bluuebunny/crossref_metadata_2025 huggingface dataset:
Modulation of the catalytic activity of free and immobilized peroxidase by extremely low frequency electromagnetic fields: dependence on frequency
Authors: Portaccio M. , De Luca P. , Durante D. , Grano V. , Rossi S. , Bencivenga U. , Lepore M. , Mita D.G.
Published: January 2005

A study of the influence of electromagnetic fields (EMF) of various frequencies, from 50 up to 400 Hz, on the catalytic activity of soluble and insoluble horseradish peroxidase (POD) was carried out. To simulate the conditions in which the enzyme operates in vivo, the POD was immobilized by entrapment on a gelatin membrane or by covalent attachment on a nylon graft membrane. The rate of inactivation of the soluble POD was found to exhibit positive and negative interactions with the 1 mT applied magnetic field, with an optimum positive effect at 130 Hz. The immobilized PODs, on the contrary, do not exhibit negative interactions, but show a maximum positive interaction at 150 Hz when entrapped and at 170 Hz when covalently attached. At 50 Hz and at frequencies higher than 250 Hz no effects were observed with insoluble POD. The optimum frequency of positive interaction between the EMF and the catalytic activity of the insoluble enzymes is shifted with respect to that of the soluble enzymes towards higher frequencies, the size of the shifts being dependent on the intensity of the physical forces involved in the immobilization process. Bioelectromagnetics 26:145–152, 2005. © 2005 Wiley‐Liss, Inc.
Morphological anomalies in pollen tubes of Actinidia deliciosa (kiwi) exposed to 50 Hz magnetic field
Authors: Dattilo Arduino M. , Bracchini Luca , Loiselle Steven A. , Ovidi Elisa , Tiezzi Antonio , Rossi Claudio
Published: January 2005

The role of the pollen grain, with respect to the reproductive process of higher plants, is to deliver the spermatic cells to the embryo sac for egg fertilisation. Delivery occurs through the pollen tube, a self produced organ that is generated when the pollen grain reaches the stigma surface. The effect of magnetic fields on pollen tube growth was reported in a recent publication by Germanà et al. Pollen tube growth is an interesting candidate for the detailed study of the effects of electromagnetic fields on cytoplasmic structures and organelles. In this research Actinidia deliciosa (kiwifruit) pollen grains were germinated in the presence of an alternating magnetic field (50 Hz). Our results, although of preliminary nature, show that pollen tube growth is affected by magnetic fields. The analysis of the observed anomalies in the pollen tube appear to be the result of changes in the ionic charges within the pollen tube cytoplasm. Bioelectromagnetics 26:153–156, 2005. © 2005 Wiley‐Liss, Inc.
A numerical and experimental comparison of human head phantoms for compliance testing of mobile telephone equipment
Authors: Christ Andreas , Chavannes Nicolas , Nikoloski Neviana , Gerber Hans‐Ulrich , Poković Katja , Kuster Niels
Published: January 2005

A new human head phantom has been proposed by CENELEC/IEEE, based on a large scale anthropometric survey. This phantom is compared to a homogeneous Generic Head Phantom and three high resolution anatomical head models with respect to specific absorption rate (SAR) assessment. The head phantoms are exposed to the radiation of a generic mobile phone (GMP) with different antenna types and a commercial mobile phone. The phones are placed in the standardized testing positions and operate at 900 and 1800 MHz. The average peak SAR is evaluated using both experimental (DASY3 near field scanner) and numerical (FDTD simulations) techniques. The numerical and experimental results compare well and confirm that the applied SAR assessment methods constitute a conservative approach. Bioelectromagnetics 26:125–137, 2005. © 2005 Wiley‐Liss, Inc.
Impulsivity, self‐control, and delay discounting in persons with acquired brain injury
Authors: Dixon Mark R. , Jacobs Eric A. , Sanders Scott , Guercio John M. , Soldner James , Parker‐Singler Susan , Robinson Ashton , Small Stacey , Dillen Jeffrey E.
Published: January 2005

The present paper describes two studies in which participants with and without acquired brain injuries were compared on a temporal discounting task involving various hypothetical amounts of money available at varying delay values. During Experiment 1, both groups of participants were presented with choices between amounts of money ranging from 1 to 1000 US dollars at delays from 1 week to 10 years. The results obtained from this procedure were consistent with previous models of temporal delay discounting for control group participants, yet not for the majority of the participants with acquired brain injuries. During Experiment 2, adjustments in hypothetical amounts and delays were made whereby the amounts of money ranged from 1 to 20 US dollars at delays from 1 day to 1 year. These manipulations yielded data generally consistent with temporal delay discounting models previously reported in the published literature. The utility of using delay discounting procedures as a means of assessing impulsivity in persons with acquired brain injuries is presented. Copyright © 2005 John Wiley & Sons, Ltd.
Effects of therapist gender and type of attention on assessment and treatment of attention‐maintained destructive behavior
Authors: LeBlanc Linda A. , Hagopian Louis P. , Marhefka Jean M. , Wilke Arthur E.
Published: January 2005

Adult attention frequently serves as a maintaining variable for problem behavior (Iwata et al., 1994). In addition, different aspects of attention such as the content of a statement or the person delivering the attention may moderate the rate of problem behavior and potentially affect treatment outcome (Fisher, Ninness, Piazza, & Owen‐DeSchryver, 1996). In the current study, we examined the effects of two variables hypothesized to affect the rate of attention‐maintained aggression in an adolescent female with profound mental retardation: gender of therapist and type of attention (physical versus verbal). The initial study examined the results of functional analyses conducted with therapists of different genders. An analysis was then conducted to determine the main and interaction effects of therapist gender and type of attention on the effectiveness of noncontingent reinforcement. The results indicate that each variable affected the rate of problem behavior (i.e., main effects) and that the two variables combined to produce an even greater effect (i.e., interaction effect) for males than for females. Next, we examined the impact of therapist gender on the effectiveness of an alternative intervention (functional communication training with extinction). The results support the initial hypotheses that therapist gender impacted both assessment and intervention results for this adolescent female. Copyright © 2001 John Wiley & Sons, Ltd.
Reducing stereotypic behavior through discrimination training, differential reinforcement of other behavior, and self‐monitoring
Authors: Shabani Daniel B. , Wilder David A. , Flood William A.
Published: January 2005

