Determination of radioactive nuclides of uranium and thorium series and estimation of α-flux in LSI constituent materials

Gamma-rays of nuclides of uranium and thorium series in silicone resin and ceramics were measured with a Ge(Li) detector. The state of radioactive equilibrium was determined by comparing the concentrations of uranium and thorium with the radioactive concentrations of²¹⁴Pb and²¹²Pb. The radioactive equilibrium was attained in silicone resin but not in ceramics. The -flux was calculated from the concentrations of uranium and thorium and their daughter nuclides. The calculated values of -flux agreed with that of -flux measured.     

Triterpene glycosides from Pulsatilla chinensis

Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.     

Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate); 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate) 23-palmitate; 24,25-dimethyl-5-cholestane-2,3,6-triol 3-(sodium sulfate); 24,25-dimethyl-5-cholestane-2,3,6-triol 6-(sodium sulfate); and 24,25-dimethyl-5-cholestane-2,3,6-triol 2,6-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 441–445, July–August, 1986.     

Porphyrins. 9. New data on the polyformylation of metal complexes of etioporphyrin I

The structures of the products of the polyformylation of Cu, Ni, and Co complexes of etioporphyrin (EP) as monoformyl-, ,-diformyl-, ,-diformyl-, and ,,-triformyl-EP were established by electronic, IR, and PMR spectroscopy and mass spectrometry. -Formyl--(N-methylformaldimine)-EP and porphyrins that contain a cyclopentane ring can be formed by alkaline treatment of the Vilsmeier formylation products.See [1] for communication 8.See [2] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 767–775, June, 1979.     

On the dynamic mechanical behavior of nylon 66

Summary The dynamic mechanical properties of nylon 66 films and fibers have been examined, as a function of annealing and drawing, with a Vibron viscoelastometer. It is found that the transition is little affected by annealing treatments, but increase in orientation causes the transition to move to a higher temperature. Experiments, with X-ray diffraction of samples at elevated temperatures, lead to the conclusion that the triclinic to hexagonal phase change does not contribute significantly to the transition. Samples cut parallel and perpendicular to the drawing direction of nylon 66 film, have been used to show that the curves of dynamic tensile modulus versus temperature, for the parallel and perpendicular directions, cross in the neighborhood of the transition. This observation is discussed in relation to the suggestion that the transition is the glass transition in nylon 66.

---

Zusammenfassung Die dynamisch-mechanischen Eigenschaften von Filmen und Fasern aus Nylon 66 wurden als Funktion der Temperung und Verstreckung mit einem Virbon-Viskoelastometer untersucht. Die -Umwandlung wird wenig durch die Temperung beeinflußt, aber erhöhte Orientierung läßt siezu höheren Temperaturen verlagern. Messungen der Röntgenstreuung bei erhöhten Temperaturen führen zu dem Schluß, daß der Übergang triklin/hexagonal nicht wesentlich zu der -Umwandlung beiträgt. Proben aus verstrecktem Nylon-66-Film, parallel und senkrecht zur Streckrichtung geschnitten, zeigen, daß die Kurven des dynamischenE-Moduls gegen die Temperatur für beide Orientierungen sich in der Nachbarschaft der -Umwandlung überkreuzen. Diese Beobachtung wird hinsichtlich der Vermutung diskutiert, daß die -Umwandlung den Glasübergang in Nylon 66 darstellt.

---

---

With 5 figures and 2 tables     

Thermodynamics of Binding of α:-Cyclodextrin to Straight-Chain Alkyl Derivatives in Aqueous Solution

Apparent standard Gibbs energy, enthalpy, entropy, and heatcapacity data of the interactions of -cyclodextrin (CD) to some n-carboxylatesH(CH₂)_nCOO^- (n = 4–6), are determined by isothermal titration microcalorimetryat different temperatures in phosphate buffer, pH 9.0, assuming a 1 : 1 model indilute solution. Modelling of contributions of the thermodynamic properties of the solutionindicates that CD undergoes conformational change upon binding to homologousseries of n-carboxylates, n-alcohols, ,-alkane dicarboxylates and ,-alkane diols.     

