bluuebunny/crossref_metadata_2025 huggingface dataset:
Terbutaline for Chronotropic Support in Heart Transplantation
Authors: Coons James C , Shullo Michael , Schonder Kristine , Kormos Robert
Published: March 2004

OBJECTIVE

To report the use of oral terbutaline for chronotropic support in a patient who had undergone heart transplantation.

CASE SUMMARY

A 54-year-old white man received a heart transplant secondary to ischemic dilated cardiomyopathy. His clinical course was uncomplicated until postoperative day 10, when he became hemodynamically compromised despite inotropic therapy (BP 88/53 mm Hg, mean HR 80 beats/min) secondary to stage IIIa rejection. Although a continuous intravenous infusion of dobutamine was maintained, therapy with oral terbutaline 2.5 mg every 6 hours was initiated. Because the patient remained bradycardic on postoperative day 11 (HR 64 beats/min; mean 75), terbutaline was titrated to a dosage of 5 mg every 8 hours. Subsequently, an improvement in the hemodynamic profile (BP 140/78 mm Hg, mean HR 91 beats/min) was noted. Treatment with terbutaline was continued for 13 days and was well tolerated.

DISCUSSION

As of February 11, 2004, this is the first case, to our knowledge, to describe the use of oral terbutaline therapy for chronotropic support in the setting of acute rejection after heart transplantation. Terbutaline is a β2-adrenergic agonist that may mediate its effects via direct β2-receptor stimulation, baroreceptor-mediated increases in sympathetic tone, or via presynaptic β2-stimulation. Although isoproterenol has been the mainstay of therapy for chronotropic support in this setting, its availability has been an issue in recent years. Terbutaline, therefore, may represent a useful alternative for chronotropic support in the setting of heart transplantation.

CONCLUSIONS

Terbutaline therapy did not appear to be associated with any significant adverse effects and warrants further application and study in this setting.
Pharmaceutical Care for HIV Patients on Directly Observed Therapy
Authors: Foisy Michelle M , Akai Peter S
Published: March 2004

BACKGROUND

Inner-city patients infected with HIV can be a challenging group to treat. Homelessness, mental illness, substance abuse, and hepatitis C infection may serve as barriers to effective treatment. A multidisciplinary team including the pharmacist can impact upon the delivery of care to the inner-city HIV patient population.

OBJECTIVE

To describe the implementation and provision of pharmaceutical care to inner-city patients taking directly observed therapy (DOT), as well as drug-related problems (DRPs) and their respective outcomes.

METHODS

Pharmaceutical care, including the prospective identification and management of DRPs, was provided by a clinical pharmacist.

RESULTS

Fifty-seven patients were followed over a 14-month period. Overall, 149 DRPs were identified and >95% were resolved. Those included (1) adverse effects (n = 56; gastrointestinal, central nervous system effects, allergies, laboratory abnormalities), (2) drug interactions (n = 32), (3) drugs indicated for comorbidities (n = 24; safety in pregnancy, tuberculosis, Pneumocystis carinii pneumonia prophylaxis, oral candidiasis, herpes zoster, nutritional supplements), (4) adherence issues (n = 20; altering timing of medication, changing formulation, decreasing pill burden), (5) drugs no longer indicated (n = 10; opportunistic infection prophylaxis, treatment of primary infection), and (6) dosage adjustment (n = 7) for weight and renal insufficiency.

CONCLUSIONS

In the provision of pharmaceutical care to HIV-infected patients on DOT, an HIV pharmacist significantly contributed to antiretroviral selection, monitoring of drug therapy, and managing DRPs. An HIV pharmacist can assist in promoting patient adherence and improved outcomes in this setting.
Nitazoxanide Treatment for Giardiasis and Cryptosporidiosis in Children
Authors: Bailey Jason M , Erramouspe John
Published: March 2004

OBJECTIVE

To review the pharmacology, pharmacokinetics, adverse effects, drug interactions, dosing recommendations, and clinical efficacy of nitazoxanide, a new antiprotozoal/anthelmintic/antibacterial agent.

DATA SOURCES

A MEDLINE search (1966-February 2004) of both human and animal research data published in the English language was conducted.

STUDY SELECTION AND DATA EXTRACTION

All primary and review articles pertaining to the MEDLINE search were reviewed for inclusion. Emphasis was placed on randomized, double-blind, placebo-controlled trials.