The effect of a treatment package designed to reduce stereotypic body rocking was examined in a child diagnosed with autism. After baseline, the participant was taught to discriminate between inappropriate (e.g. sitting in a chair and rocking) and appropriate (e.g. sitting in a chair without rocking) behavior. During intervention, both a therapist and the participant himself monitored the occurrence of rocking behavior. A non‐resetting 5 min differential reinforcement of other behavior (DRO) schedule was also introduced. A multiple baseline across behaviors (sitting and standing) design was used to evaluate the effects of the intervention package. The results indicated that the intervention was effective in eliminating body rocking. In addition, the DRO schedule was successfully increased to 20 min for sitting and 17 min for standing and the treatment was successfully introduced at the child's school. Copyright © 2001 John Wiley & Sons, Ltd.
Inclusion complexes of nabumetone with β‐cyclodextrins: thermodynamics and molecular modelling studies. Influence of sodium perchlorate
Authors: Goyenechea Nerea , Sánchez Miguel , Vélaz Itziar , Martín Carmen , Martínez‐Ohárriz Ma Cristina , González‐Gaitano Gustavo
Published: January 2005

Fluorescence, 1H‐NMR and molecular mechanics have been used to study the inclusion complexes of nabumetone (4,6‐methoxy‐2‐naphthyl‐butan‐2‐one; NAB) with β‐cyclodextrin (β‐CD), randomly methylated‐β (Mβ‐CD) and hydroxypropyl‐β‐cyclodextrins (HPβ‐CD). The emission spectrum of NAB shows a maximum whose fluorescence intensity increases with the different β‐CDs growing concentrations. This phenomenon allows calculation of the stability constants at 15, 25, 37 and 45°C. The thermodynamic parameters ΔH° and ΔS° for the inclusion process were obtained from the temperature dependence of the stability constants. Molecular mechanics calculations, together with proton NMR measurements, for the complex with β‐CD prove that the complex can be formed by penetration through any of the rims, with the naphthalene nucleus included and the substituents outside the cavity. The influence of NaClO4 in the aforementioned complexes has been analysed by spectrofluorimetric measurements. It has been found that the stability constants for the complexes decrease with the salt concentration; the causes are discussed. Copyright­© 2001 John Wiley & Sons, Ltd.
Extraordinary hyperconjugation of the methyl group in the S1 state of 8‐methylquinoline
Authors: Yang Rong , Schulman Stephen G.
Published: January 2005

8‐Methylquinoline is unique among the monomethylquinolines in the red‐shift it shows in the absorption band derived from the short axis polarized (1La ← 1A) electronic transition, relative to that in quinoline itself. The effect is even more pronounced in the 8‐methylquinolinium cation, with the 1La band clearly emerging on the long‐wavelength side of the 1Lb band, which is normally the longest wavelength absorption band in quinolines substituted with weakly interacting functional groups. The fluorescences of 8‐methylquinoline and its conjugate acid show a pH dependence which is typical of N‐heterocylic bases that undergo hydrolysis in the lowest excited singlet state. These observations are explained in terms of hyperconjugation in the lowest excited singlet state, with electronic charge being swept into the quinoline ring by coupling of the short‐axis polarized transition of the ring system with the electrons of the methyl group in the 8‐position of the ring. Copyright © 2001 John Wiley & Sons, Ltd.
Membrane fusion induced by a lipopeptidic epitope from VP3 capside protein of hepatitis A virus
Authors: Chávez Abelardo , Pujol Montserrat , Alsina M. Asunción , Cajal Yolanda
Published: January 2005

Palmitoyl‐VP3(110–121) (PVP3) is a synthetic lipopeptide derivative of a continuous epitope from the VP3 capsid protein of hepatitis A virus, and it is highly immunogenic in vivo. We have investigated the interaction of PVP3 with lipid model membranes of varying surface charge. Binding of PVP3 to anionic vesicles of PC/SM/PE/PS; (PC) 1‐palmitoyl‐2‐oleoyl‐phosphatidylcholine, (SM) sphingomyelin, (PE) 1,2‐dipalmitoyl‐phosphatidylethanolamine and (PS) L‐α‐phosphatidyl‐L‐serine, a composition that mimics the lipid component of natural membranes, was determined by tryptophan fluorescence and quenching experiments. In addition, and given the anionic net charge of the lipopeptide, binding to zwitterionic (PC/SM/PE) and cationic PC/SM/PE/DOTAP (DOTAP) 1,2‐dioleoyl‐3‐trimethylammonium‐propane mixtures was also determined. PVP3 binds to all three types of vesicles, but it adopts different forms depending on the electrical charge of the interface. This conclusion is supported by the insertion of PVP3 into lipid monolayers of the same charges spread at the air–water interface. The bound lipopeptide has membrane‐destabilizing effects in all three vesicle compositions, as demonstrated by leakage of vesicle contents, whereas lipid mixing only occurs in cationic liposomes. Our results provide useful information for the design of a liposomal system that promotes a direct delivery of the membrane‐incorporated immunogen to the immunocompetent cells, potentially increasing the immune response from the host. Copyright © 2001 John Wiley & Sons, Ltd.
Reporter cell lines are useful tools for monitoring biological activity of nuclear receptor ligands
Authors: Balaguer Patrick , Boussioux Anne‐Marie , Demirpence Ediz , Nicolas Jean‐Claude
Published: January 2005

