The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 11. Synthesis and total assignment of the 1H and 13C NMR spectra of isomeric benzothienonaphthoquinolines using multiple inverse detected two-dimensional NMR methods

Two novel heterocyclic ring systems, namely, [1]benzothieno[2,3-c]naphtho[1,2-f]quinoline and [1]benzothieno[2,3-c]naphtho[2,1-g]quinoline have been synthesized and characterized by inverse detected two-dimensional nmr methods. Unequivocal total assignments of the proton and carbon nmr spectra were made through the concerted utilization of HMQC (Heteronuclear Multiple Quantum Correlation) and a combination of HMBC (Heteronuclear Multiple Bond Correlation) and HMQC-TOCSY (HMQC with proton TOtal Correlation Spectroscopy).     

Autocorrelated 13c-13c double quantum coherence two-dimensional nmr spectroscopy: Utilization of a modified version of the technique as an adjunct in the total assignment of the 1h- and 13c-nmr spectra of the mutagen phenanthro[3,4-b]thiophene

Development of successively higher field nmr spectrometers has facilitated the study of increasingly more complex molecules, although smaller molecules such as phenanthro[3,4-b]thiophene still offer very substantial assignment problems because of the highly congested nature of their ¹H- and ¹³C-nmr spectra. Assignments of such spectra, if they are to be unequivocal, frequently require the utilization of two-dimensional nmr spectroscopic techniques. Total assignments of the ¹H- and ¹³C-nmr spectra of phenanthro[3,4-b]thiophene are reported. Assignments were based on a conventional high resolution 500 MHz ¹H-nmr spectrum, autocorrelated two-dimensional ¹H-nmr spectra (COSY), two-dimensional ¹H-¹³C chemical shift correlation spectra and a modified version of autocorrelated ¹³C-¹³C double quantum coherence two-dimensional nmr spectroscopy. From NOE measurements, a separation of 1.99 Å between H1 and H11 was computed, suggesting that phenanthro[3,4-b]thiophene has a pronounced helical conformation in solution.     

Investigation of bicyclic thioketones as triggers for liquid crystal optical switches

The axially chiral bicyclic thioketones 11 and 15 were prepared and investigated for suitability as chiroptical triggers in a liquid crystal optical switch. Irradiation of partially resolved 15 with unpolarized light leads to its conversion to the racemic form (photoracemization). However, irradiation of racemic thioketones 11 and 15 with circularly polarized light does not lead to detectable photoresolution. The lack of photoresolution was traced to inefficiency in intramolecular, through-bond triplet energy transfer. These thioketones are not suitable for use as phototriggers.     

Synthesis, characterization, and stability of Fe-MCM-41 for production of carbon nanotubes by acetylene pyrolysis

Fe-substituted MCM-41 molecular sieves with ca. 1, 2, and 3 wt % Fe were synthesized hydrothermally using different sources of colloidal silica (HiSil and Cab-O-Sil) and characterized by ICP, XRD, N2 physisorption, UV-vis, EPR, TPR, and X-ray absorption. Catalysts synthesized from Cab-O-Sil showed higher structural order and stability than those from HiSil. The local environment of Fe in the mesoporous material as studied by UV-vis reveals the dominance of framework Fe in all the as-synthesized Fe-MCM-41 samples. Dislodgement of some Fe species to extraframework location occurs upon calcination, and this effect is more severe for Fe-MCM-41 (2 wt %) and Fe-MCM-41 (3 wt %), as confirmed by EPR and X-ray absorption. These materials have been used as catalytic templates for the production of carbon nanotubes (CNTs) by acetylene pyrolysis at atmospheric pressure. A relationship between the Fe loading in MCM-41 and the carbon species produced during this reaction has been established. Using our optimized conditions for this system, Fe-MCM-41 with ca. 2 wt % Fe showed the best results with particularly high selectivity for single-wall carbon nanotube (SWNT) production. This catalyst was selective for carbon nanotubes with a low amount of amorphous carbon for a narrow range of temperatures from 1073 to 1123 K. To account for the different selectivity of these catalysts for CNTs production, the local environment and chemical state of Fe in the used catalyst was further probed by X-band EPR.     

The assembly of organic radical anions between metal-borate scaffolds

Metal-organic frameworks based on the Pb[B(Im)(4)](+) unit form layered structures analogous to those observed in clays and double layered hydroxide minerals. These layers can act as scaffolds for the organization of anionic organic guests. In this report, we use this scaffold to assemble TEMPO and PROXYL carboxylates in the interlayer spacings of Pb[B(Im)(4)](4-carboxy-TEMPO) 1 and Pb[B(Im)(4)](3-carboxy-PROXYL)(H(2)O)2, respectively. The resultant materials are paramagnetic, and the organization of the radical units differs between the two compounds. This results in changes in electronic structure of the radical unit, as observed by EPR spectroscopy.     