DATA SYNTHESIS

Nitazoxanide is approved for the treatment of giardiasis and cryptosporidiosis (first drug approved for the latter indication) in immune-competent children <12 years of age. Most studies in immune-competent patients have reported clinical and parasitologic response rates close to 80% and 70%, respectively, for both indications. Response rates have been lower in immune-compromised patients.

CONCLUSIONS

Nitazoxanide should be available for patients unable to tolerate or adhere to first-line therapy employed for these intestinal protozoa. THIS ARTICLE IS APPROVED FOR CONTINUING EDUCATION CREDIT ACPE UNIVERSAL PROGRAM NUMBER: 407-000-04-014-H01
Telling a story or telling it straight: the effects of entertaining versus accurate retellings on memory
Authors: Dudukovic Nicole M. , Marsh Elizabeth J. , Tversky Barbara
Published: March 2004

People retell events for different reasons. Sometimes they try to be accurate, other times entertaining. What characterizes retellings from different perspectives? How does retelling perspective affect later recall of events? In the current research, participants retold a story either three times or not at all. By instruction, retellings were either entertaining or accurate. Compared to accurate retellings, entertaining retellings contained more affect, but fewer sensory references. On a subsequent memory test, participants who retold with an accuracy goal recalled the greatest number of story events, and their recall protocols were the most accurate and detailed, and least exaggerated. However, recognition memory did not differ across groups, suggesting that differences in retrieval structures (necessary for recall but not recognition) were key to understanding later differences in memory. Compared to telling it straight, the creative process of telling a story leads to qualitative and quantitative changes in later recall. Copyright © 2004 John Wiley & Sons, Ltd.
The effects of anxious mood induction on suggestibility to misleading post‐event information
Authors: Ridley Anne M. , Clifford Brian R.
Published: March 2004

Little research has been carried out into the effects of anxious mood at the time of either the encoding of misleading post‐event information or the time of its possible retrieval, on subsequent suggestibility. Participants comprised 160 first‐year undergraduates. Using a standard suggestibility paradigm, half of all participants were exposed to misleading information while half were non‐misinformed controls. In addition there were four state anxiety conditions, dependent on the timing of the anxious mood induction: at the time of encoding misleading information; at retrieval only; at both encoding and retrieval; or at neither encoding nor retrieval (controls). Results showed memory accuracy for non‐suggestible items was unaffected by the anxious mood induction. With respect to suggestibility, there was a strong effect of misleading information. In addition, within the misinformed group, all three groups who experienced the anxious mood induction were significantly less suggestible than controls. These findings are discussed both in terms of theories of anxiety and cognition and the applied implications for the increasing use by the police of video‐recorded witness interviews. Copyright © 2004 John Wiley & Sons, Ltd.
Adaptive robust force control for vehicle active suspensions
Authors: Chantranuwathana Supavut , Peng Huei
Published: March 2004

In this paper, the modular adaptive robust control (MARC) technique is applied to design the force loop controller of an electro‐hydraulic active suspension system. A key advantage of this modular design approach lies in the fact that the adaptation algorithm can be designed for explicit estimation convergence. The effect of parameter adaptation on force tracking performance can be compensated and thus it is possible to guaranteed certain control performance. Experimental results from a quarter‐car active suspension test rig show that when realistic external disturbances and measurement noises exist, the modular design achieves a better estimate than the non‐modular ARC design. The improved estimation was found to result in control signals with slightly lower magnitude while maintaining similar tracking performance. Copyright © 2004 John Wiley & Sons, Ltd.
Aftertreatment control and adaptation for automotive lean burn engines with HEGO sensors
Authors: Sun Jing , Kim Yong Wha , Wang Leyi
Published: March 2004

Control of aftertreatment systems for lean burn technology engines represents a big challenge, due to the lack of on‐board emission measurements and the sensitivity of the hardware components to ageing and sulphur poisoning. In this paper, we consider the control and adaptation of aftertreatment systems involving lean NOx trap (LNT). A phenomenological LNT model is presented to facilitate the model‐based control and adaptation. A control strategy based on the LNT model and HEGO (heated exhaust gas oxygen) sensor feedback is discussed. A linear parametric model, which is derived by exploiting the physical properties of the LNT is used for adaptation of trap capacity and feedgas NOx emission models. The conditions under which parameter convergence will be achieved are derived for the proposed adaptive scheme. Simulation results for different scenarios are included to demonstrate the effectiveness of control and adaptation. Copyright © 2004 John Wiley & Sons, Ltd.
Closed‐loop combustion control of homogeneous charge compression ignition (HCCI) engine dynamics
Authors: Bengtsson J. , Strandh P. , Johansson R. , Tunestål P. , Johansson B.
Published: March 2004

