix[4]arenes

The dimerization of tetratolyl- and tetratosyl-urea derivatives 1 and 2, derived from a tetrapentoxy calix[4]arene in the cone conformation and of the corresponding tetra-urea derivatives 3 and 4, in which the cone conformation is rigidified by the two crown-3 tethers, have been studied. All six possible equimolar mixtures were examined by 1H NMR using CDCl3 and CD2Cl2 as solvents. While no heterodimers are found for the combinations 1/3 and 2/4 in either solvent, all remaining combinations lead to the (exclusive) formation of heterodimers in CD2Cl2. In CDCl3 heterodimers are only observed for the combinations of 3 with 2 or 4. These results are discussed in terms of entropic and enthalpic contributions and compared with MD-simulations in a box of chloroform solvent molecules.     

1,8-bis(dimethylethyleneguanidino)naphthalene: tailoring the basicity of bisguanidine "proton sponges" by experiment and theory

1,8-bis(dimethylethyleneguanidino)naphthalene (DMEGN), the second example of a peralkyl guanidine "proton sponge" based on the 1,8-naphthalene backbone, was prepared and fully characterized. The crystal structure analysis of monoprotonated DMEGN reveals an unsymmetrical intramolecular hydrogen bridge. A decrease in the basicity with respect to the noncyclic parent 1,8-bis(tetramethylguanidino)naphthalene was found. Nevertheless, a new proton sponge provides a new crossbar in the ladder of highly basic neutral organic compounds. A detailed theoretical study of DMEGN and related cyclic guanidines explains this surprising experimental result. Homodesmotic reactions reveal that the intramolecular hydrogen bond contributes effectively 10 kcal/mol to proton affinity of DMEGN.     

Carbon nanodots revised: the thermal citric acid/urea reaction

Luminescent compounds obtained from the thermal reaction of citric acid and urea have been studied and utilized in different applications in the past few years. The identified reaction products range from carbon nitrides over graphitic carbon to distinct molecular fluorophores. On the other hand, the solid, non-fluorescent reaction product produced at higher temperatures has been found to be a valuable precursor for the CO₂-laser-assisted carbonization reaction in carbon laser-patterning. This work addresses the question of structural identification of both, the fluorescent and non-fluorescent reaction products obtained in the thermal reaction of citric acid and urea. The reaction products produced during autoclave–microwave reactions in the melt were thoroughly investigated as a function of the reaction temperature and the reaction products were subsequently separated by a series of solvent extractions and column chromatography. The evolution of a green molecular fluorophore, namely HPPT, was confirmed and a full characterization study on its structure and photophysical properties was conducted. The additional blue fluorescence is attributed to oligomeric ureas, which was confirmed by complementary optical and structural characterization. These two components form strong hydrogen-bond networks which eventually react to form solid, semi-crystalline particles with a size of ∼7 nm and an elemental composition of 46% C, 22% N, and 29% O. The structural features and properties of all three main components were investigated in a comprehensive characterization study.

Products of the thermal reaction of citric acid and urea have been identified as a complex mixture of fluorophores and particles.     

Deuterated ammonium formate as deuterium source in a mild catalytic deuterium transfer reaction of pyridines, pyrazines and isoquinolines

The application of deuterated ammonium formate as deuterium source in transfer deuteration reactions of aromatic heterocycles (4-6) for the synthesis of highly deuterated, substituted piperidines (1), piperazines (2) and tetrahydroisoquinolines (3) has been developed.     

Novel Redox-Active Cyclophanes Based on 3,3'-Biindolizines: Synthesis and Chirality

The first compounds of a new series of redox-active cyclophanes were prepared by dehydrocyclization of bridged indolizines of type 1. The bridged dipyridino-compounds 2a and 2b obtained by reaction of 2 mol of lithiated alpha-picolines with dihalides were used as starting materials. Subsequent treatment of 2a,b with 2 mol of alpha-bromo ketones gave quaternary pyridinium halides. Ring closure in an alkaline medium (Chichibabin reaction) yielded the starting material for the synthesis of the macrocycles. Oxidative C-C coupling gave the diastereomeric cyclophanes of type 3. In all cases one pair of the enantiomers was obtained in excess. CV-investigations have shown that the main products are reversible redox systems. To clarify their conformations, compounds 3c, 3d/1, and3d/2 were subjected to X-ray analysis.     

A Bruen chain forq=19

The one-to-one correspondence between the class of two-dimensional translation planes of orderq ² and the collection of spreads ofPG(3,q) has long provided a natural context for describing new planes. The method often used for constructing interesting spreads is to start with a regular spread, corresponding to a desarguesian plane, and then replace some nice subset of lines by another partial spread covering the same set of points. Indeed the first approach was replacing the lines of a regulus by the lines of its opposite regulus, or doing this process for a set of disjoint reguli. Nontrivial generalizations of this idea include thechains of Bruen and thenests of Baker and Ebert. In this paper we construct a replaceable subset of a regular spread ofPG (3, 19) which is the union of 11 reguli double covering the lines in their union, hence is a chain in the terminology of Bruen or a 11-nest in the Baker-Ebert terminology.     

Polymer diffusion in quenched disorder: A renormalization group approach

We study the diffusion of polymers through quenched short-range correlated random media by renormalization group (RG) methods, which allow us to derive universal predictions in the limit of long chains and weak disorder. We take local quenched random potentials with second momentv and the excluded-volume interactionu of the chain segments into account. We show that our model contains the relevant features of polymer diffusion in random media in the RG sense if we focus on the local entropic effects rather than on the topological constraints of a quenched random medium. The dynamic generating functional and the general structure of its perturbation expansion inu andv are derived. The distribution functions for the center-of-mass motion and the internal modes of one chain and for the correlation of the center of mass motions of two chains are calculated to one-loop order. The results allow for sufficient cross-checks to have trust in the one-loop renormalizability of the model. The general structure as well as the one-loop results of the integrated RG flow of the parameters are discussed. Universal results can be found for the effective static interactionwu–v0 and for small effective disorder coupling on the intermediate length scalel. As a first physical prediction from our analysis, we determine the general nonlinear scaling form of the chain diffusion constant and evaluate it explicitly as for .