To characterize the specificity of synthetic compounds for nuclear receptors, we established stable cell lines expressing the luciferase gene and different wild‐type or chimaeric receptors. MCF‐7 cells, which express the oestrogen receptor α (ERα), and HeLa cells, which do not express the oestrogen receptor, were transfected with a plasmid containing the luciferase gene downstream from a minimum promoter (β‐globin) and an oestrogen‐responsive element, generating the MELN and the HELN cell lines, respectively. MELN cells enabled the detection of compounds that bind to the ERα or interfere with its pathway. HELN cells were used to establish stable transfectants expressing different nuclear receptors containing the DNA‐binding domain of the oestrogen receptors. We thus established ERα or ERβ reporter cell lines by transfecting ERα or ERβ expression plasmids, and also retinoic acid receptor α, β or γ reporter cell lines by transfecting the chimaeric RAR gene, in which the DNA‐binding domain was replaced by the ERα DNA‐binding domain. Copyright © 2001 John Wiley & Sons, Ltd.
Interaction study of peptide from VP3 capsid protein of hepatitis A virus through monolayers and fluorescence spectroscopy
Authors: Sospedra P. , Prat J. , Haro I. , Mestres C. , Busquets M. A.
Published: January 2005

A synthetic peptide with the sequence [Lys113]VP3(110–121): FWRKDLVFDFQV, corresponding to an epitope of the VP3 capsid protein of hepatitis A virus (HAV), was synthesized by solid phase and characterized. To obtain insight into its physicochemical properties and to understand its possible mechanism of action at the membrane level, interaction with DPPC or DPPC/DPPG (95/5) liposomes and lipid monolayers of DPPC, DPPG, SA, PS, PA and SM were studied by fluorescence spectroscopy and Langmuir–Blotgett films technique, respectively. Fluorescence studies showed that the peptide was in a hydrophobic environment when DPPC liposomes were used. The addition of a 5% of a charged lipid, DPPG, to the preparations changed the preference of the peptide towards a polar surrounding. However, the peptide had a high surface activity (nmol/L) and was able to incorporate into lipid monolayers. Interaction was higher with charged phospholipids than with neutral ones. These results may have physiological significance in the mechanism of infection of host hepatic cells by HAV. Copyright © 2001 John Wiley & Sons, Ltd.
Attempt to separate the fluorescence spectra of adrenaline and noradrenaline using chemometrics
Authors: Nikolajsen Rikke P.H. , Hansen Åse Marie , Bro Rasmus
Published: January 2005

An investigation was conducted on whether the fluorescence spectra of the very similar catecholamines adrenaline and noradrenaline could be separated using chemometric methods. The fluorescence landscapes (several excitation and emission spectra were measured) of two data sets with respectively 16 and 6 samples were measured, the smaller data set with higher resolution and i.e. precision. The samples were artificial urine (pH ≃ 3) spiked with the catecholamines in the concentration ranges 40–1200 nmol/L and 5.5–18 µmol/L, respectively. Unfold partial least squares regression (Unfold‐PLSR) on the larger data set and parallel factor analysis (PARAFAC) of the six samples of the smaller set showed that there was no difference between the fluorescence landscapes of adrenaline and noradrenaline. It can be concluded that chemometric separation of adrenaline and noradrenaline is not obtainable using this type of fluorescence measurement. Raman scatter, which overlaps the catecholamine spectra, was shown not to have any influence on the models calculated. Copyright © 2001 John Wiley & Sons, Ltd.
A fibre‐optic calcium ion sensor using a calcein derivative
Authors: Sloan W. D. , Uttamlal M.
Published: January 2005

This paper describes the development of a new fibre‐optic calcium ion sensor based on the immobilization of the calcein derivative, calcein acrylamide (CA) onto an optical fibre. The method involves the covalent attachment of CA in a polymer which itself is covalently bonded to an optical fibre. The fluorescence of CA is pH‐sensitive in the region 4–12 and also increases as a function of Ca2+ concentration at pH > 12. Typically, the indicator is sensitive to Ca2+ in the concentration range 0–20 µmol/L, with a linear region occurring when the concentration of calcium is equal to or below that of CA. The binding ratio of Ca2+ to CA in the linear calibration region is 1:1 and beyond the linear region is 2:1. The calcium‐sensitive polymer is prepared using photo‐initiated polymerization of a stock solution containing CA, monomer, a crosslinker and a photo‐initiator. The monomer units used were acrylamide and acrylamide doped with MAPTAC. The fluorescence characteristics of bound CA in acrylamide are similar to that of CA in solution. However, the cationic nature of the polymer doped with MAPTAC allows analysis of Ca2+ to be carried out in pH 8.5 solution. The Ca2+ sensing range of the sensor is typically 0–12 µmol/L. Copyright © 2001 John Wiley & Sons, Ltd.
Thiols enhance the sensitivity of luminescent assays for non‐cross‐linked and covalently cross‐linked aminophthalhydrazides
Authors: Achyuthan Komandoor E.
Published: January 2005