Homogeneous charge compression ignition (HCCI) is a hybrid of the spark ignition and compression ignition engine concepts. As in a spark ignition engine, a homogeneous fuel–air mixture is created in the inlet system. During the compression stroke the temperature of the mixture increases and reaches the point of auto ignition, just as in a compression ignition engine (or diesel). One challenge with HCCI engines is the need for good timing control of the combustion. Auto ignition of a homogeneous mixture is very sensitive to operating condition. Even small variations of the load can change the timing from too early to too late combustion. Thus a fast combustion timing control is necessary since it sets the performance limitation of the load control. As measurement for combustion timing feedback, the crank angle of 50% burnt has been used. This paper performs a comparative study of different cylinder‐pressure based methods for estimating the crank angle of 50% burnt, CA50. The estimates are compared in terms of accuracy, robustness and feasibility for cycle‐to‐cycle real‐time control. Dynamic models of CA50 are estimated using system identification as a means to find models relevant to engine control. Copyright © 2004 John Wiley & Sons, Ltd.
Advanced misfire detection using adaptive signal processing
Authors: Naik Sanjeev
Published: March 2004

This article addresses the problem of internal combustion engine misfire detection. Specific attention is paid to misfire detection using crankshaft speed measurements. After an initial analysis of the problem, the applicability of advanced signal processing methods to its solution is discussed. We demonstrate how adaptive filtering techniques can lead to improved misfire detection accuracy. This can lead to reduced mis‐detection as well as false alarm rates. The general concept of estimating and removing periodic, time‐varying components may also be applied to other automotive problems. Copyright © 2004 John Wiley & Sons, Ltd.
Titelbild: Emergence of Morphological Chirality from Twinned Crystals (Angew. Chem. 11/2004)
Authors: Imai Hiroaki , Oaki Yuya
Published: March 2004

Die helicale Morphologie die auf dem Titelbild gezeigt ist, entsteht durch das diffusionskontrollierte Wachstum trikliner Kristalle. Das Rückgrat der helicalen Architektur enthält verdrillte Zwillinge aus Kristalluntereinheiten, deren Verkippung eine Folge des triklinen Systems ist. Diese Ergebnisse bieten eine fundierte Erklärung für die Entstehung verschiedener helicaler Morphologien. Weiteres zu diesem Thema entnehmen Sie der Zuschrift von H. Imai und Y. Oaki auf S. 1387 ff.
Cover Picture: Emergence of Morphological Chirality from Twinned Crystals (Angew. Chem. Int. Ed. 11/2004)
Authors: Imai Hiroaki , Oaki Yuya
Published: March 2004

The helical morphology shown in the cover picture, emerges from triclinic crystals through diffusion‐limited growth. The backbone of the helical architecture comprises twisted twins of the tilted subunit crystal originating from the triclinic system. The results provide a fundamental basis for the formation of various helical morphologies that have already been reported. For more information see the Communication by H. Imai and Y. Oaki on page 1363 ff.
Comparing single and serial homicide offenses
Authors: Kraemer Gretchen W. , Lord Wayne D. , Heilbrun Kirk
Published: March 2004

Serial homicide has attracted much attention, but little empirical scientific investigation. This exploratory study reports demographic information on a large sample of serial homicide offenders (157 offenders, 608 victims), and compares a subsample of serial homicide offenses with a control group of single homicide offenses. Results show that serial homicide offenders target more women than men, and kill more strangers than family or friends. Single homicide offenders kill men and women in equal frequency, but kill family and friends more often than strangers. Serial homicide offenders kill for apparent sexual motivation more often than for any other reason, while single homicide offenders kill most often out of anger. Copyright © 2004 John Wiley & Sons, Ltd.
The effects of isosorbide dinitrate on methemoglobin reductase enzyme activity and antioxidant states
Authors: İnal Mi̇ne Erden , Egüz Ayşe Meral
Published: March 2004

