Terahertz vibration-rotation-tunneling spectroscopy of the ammonia dimer. II. A-E states of an out-of-plane vibration and an in-plane vibration

Terahertz vibration-rotation-tunneling transitions have been measured between ca. 78.5 and 91.9 cm-1, and assigned to A-E (ortho-para) combinations of NH3 monomer states. The spectrum is complicated by inversion splittings that correlate to E symmetry monomer rovibronic states. Twenty progressions have been assigned to six excited states involving an out-of-plane vibration and an in-plane intermolecular vibration. The quality of the fit was affected by strong Coriolis interactions among these states and possibly an additional K = 2 state that was not explicitly observed in the data.     

Development of an ultra-micro sample injector for gas chromatography using an ink-jet microchip.

An ultra-micro sample injector for gas chromatography (GC) was developed. An ink-jet microchip, originally used for industrial recorder, was modified at the edge near to an orifice, and fixed into the GC. In order to evaluate the characteristics of this injector, a sample injector and a thermal conductive detector (TCD) were connected directly, while water was used as the test sample. The volume of the droplet, the interval time and the back-pressure to the ink-jet microchip were investigated. Within the range of 1 - 5 nL volume injected sample, the TCD response according to the amount of the sample volume (the volume of one droplet from the ink-jet microchip was about 1 nL) was obtained. A good reproducibility of the peak area was obtained to be about 1.0% of the RSD value. In order to compare the injection method of the ink-jet chip with that using a micro-syringe, the method using the ink-jet chip could introduce 1/1000 of the amount of the sample and gave reproducible results.     

Bicarbonate as an interference in B. stearothermophilus assays.

The screening analysis of antibiotic residues in meat products is readily accomplished by a suite of bacterial inhibition assays. Inhibition of B. stearothermophilus is a standard assay noted for its sensitivity to penicillins. In New Zealand, a test kidney from slaughtered animals is accompanied by a urine sample. Generally, penicillins and tetracyclines are both richer in the urine sample, which is applied directly to wells cut in bacterially seeded agar plates. An interference in the assay for B. stearothermophilus has been traced to excessive amounts of bicarbonate in the urine. It is the bicarbonate, not the pH nor the ionic strength that causes the problem. Removal of the bicarbonate was by mild acetic acid treatment to pH 5.5 and vortex mixing to de-gas carbon dioxide. This resulted in complete eradication of the interference without affecting the ability to detect penicillin. The pH change was readily monitored by the indicator bromcresol purple and no complex equipment was needed.     

High-performance liquid chromatography-mass spectrometry of an osteocalcin derivative.

High-performance liquid chromatography (HPLC) was combined on-line with electrospray ionization mass spectrometry (ESI-MS) for structural analysis of a synthetic osteocalcin derivative and its degradation products. Initial determination of amino acid sequence of the synthetic peptide was performed after tryptic degradation. Hydrolytic degradation of the osteocalcin derivative was studied under different pH conditions: pH 2, pH 7 and pH 10 at 60 degrees C up to 20 h. According the HPLC-ESI-MS results, the chemical stability was dependent on pH. Two major degradation products and a number of other fragments were obtained in acidic solution, whereas the osteocalcin molecule was rather stable in neutral and alkaline conditions.     

Incident-angle dependence of the sensitivity of second-harmonic generation of an oxacyanine dye in an LB film.

The second-harmonic generation of a cyanine dye in an LB film was investigated by varying the incident angle of the excitation laser. There was a clear dependence on the incident angle, which was simulated by a simple model. Thus, a highly sensitive determination should be carried out at such an angle where the efficiency of the second-harmonic generation shows its maximum.     

Aktivierungsanalytische Untersuchungen an standardisierten Eisenlegierungen. I

Zusammenfassung In zwei standardisierten Legierungen, und zwar in NBS-1138 Cast Steel 1 und NBS-1140 Ductile Iron 1, wurde Vanadin mit Hilfe der Neutronenaktivierungsanalyse und der Gamma-Spektrometrie zerstörungsfrei bestimmt.Bei den Vorversuchen zur Optimierung der Meßbedingungen wurden außer den in den provisorischen Zertifikaten angegebenen Elementen in NBS-1138 zusätzlich noch Arsen und Antimon, in NBS-1140 Antimon und Lanthan qualitativ nachgewiesen.