Transglutaminases catalyse an acyl‐transfer reaction between the γ‐carboxamide of a protein or peptide‐bound glutamine (P‐CH2‐γCH2‐CO‐1NH2) and the primary amino group of mono‐ or polyamines (R‐2NH2), covalently cross‐linking the reactants by an isopeptide bond: P‐CH2‐γCH2‐CO‐1NH2 + R‐2NH2 → P‐CH2‐γCH2‐CO‐2NH‐R + 1NH3. We reported that N‐(4‐aminobutyl)‐N‐ethylisoluminol (ABEI) was a chemiluminescent (CL) amine substrate for transglutaminases. We now identified N‐(6‐aminohexyl)‐N‐ethylisoluminol (AHEI) as a second, less reactive, transglutaminase substrate. A structure‐based explanation is offered for the lower reactivity of AHEI. Optimum CL from non‐cross‐linked or cross‐linked ABEI or AHEI was elicited in the presence of 10 mmol/L dithiothreitol, by oxidizing with a mixture of 20 mmol/L potassium ferricyanide and 10 mmol/L hydrogen peroxide in 100 mmol/L NaOH. The limits of detection and quantitation for non‐cross‐linked aminophthalhydrazides obtained in this system were: 20 fmol and 60 fmol for ABEI and 10 fmol and 30 fmol for AHEI. These values represented a 500–800‐fold improved sensitivity. Delayed peak CL and CL decay in the presence of dithiothreitol contributed to improving the sensitivity. The data could be useful for improving the immunoassays for aminophthalhydrazides and facilitate the development of high throughput assays for transglutaminases. Copyright © 2001 John Wiley & Sons, Ltd.
Analysis of single‐cell cultures by immunoaffinity capillary electrophoresis with laser‐induced fluorescence detection
Authors: Phillips Terry M.
Published: January 2005

Neuropeptide regulation of immunological activity is becoming an important issue in both basic and clinical sciences, necessitating the need for analysis to be performed at the single‐cell level. A microsampling procedure has been developed for studying secretion of biologically important peptides from neuropeptide‐stimulated lymphocytes, based on microdialysis sampling coupled to immunoaffinity capillary electrophoresis (ICE), with laser‐induced fluorescence (LIF) detection using a fibre‐optic spectrometer and diode laser excitation. The system demonstrated a limit of detection in the high attomole (10−18 mol/L) range with pure standards and was capable of monitoring secretion from a single cell over time. Using this system it was possible to differentiate the effects of four neuropeptides on both T and B cell release of regulatory cytokines. CD4+ lymphocytes demonstrated a 7.5‐fold increase in cytokine secretion over baseline following stimulation with substance P (SP) and calcitonin gene‐related peptide (CGRP). B cells responded to CGRP and vasoactive intestinal peptide (VIP) stimulation (5.5‐fold increase), but not to SP. These changes took place 12–20 h post‐stimulation and, once the peak secretion had been reached, remained at that level for the duration of the experiment. This system demonstrates the ability to perform high sensitivity measurements on microsamples of biological fluids. Copyright © 2001 John Wiley & Sons, Ltd.
Applications of biochemiluminescence to HACCP
Authors: Champiat Dominique , Matas Nada , Monfort Bertrand , Fraass Hervé
Published: January 2005

The hazard analysis critical control point) (HACCP) system is set up with the aim of ensuring the harmlessness of food along the process chain, from the producer to the ultimate consumer. To set up this system, it is necessary to perform an analysis to identify the dangers and the critical points of the process in real time. Living organisms are detected on the principle of measurement of cellular energy in the form of adenosine triphosphate (ATP), which is produced by all living cells and of particularly by microorganisms. The principle of the bioluminescence of firefly luciferase is applied, whereby a reduced form of luciferin, together with a molecule of oxygen and ATP in the presence of the enzyme luciferase, produces a reaction in which oxyluciferine is released, together with AMP. This is accompanied by a simultaneous release of photons, which are then quantified. The emission spectra recorded with the firefly luciferin/luciferase system is obtained with absolute sensitivity. The method of ATP assays here proposed is adapted for measuring the total content of different adenylates in the cell, i.e. the adenylate pool. ATP concentration is then measured through bioluminescence, i.e. the light is measured by a photomultiplier tube detector and the signal is converted to relative light units (RLU). Thus, RLU have a relationship with the amount of ATP present in the sample, which is not the case with traditional methods. Adequate levels of sensitivity are calculated with appropriate controls and the readings are translated into a statistical designation of positive or negative result. There are numerous illustrations of HACCP applications using biochemiluminescence (BCL) techniques as detection technology in food industry production lines and in control of critical points in real time in industrial applications. Copyright © 2001 John Wiley & Sons, Ltd.
Development of ultra‐high sensitivity bioluminescent enzyme immunoassay for prostate‐specific antigen (PSA) using firefly luciferase
Authors: Seto Yoshiaki , Iba Toshihiko , Abe Katsushi
Published: January 2005

A bioluminescent enzyme immunoassay (BLEIA) for prostate‐specific antigen (PSA) using biotinylated firefly luciferase‐labelled antibody was developed. PSA is an important marker for the diagnosis and management of prostate cancer. Our BLEIA for PSA, based on the two‐step sandwich method, had ultra‐high sensitivity and a very wide measurable range. The detection limit (mean of nine replicates of the zero standard +2 SD) for PSA was 0.25 pg/mL and the measurable range for PSA was 0.25 pg/mL–100 ng/mL. Generally, PSA in the serum exists on two forms, called free PSA (f‐PSA) and complex PSA (c‐PSA), which is formed with α‐antichymotripsin. Thus, the response of the PSA assay to these two forms has to be equimolar in the construction of the assay system. Our BLEIA for PSA also had an equimolar response to them. Copyright © 2001 John Wiley & Sons, Ltd.
Potential of NIR‐FT‐Raman spectroscopy in natural carotenoid analysis
Authors: Schulz H. , Baranska M. , Baranski R.
Published: January 2005

This paper demonstrates the special advantages of FT‐Raman spectroscopy for in situ studies of several carotenoids that occur ubiquitously in the plant kingdom. Spectra obtained from various tissues of a range of plant species indicate that the wavenumber location of CC stretching vibrations is mainly influenced both by the length as well as by the terminal substituents of the polyene chain of carotenoids and by their interaction with other plant constituents. The obtained results show also the usefulness of Raman spectroscopy in the investigation of cis–trans isomerization of carotenoids during processing. Additionally, 2‐D Raman mappings present a unique possibility to evaluate the individual distribution of carotenoids in the intact plant tissue; in this context different 7‐, 8‐, and 9‐double bond conjugated carotenoids can be analyzed independently in the same sample. Furthermore, the use of Raman spectroscopy for in situ detection of unstable substances such as epoxycarotenoids is discussed. © 2005 Wiley Periodicals, Inc. Biopolymers, 2005
Solid‐state NMR studies of collagen‐based parchments and gelatin
Authors: Aliev Abil E.
Published: January 2005