Isosorbide dinitrate (ISDN) has been used in the treatment of ischaemic cardiovascular diseases for many years. ISDN is the most popular nitric oxide donor and causes methemoglobinemia as an important side‐effect. The purpose of this study was to examine antioxidant states and methemoglobin reductase activity after giving ISDN and ISDN plus vitamin E. Rats were divided into three groups according to the treatment: control group, ISDN group and ISDN plus vit. E group. We measured reduced glutathione in blood (GSH), plasma malondialdehyde (MDA), erythrocyte superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) and NADH‐dependent methemoglobin reductase activities. In the ISDN group, plasma MDA levels were significantly high compared to the control and ISDN+vit. E groups (p < 0.001). In the ISDN and ISDN+vit. E groups, blood GSH levels were higher than those of the control group (p < 0.05). Changes of SOD and GPx activities were not significant. In the ISDN and ISDN+vit. E groups the erythrocyte catalase and NADH‐dependent methemoglobin reductase activities were significantly higher than that in the control group (p < 0.001). We conclude that oxidant drugs such as ISDN need to be carefully used because of lipid peroxidation and methemoglobinemia. These findings support the notion that vitamine E protects tissues against oxidative stress. Copyright © 2004 John Wiley & Sons, Ltd.
On the Nature of the Plateau in Two‐Step Dinuclear Spin‐Crossover Complexes
Authors: Ksenofontov Vadim , Gaspar Ana B. , Niel Virginie , Reiman Sergey , Real José A. , Gütlich Philipp
Published: March 2004

A remarkable feature of the spin‐crossover process in several dinuclear iron(II) compounds is a plateau in the two‐step transition curve. Up to now, it has not been possible to analyse the spin state of dinuclear pairs that constitute such a plateau, due to the relative high temperatures at which the transition takes place in complexes investigated so far. We solved this problem by experimentally studying a novel dinuclear spin‐crossover compound [{Fe(phdia)(NCS)2}2(phdia)] (phdia: 4,7‐phenanthroline‐5,6‐diamine). We report here on the synthesis and characterisation of this system, which exhibits a two‐step spin transition at Tc1=108 K and Tc2=80 K, displaying 2 K and 7 K wide thermal hysteresis loops in the upper and the lower steps, respectively. A plateau of approximately 20 K width centred at about 90 K, which corresponds to the 50 % of the spin conversion, separates the two transitions. The composition of the plateau was identified in metastable state after quenching to 4.2 K by means of Mössbauer spectroscopy in an external magnetic field. Such experiments revealed that the plateau consists mainly of [HS–LS] pairs (HS=high spin, LS=low spin) and confirmed the hypothesis that the spin conversion in dinuclear entities proceeds through [LS–LS]↔[HS–LS]↔[HS–HS] pairs. The results are discussed in terms of a thermodynamic model based on the regular solution theory adapted for dinuclear spin‐crossover compounds.
AlIII Ion Complexes of Saccharic Acid and Mucic Acid: A Solution and Solid‐State Study
Authors: Lakatos Andrea , Bertani Roberta , Kiss Tamas , Venzo Alfonso , Casarin Maurizio , Benetollo Franco , Ganis Paolo , Favretto Donata
Published: March 2004

The AlIII‐binding abilities of two aldaric acids, D‐saccharic acid and mucic acid (the neutral form is denoted as H2L), were studied in solution by means of pH potentiometric, 1H and 13C NMR, and ESI‐MS techniques. The most probable conformations and isomeric binding modes of the complexes formed in solution were determined by density functional theory (DFT) calculations. A solid D‐saccharic acid complex K2[{Al(LH−2)(H2O)}2]⋅H2O was isolated and crystallographically characterised. The two alcoholic hydroxy groups α to the terminal COO− groups were found to take part in the coordination, but in different ways. One of them coordinates in a bridging mode. Detailed ESI‐MS and NMR studies proved that the complex retains its structure in solution. However, depending on the ligand and the pH, such complexes may exist in two isomeric forms. DFT calculations on the ion [{Al(LH−2)(H2O)}2]2− revealed that several orbitals participate in stabilizing the dimeric arrangement.
Chiroptical Analysis of Marine Sponge Alkaloids Sharing the Pyrrolopyrazinone Core
Authors: Jacquot Delphine E. N. , Mayer Peter , Lindel Thomas
Published: March 2004

