Synthetic studies in the alkaloid field—VII: Stereochemistry of 1,2,3,4,6,7,12,12b-octahydroindolo [2,3-a]quinolizine derivatives prepared by alkaline decarboalkoxylative cyclization or acid-induced cyclization of appropriate tetrahydropyridines

The C(12b)-C(1)-C(2) stereochemical relationship in several racemic 1,2,3,4,6,7,12,12b-octahydroindolo [2,3-a]quinolizine derivatives has been determined by ¹³C NMR spectral analysis. The proper shift assignment was confirmed by recording the spectra of selectively deuterated derivatives. The C(12b)-C(1)-C(2) stereochemical relationship in indolo[2,3-a]quinolizines obtained either by alkaline decarboalkoxylative cyclization or by acid-induced cyclization of partially hydrogenated 1-[2-(3-indolyl)ethyl]-3-methoxycarbonylpyridine derivatives is discussed. The ambiguity existing in the preparation of dl-18,19-dihydroantirhine 2 by analogous decarboalkoxylative cyclization is considered.     

INCREASED UV EXPOSURE IN FINLAND IN 1993

Abstract—
Exceptionally low total ozone, up to 40% below the normal level, was measured over Northern Europe during winter and spring in 1992 and 1993. In 1993 the depletion persisted up to the end of May, resulting in a significant increase of biologically effective UV radiation. The increases were significantly smaller in 1992 and 1994 than in 1993. The UV exposure of the Finnish population was evaluated through measurements and theoretical calculations. The increase in measured erythemal (International Lighting Commission) UV falling onto horizontal surfaces on clear days was determined relative to model calculations for an average ozone amount. The increase was on average 10% from April to May 1993, and the maximal measured increase was 34%. Theoretical calculations for both erythemal and carcinogenic (Skin Cancer Utrecht-Philadelphia) UV indicated that in 1993 the theoretical annual increase to a vertical (cylinder) surface ranged from 8 to 13% in Finland. The reflection of UV from snow considerably increases facial UV doses in Northern Finland.     

JT-60U装置温度分布剖面不变性的实验研究

在一系列H模放电条件下，建立了一个旨在研究等离子体温度分布剖面不变性的数据库。介绍了数据库建立过程中要解决的关键问题和所用软件，对等离子体温度分布剖面不变性及芯部约束与边缘参数的关系进行了研究。     

Effect of the initial matrix material on the structure of radiation‐grafted ion‐exchange membranes: Wide‐angle and small‐angle X‐ray scattering studies

Seven different fluoropolymer films were used as matrix materials for radiation‐grafted ion‐exchange membranes. The crystallinity and preferred orientation of these membranes were studied with wide‐angle X‐ray scattering, and the lamellar structure of the membranes was examined with small‐angle X‐ray scattering. The crystallinity of poly(vinylidene fluoride) (PVDF)‐based matrix materials varied between 57 and 40%, and the crystallinity of the sulfonated samples varied between 34 and 23%. The lamellar periods of PVDF‐based matrix materials were about 115 Å, and the lamellar periods of poly(ethylene‐alt‐tetrafluoroethylene) and poly(tetrafluoroethylene‐co‐hexafluoropropylene) were 250 and 212 Å, respectively. When the samples were grafted, the lamellar periods increased. Correlation function analysis showed very clearly that the long‐range order decreased because of grafting and sulfonation processes. For those samples that showed good proton conductivity, the lamellar period also increased because of sulfonation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1539–1555, 2002     

Detector-Based Calibration Method for High-Accuracy Solar UV Measurements

A novel method for calibrating the absolute responsivity of solar UV spectroradiometers has been developed and tested. The method is based on calibrated filter radiometers constructed from a detector, a precision aperture, a band-pass filter and devices for temperature stabilization. The filter radiometers utilize a trap detector with very low reflectance. The filter and the detector can therefore be characterized separately. As an example the detector-based calibration is compared at 312 nm wavelength with lamp-based calibration by measuring the irradiance of a deuterium lamp with both the filter radiometer and the lamp-calibrated spectroradiometer. The agreement between the results is at the level of 1%, well within the estimated uncertainties of both methods.     