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Activation analytical studies of standardized iron alloys. I

Summary Vanadium was determined without interference by means of neutronactivation analysis and gamma spectrometry in two standardized alloys, namely in NBS-1138 Cast Steel 1 and NBS-1140 Ductile Iron 1. In the preliminary trials for determining the optimation of the measurement conditions the presence of arsenic and antimony was established qualitatively in addition to the elements stated provisionally in the certificate describing NBS-1138, and likewise antimony and lanthanum were found in the NBS-1140.

     

Polymerization of propiolaldehyde. IV. Synthesis of a functional polymer having an ethynyl group

The cationic homopolymerization and copolymerization of propiolaldehyde were carried out with use of boron trifluoride etherate as an initiator at the temperatures of 0 to ?78°C. Poly(ethynyl)oxymethylene was prepared by the homopolymerization at ?78°C, but it was readily depolymerized to the monomer. The cationic copolymerization with styrene at ?78°C proceeded almost exclusively through the aldehyde addition and a new functional copolymer was obtained. With a rise in polymerization temperature, the ethynyl addition was mixed slightly.     

Hydroxidgruppen an Zeolithen. I. Zahl und Eigenschaften von Hydroxidgruppen an CaNaY- und MgNaY-Zeolithen unterschiedlichen Austauschgrades

Hydroxide Groups on Zeolites. I. Number and Properties of Hydroxide Groups on CaNaY and MgNaY Zeolites of Different Degree of Ion Exchange The number of hydroxide groups was studied on CaNaY and MgNaY zeolites by D₂ exchange in dependence on the degree of exchange, and their properties were examined by infrared spectroscopy. At these zeolites there exist five types of hydroxide groups which differ by their concentration, their acidic strength, and their thermal stability. The OH-groups are produced mainly by dissociative chemisorption of water at the bivalent cations. The concentration of OH groups shows a characteristic dependence on the degree of ion exchange. There are OH groups which are strongly acid BRÖNSTED centers, capable of protonisation of pyridine, and others which are only capable of weak interactions with pyridine. The number of the acid BRÖNSTED centers increases with the degree of ion exchange analogous to the total number of the hydroxide groups and is highly dependent on the species of the cations exchanged and on the preheating temperature. Compared with CaNaY zeolites, MgNaY zeolites posess a greater number of hydroxide groups which are thermally more stable.     

NMR-spektroskopische Untersuchungen an Mercaptophosphazenen. II. NMR-spektroskopische Untersuchungen an 15N-markierten Mercaptophosphazenen

N.M.R. Spectroscopic Investigations of Thiophosphazenes. II. N.M.R. Spectroscopic Investigations of ¹⁵N Labelled Thiophosphazenes Completely ¹⁵N labelled compounds of the type ¹⁵N₃P₃Cl_6?n(SR)_n, R = Et or Ph; n = 0, 2, 4, or 6, and of the type ¹⁵N₄P₄Cl_8?n(SR)_n, R = Et; n = 0, 4, or 8, were prepared and investigated by means of both ³¹P n.m.r. spectroscopy and ¹⁵N n.m.r. spectroscopy respectively. The coupling constants ²J_PP, in some cases only found by simulating the spectra, and the coupling constants ¹J_PN are given. The values of these coupling constants and their relation are discussed. The general tendency is visible, that with increasing coupling constant ¹J_PN the coupling constant ²J_PP decreases. With increasing grade of substitution n the ¹⁵N chemical shifts are changed to higher fields.     

Metal chelates in vinyl polymerization. I. Ferric dipivaloylmethide as an initiator

The behavior of the chelate, ferric dipivaloylmethide, Fe(DPM)₃, in vinyl polymerization systems was investigated. The polymerization was found to be of free-radical nature. The rate of polymerization was proportional to the square root of the concentration of the chelate. The monomer exponent was close to 1.5 for the Fe(DPM)₃-initiated polymerization of styrene and methyl methacrylate. The kinetic and transfer constants and activation energies for these systems have been evaluated. Spectral studies revealed the possibility of a complex formation between the chelate and the monomer. A kinetic scheme for the Fe(DPM)₃-initiated polymerization is derived based on this initial complex formation.     

