IN VIVO CHLOROPHYLL a FLUORESCENCE TRANSIENTS AND THE CIRCADIAN RHYTHM OF PHOTOSYNTHESIS IN GONYAULAX POLYEDRA

Abstract— The intensity of chlorophyll a fluorescence during the early part of fluorescence induction at O , initial fluorescence, and P, peak fluorescence, was higher during the day phase of the circadian cycle than during the night phase in continuous light (LL) conditions and was positively correlated with the rate of oxygen evolution. The circadian rhythm in fluorescence in LL persisted in the presence of 10μM 3–(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), which blocks electron flow from photo-system (PS) II in photosynthesis. The rhythmic changes in fluorescence intensity are consistent with a lower rate constant for radiationless transitions during the day phase than during the night phase of the circadian rhythmicity. The circadian changes in the intensity of fluorescence were abolished at 77K, which may indicate the importance of structural changes in membranes in circadian oscillations.     

Poly(4‐vinylpyridine) as the host ligand of metal‐containing chromophores for second‐order nonlinear optical active materials

Two formulas of grafted polymers with metal‐containing chromophores, potentially suitable for second‐order nonlinear optics applications, are described. Two chromophores were obtained from a tridentate ligand coordinated to Cu(II) or Pd(II) ions. The organometallic chromophore fragments were grafted to poly(4‐vinylpyridine) by the pyridinic nitrogen of the host polymer. Some qualities displayed by the new metallated polymers are remarkable: (1) a high value of the first hyperpolarizability coefficient of the chromophores, (2) a high content of the grafted chromophore in the polymers (up to 60 wt %), (3) a considerable increase in the glass‐transition temperatures (up to 240 °C), (4) good thermal stability in air (ca. 280 °C), and (5) good optical transparency of the films. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2987–2993, 2002     

REASSESSMENT OF THE DIFFERENTIAL EFFECTS OF ULTRAVIOLET AND IONIZING RADIATION ON HIV PROMOTER: THE USE OF CELL SURVIVAL AS THE BASIS FOR COMPARISONS

Abstract: Effects of different radiation treatments on the human immunodeficiency virus-1 (HIV) promoter were reassessed for exposures comparable to those encountered in clinical or cosmetic practice, using survival of the host cell as a basis for comparisons. The exposures were performed with two ultraviolet radiation sources commonly used as medical or cosmetic devices (UVASUN 2000 and FS20 lamps), a germicidal (G15T8) lamp and an X-ray machine. The UVC component of the FS20 lamp was filtered out. The emission spectra of the lamps were determined. The characteristics of these sources allowed us to discriminate among effects of UVA1 (340–400 nm), UVB + UVA2 (280–340 nm) and UVC (254 nm) radiations. Effects of irradiation were ascertained using cultures of HeLa cells stably transfected with the HIV promoter linked to a reporter—chloramphenicol acetyl transferase—gene. The exposures used caused at least two logs of cell killing. In this cytotoxicity range, UVA1 or X radiations had no effect on the HIV promoter, whereas UVB + UVA2 or UVC radiations activated the HIV promoter in a fluence-dependent manner. Survivals following exposure to UVB + UVA2 or UVC radiation were (1) at the lowest measurable HIV promoter activation, 30 and 20%, respectively, (2) at one-half maximal activation, 6 and 3%, respectively and (3) at the maximal activation, 0.5 and 0.2%, respectively. The results suggest that, among the radiations studied, UVB is the most important modality from the viewpoint of its potential effects on HIV-infected individuals, since (1) UVA1 or X radiations have no effects on the HIV promoter, (2) human exposure to UVC radiation is infrequent and (3) human UVB exposure is very common.     

Method validation and qualification of instruments for atomic spectrometry

This work describes the analytical procedures for atomic absorption and inductively coupled plasma (ICP) techniques that have to be used in order to obtain a license to sell drugs in the USA. The qualification of atomic absorption spectrometers and ICP instruments is described. The method validation characteristics, e.g., accuracy, precision, linearity, range, detection limits, and quantification are discussed. The time involved and the quality of documentation are pointed out. The consequences for laboratory personnel and operating costs are also discussed.     

Fragmentation of 1-aryl-5-(2-dialkylaminovinyl)-1H-tetrazoles upon electron impact

The mass spectrometric behaviour of 1-aryl-5-(2-dialkylaminovinyI)-lH-tetrazoles was studied, especially 1-phenyl-5-(2-dimethylaminovinyl)-l H-tetrazole as a typical example of D- and ¹⁵N-labelled derivatives revealed a rearrangement via a carbodiimide-like intermediate ion.     