A systematic experimental study has been conducted on the chiroptical properties of bi‐ and tricyclic pyrrolopyrazinones, which occur as the core in a variety of marine pyrrole–imidazole alkaloids, such as the immunosuppressive palau'amine. On the basis of the chiral‐pool synthesis of conformationally fixed dipyrrolopyrazinones, it was possible to predict the CD spectrum of (−)‐dibromophakellin above 240 nm. 2,2,2‐Trifluoroethanol was identified as a superior solvent for this analysis. Positive Cotton effects at 250 nm can be used to determine the helicity of dibrominated pyrrolopyrazinones, while the intensity of the Cotton effect at 285 nm is governed by the relative stereochemistry. The influence of bromination of the pyrrole ring also becomes predictable. One of the tricycles can be considered as “conformationally frozen longamide A”. Our study also gives the first comparative Röntgen analyses of diastereomeric Mosher esters of N,O‐hemiacetals, with the results underlining the fact that caution is advised in the application of the advanced Mosher method.
Metal Ion Complexation: A Route to 2 D Templates?
Authors: De Feyter Steven , Abdel‐Mottaleb Mohamed M. S. , Schuurmans Norbert , Verkuijl Bas J. V. , van Esch Jan H. , Feringa Ben L. , De Schryver Frans C.
Published: March 2004

The two‐dimensional ordering of a number of 2,2′‐bipyridine derivatives at the liquid/solid interface has been investigated by scanning tunneling microscopy. By appropriate functionalization of the bipyridine units, their intermolecular distance can be tuned, which has proved to be crucial for complexation with metal ions. The in situ addition of metal salts (Pd2+, Cu2+), leading to the formation of metal‐bipyridine complexes, has a dramatic influence on the two‐dimensional ordering of the molecules and suggests that these complexes could be used as templates.
Elevated‐Temperature Metathesis Syntheses of Structurally Novel Alkali‐Metal Tetrakis(3,5‐di‐tert‐butylpyrazolato)lanthanoidate(III) Complexes: Toluene‐Coordinated Discrete Bimetallic Complexes and Supramolecular Chains
Authors: Deacon Glen B. , Delbridge Ewan E. , Evans David J. , Harika Rita , Junk Peter C. , Skelton Brian W. , White Allan H.
Published: March 2004

Sodium and potassium tetrakis(3,5‐di‐tert‐butylpyrazolato)lanthanoidate(III) complexes [M{Ln(tBu2pz)4}] have been prepared by reaction of anhydrous lanthanoid trihalides with alkali metal 3,5‐di‐tert‐butylpyrazolates at 200–300 °C, and a 1,2,4,5‐tetramethylbenzene flux for M=K. On extraction with toluene (or occasionally directly from the reaction tube) the following complexes were isolated: [Na(PhMe){Ln(tBu2pz)4}] (1 Ln; 1 Ln=1 Tb, 1 Ho, 1 Er, 1 Yb), [K(PhMe){Ln(tBu2pz)4}]⋅2 PhMe (2 Ln; 2 Ln=2 La, 2 Sm, 2 Tb, 2 Ho, 2 Yb, 2 Lu), [Na{Ln(tBu2pz)4}]n (3 Ln; 3 Ln=3 La, 3 Tb, 3 Ho, 3 Er, 3 Yb), [K{Ln(tBu2pz)4}]n (4 Ln; 4 Ln=4 La, 4 Nd, 4 Sm, 4 Tb, 4 Ho, 4 Er, 4 Yb, 4 Lu), with the last two classes generally being obtained by loss of toluene from 1 Ln or 2 Ln, and [Na(tBu2pzH){Ln(tBu2pz)4}]⋅PhMe (5 Ln; 5 Ln=5 Nd, 5 Er, 5 Yb). Extraction with 1,2‐dimethoxyethane (DME) after isolation of 2 Ho yielded [K(dme){Ho(tBu2pz)4}] (6 Ho). X‐ray crystal structures of 1 Ln (=1 Tb, 1 Ho; P21/c), 2 Ln (=2 La, 2 Sm, 2 Tb, 2 Yb, 2 Lu; Pnma), 3,4 Ln (=3 La, 3 Er, 4 Sm; P21/m), and 5 Ln (=5 Nd, 5 Er, and 5 Yb; P$\bar 1$) show each group to be isomorphous regardless of the size of the Ln3+ ion. All complexes contain eight‐coordinate {Ln(η2‐tBu2pz)4} units. These are further linked to the alkali metal by bridging through two (1,2,5 Ln) or three (3,4 Ln) tBu2pz groups which show striking coordination versatility. Sodium is coordinated by an η4‐PhMe, a μ‐η2:η2‐tBu2pz, and a μ‐η4(Na):η2(Ln)‐tBu2pz ligand in 1 Ln, and by one η1‐tBu2pzH and two μ‐η3(Na):η2(Ln) ligands in 5 Ln. By contrast, potassium has one η6‐PhMe and two μ‐η5(K):η2(Ln) ligands in 2 Ln. Classes 3,4 Ln form polymeric chains with the alkali metal bonded by two μ‐η3(NNC‐M):η2(Ln)‐tBu2pz ligands within [MLn(tBu2pz)4] units which are joined together by η1(C)‐tBu2pz‐Na, K linkages.
Programming Heteropolymetallic Lanthanide Helicates: Thermodynamic Recognition of Different Metal Ions Along the Strands
Authors: Floquet Sébastien , Borkovec Michal , Bernardinelli Gérald , Pinto André , Leuthold Luc‐Alexis , Hopfgartner Gérard , Imbert Daniel , Bünzli Jean‐Claude G. , Piguet Claude
Published: March 2004