GC-FTIR and GC-MS in odour analysis of essential oils

The analysis of odour components in East Indian Sandalwood Oil (Santalum album L.) and in Patchouli Oil (Pogostemon cablin Benth.) based on GC-, GC-FTIR- and GC-MS-data resulted in the identification of-santalene,-santalal,-santalal, epi--santalal,-santalol,-santalol, (E)--santalol,-bergamotol and spirosantalol in Sandalwood Oil and of (–)-patchoulol,-guaiene,-patchoulene, seychellene,-bulnesene, norpatchoulenol and pogostol in Patchouli Oil as the most intense aroma compounds of these oils.     

Extraction of Polonium from Aqueous α-Hydroxyisobutyric Acid Solutions Using Dioctyl Sulphide, Cyanex 272, Cyanex 301 or Cyanex 302 in Toluene

A study of the extraction of polonium from aqueous solutions containing -hydroxyisobutyric acid (-HIBA) was performed with four different extractants, di-n-octyl sulphide (DOS), Cyanex 272, Cyanex 301 and Cyanex 302, dissolved in toluene. The extracted complex for DOS at low -HIBA concentrations is most likely PoO(-HIB)₂·2DOS, while at higher -HIBA concentrations there seems to be a solvating effect implicating an extracted complex of the type PoO(-HIB)₂(-HIBA)₂·2DOS. For the extraction of polonium with Cyanex 272 the results are inconclusive. The extracted complex is either PoOA₂ or PoO(-HIB)₂·2HA. For extraction with Cyanex 301 or Cyanex 302 the major extracted species does not contain any -HIBA molecules. The neutral species in both cases is PoOA₂, extracted at low extractant concentrations, while at higher extractant concentrations a complex of the type PoOA₂·xHA is extracted. The extraction of polonium increases in the order Cyanex 272 < DOS < Cyanex 302 < Cyanex 301.     

Glass capillary gas chromatography of hop bitter acids. II. Desoxy-α-acids in hop extracts

Summary The presence of about 0.5 to 1% desoxy--acids in hops and hop extracts is confirmed. Desoxy--acids are supposed to be biogenetic precursors and these compounds could be present in the hops as a surplus to this activity, but it is more likely that they have been formed from -and -acids. A gas chromatographic method for analysing the desoxy--acids amount in hops and in hop extracts is described.     

Low-pressure decomposition of ammonia on rhodium

Kinetics of ammonia decomposition and adsorption of reactants on a polycrystalline rhodium wire have been studied by thermal desorption and mass-spectrometric methods. Qualitive discussion of the mechanism of ammonia interaction with rhodium is presented.

---

- . .

     

Complex polarizability as used to analyze dielectric relaxation measurements

The effect of representing dielectric properties in terms of the complex polarizability ^c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.     

Preparation of rare metallic actinides (248Cm,249Bk,249Cf) and investigation of their crystal structure

²⁴⁸Cm and²⁴⁹Bk metals were prepared by thermal reduction of their oxides with thorium and metallic²⁴⁹Cf with metallic lanthanum. These rare actinide samples of 1.0 mg in mass were thin layers on a flat substrate and were investigated by X-ray technique. Dhcp lattice parameters of -Cm, -Bk and -Cf as main phases in X-ray diagrams are presented. The effect of impurities on the -Cm lattice parameters is shown. Fcc lattices for the high temperature form of Cm metal (-Cm) with a=0.4933 nm, and of Cm and Bk monoxides (a=0.502–0.504 nm and a=0.5002 nm, respectively) have been observed. Thermal expansion coefficients for -Cm and -Bk at 80–300 K were calculated. Identification problems of fcc lattices and oxidation features of metals prepared are discussed.     