EFFECTS OF ARCTIC OZONE DEPLETION AND SNOW ON UV EXPOSURE IN FINLAND

The increase in the UV exposure of the Finnish population associated with the combined effects of ozone depletion and snow reflection was studied with the aid of theoretical calculations based on Green's clear sky UV model. A simple formula was utilized to transform horizontal irradiances to vertical irradiances averaged over 360 azimuth angle. The model was verified with spectral and broadband measurements. The difference between the theoretical and measured UV radiation falling to horizontal surfaces was in most cases less than ±10%, and the additional error to theoretical vertical irradiances was less than ± 10%. The calculations show that the annual horizontal doses in Helsinki (60.2°N, 25°E) are about 35% higher than in Saariselkä (68.4°N, 27.5°E), but the difference is only 16% for vertical doses owing to the stronger contribution to vertical (facial) surfaces of the reflection of UV from snow. At Saariselkä, the maximum vertical irradiance at the end of April approaches the midsummer values. The ozone depletions up to 40% in February and March 1992 had no significant effect on the annual doses because the total ozone returned to normal before the UV increased to biologically significant levels.     

Identification of the hydrolysis products of AlCl3.6H2O by electrospray ionization mass spectrometry

The hydrolysis reactions of AlCl3 in 0.1 M aqueous solutions at pH 3.27-4.20 were monitored by electrospray ionization time-of-flight mass spectrometry (ESI-ToF MS) as a function of time. The cationic and anionic ESI mass spectra of aluminum(III) solutions gave strong evidence of the presence of a variety of monomeric and polymeric complexes. Competition between the OH- and Cl- ligands within the same aluminum core was observed. The influence of the sample cone voltage on the product distribution was also explored. The optimum sample cone voltage for the cationic spectra was 70 V. For the anionic spectra no optimum sample cone voltage was found and the appearance of the anionic spectra was strongly dependent on the sample cone voltage within the whole range explored.     

Chromatographic separation of nucleosides using a cross-linked xylose isomerase crystal stationary phase

Cross-linked xylose isomerase (EC 5.3.1.5., from Streptomyces rubiginosus) crystals (CLXIC) packed into a 7.8 x 300 mm steel column showed specific affinity towards uridine (Urd), cytidine (Cyd), adenosine (Ado), guanosine (Guo), and thymidine. These nucleosides eluted out of the CLXIC column in the same order as the corresponding nucleoside bases, indicating that the retention depends mainly on the base component of the molecule. The interaction of nucleosides with the CLXIC material was not based merely on ion exchange or hydrophobic interactions but also on the unique properties of the CLXIC column. Decrease in temperature increased the retention but not the resolution factors of the adjacent nucleosides. The CLXIC column maintained its separation capacity even when 100 mg of ribonucleosides in equimass amounts were injected into the column in a volume of 1 mL corresponding to 10% of the total column volume. Analysis of sugar beet molasses, a side stream from sucrose production, showed it to contain 1-2.5 mg mL(-1) of Urd, Cyd, Ado, and Guo. The CLXIC column was able to separate and enrich these nucleosides also from highly viscous sugar beet molasses. The CLXIC column was especially efficient in the purification of guanosine. Other commercially interesting sugar beet molasses components such as the acidic compounds betaine, gamma-amino butyric acid, and D- and L-pyroglutamic acids or neutral sucrose did not interact with the CLXIC material.     

Total synthesis of (±)-desmethylhexahydrovallesiachotaminelactones

Total synthesis of (±)-desmethylhexahydrovallesiachotaminelactones 1a and 1b, and their isomers 2a and 2b is described. The formation of other epimeric pairs of lactones (1a and 3a, and 1b and 3b) from vallesiachotamine 4 is also described.     

Ultrasound assisted method to increase soluble chemical oxygen demand (SCOD) of sewage sludge for digestion

The aim of this study was to clarify the possibilities to increase the amount of soluble chemical oxygen demand (SCOD) and methane production of sludge using ultrasound technologies with and without oxidising agents. The study was done using multivariate data analyses. The most important factors affected were discovered. Ultrasonically assisted disintegration increased clearly the amount of SCOD of sludge. Also more methane was produced from treated sludge in anaerobic batch assays compared to the sludge with no ultrasonic treatment. Multivariate data analysis showed that ultrasonic power, dry solid content of sludge (DS), sludge temperature and ultrasonic treatment time have the most significant effect on the disintegration. It was also observed that in the reactor studied energy efficiency with high ultrasound power together with short treatment time was higher than with low ultrasound power with long treatment time. When oxidising agents were used together with ultrasound no increase in SCOD was achieved compared the ultrasonic treatment alone and only a slight increase in total organic carbon of sludge was observed. However, no enhancement in methane production was observed when using oxidising agents together with ultrasound compared the ultrasonic treatment alone. Ultrasound propagation is an important factor in ultrasonic reactor scale up. Ultrasound efficiency rose linearly with input power in sludge at small distances from the transducer. Instead, ultrasound efficiency started even to decrease with input power at long distances from the transducer.