Absolute infrared intensities of hydrocarbons

Dipole-moment derivatives, calculated by both the CNDO/2 method with different parameterizations and the INDO method, are compared to the experimental values determined from absolute infrared intensity measurements for the IR active modes of methane, ethane, ethylene and acetylene. A parameter refinement procedure is introduced in which the CNDO/2 molecular orbital parameters are adjusted through a damped least-squares treatment to give best agreement with the observed dipole-moment derivatives. It is found that the refinement does not substantially improve the agreement obtained with the original CNDO/2 parameterization. The INDO method gives somewhat poorer agreement than the CNDO/2 calculations. As an example of the applicability of the molecular orbital methods toward reproducing relative infrared intensities, the spectrum of cyclopropane in the gasphase is examined.

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Zusammenfassung Die Ableitungen des Dipol-Moments, die nach der CNDO/2-Methode mit verschiedenen Parametrisierungen sowie der INDO-Methode berechnet wurden, werden mit den experimentellen Ergebnissen aus Messungen der absoluten Infrarot-Intensitäten für die IR-aktiven Schwingungen von Methan, Äthan, Äthylen und Azetylen verglichen. Die CNDO/2-Parameter werden mit einer Methode der kleinsten Quadrate den beobachteten Dipol-Moment-Ableitungen angepaßt. Die Ergebnisse sind jedoch nicht wesentlich von denen der ursprünglichen CNDO/2-Methode verschieden. Die INDO-Ergebnisse sind nicht so gut wie die CNDO/2-Ergebnisse. Als Beispiel der Anwendbarkeit der MO-Methoden zur Berechnung von relativen IR-Intensitäten wird das Spektrum des Cyclopropans in der Gasphase untersucht.

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Résumé Les dérivées du moment dipolaire, calculées par la méthode CNDO/2 avec différentes paramétrisations et par la méthode INDO, sont comparées aux valeurs expérimentales déterminées à partir de mesures d'intensité absolue pour les modes actifs dans l'infra-rouge dans le méthane, l'éthane, l'éthylène et l'acétylène. Les paramètres sont ajustés de manière à donner le meilleur accord avec les dérivées du moment dipolaire. Cet ajustement n'améliore pas sensiblement l'accord obtenu avec la paramétrisation CNDO/2 originale. La méthode INDO donne des résultats moins bons que les calculs CNDO/2. Le spectre du cyclopropane en phase gazeuse est étudié comme exemple de l'applicabilité de la méthode des orbitales moléculaires au calcul des intensités relatives infra-rouge.

     

PHOTOSENSITIZED INHIBITION OF PHOTOSYNTHETIC 14CO2 FIXATION BY α-TERTHIENYL AND ULTRAVIOLET-A*

Abstract: A variety of naturally occurring photosensitizers of plant origin were tested for their ability to cause ultraviolet-A (UVA)-dependent inhibition of photosynthetic ¹⁴CO₂ fixation in leaf disks of Pisum sativum L. At 0.1 mM concentrations and 60 min UVA irradiation, α-terthienyl was strongly inhibitory, harmine and sanguinarine inhibited to a lesser degree, and curcumin, 8-methoxypsoralen and nordihydroguaiaretic acid had no effect under the conditions tested. Alpha-terthienyl + UVA treatments that fully inhibited ¹⁴CO₂ fixation had no effect on fresh weight, chlorophyll or protein content of the tissue. Chloroplast malate dehydrogenase and glyceraldehyde-3-phosphate dehydrogenase were inhibited 45% and 29%, respectively, by α-terthienyl + UVA treatment. Electron transport from H₂O to the reducing side of photosystem I was inhibited to a similar extent, suggesting interference with the reductive activation of chloroplast enzymes. Alpha-terthienyl + UVA-treated tissue exhibited a seven-fold increase in leakage of labeled photosynthate into the external medium. Treated leaf disks showed no ability to recover ¹⁴CO₂ fixing ability over a 24 h period. These results indicate photosensitized damage at the level of the thylakoid membranes resulting in partial loss of electron transport capability and more general damage to chloroplast and cell membranes.     