Historical collagen‐based parchments have been studied by solid‐state NMR. In addition, new parchment (produced according to traditional methods) and gelatin from bovine skin were also studied. Wideline 1H and MAS 13C measurements were carried out directly on intact parchments. A simple approach is proposed for evaluation of the extent of parchment degradation based on the linewidth changes in the 13C CPMAS spectra relative to new parchment and gelatin. Structural (bound) water content was estimated from wideline 1H NMR lineshape and relaxation time measurements. It was found that the relative water content in parchments correlates linearly with 13C MAS linewidths. Its decrease on parchment degradation indicates that structural water molecules are of primary importance in stabilizing higher order collagen structures. Backbone and side chain dynamics of collagen in parchments were compared to those of gelatin based on the 13C dipolar‐dephased experiments. Carbonyl 13C chemical shift anisotropies were measured to deduce the geometry of the collagen backbone motion. Unlike previous studies, we found that the collagen backbone motion is similar to that found in other proteins and occurs primarily via small‐angle librations about internal bond directions. © 2005 Wiley Periodicals, Inc. Biopolymers, 2005
Production of high‐purity isomalto‐oligosaccharides syrup by the enzymatic conversion of transglucosidase and fermentation of yeast cells
Authors: Pan Yen‐Chung , Lee Wen‐Chien
Published: January 2005

A method for the production of high‐purity isomalto‐oligosaccharides (IMO) involving the transglucosylation by transglucosidase and yeast fermentation was proposed. The starch of rice crumbs was enzymatically liquefied and saccharified, and then converted to low‐purity IMO syrup by transglucosylation. The low‐purity IMO produced either from rice crumbs or tapioca flour as the starch source could be effectively converted to high‐purity IMO by yeast fermentation to remove the digestible sugars including glucose, maltose, and maltotriose. Both Saccharomyces carlsbergensis and Saccharomyces cerevisiae were able to ferment glucose in the IMO syrup. Cells of S. carlsbergensis harvested from the medium of malt juice were also able to ferment maltose and maltotriose. A combination of these two yeasts or S. carlsbergensis alone could be used to totally remove the digestible sugars in the IMO, coupled with the production of ethanol. The resultant high‐purity IMO, including mainly isomaltose, panose, and isomaltotriose made up more than 98% w/w of the total sugars after a 3‐day fermentation. When the low‐purity IMO was produced from the starch of tapioca flour, 3‐day fermentation under the same conditions resulted in IMO with purity lower than that from rice crumbs. For low‐purity IMO from rice crumbs, fermentation with washed S. carlsbergensis cells harvested at log phase was the most effective. However, for the low‐purity IMO from tapioca flour, incubation with S. cerevisiae for the first 24 h and then supplementing with an equal amount of S. carlsbergensis cells for further fermentation was the most effective approach for producing high‐purity IMO. © 2005 Wiley Periodicals, Inc.
Fluorogenic and fluorescent labeling reagents with a benzofurazan skeleton
Authors: Uchiyama Seiichi , Santa Tomofumi , Okiyama Natsuko , Fukushima Takeshi , Imai Kazuhiro
Published: January 2005

Fluorogenic and fluorescent labeling reagents having a benzofurazan (2,1,3‐benzoxadiazole) skeleton such as 4‐fluoro‐7‐nitro‐2,1,3‐benzoxadiazole (NBD‐F), 4‐N,N‐dimethylaminosulfonyl‐7‐fluoro‐2,1,3‐benzoxadiazole (DBD‐F), 4‐aminosulfonyl‐7‐fluoro‐2,1,3‐benzoxadiazole (ABD‐F), ammonium 7‐fluoro‐2,1,3‐benzoxadiazole‐4‐sulfonate (SBD‐F), 4‐hydrazino‐7‐nitro‐2,1,3‐benzoxadiazole (NBD‐H), 4‐N,N‐dimethylaminosulfonyl‐7‐hydrazino‐2,1,3‐benzoxadiazole (DBD‐H), 4‐nitro‐7‐N‐piperazino‐2,1,3‐benzoxadiazole (NBD‐PZ), 4‐N,N‐dimethylaminosulfonyl‐7‐N‐piperazino‐2,1,3‐benzoxadiazole (DBD‐PZ), 4‐(N‐chloroformylmethyl‐N‐methyl)amino‐7‐N,N‐dimethylaminosulfonyl‐2,1,3‐benzoxadiazole (DBD‐COCl) and 7‐N,N‐dimethylaminosulfonyl‐4‐(2,1,3‐benzoxadiazolyl) isothiocyanate (DBD‐NCS) are reviewed in terms of synthetic method, reactivity, fluorescence characteristics, sensitivity and application to analytes. Copyright © 2001 John Wiley & Sons, Ltd.
High‐performance liquid chromatographic assay for glucuronidation activity of 7‐ethyl‐10‐hydroxycamptothecin (SN‐38), the active metabolite of irinotecan (CPT‐11), in human liver microsomes
Authors: Hanioka Nobumitsu , Jinno Hideto , Nishimura Tetsuji , Ando Masanori , Ozawa Shogo , Sawada Jun‐ichi
Published: January 2005

