Relation between asymmetrical orbital angular momentum and irradiance-profile rotation for partially coherent beams

On the basis of the irradiance-moment formalism for describing general partially coherent beams, we investigate the relation between the spatial orientation of the transverse beam profile upon propagation and the asymmetrical part of its orbital angular momentum (OAM). More specifically, a necessary and sufficient condition (one-to-one correspondence) is shown between freely propagating non-rotating beams and vanishing asymmetrical OAM. As a corollary, it is obtained that any beam emerging from optical systems that transform a rotating field into a non-rotating beam exhibits vortex OAM only.     

The determination of certain major and minor elements in geological samples by inductively coupled plasma atomic emission spectrometry. Some interference problems with the analysis of geological standard reference materials and nutrition supplements

Direct ICP-AES measurements of the digested geological standard reference material samples yielded the wrong information about their composition. The differences between certified and measured concentrations of the samples were due to the complicated sample matrix. The measured concentrations can be successfully corrected by using a multiple linear regression technique. The correction is based on the multiple regression line calculated from the analytical results at synthetic mixtures of matrix elements, where concentrations varied on five levels. There were no significant (P = 0.05) differences between certified and measured concentrations in standard reference materials after the correction. The same method was used in the analysis of nutrition supplements. Received: 25 January 2000 / Revised: 15 March 2000 / Accepted: 31 March 2000     

Synthesis,Characterization and Photocleavage of Bis-decyl Pteroic Acid: A Folate Derivative with Affinity to Biomembranes†

Here, we provide mechanistic insight to the photocleavage of a compound in the folate family, namely pteroic acid. A bis-decyl chain derivative of pteroic acid was synthesized, structurally characterized and photochemically investigated. We showed that, like folic acid, pteroic acid and the decylated derivative undergo a photocleavage reaction in the presence of H₂O, while no reaction was observed in methanol solution. Furthermore, density functional theory calculations were carried out to predict relative stabilities of hypothetical mono-, bis- and tris-decylated pteroic acid derivatives to help rationalize the regioselectivity of the bis-decyl pteroic acid product. Additionally, the lipophilicity of the bis-decyl pteroic acid appears to confer a hydrophobic property enabling an interaction with biomembranes.     

Determination of 2,4-D and Dicamba in food crops by MEKC

Summary The determination of 2,4-D (2,4-dichlorophenoxyacetic acid) and Dicamba (2-methoxy-3,6-dichlorobenzoic acid) residues in sugar cane, rice and corn was performed by a supercritical fluid extraction (SFE) method using CO₂/acetone as extraction mix and an SFE apparatus developed in our laboratory. The extracts were cleaned up after extraction by both liquid-liquid partition and a Florisil column. Micellar electrokinetic capillary chromatography (MEKC) coupled with ultraviolet on-column detection was used for the analysis of these pesticides. The detection limits were improved by the preparation of a special detection cell with an increased pathlength that gave detection limits of ca. 0.6 pg for 2,4-D and Dicamba. Our results demonstrated that capillary electrophoresis can be a powerful new analytical tool for pesticide residue analysis.     

Distinct dynamic behaviors of water molecules in hydrated pores

Water molecules confined inside narrow pores are of great importance in understanding the structure, stability, and function of water channels. Here we report that besides the H-bonding water that structures the pore, the permanent presence of a significant, fast-moving fraction of incompletely H-bonded water molecules inside the pore should control the free entry and exit of water. This is achieved by means of complementary DSC and solid-state NMR studies. We also present compelling evidence from X-ray diffraction data that the cluster formed by six water molecules in the most stable cage-like structure is sufficiently hydrophobic to be stably adsorbed in a nonpolar environment.     

Principles of analytical calibration/quantification for the separation sciences

Calibration is an operation whose main objective is to know the metrological status of a measurement system. Nevertheless, in analytical sciences, calibration has special connotations since it is the basis to do the quantification of the amount of one or more components (analytes) in a sample, or to obtain the value of one or more analytical parameters related with that quantity. Regarding this subject, the aim of analytical calibration is to find an empiric relationship, called measurement function, which permits subsequently to calculate the values of the amount (x-variable) of a substance in a sample, from the measured values on it of an analytical signal (y-variable). In this paper, the metrological bases of analytical calibration and quantification are established and, the different work schemes and calibration methodologies, which can be applied depending on the characteristic of the sample (analyte+matrix) to analyse, are distinguished and discussed. Likewise, the different terms and related names are clarified. A special attention has been paid to those analytical methods which use separation techniques, in relation with its effect on calibration operations and later analytical quantification.     

Coexistence of Two Thermally Induced Intramolecular Electron Transfer Processes in a Series of Metal Complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)2] (M=Co,Fe, and Ni) bearing Non‐Innocent Catechol‐Based Ligands: A Combined Experimental and Theoretical Study

The different thermally induced intermolecular electron transfer (IET) processes that can take place in the series of complexes [M(Cat‐N‐BQ)(Cat‐N‐SQ)]/[M(Cat‐N‐BQ)₂], for which M=Co ( 2 ), Fe ( 3 ) and Ni( 4 ), and Cat‐N‐BQ and Cat‐N‐SQ denote the mononegative (Cat‐N‐BQ^?) or dinegative (Cat‐N‐SQ^2?) radical forms of the tridentate Schiff‐base ligand 3,5‐di‐tert‐butyl‐1,2‐quinone‐1‐(2‐hydroxy‐3,5‐di‐tert‐butylphenyl)imine, have been studied by variable‐temperature UV/Vis and NMR spectroscopies. Depending on the metal ion, rather different behaviors are observed. Complex 2 has been found to be one of the few examples so far reported to exhibit the coexistence of two thermally induced electron transfer processes, ligand‐to‐metal (IET^LM) and ligand‐to‐ligand (IET^LL). IET^LL was only found to take place in complex 3 , and no IET was observed for complex 4 . Such experimental studies have been combined with ab initio wavefunction‐based CASSCF/CASPT2 calculations. Such a strategy allows one to solicit selectively the speculated orbitals and to access the ground states and excited‐spin states, as well as charge‐transfer states giving additional information on the different IET processes.     

Fluorescence-quenching of Tryptophan Ion-18-crown-6 Complex——A Different Observation from Its Neutral Counterpart

It is well-known that primary amines form inclusive complexes with crown ethers. This kind of noncova-lently inclusive complexes,exemplified tryptophan complex with 18-crown-6,was studied by combination of two experimental methods,fluorimetry and mass spectrometry,with theoretical calculation. Fluorescence intensity of tryptophan in the absence and the presence of 18-crown-6 in aqueous HAc-NaAc buffer solution at pH=3.73 has been studied by fluorometry. The fluorescence intensity decreases significantly wit...     

Two new bromoindoles from red alga Laurencia similis

Two new bromoindole alkaloids have been isolated from the ethanolic extract of the red alga Laurencia similis.On the basis of chemical and spectroscopic methods(including 1D and 2D NMR technique),their structures have been elucidated as 2,2′,5,5′,6,6′-sixibromo -3,3′-bi-1H-indole and 3,5-dibromo-1-methylindole,respectively.