Vibrational spectroscopy of 3,4-difluorocyclobutenes: cis-d0, trans-d0 and trans-d4 species

Infrared and Raman spectra were recorded for cis-3,4-difluorocyclobutene (cDFCB) and trans-3,4-difluorocyclobutene-d4. Unscaled density functional theory (DFT) calculations of frequencies and intensities at the B3LYP/6-311++G(d,p) level supported the complete assignment of the vibrational fundamentals. The previous assignment of fundamentals of trans-3,4-difluorocyclobutene was revised. An unusual blue shift occurs for the methylenic CH-stretching frequencies of cis-3,4-difluorocyclobutene in going from the gas phase to the liquid phase. This hydrogen bond effect is related to similar observations recently reported and interpreted. The blue shift does not occur for the vinylic CH bonds of the cis isomer and does not occur for either type of CH bond in the trans isomer.     

Enantioselective [4 + 2] cycloadditions of o-quinone methides: total synthesis of (+)-mimosifoliol and formal synthesis of (+)-tolterodine

The first example of an enantioselective cycloaddition of an o-quinone methide (o-QM) with a chiral enol ether is described along with the total synthesis of (+)-mimosifoliol and the formal synthesis of (+)-tolterodine. These syntheses exemplify a three-component, one-pot benzopyran approach for the construction of chiral benzylic junctions. Cycloadditions of various enol ethers and o-QMs are examined, and diastereoselectivities >95% are obtained with trans-2-phenyl-1-cyclohexanol and 2,2-diphenylcyclopentanol vinyl ethers.     

Application of ESCA to polymer chemistry. XVI. Electron mean free paths as a function of kinetic energy in polymeric films determined by means of ESCA

Electron mean free paths as a function of kinetic energy have been measured by the substrate overlayer technique for in situ-polymerized films of poly(p-xylylene) and the monochloro- and monobromo-substituted derivatives. The results are compared with previous estimates of mean free paths available in the literature for organic materials. Comparison is also drawn with corresponding experimental data for typical metals and semiconductors, and it is shown that organic polymers fit into a consistent picture which may be rationalized on the basis of existing theory. For electrons of kinetic energy ～969 eV, ～1170 eV, 1202 eV, and 1403 eV, mean free paths of ～14 Å, ～22 Å, ～23 Å, and ～29 Å, respectively, are obtained for the poly(p-xylylene) polymer films studied in this work.     

Optical rotatory dispersion and circular dichroism. LXXV. Circular dichroism of some aryl-amino acids

CD. curves have been recorded for α-aryl-α-amino acids, esters and amides related to α-phenylglycine, α-phenyl-alanine and their N-dimethyl derivatives, and for the corresponding α-cyclohexyl-α-amino acids and esters. Compounds with the (S)-configuration at the single asymmetric carbon atom give strong positive Cotton effects near 220 nm. The conformations of the acids are discussed and compared with those of other α-amino acids.     

Programmable gate delayed ion mobility spectrometry-mass spectrometry: a study with low concentrations of dipropylene-glycol-monomethyl-ether in air

The concept of using a short ionisation event, in this case a pulsed corona discharge, in conjunction with programmed gate delay is described. This technique is proposed for the selective study of different ionisation processes within the reaction region of an ion mobility spectrometer. The utility of such an approach was tested in a study of the ionisation of dipropylene-glycol-monomethyl-ether (DPM); a compound commonly used to test the operation of ion mobility spectrometers. Dipropylene-glycol-monomethyl-ether at a concentration of 113 microg m(-3) in air, with a water level of 75 mg m(-3) in air, was analysed using a switchable, high resolution ion mobility spectrometer, operating in the positive mode at 40 degrees C at ambient pressure. The ion mobility spectrometer was fitted with a pulsed corona discharge ionisation source, doped with ammonia at a concentration of 1.3 mg m(-3) in the reaction region, and interfaced to a mass spectrometer. Synchronisation of the ionisation event to the operation of the shutter grids for the drift region enabled different parts of the product ion population to be injected into the drift tube, and programming the gate delays produced a map of the gate delay verses drift time response surface. Ammonium bound dipropylene-glycol-monomethyl-ether was observed, [(DPM)NH4]+ (m/z 166) as well as the ammonium bound dimer [(DPM)2NH4]+ (m/z 314), the same as those observed with a 63Ni source. Two other species were also observed, but their molecular identity was not elucidated. One of them m/z 146, also observed with 63Ni, formed ammonium bound ions [(m/z 146)NH4]+ (K0= 1.49 cm2 V(-1) s(-1)), ammonium bound dimer ions [(m/z 146)2NH4]+(K0= 1.18 cm2 V(-1) s(-1)) and a mixed cluster ion with DPM [(m/z 146)(DPM)NH4]+(K0= 1.18 cm2 V(-1) s(-1)); while the other, m/z 88 a decomposition product, formed ammonium bound monomer [(m/z 88)NH4]+(K0= 1.68 cm2 V(-1) s(-1)), dimer ions [(m/z 88)2NH4]+(K0= 1.40 cm2 V(-1) s(-1)) and a mixed cluster ion containing DPM and ammonium, [(DPM)(m/z 88)2NH4]+(K0= 1.40 cm2 V(-1) s(-1)). The assignment of responses to these ions required the additional dimensionality in the data provided from the gate delay studies. The relationships evident in the programmable gate delay data enabled these ions to be differentiated from alternative assignments of possible nitrogen clusters, formed at the interface of the mass spectrometer.     