A simple and sensitive assay for glucuronidation activity of 7‐ethyl‐10‐hydroxycamptothecin (SN‐38), the active metabolite of irinotecan (CPT‐11), in human liver microsomes by high‐performance liquid chromatography (HPLC) with fluorescence detection is reported. The method was validated for the determination of SN‐38 glucuronide (SN‐38G) with respect to specificity, linearity, recovery, stability, precision, accuracy, and limits of detection and quantitation. There was no interference from matrix and non‐enzymatic reactions. The calibration curve for SN‐38G was linear from 5 to 500 nM. Average recoveries ranged from 98 to 100% in spiked human liver microsome samples, and the SN‐38G was stable at 4°C for at least 72 h. The newly developed method was found to be more sensitive and selective than previous methods using thin layer chromatography and HPLC. The limit of quantitation for SN‐38G was 5 nM (2.5 pmol/assay). The intra‐ and inter‐day precision and accuracy were less than 7 and 4%, respectively. The intra‐ and inter‐day precision of enzyme assay for UDP‐glucuronosyltransferase (UGT) activity toward SN‐38 in human liver microsomes was less than 4%. With this improved sensitivity, the kinetics of SN‐38 glucuronidation in human liver microsomes could be determined more precisely. Therefore, this method is applicable to in vitro study on the side effects and drug interactions of CPT‐11 using small amounts of biological sample. Copyright © 2001 John Wiley & Sons, Ltd.

Abbreviations used:

CPT‐11

7‐ethyl‐10‐[4‐(1‐piperidino)‐1‐piperidino]carbonyloxycamptothecine

SN‐38

7‐ethyl‐10‐hydroxycamptothecin

UGTs

UDP‐glucuronosyltransferases.
Detection of perfluorocarbons in blood by headspace solid‐phase microextraction combined with gas chromatography/mass spectrometry
Authors: Mathurin Jean‐Charles , Ceaurriz Jacques de , Audran Michel , Krafft Marie‐Pierre
Published: January 2005

A new method of detection of perfluorocarbon molecules (PFCs) in blood sample has been established. After an extraction and pre‐concentration step performed by headspace solid‐phase microextraction (HS‐SPME), the PFCs are detected by gas chromatography‐mass spectrometry (GC/MS) with an ion trap mass spectrometer in MS and MS/MS modes. The influence of different parameters on the SPME process is discussed. The limit of detection and the linearity of the procedure have been determined for two PFCs. Copyright © 2001 John Wiley & Sons, Ltd.

Abbreviations used:

EI

electron impact

EPO

erythropoietin

FDC

F‐decaline

HS‐SPME

headspace solid‐phase extraction

IOC

International Olympic Committee

LOD

Limit of detection

PDMS

polydimethylsiloxane

PFCs

perfluorocarbon molecules
The relationship between criminal charges, diagnoses, and psycholegal opinions among federal pretrial defendants
Authors: Cochrane Robert E. , Grisso Thomas , Frederick Richard I.
Published: January 2005

This study analyzed data from 1710 criminal defendants referred by federal courts throughout the United States. We examined 12 categories of criminal charges with respect to diagnosed psychopathology and opinions related to competence to stand trial (CST) and criminal responsibility (CR) at the time of the alleged offense. Overall, 18% of the present sample were found to be incompetent to stand trial, while 12% were found to be not criminally responsible or ‘insane.’ In this study, crimes were associated with rates of psychopathology and rates of opinions regarding CST and CR. The findings of this study suggest that individuals who are charged with different crimes have different mental states and psychopathology and are therefore found to have differential rates of competence and sanity. Copyright © 2001 John Wiley & Sons, Ltd.
The “Invisible” 13C NMR Chemical Shift of the Central Carbon Atom in [(Ph3PAu)6C]2+: A Theoretical Investigation
Authors: Le Guennic Boris , Neugebauer Johannes , Reiher Markus , Autschbach Jochen
Published: January 2005

The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage‐like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p‐C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at δ=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close‐lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally.
Solid‐State Molecular Organization and Solution Behavior of Methane‐1,1‐Diphosphonic Acid Derivatives of Heterocyclic Amines: The Role of the Topochemical Ring Modification and the Intramolecular Hydrogen Bonds in Monosubstituted Piperid‐1‐ylmethane‐1,1‐diphosphonic Acids
Authors: Matczak‐Jon Ewa , Videnova‐Adrabińska Veneta , Burzyńska Agnieszka , Kafarski Paweł , Lis Tadeusz
Published: January 2005

The crystal structures of 3‐methylpiperid‐1‐ylmethane‐1,1‐diphosphonic (2), 4‐methylpiperid‐1‐ylmethane‐1,1‐diphosphonic (3), 2‐ethylpiperid‐1‐ylmethane‐1,1‐diphosphonic (4), and 2‐methylpiperid‐1‐ylmethane‐1,1‐diphosphonic (5) acids have been determined and are discussed with respect to their molecular organization and crystal‐packing preferences. The chair conformation, predominant also in solution, favors equatorial positioning of the bulky subsituents of the heterocyclic N and C atoms. The molecular geometry also provides access to intramolecular hydrogen‐bond formation between the axial protons located on the nitrogen atoms, as well as the carbon atoms closest to it, and phosphonic/phosphonate oxygen atoms. The molecules preferably arrange in monolayers, observed in all crystals with an exception of 3. The layers are held in place in the third direction through van der Waals interactions. The analysis of two‐dimensional hydrogen‐bonded networks is concentrated on revealing how the substituent's topology of the molecule affects the solid‐state organization in well‐defined structures and is aimed at unraveling the consequences and the possible conformational changes by stepwise network disruption upon crystal dissolution in water. The solution NMR studies are focused on revealing the role that the topochemistry of the substituent plays for the stereodynamics in 2–5. It is demonstrated that in constrast to piperid‐1‐ylmethane‐1,1‐diphosphonic acid (1), in which the ring inversion/rotation around the CN bond concerted with the NH⋅⋅⋅O hydrogen‐bond breaking/formation process leads to a mixture of two interconverting conformers, the concerted NH⋅⋅⋅O breaking/rotation/NH⋅⋅⋅O formation process in 2 and 3 allows for a predominance of one conformer in solution. However, placement of a substituent at 2‐position in the ring hampers the rotation around the CN bond; this makes 4 and 5 significantly less flexible relative to compounds 1–3. In addition, both compounds 4 and 5 are proved to exist as a mixture of two conformers, the equilibrium of which in acidic solution is shifted towards the conformer found in solid state. In alkaline solutions of 4 and 5, the equilibrium is shifted towards the conformer that is forced by the flipping of the heterocyclic ring. These results correlate well with recently documented differences in the biological potency of this group of compounds.
Anion Control over Interpenetration and Framework Topology in Coordination Networks Based on Homoleptic Six‐Connected Scandium Nodes
Authors: Long De‐Liang , Hill Robert J. , Blake Alexander J. , Champness Neil R. , Hubberstey Peter , Wilson Claire , Schröder Martin
Published: January 2005