Geometry of α-cyclodextrin inclusion complex with m-nitrophenol deduced from quantum chemical analysis of carbon-13 chemical shifts

The host-guest orientation and the position of the guest m-nitrophenol (MNP) in the -cyclodextrin (-CD)-MNP inclusion-complexation induced carbon-13 NMR chemical shifts of MNP with those predicted by quantum chemical calculation. In the calculation, the non-polar environmental effect produced by the -CD cavity on the carbon-13 shifts of included guest molecule has been formulated by the so-called NMR solvent effect theory. Here, carbon-13 shift displacements are assumed to be induced by transference of the guest from polar aqueous phase with higher dielectric constant to the non-polar -CD cavity with lower dielectric constant. Among a variety of host-guest orientation investigated, only the geometry in which the nitrophenyl group is located in the -CD cavity and the hydroxyl groups is exposed to the aqueous phase can reproduce qualitatively the observed carbon-13 shift displacements of MNP. This geometry is consistent with that in the solid state determined by the X-ray method.     

On the preparation of bilirubins of the natural α series substituted with a propionic acid residue and a hydroxypropyl group

Summary The reduction of mesobiliverdin XIII propan-1,3-diyl diester with NaBH₄ affords mesobilirubin XIII propan-1,3-diyl diester. The same reduction of mesobiliverdin XIII methylen diester. The same reduction of mesobiliverdin XIII methylen diester affords 8-(2-carboxyethyl)-3,17-diethyl-12-(3-hydroxypropyl)-2,7,13,17-tetramethylbiladien-ac-1,19-(21H, 24H)-dione (MBR-mc). The UV/Vis and¹H NMR spectra ofMBR-mc show that its structure in solution is similar to that of the natural bilirubins of the series.

---

Zur Herstellung von Bilirubinen der natürlichen -Reihe mit Propionsäure- und Hydroxypropylsubstituenten

Zusammenfassung Reduktion von Mesobiliverdin-XIII-propan-1,3-diyl-diester mit NaBH₄ liefert Mesobilirubin-XIII-propan-1,4-diyl-diester. Die analoge Reaktion des Mesobiliverdin-XIII-methylen-diesters führt zu 8-(2-Carboxyäthyl)-3,17-diäthyl-12-(3-hydroxypropyl)-2,7,13,17-tetramethylbiladien-ac-1,19-(21H,24H)-dion (MBR-mc).MBR-mc weist in Lösung (UV/Vis und 1H-NMR Spektren) eine ähnliche Struktur auf wie die der natürlichen Bilirubine der -Serie.

     

Nuclear Recoil Implosion for Generating Radioisotopically Labeled Fullerene Endohedrals and Cages

The use of nuclear recoil for producing radioactive endohedral and cage-labeled fullerenes is presented, with special emphasis on the energy of chemical effects after nuclear particle capture. The different possibilities using (n,), (n,), (p,n), (g,n) and (,n) and (,n) nuclear reactions are treated in detail.     

Über halogen- und stickstoffhaltige Derivate aliphatischer Carbonsäuren, 6. Mitt.: Über die Gewinnung von α-Oximino- und α-Nitrodicarbonsäureestern

Zusammenfassung Aus den entsprechenden -Bromestern werden durch Umsetzung mit Natriumnitrit die -Oximinodicarbonsäuredimethylester C₇ und C₉ und der , -Dioximinoazelainsäuredimethylester erhalten. -Methyladipinsäure wird zum Gemisch aus -Bromund -Bromester umgesetzt. Mit Natriumnitrit wird -Nitro-und -Oximino--methyladipinsäuredimethylester erhalten.

---

The -oximino dicarboxylic dimethyl esters of C₇ and C₉ and the , -dioximino azelaic acid dimethyl ester are received from the corresponding -bromo esters by reaction with sodium nitrite. -Methyladipic acid is reacted with bromine to a mixture of the -bromo and -bromo ester. Reaction with sodium nitrite gives the -nitro ester and the -oximino ester of -methyl adipic acid.