Under stoichiometric conditions, the segmental tris‐tridentate ligand L9 assembles with two different lanthanide metal ions Ln1 and Ln2 (Ln1, Ln2=La, Nd, Sm, Eu, Yb, Lu, Y) to give mixtures of the heterotrimetallic triple‐stranded helicates [(Ln1)x(Ln2)3−x(L9)3]9+ (x=0–3) in acetonitrile. The combination of qualitative (ESI‐MS) and quantitative (1H NMR) speciations provides a set of thermodynamic data that were analysed with various statistical chemical models. A satisfying description requires the consideration of different affinities for the terminal N6O3 sites (k${{{\rm t}\hfill \atop {\rm Ln}\hfill}}$) and for the central N9 site (k${{{\rm c}\hfill \atop {\rm Ln}\hfill}}$) for each specific lanthanide. The nontrivial dependence of these parameters on the ionic radius provides size‐discriminating effects that favour the formation of heterotrimetallic helicates in which the central site is occupied by the larger metal of the pair. Combining the latter enthalpic driving forces with entropic contributions due to specific stoichiometric conditions allows partial selection (i.e., programming) of a specific heterotrimetallic species in solution, which can be isolated by crystallisation, as demonstrated for [Eu2.04La0.96(L9)3](CF3SO3)9(CH3NO2)9 (1, Eu2.04La0.96C207H222N48O51S9F27, monoclinic, P21/c, Z=4) in which the cation [EuLaEu(L9)3]9+ is the major component in the crystal. The scope and limitation of this approach is discussed together with the conditions for explicitly considering intermetallic interaction parameters uLn1Ln2 in more sophisticated chemical models.
Photocontrolled Release and Uptake of a Porphyrin Guest by Dithienylethene‐Tethered β‐Cyclodextrin Host Dimers
Authors: Mulder Alart , Juković Amela , van Leeuwen Fijs W. B. , Kooijman Huub , Spek Anthony L. , Huskens Jurriaan , Reinhoudt David. N.
Published: March 2004

Two photoswitchable dithienylethene‐tethered β‐cyclodextrin dimers were synthesized to function as host molecules with an externally controllable binding affinity. The cyclodextrin cavities of these dimers are linked through their secondary sides by a photochromic dithienylethene unit that is connected to the secondary rim either directly (4) or through propyl spacers (9). Irradiation with light switches these dimers between a relatively flexible (open) and a rigid (closed) form. The binding properties of the dimers depend on the configuration of the dithienylethene spacer, as is shown by microcalorimetry performed with tetrakis‐sulfonatophenyl porphyrin (TSPP) as a guest molecule. The differences in binding properties are most pronounced for the more rigid dimer 4, which binds TSPP 35 times more strongly in the open form (4 a) than in the closed form (4 b). The values found for the enthalpy of binding (ΔH°) indicate that this difference in binding is due to the loss of cooperativity between the two β‐cyclodextrin cavities in the closed form. Molecular modeling shows that 4 b is not able to bind TSPP effectively in both cyclodextrin cavities. The open and closed forms of the more flexible dimer 9 show no substantial difference in their binding of TSPP. Thermodynamic values indicative of strong binding of TSPP by two β‐cyclodextrin cavities were measured for both forms of the dimer, and molecular modeling confirms that both are flexible enough to tightly bind TSPP. The binding differences between the forms of dimer 4 allow the photocontrolled release and uptake of TSPP, which renders control of the ratio of complexed to free TSPP in solution possible.
Sterically Hindered Triacylglycerol Analogues as Potent Inhibitors of Human Digestive Lipases
Authors: Constantinou‐Kokotou Violetta , Magrioti Victoria , Verger Robert
Published: March 2004