Reaction of ScX3 (X=NO3−, CF3SO3−, ClO4−) with 4,4′‐bipyridine‐N,N′‐dioxide (L) affords topologically distinct six‐connected three‐dimensional coordination frameworks, {[Sc(L)3](NO3)3}∞ (1), {[Sc(L)3](CF3SO3)3(CH3OH)2.7(H2O)3}∞ (2), {[Sc(L)3](ClO4)3}∞ (3) and {[Sc(L)4(H2O)2](ClO4)3}∞ (4). Compounds 1, 2 and 3 are networks based on octahedrally co‐ordinated ScO6 centres bound through six oxygen atoms from six separate N‐oxide ligands L. Compounds 1 and 3 are doubly interpenetrated and have α‐polonium‐type structures of 41263 topology based upon three intersecting (4,4) nets. The structure of 2 is unusual and shows parallel, co‐planar layers of (4,4) nets connected in a criss‐crossed fashion to afford a new 48668 topology. In 4 only four ligands L bind to each ScIII centre with two additional water molecules bridging metal nodes. Significantly, the bridges formed by L do not sit in a plane and if connections through L are considered alone the resultant structure is a diamondoid array typically based upon a tetrahedral connecting node at Sc. Five interpenetrating diamondoid networks are observed that are cross‐bridged by water molecules to form a single three‐dimensional array of 4867 topology. Compound 4 can also be viewed as incorporating two intersecting (4,4) grids based upon two ligands L and two bridging waters. Thus, variation of anion, solvent and conditions critically affects the structures of products formed, and the series of polymers reported herein illustrates how tectons based upon (4,4) grids can be combined and distorted to form non‐NaCl topologies and even cross‐bridged, multiply interpenetrated diamondoid materials. Both compounds 2 and 4 represent unusual examples of self‐penetrated coordination frameworks.
Synthesis of Two Linear PADRE Conjugates Bearing a Deca‐ or Pentadecasaccharide B Epitope as Potential Synthetic Vaccines against Shigella flexneri Serotype 2a Infection
Authors: Bélot Frédéric , Guerreiro Catherine , Baleux Françoise , Mulard Laurence A.
Published: January 2005

The blockwise synthesis of the 2‐aminoethyl glycosides of a deca‐ and a pentadecasaccharide made of two and three repeating units, respectively, of the Shigella flexneri serotype 2a specific polysaccharide is reported. The strategy relies on trifluoromethanesulfonic acid mediated glycosylation of a pentasaccharide building block acting as a glycosyl donor and a potential glycoside acceptor. Both targets were made available in amounts large enough for their subsequent conversion into glycoconjugates. Indeed, efficient elongation of the spacer through an acetylthioacetyl moiety and subsequent conjugation onto a Pan HLA DR‐binding epitope (PADRE) T‐cell‐universal peptide resulted in two fully synthetic neoglycopeptides, which will be evaluated as potential vaccines against S. flexneri serotype 2a infections.
Towards Supramolecular Fixation of NOX Gases: Encapsulated Reagents for Nitrosation
Authors: Kang Yanlong , Zyryanov Grigory V. , Rudkevich Dmitry M.
Published: January 2005

The use of simple calix[4]arenes for chemical conversion of NO2/N2O4 gases is demonstrated in solution and in the solid state. Upon reacting with these gases, calixarenes 1 encapsulate nitrosonium (NO+) cations within their cavities with the formation of stable calixarene–NO+ complexes 2. These complexes act as encapsulated nitrosating reagents; cavity effects control their reactivity and selectivity. Complexes 2 were effectively used for nitrosation of secondary amides 5, including chiral derivatives. Unique size–shape selectivity was observed, allowing for exclusive nitrosation of less crowded N‐Me amides 5 a–e (up to 95 % yields). Bulkier N‐Alk (Alk>Me) substrates 5 did not react due to the hindered approach to the encapsulated NO+ reagents. Robust, silica gel based calixarene material 3 was prepared, which reversibly traps NO2/N2O4 with the formation of NO+‐storing silica gel 4. With material 4, similar size–shape selectivity was observed for nitrosation. The N‐Me–N‐nitroso derivatives 6 d,e were obtained with ∼30 % yields, while bulkier amides were nitrosated with much lower yields (<8 %). Enantiomerically pure encapsulating reagent 2 d was tested for nitrosation of racemic amide 5 t, showing modest but reproducible stereoselectivity and ∼15 % ee. Given high affinity to NO+ species, which can be generated by a number of NOX gases, these supramolecular reagents and materials may be useful for NOX entrapment and separation in the environment and biomedical areas.
Synthesis, Characterization, and Complexation of Tetraarylborates with Aromatic Cations and Their Use in Chemical Sensors
Authors: Alaviuhkola Terhi , Bobacka Johan , Nissinen Maija , Rissanen Kari , Ivaska Ari , Pursiainen Jouni
Published: January 2005