Groups of paramagnetic centres in coal samples with different carbon contents

Complex systems of paramagnetic centres existing in demineralised flame coal (71.4 wt% C), medium-rank coal (85.6 wt% C) and anthracite (94.9 wt% C) were analysed by electron paramagnetic resonance spectroscopy (EPR). Different groups of paramagnetic centres were searched in macerals (exinite, vitrinite, inertinite) of coals with carbon contents of 73.8 wt% C and 85.6 wt% C. Experimental EPR spectra were fitted by different superposition of theoretical lines. Total concentration of paramagnetic centres both in coal and macerals increases with carbon content in the sample. Total concentration of paramagnetic centres in macerals increases from exinite to inertinite. Four groups of paramagnetic centres were found in medium-rank coal, and only two groups exist in flame coal and anthracite. The EPR spectrum of medium-rank coal is a superposition of two broad and two narrow lines. Both broad and narrow, and two narrow lines were measured in EPR spectra of flame coal and anthracite, respectively. Two types of paramagnetic centres with broad lines and one group with narrow lines exist in exinite and vitrinite from medium-rank coal. Two narrow components were observed in EPR spectra of its inertinite. Two different broad electron paramagnetic resonance signals were detected for macerals from low-coalificated coal. Paramagnetic centres systems of medium-rank coal samples reveal the most complex character. Broad EPR lines were not observed for the higher coalificated samples, i.e., anthracite and inertinite from medium-rank coal. Narrow lines do not occur in EPR spectra of low-coalificated macerals. Strong dipolar interactions and fast spin-lattice relaxation processes are characteristic for paramagnetic centres with broad lines. Strong exchange interactions and short spin-lattice relaxation time were measured for paramagnetic centres with the narrowest EPR signals.     

Sequential determination of platinum, ruthenium, and molybdenum in carbon-supported Pt, PtRu, and PtMo catalysts by atomic absorption spectrometry

A simple accurate and precise analytical method for the determination of platinum, ruthenium, and molybdenum in Pt, PtRu, and PtMo nanoparticles catalysts deposited on high-surface area carbon by flame atomic absorption spectrometry (FAAS) and graphite furnace atomic absorption spectrometry (GFAAS) is described. The complete digestion of samples (0.010-0.020 g), which contain noble metals (NMs) in the range between 0 and 30% in combination among them or with other non-NMs, is obtained under mild conditions using both concentrated HCl and HCl+HNO₃ (1+1 (v/v)) mixture to boiling for 30 min in an open vessel. Carbon is separated from the solution by filtering it. Under optimized conditions of the flame, the poor sensitivity of platinum is enhanced 50-fold in presence of 1% (m V⁻¹) ascorbic acid, whereas the analytical signal of ruthenium increased by the presence of co-existing platinum. Any kind of interference is observed on the analytical signal of molybdenum. Recovery test obtained by analyzing commercial powder catalysts ranged from 99 to 101%. The precision, expressed as relative standard deviation of five measurements, is better than 1%. Electrode catalysts, made by using the carbon-supported platinum-based powder catalysts, have been analyzed for the metal loadings onto the electrode by GFAAS after dissolution under the same conditions used for the powder catalysts. The precision, expressed as relative standard deviation of three measurements, is better than 2%.     

Synthese,Struktur und einige Reaktionen [N-(N′,N′,N″,N″-tetramethyl)-guanidinyl]-substituierter Phosphorylverbindungen

Synthesis, Structure, and some Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphoryl Compounds The tetramethylguanidinyl-substituted phosphoryl compounds 1 – 10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N′,N′,N″,N″-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N′,N′,N″,N″-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF₃ · Et₂O at both imino nitrogen atoms with formation of the bis-BF₃-adduct 12 . The X-ray structure determination of phenylphosphonic acid-bis(N′,N′,N″,N″-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond.     

GIAO/DFT evaluation of 13C NMR chemical shifts of selected acetals based on DFT optimized geometries

DFT/B3LYP calculations of the ground-state conformation of eight cyclic and acyclic acetals are presented and compared with experimental data. Results of single-point GIAO/DFT calculations at five different levels of theory show that isotropic shieldings need to be empirically scaled to achieve agreement with experimental chemical shifts. Statistical evaluation of data indicates that the most accurate prediction of 13C chemical shifts is achieved at the MPW1PW91/6-311G** level of theory. An empirical equation describing the relationship between delta values and shielding constants is postulated. This equation has been applied to the non-chair ground-state conformation of the six-membered acetonide and to the conformationally flexible benzodioxonine derivative. The agreement observed between the experimental and predicted chemical shifts shows that calculations at the MPW1PW91/6-311G** level of theory are adequate for addressing questions of conformation.