A novel class of inhibitors of human digestive lipases have been developed. Various sterically hindered triacylglycerols based on 2‐methyl‐ and 2‐butylglycerol, and/or 2‐methyl fatty acids were synthesized. The triacylglycerol analogues were tested for their ability to form stable monomolecular films at the air/water interface by recording their surface‐pressure/molecular‐area compression isotherms. The inhibition of human pancreatic and gastric lipases by the sterically hindered triacylglycerol analogues was studied by using the monolayer technique with mixed films of 1,2‐dicaprin, which contained variable proportions of each inhibitor. Triolein analogues that contain a butyl group at the 2‐position of the glycerol backbone or methyl groups both at the 2‐position of glycerol, and the α‐position of each oleic acid residue were potent inhibitors; this caused a 50 % decrease in HPL activity at 0.003 molar fraction.
Synthesis and Esterolytic Activity of Catalytic Peptide Dendrimers
Authors: Lagnoux David , Delort Estelle , Douat‐Casassus Céline , Esposito Annamaria , Reymond Jean‐Louis
Published: March 2004

Peptide dendrimers were prepared by solid‐phase peptide synthesis. Monomeric dendrimers were first obtained by assembly of a hexapeptide sequence containing alternate standard α‐amino acids with diamino acids as branching units. The monomeric dendrimers were then dimerized by disulfide‐bridge formation at the core cysteine. The synthetic strategy is compatible with functional amino acids and different diamino acid branching units. Peptide dendrimers composed of the catalytic triad amino acids histidine, aspartate, and serine catalyzed the hydrolysis of N‐methylquinolinium salts when the histidine residues were placed at the outermost position. The dendrimer‐catalyzed hydrolysis of 7‐isobutyryl‐N‐methylquinolinium followed saturation kinetics with a rate constant of catalysis/rate constant without catalysis (kcat/kuncat) value of 3350 and a rate constant of catalysis/Michaelis constant (kcat/KM) value 350‐fold larger than the second‐order rate constant of the 4‐methylimidazole‐catalyzed reaction; this corresponds to a 40‐fold rate enhancement per histidine side chain. Catalysis can be attributed to the presence of histidine residues at the surface of the dendrimers.
Perceived in‐group threat as a factor moderating the influence of in‐group norms on discrimination against foreigners
Authors: Falomir‐Pichastor Juan Manuel , Muñoz‐Rojas Daniel , Invernizzi Federica , Mugny Gabriel
Published: March 2004

Within the framework of an intergroup relations paradigm, three studies analysed the role of in‐group threat in intergroup discrimination and the influence of in‐group norms on intergroup discrimination. The first study showed that perceived socio‐economic threat underlies Swiss nationals' prejudice and discrimination toward foreigners in Switzerland. The second and third studies experimentally tested the hypotheses, first, that variations in perception of in‐group threat will produce change in initial discrimination, and, second, that the influence of an in‐group norm (pro‐ vs. anti‐ discriminatory) is moderated by the perception of in‐group threat. In support of these predictions, results of both studies indicated that discrimination was reduced when perceived in‐group threat was low. However, the anti‐discriminatory in‐group norm reduced discrimination only when perceived in‐group threat was low. No influence was observed for the pro‐discriminatory in‐group norm. Copyright © 2004 John Wiley & Sons, Ltd.
When the past becomes history: effects of temporal order on explanations of trends
Authors: Teigen Karl Halvor
Published: March 2004

When people are asked to ‘explain’ a time series consisting of population statistics, they will suggest factors responsible for later events rather than for earlier events. This is shown in Experiment 1 for pairs of events and in Experiment 2 for triads of events with one deviant member. When the deviant statistic is the most recent one, it will in most cases be singled out for explanation. When it comes first, it is rarely explained, but accepted as a given fact. This is seen as an instance of the temporal order effect, where the first event in a pair or a series is taken for granted, whereas later events are considered more ‘mutable’, i.e. they could have been different. In line with this, later statistics are considered to be more in need of support from additional information than earlier statistics (Experiment 3). The focus on temporally later events can be distinguished from other primacy and recency effects by being due to chronological order, rather than order of presentation. Copyright © 2004 John Wiley & Sons, Ltd.
Back to caring after being hurt: the role of forgiveness
Authors: Karremans Johan C. , Van Lange Paul A. M.
Published: March 2004