P and H NMR studies of the transesterification polymerization of polyphosphonate oligomers

Polymeric phosphonate esters are an interesting class of organophosphorus polymers because both the polymer backbone and phosphorus substituents can be modified. These polymers have been prepared by ring-opening polymerizations of cyclic phosphites, stoichiometric polycondensations of dimethyl phosphonate with diols in conjunction with diazomethane treatment and by transesterification of polyphosphonate oligomers. Our initial attempts to prepare high molecular weight polymeric phosphonate esters by the transesterification methods were unsuccessful. Results indicate that the reactions of dimethyl phosphonate with diols to form polyphosphonate oligomers with only methyl phosphonate end groups are plagued by a serious side reaction that forms phosphonic acid end groups. These end groups do not participate in the transesterification reaction and limit the molecular weights of the polymers that can be obtained. The phosphonic acid end groups can be converted into reactive methyl phosphonate end groups by treatment with diazomethane, however diazomethane is explosive and the polymerization is slow. An alternative route for the production of high molecular weight polymers is the transesterification of the 1,12-bis(methyl phosphonato)dodecane, formed by the reaction of excess dimethyl phosphonate and 1,12-dodecanediol, with a Na₂CO₃ promoter. This allows polymers with molecular weights of up to 4.5×10⁴ to be prepared, and no phosphonic acid end groups are observed in these polymers. Thermal analyses of the poly(1,12-dodecamethylene phosphonate) have shown that this polymer has reasonable thermal stability (onset of thermal decomposition at 273 °C). This polymer also undergoes a cold crystallization process at 15 °C similar to that which has been observed in some polyesters, polyamides and elastomers.     

Two dimensional reversed-phase-reversed-phase separations isomeric separations incorporating C18 and carbon clad zirconia stationary phases

Informational theory and a geometric approach to factor analysis were employed to evaluate the degree of orthogonality of a two-dimensional reversed-phase-reversed-phase chromatographic system. The system incorporated a C18 column as one dimension and a carbon clad zirconia column as the second dimension. In order to study the resolving power of this system, the separation of a sample matrix containing an artificial mix of 32 isomers (structural and diastereoisomers) was evaluated. Using this system, between 25 and 28 of the 32 isomers could be separated, depending on the mobile phase combinations--with resolution that could not possibly be achieved in a single one dimensional separation. The results from this study indicate that in order to fully evaluate the resolving power of a 2D system multiple methods of analysis are most appropriate. This becomes increasingly important when the sample contains components that are very closely related and the retention of solutes is clustered in one quadrant of the 2D space. Ultimately, the usefulness of the 2D separation is determined by the goals of analyst.     

Nitrotyrosine-modified proteins and oxidative stress induced by diesel exhaust particles

Protein tyrosine nitration is a post-translational modification that occurs under conditions of oxidative stress and may play a role in the pathogenesis of diseases such as asthma. Through their ability to generate reactive oxygen species in macrophages and epithelial cells, particulate pollutants, such as diesel exhaust particles (DEPs), may lead to a worsening of the asthmatic condition. In this study, we looked for evidence of oxidative modification of proteins in RAW 264.7 cell line treated with DEP chemicals. We show that the induction of oxidative stress is accompanied by 53 newly expressed proteins which are suppressed by a thiol antioxidant, N-acetylcysteine. These include antioxidant enzymes, pro-inflammatory components, and products of intermediary metabolism. In addition, inducible nitric oxide synthase (iNOS) was identified as a biologically relevant oxidative stress protein that is induced concurrent with increased NO production and protein tyrosine-nitration in DEP-exposed RAW 264.7 cells. Utilizing two-dimensional gel electrophoresis, anti-nitrotyrosine immunoblotting, and mass spectrometry led to the identification of an additional ten nitrotyrosine modified proteins, including oxidative stress proteins involved in intermediary metabolism (e.g., GAPDH and enolase), antioxidant defense (e.g., MnSOD) and inhibition of proteosomal activity (e.g., Hsp 90alpha). These oxidative proteins may serve as markers for oxidative stress generation in vivo.     

Multiple-quantum NMR in anisotropic phases: Projections of two-dimensional MQNMR spectra

The use of two-dimensional transform techniques in the observation of multiple-quantum transitions in large spin systems in anisotropic environments is described. In the case of partial resolution in the ω₂ dimension, it is shown that the signal to noise of the projection onto ω₁ of the absolute magnitude two-dimensional multiple-quantum spectrum is considerably greater than that of the Fourier transform of the t₂ = 0 cross section. In practical terms, multiple- quantum transitions of very high order may be observed with good signal to noise after acquisition periods much shorter than previously reported by cross section methods.     

Novel heterocycles. I. Synthesis and reactions of 6,7-dihydro-1H,3H,5H-pyrido[3,2,l-ij] [3,1]benzoxazine-1,3-dione

6,7-Dihydro-1H,3H,5H-pyrido[3,2,l-ij][3,1 ]benzoxazine-1,3-dione ( 1b ) was synthesized by a new route and its reactions with various nueleophiles are described.