Isosteres of natural phosphates. 11. Synthesis of a phosphonic acid analogue of an oligonucleotide

The synthesis of an isosteric phosphonic acid analogue of UpUpU has been accomplished. In this analogue each of the normal 3'-phosphate esteric oxygen atoms has been replaced with a methylene group. The synthesis began with diacetone-D-glucose which was converted in a series of reactions to a 3'-deoxy-3'-dihydroxyphosphinylmethyluridine derivative, which bore protection as a 3-benzoylpropionate at the 5'-hydroxyl and as an acetate at the 2'-hydroxyl. This critical intermediate (A) was condensed with 2',3'-O-isopropylidene uridine to generate a protected analogue of a dinucleoside phosphate. Selective removal of the 3-benzoylpropionate followed by condensation with another unit of (A) yielded the protected oligonucleotide. Deprotection was accomplished in two steps.     

Fluorimetric determination of peroxynitrite based on an enzymatic reaction.

A novel fluorimetric method for the determination of peroxynitrite (ONOO-) using hemoglobin (Hb) as a catalyst is described. The method employs the reaction of ONOO with thiamine (TM), a colorless, non-fluorescent reagent in a glycine-NaCl-NaOH buffer solution (pH 12.7), to generate a highly fluorescent product, thiochrome (TC). The fluorescent product was monitored by fluorimetry. A linear calibration graph was obtained over an ONOO- concentration range from 4.95 x 10(-7) mol L(-1) to 2.97 x 10(-5) mol L(-1), with a detection limit of 9.78 x 10(-9) mol L(-1) ONOO-. The relative standard deviation at an ONOO- concentration of 2.11 x 10(-6) mol L(-1) was 4.15% (n = 9).     

Hydroxidgruppen an Zeolithen. II. Zahl und Eigenschaften von Hydroxidgruppen an CeNaY- und HNaY-Zeolithen unterschiedlichen Austauschgrades

Hydroxide Groups on Zeolites. II. Number and Properties of Hydroxide Groups on CeNaY and HNaY Zeolites of Different Exchange Degree The number of hydroxide groups on CeNaY and HNaY zeolites was examined by D₂ exchange, and their properties in dependence of the cation exchange degrees were studied by IR spectroscopy. On CeNaY zeolites there exist six kinds and on HNaY zeolites at least seven kinds of hydroxide groups. On the CeNaY zeolites, the hydroxide groups are produced by dissociative chemisorption of water on Ce³⁺ ions. Their total number increases continuously with increasing exchange degree. Some of the hydroxide groups are acid BRÖNSTED centers whose number increases with increasing exchange degree and decreases with the temperature of preheating increasing to about 600°C. On the HNaY zeolites, the hydroxide groups are produced by thermal decomposition of the NH⁺₄ ions, by dealumination and interaction of the Al³⁺ ions produced in this way in the place of cations with water. Above the threshold value of 35% the total number of the hydroxide groups increases very rapidly with increasing exchange degree. One part of the hydroxide groups decreasing with increasing exchange degree acts as acid BRÖNSTED centers. The number of these centers does not decrease until at preheating temperatures above 450°C.     

Monitoring the stability of an emulsion by high-frequency spectroscopy.

High-frequency spectroscopy has been applied to monitoring the stability of oil-in-water emulsions. It was found that stable emulsions showed absorption peaks at around 550 MHz; further, they shifted from lower to higher frequencies with time. The rate of increase of the frequencies was dependent on the amount of emulsifier added. These results show that the stability of emulsions can be monitored by the amount of the frequency shift.     

Electrochemical immunoassay: an ultrasensitive method.

Hydrodynamic electrochemical techniques such as liquid chromatography and flow injection analysis with electrochemical detection are very effective for the rapid determination of the enzyme-generated product in enzyme immunoassays. The authors have used this detection method in various assay formats using both alkaline phosphatase and glucose-6-phosphate dehydrogenase as labels. Assays for digoxin will be used illustratively. Recently, the authors have used 70 mL microcapillary hematocrit tubes as the immunoassay reaction vessel and alkaline phosphatase as the labeling enzyme. The assay, complete in 30 min, had a detection limit of 5,6 x 10 -20 moles of IgG in serum. The linear range was four orders of magnitude. This low detection limit is due to a combination of the favorable geometry of the reaction vessel and the suppression of nonspecific adsorption by the addition of ion-pairing blocking agents. Even lower detectable amounts should be achievable with smaller reaction vessels. The capability for detecting such small amounts of analyte is potentially useful for the analysis of extremely small samples such as single cells and blood samples from premature infants.     