Five aromatic borate anions, namely tetrakis(4‐phenoxyphenyl)borate (1), tetrakis(biphenyl)borate (2), tetrakis(2‐naphthyl)borate (3), tetrakis(4‐phenylphenol)borate (4), and tetrakis(4‐phenoxy)borate (5), have been prepared and tested as ion‐recognition sites in chemical sensors for certain aromatic cations and metal ions. To gain further insight into the complexation of the cations, some complexes have been prepared and structurally characterized. The complexation behavior of 1 and 2 towards N‐methylpyridinium (6), 1‐ethyl‐4‐(methoxycarbonyl)pyridinium (7), tropylium (8), imidazolium (9), and 1‐methylimidazolium (10) cations has been studied, and the stability constants of the complexes of 1 with cations 6 and 8 have been measured to compare them with the values for the previously studied complexes of tetraphenylborate. The structures of the borate anions and their complexes have been characterized by NMR and mass spectrometric methods. X‐ray crystal structures have been determined for potassium tetrakis(4‐phenoxyphenyl)borate (K+⋅1), N‐methylpyridinium tetrakis(4‐phenoxyphenyl)borate (6⋅1), 1‐ethyl‐4‐(methoxycarbonyl)pyridinium tetrakis(4‐phenoxyphenyl)borate (7⋅1), tropylium tetrakis(4‐phenoxyphenyl)borate (8⋅1), and imidazolium tetrakis(biphenyl)borate (9⋅2). The results show that borate derivatives are potential candidates for a completely new family of charged carriers for use in cation‐selective electrodes.
Direct Assignment of Enantiofacial Discrimination on Single Heterocyclic Substrates by Self‐induced CD
Authors: Siering Carsten , Grimme Stefan , Waldvogel Siegfried R.
Published: January 2005

The first direct assignment of highly dynamic enantiofacial discrimination acting on a single heterocyclic substrate has been achieved by a combination of experimental and theoretical CD spectroscopy. The interaction of chirally modified hosts based on triphenylene ketals with appropriate prochiral guests can lead to the preferential formation of one diastereomeric host–guest complex. This reversible stereoselective binding transmits the chiral information from remote chiral groups in the host to the strongly absorbing triphenylene chromophore, which gives rise to self‐induced CD. This effect was exploited for the determination of the enantiofacial recognition in various host–guest systems. Inversion of the steric demand either of the chiral substituents at the host or of the prochiral guest leads to almost complete inversion of the resulting CD spectra. For the assignment of the absolute stereochemistry of the complexes, a combined molecular dynamics/quantum‐chemical approach was successfully employed. Despite the size and the highly dynamic character of the supramolecular systems, fundamental properties of the systems and details of the spectra were simulated accurately, providing access to fast and reliable assignment of the enantiofacial preference. The results are highly consistent with available X‐ray data.
Evaluation of the impact of the Webster‐Stratton Parent‐Child Videotape Series on participants in a Midlands town in 2001–2002
Authors: Manby Martin
Published: January 2005

Small groups of parents experiencing problems in managing the behaviour of young children took part in parenting programmes in a Midlands city in 2001–2002 based on the Webster Stratton Parent‐Child Videotape Series. Programmes were evaluated using standardised measures and qualitative data. Most participants who completed the programme (N = 29) in this small scale study had improved scores on all measures. The largest (positive) effects were in reductions in mean total parenting stress levels. Qualitative data confirmed high participant ratings for the facilitators and appreciation for group support; and indicated that partners' views were an important variable. Further research is needed about programme impact on non‐completers (including fathers and minority ethnic participants) and about the influence of non‐participating partners.
The first preparation of enantiopure 1‐methyl‐7‐oxabicyclo[2.2.1]heptan‐2‐one, a versatile chiral building block for terpenoids
Authors: Guan Yu‐Kun , Li Yu‐Lin
Published: January 2005

Methods for the resolution of (±)‐1‐methyl‐7‐oxabicyclo[2.2.1]heptan‐2‐one 1, a versatile chiral building block for terpenoids, have been investigated. While no efficient result was obtained with kinetic resolution methods, both enantiomers of 1 were prepared optically pure for the first time via esterification of the reductive products of 1 with (+)‐mandelic acid and oxidation of the saponified products of diastereomer esters, in an overall yield of 70%. The absolute configurations of (−)‐1 and (+)‐1 were determined as (1S,4R)‐(−)‐1 and (1R,4S)‐(+)‐1 by the CD exciton chirality method and confirmed by Moshers 1H‐NMR method. Chirality 17:113–118, 2005. © 2005 Wiley‐Liss, Inc.
Photoeletrochemical Properties of TiO2 Films Modified with Gold Nanoparticles
Authors: Xu Hong , Liu Ling , Jia Neng‐Qin , Yang Jie , Yan Man‐Ming , Jiang Zhi‐Yu
Published: January 2005

A nano‐Au modified TiO2 electrode was prepared via the oxidation of Ti sheet in flame and subsequent modification with gold nanoparticles. The results of SEM and TEM measurements show that the Au nanoparticles are well dispersed on TiO2 surface. A near 2‐fold enhancement in photocurrent was achieved upon the modification with Au nanoparticles. From the results of photocurrent and electrochemical impedance experiments it was found that the flatband potential of nano‐Au/TiO2 electrode negatively shifted about 100 mV in 0.5 mol/L Na2SO4 solutions compared with that of bare TiO2 electrode. The improvement of photoelectrochemical performance was explained by the inhibition for charge recombination of photo‐induced electrons and holes, and the promotion for interfacial charge‐transfer kinetics at nano‐Au/TiO2 composite film. Such nanometal‐semiconductor composite films have the potential application in improving the performance of photoelectrochemical solar cells.