Synthesis of a giant 222 carbon graphite sheet

In this paper we present the synthesis and characterization of the so far largest polycyclic aromatic hydrocarbon (PAH), containing 222 carbon atoms or 37 separate benzene units. First a suitable three-dimensional oligophenylene precursor molecule is built up by a sequence of Diels-Alder and cyclotrimerization reactions and then planarized in the final step by oxidative cyclodehydrogenation to the corresponding hexagonal PAH. Structural proof is based on isotopically resolved MALDI-TOF mass spectra and electronic characteristics are studied by UV/Vis spectroscopy.     

Pyrolytisch-gaschromatographische Untersuchungen an Polymeren

Zusammenfassung Es wird gezeigt, daß durch Kombination des Pyrolysators nach Simon mit einem temperaturprogrammierten, mit einer Capillarsäule ausgestatteten Gaschromatographen die Charakterisierung polymerer Kunststoffe nach dem Fingerprintsystem möglich ist. Dabei können Copolymerisate und Mischungen entsprechender Homopolymerisate ebenso leicht voneinander unterschieden werden wie die einzelnen Glieder homologer Reihen. Besonders erwähnt werden die Mischpolymerisate Vinylacetat-Acrylsäure-n-butylester bzw. Vinylacetat-Malein- oder Fumarsäuredi-n-butylester, die bisher weder durch IR-Untersuchung noch durch Elementaranalyse unterschieden werden konnten.

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Summary The characterization of high polymers in a finger-print system has been made possible by a combination of the pyrolysator according to Simon and a temperature-programmed gas-chromatograph with a macro-capillary column. Copolymers and mixtures of the corresponding homopolymers can be distinguished easily in this way, as well as the single members of homologous series of polymer esters. The investigation of the copolymers vinyl acetate—n-butyl acrylate and vinyl acetate—di-n-butyl maleinate or -fumarate, which could hitherto be distinguished neither by IR nor by elemental analysis, is particularly mentioned.

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Wir danken Herrn Dr. Benz, Ammoniaklaboratorium der BASF, für die Ausführung der mühevollen massenspektrometrischen Untersuchungen, sowie Herrn Götz für die sorgfältige Ausführung der gaschromatographischen Experimente.     

Background noise cancellation for improved acoustic detection of manatee vocalizations

The West Indian manatee (Trichechus manatus latirostris) has become endangered partly because of an increase in the number of collisions with boats. A device to alert boaters of the presence of manatees, so that a collision can be avoided, is desired. A practical implementation of the technology is dependent on the hydrophone spacing and range of detection. These parameters are primarily dependent on the manatee vocalization strength, the decay of the signal's strength with distance, and the background noise levels. An efficient method to extend the detection range by using background noise cancellation is proposed in this paper. An adaptive line enhancer (ALE) that can detect and track narrow band signals buried in broadband noise is implemented to cancel the background noise. The results indicate that the ALE algorithm can efficiently extract the manatee calls from the background noise. The improved signal-to-noise ratio of the signal can be used to extend the range of detection of manatee vocalizations and reduce the false alarm and missing detection rate in their natural habitat.     

Determination of West Indian manatee vocalization levels and rate

The West Indian manatee (Trichechus manatus latirostris) has become endangered partly because of a growing number of collisions with boats. A system to warn boaters of the presence of manatees, based upon the vocalizations of manatees, could potentially reduce these boat collisions. The feasibility of this warning system would depend mainly upon two factors: the rate at which manatees vocalize and the distance in which the manatees can be detected. The research presented in this paper verifies that the average vocalization rate of the West Indian manatee is approximately one to two times per 5-min period. Several different manatee vocalization recordings were broadcast to the manatees and their response was observed. It was found that during the broadcast periods, the vocalization rates for the manatees increased substantially when compared with the average vocalization rates during nonbroadcast periods. An array of four hydrophones was used while recording the manatees. This allowed for position estimation techniques to be used to determine the location of the vocalizing manatee. Knowing the position of the manatee, the source level was determined and it was found that the mean source level of the manatee vocalizations is approximately 112 dB (re 1 microPa) @ 1 m.     