---

---

5. Mitt.:H. Reinheckel, Mh. Chem.98, 1217 (1967).     

Telomerization of ethylene and carbon tetrachloride or chloroform in the presence of the hexacarbonyls of chromium,molybdenum, and tungsten

summary The reaction of telomerization of ethylene with carbon tetrachloride or chloroform is initiated by hexacarbonyls of chromium, molybdenum, and tungsten at 115–120, forming ,,,-tetrachloroalkanes and ,,-trichloroalkanes. respectively.     

Effect of α-methylstyrene of the curing behaviour of vinyl ester resins

The curing behaviour of bismethacryloxy derivative of diglycidyl ether of bisphenol A (vinyl ester resin) containing styrene as the reactive diluent (40% w/w) was studied using gel point determination method and DSC. Seven samples of styrene/-methylstyrene in the ratio 400, 355, 3010, 2515, 2020, 1525 and 040 were studied. Delayed curing was observed in samples containing increasing proportions of -methylstyrene. The energy of activation decreased from 869 kJ mol^–1 to 333 kJ mol^–1 as the concentration of -methylstyrene increased in the formulations. However, no difference in thermal stability was observed by replacement of styrene by -methylstyrene. It was concluded that in vinyl ester resin samples 10–15% -methylstyrene and 30-25% styrene can be used as reactive diluent.

---

Zusammenfassung Mittels DSC und Bestimmung der Gelierungstemperatur wurde das Aushärteverhalften des Bismethakryloxyderivaten des Diglycidyläthers von Bisphenol A (Vinylesterharz) mit 40 Gewichtsprozenten Styrol als reaktives Streckmittel untersucht. Es würden sieben Proben mit einem Styrol/-Methylstyrol Verhältnis von 400, 355, 3010, 2515, 2020, 1525 und 040 untersucht. Mit steigendem Anteil an -Methylstyrol konnte eine Verzögerung der Aushärtung sowie ein Absinken der Aktivierungsenergie von 869 kJ · mol^–1 auf 333 kJ · mol^–1 beobachtet werden. Der Ersatz von Styrol durch -Methylstyrol veränderte jedoch die thermische Stabilität in keiner Weise. Vinylesterharzproben mit 10–15% -Methylstyrol und 30–25% Styrol können als reaktive Streckmittel in Vinylesterharzen verwendet werden.

---

- - , 40 .% . /-, 400, 355, 3010, 2515, 2020, 1525 040. - . - 869 333 · ^–1. , .. , , 10–15% - 30–25% .

     

A novel synthesis of N-acetyl-α-d-fucosamine 1-phosphate and uridine 5"-diphospho-N-acetyl-α-d-fucosamine

In connection with studies on the biosynthesis of capsular polysaccharides from Staphylococcus aureus, a new synthesis of uridine 5"-(2-acetamido-2,6-dideoxy--d-galactopyranosyl diphosphate) (uridine 5"-diphospho-N-acetyl--d-fucosamine) using 2-azido-3,4-di-O-acetyl-2,6-dideoxy--d-galactopyranosyl nitrate as the key intermediate was carried out. The reaction of this product with cesium dibenzyl phosphate smoothly affords the corresponding -glycosyl dibenzyl phosphate, which undergoes anomerization on treatment with BF₃·Et₂O and 2-bromopyridine to give -glycosyl dibenzyl phosphate in high yield. This product was then transformed into 2-amino-3,4-di-O-acetyl-2,6-dideoxy--d-galactopyranosyl phosphate, subsequently converted into 2-acetamido-2,6-dideoxy--d-galactopyranosyl phosphate and the target nucleoside diphosphate sugar.     

Synthesis of α-alkyl- and α,α-dialkyl-β-phenyltryptamines

A new method was developed for the synthesis of -alkyl- and ,-dialkyl--phenyltryptamines based on alkylation of nitroalkanes with -phenyl-nor-gramine.