Synthesis of 3-nitro- and 3-aminoquinoline-2,4-diones. An unexpected route to 3-hydroxyquinoline-2,4-diones

Nitration of 3-substituted-4-hydroxy-2(1H)-quinolones 1 with nitric acid leads either to 3-nitro- 2 or 3-hydroxyquinolinediones 3 , depending on the reaction conditions. 3-Substituted-3-hydroxyquinolinediones 3 are also obtained by oxidative hydroxylation with peracetic acid. Amination of 3-substituted-3-chloroquinolinediones 4 with ammonium hydroxide predominantly leads again to 3-substituted-3-hydroxyquinolinediones 3 , only in one case the 3-aminoquinolinedione 5 could be isolated. With morpholine or pyridine as amines the expected 3-aminoquinolinediones 6 and 7 were obtained.     

Nucleophile Ringöffnung von α-Nitrocyclopropancarbonsäure-arylestern mit sterisch geschützter,aber elektronisch wirksamer Carbonyl- und Nitro-Gruppe. Ein neues Prinzip der α-Aminosäure-Synthese (2-Aminobutansäure-a4-Synthon)

Nucleophilic Ring Opening of Aryl α-Nitrocyclopropanecarboxylates with Sterically Protected but Electronically Effective Carbonyl and Nitro Group. A New Principle of α-Amino Acid Synthesis (2-Aminobutanoic Acid a⁴-Synthon) The readily available 2,4,6-tri(tert-butyl)-and 2,6-di(tert-butyl)-4-methoxypahenol esters 2 of α-nitrocyclo-propanecarboxaylic acid ring opening with C-, N-, O-, and S-nucleophiles (cyanide, malonate, azide, anilines, alkoxides, phenoxides, thiolates) in DMF or alcohol solvents (80–95% yield). The products 6 – 14 are 2-nitrobutanoates with the newly introduced substituent in the 4-position. Reduction of the NO₂ group with Zn/AcOH/Ac₂O gives N-acetyl-α-amino acid esters 16 – 22 (40–90% yield). Subsequent oxidative cleavage (H₂O₂/HCOOH) of The p-methoxy-phenyl esters 18 and 20 produces free amino acids (65% 23 and 67% 24 , respectively). Thus, the nitro ester 2 corresponds to a 2-aminobutanoic-acid a⁴-synthon, it is a ‘homo-Michael acceptor’ producing γ-substituted α-amino acids.     

Reactivity ratios for copolymerization of vinyl chloride with 2-methylpentyl vinyl brassylate by computerized linearization

A computerized version of the Fineman-Ross linearization procedure was used to determine reactivity ratios for copolymerization of vinyl chloride (monomer 1) and 2-methylpentyl vinyl brassylate (monomer 2). From differential refractometry data for the products of low-conversion copolymerization, the procedure gave r₁ = 1.06 and r₂ = 0.234. The ratios computed from chlorine contents of the same products were r₁ = 1.10 and r₂ = 0.239. The polarity factor (e₂) and general monomer reactivity (Q₂) calculated for monomer 2 from these ratios were, respectively, ?0.95 to ?0.98 and 0.032–0.033. The interquartile range for the copolymerization of a mixture of 60% monomer 1 and 40% monomer 2 was 1.4%. These values suggest that from suitable proportions of reactants, sufficiently homogeneous distribution of monomers can be achieved in copolymers of vinyl chloride and 2-methylpentyl vinyl brassylate to offer the possibility of effective internal plasticization.