Defective Continuous Hydrogen‐Bond Networks: An Alternative Interpretation of IR Spectroscopy

We apply our previously developed deconvolution method and interpretation to analyze changes in the OH stretching band [ν(OH) band] of low‐concentration (≤0.2 m) aqueous solutions of NaCl and KCl. We treat these simple, monovalent ions as defects in the hydrogen‐bond network of pure water and quantify the changes in the spectra at low defect concentration with an “order parameter”. Order‐parameter analysis of difference spectra of the two solutions leads to hydration numbers of 7.0±1.0 and 5.9±0.3 for K⁺ and Na⁺, respectively. Additionally, we find that changes in the ν(OH) band due to low concentrations of ions result from changes in the topology of the hydrogen‐bond network.     

Evaluation of light scattering data from bimodal turbid suspensions: a simple fit procedure

Whereas correlation spectroscopy gives reliable information on the size of immersed particles in those cases where the size distribution is narrow, large problems arise for more complex particle distributions. For instance, samples containing distinctly different particles of rather similar size lead to correlation functions which are very close to those of monodisperse samples. We present a measurement technique which is based on angle dependent measurements of 3D cross correlation functions and an evaluation scheme which uses the results of the Mie theory. The experimental technique warrants applications to strongly scattering samples. Having tested this procedure with mixtures containing standard latex particles we applied it to a sample of skimmed, homogenized milk.     

Metallosupramolecular chemistry with bis(benzene-o-dithiolato) ligands

The bis(benzene-o-dithiol) ligands H(4)-1, H(4)-2, and H(4)-3 react with [Ti(OC(2)H(5))(4)] to give dinuclear triple-stranded helicates [Ti(2)L(3)](4)(-) (L = 1(4)(-), 2(4)(-), 3(4)(-)). NMR spectroscopic investigations revealed that the complex anions possess C(3) symmetry in solution. A crystal structure analysis for (PNP)(4)[Ti(2)(2)(3)] ((PNP)(4)[14]) confirmed the C(3) symmetry for the complex anion in the solid state. The complex anion in Li(PNP)(3)[Ti(2)(1)(3)] (Li(PNP)(3)[13]) does not exhibit C(3) symmetry in the solid state due to the formation of polymeric chains of lithium bridged complex anions. Complexes [13](4)(-) and [14](4)(-) were obtained as racemic mixtures of the Delta,Delta and Lambda,Lambda isomers. In contrast to that, complex (PNP)(4)[Ti(2)(3)(3)] ((PNP)(4)[15]) with the enantiomerically pure chiral ligand 3(4)(-) shows a strong Cotton effect in the CD spectrum, indicating that the chirality of the ligands leads to the formation of chiral metal centers. The o-phenylene diamine bridged bis(benzene-o-dithiol) ligand H(4)-4 reacts with Ti(4+) to give the dinuclear double-stranded complex Li(2)[Ti(2)(4)(2)(mu-OCH(3))(2)] containing two bridging methoxy ligands between the metal centers. The crystal structure analysis and the (1)H NMR spectrum of (Ph(4)As)(2)[Ti(2)(4)(2)(mu-OCH(3))(2)] ((Ph(4)As)(2)[(16]) reveal C(2) symmetry for the anion [Ti(2)(4)(2)(mu-OCH(3))(2)](2)(-). For a comparative study the dicatechol ligand H(4)-5, containing the same o-phenylene diamine bridging group as the bis(benzene-o-dithiol) ligands H(4)-4, was prepared and reacted with [TiO(acac)(2)] to give the dinuclear complex anion [Ti(2)(5)(2)(mu-OCH(3))(2)](2)(-). The molecular structure of (PNP)(2)[Ti(2)(5)(2)(mu-OCH(3))(2)] ((PNP)(2)[17]) contains a complex anion which is similar to [16](2)(-), with the exception that strong N-H...O hydrogen bonds are formed in complex anion [17](2)(-), while N-H...S hydrogen bonds are absent in complex anion [16](2)(-).