Vinylferrocene homopolymer and copolymers: an electrochemical comparison.

Poly(vinylferrocene) (pVFc) homopolymer was synthesized by free radical polymerization, along with a series of pVFc-based copolymers containing either styrene, vinylanthracene or methylmethacrylate. This report details the electrochemical experiments conducted to examine the stability of the various pVFc based polymers, which is shown to be critically dependent on the extent of copolymerization. A trend was found that when the concentration of co-monomer was decreased, electrochemical stability was enhanced. Furthermore incorporation of a second monomer into the polymer chain produced a profound effect on the scan rate behaviour of the vinylferrocene moiety. As the concentration of co-monomer was decreased, the behaviour tended towards that of a diffusion controlled process. These results are of vital significance for the development of pVFc-based electrochemical sensors.     

Purification and Characterization of an Antifungal Chitinase from Citrobacter freundii str. nov. haritD11

The purpose of the research was to study the purification and partial characterization of antifungal alkaline chitinase from a newly isolated Citrobacter freundii haritD11. The enzyme was purified in a three-step procedure involving ammonium sulfate precipitation, dialysis, and Sephadex G-100 gel filtration chromatography. The enzyme was shown to have a relative high molecular weight of 64 kDa by sodium dodecyl sulfate polyacrylamide gel electrophoresis and was purified 7.3-fold with a yield of 18.8 %. It was most active at 35 °C, pH 8.0, with colloid chitin as substrate and was very stable at alkaline pH contradicting the characteristic that most of the bacterial chitinases are active at acidic pH. Further, the purified chitinase exhibited remarkable antifungal activity against pathogenic fungi Aspergillus flavus MTCC 2798 and Aspergillus niger MTCC 9652 showing diametric inhibition zones of 27 mm and 21 mm, respectively.     

Tumorigenicity of revertant from an SV40-transformed line.

A syndrome of in vitro properties correlates with the tumorigenicity of SV40-transformed rodent cells. These properties are: plasminogen activator production, loss of large actin cables, and anchorage-independent growth. An established rat fibroblast line, its SV40 transformant, several T-antigen negative revertants, and a spontaneous retransformant isolated from one of the revertants were analyzed in vivo for their tumorigenicity and in vitro for the syndrome. The two transformed lines were highly tumorigenic, and had clearly abnormal in vitro properties. The parental rat line was weakly tumorigenic in nude mice and demonstrated a slightly transformed response in the in vitro assays. The revertants were completely nontumorigenic. Expression of the in vitro syndrome was not uniform for all revertants; however, most cell lines maintained the correlation of the syndrome and tumorigenicity.     

Triaziridine. 6. Mitteilung. Substituententransformationen an Triaziridinen

Substituent Transformations on Triaziridines Several novel triaziridines were prepared by substituent transformations starting from the known dialkyl-triaziridine-carboxylates 1a – c , with the aim to study the influence of the substitution pattern on the properties of the triaziridine ring. The dialkyl-triaziridines 2a – c were obtained by (t-BuO^?)-mediated demethylation and decarboxylation and the dialkyl-triaziridine-methanols 4a – c by LiAlH₄ reduction. Further reduction of the tosylates of 4a , b with LiAlH₄ gave the methyl-dialkyl-triaziridines 3a , b . The dialkyl-triaziridines 2a , c could not be N-methylated directly with CH₃I, but the anions 10a , c , obtained from 2a, c with CH₃Li, yielded 3a , c . N-Methylation of 2a with (CH₃)₃OBF₄ did not afford 3a but rather the methyl-triaziridinium salt 11 . The dialkyl-triaziridine 2c has pK_a > 14, its protonated species < 2. A concept that the electron pairs on the triaziridine N-atoms are more strongly localized than on amine N-atoms explains (a) that the dialkyl-triaziridine 2c is hardly basic, (b) that the LiAlH₄ reductions of the esters 1 stop at the stage of the methanols 4 , and (c) that the methanols 4a , b do not cleave like aminomethanols.