While the topic of forgiveness has only recently started to receive empirical attention, little research has been conducted to examine the notion that forgiveness predicts pro‐relationship responses, motivated by a willingness to set aside personal well‐being to enhance the well‐being of the partner or relationship. The purpose of the present research was to examine whether forgiveness predicts pro‐relationship responses, and whether it does so above and beyond commitment to the offender. Consistent with hypotheses, three studies revealed that forgiveness is significantly associated with (a) willingness to accommodate (i.e. to respond constructively rather than destructively when the partner has engaged in a potentially destructive act), (b) willingness to sacrifice, and (c) level of intended cooperation. Moreover, these associations were independent of commitment to the offender, providing initial evidence for the unique role of forgiveness in understanding pro‐relationship motivation and behaviour. Finally, the results of Study 3 suggested that forgiveness restores, rather than increases, levels of pro‐relationship motivation, compared to baseline levels of pro‐relationship motivation. Copyright © 2004 John Wiley & Sons, Ltd.
Who's the one in trouble? experimental evidence for a ‘psychic state’ bias in lineups
Authors: Weigold Arne , Wentura Dirk
Published: March 2004

In two experiments, a bias in lineups was examined, which has mostly been ignored in previous research. The psychic state of the suspects differs from the state of the fillers, in that they face a situation that can lead to personal loss (if they are identified) or relief (if they are not identified). This state might result in detectable behavioural cues, thus making the lineup unfair. Lineups were conducted with randomly chosen mock suspects who were promised money if they were not identified. Lineup samples were recorded on videotape once before the selection of the mock suspect (serving as a control) and once afterwards. The probability of identification of the mock suspect was significantly increased in the latter compared to the former condition. Copyright © 2004 John Wiley & Sons, Ltd.
High‐throughput single nucleotide polymorphism typing by fluorescent single‐strand conformation polymorphism analysis with capillary electrophoresis
Authors: Doi Kent , Doi Hitomi , Noiri Eisei , Nakao Akihide , Fujita Toshiro , Tokunaga Katsushi
Published: March 2004

In this study, we performed high‐throughput and precise single nucleotide polymorphism (SNP) typing by fluorescent capillary electrophoresis single‐strand conformation polymorphism (CE‐SSCP) analysis. A system composed of a multicapillary DNA analyzer, a newly developed sieving matrix, four different colors of fluorescent labels, and a multiplex polymerase chain reaction (PCR) enabled low‐cost and highly reliable SNP typing. Moreover, this system enabled the estimation of SNP allele frequencies using pooled DNA samples, which should be beneficial for large‐scale association studies. Thus, fluorescent CE‐SSCP analysis is a useful method for large‐scale SNP typing.
Different binding thermodynamics of Ni2+, Cu2+, and Zn2+ to bacitracin A1 determined by capillary electrophoresis
Authors: Castagnola Massimo , Rossetti Diana V. , Inzitari Rosanna , Lupi Alessandro , Zuppi Cecilia , Cabras Tiziana , Fadda Maria B. , Onnis Giuseppina , Petruzzelli Raffaele , Giardina Bruno , Messana Irene
Published: March 2004

Thermodynamics of the binding of Ni2+, Cu2+ and Zn2+ to bacitracin A1 was studied by capillary electrophoresis measuring the peptide effective mobility at different pH in the presence of increasing concentration of the three ligands. The affinity follows the order Ni2+ > Cu2+ > Zn2+, with association constant values of (2.3 ± 0.1)×104, (4.9 ± 0.2)×103, and (1.5 ± 0.1)×103 M−1, respectively. The only model able to rationalize mobility data implies that metal ion binds to the P0 peptide form. Moreover, mobility values indicated a change of bacitracin A1 acidic properties on Ni2+ and Cu2+ binding, with a shift of the pKa of N‐terminal Ile‐1 from 7.6 to about 5 and of the pKa of the δ‐amino group of D‐Orn‐7 from 9.7 to about 7. Even though on Zn2+ binding a shift of the N‐terminal Ile‐1 pKa was observed, restrictions in the pH range suitable for investigation, due to precipitation phenomena, did not allow establish if the shift of D‐Orn‐7 lateral chain pKa also occurred. Nonetheless, if present, the shift should be limited to the 7.8–9.7 range. Mobility data indicated that the Stokes radius of the complexes is ca. 3 Å lower than that of the free peptide. The present results indicate that metal‐ion binding to bacitracin A1 is more complex than previously assumed.
Capillary electrophoresis analysis of glucooligosaccharide regioisomers
Authors: Joucla Gilles , Brando Thérèse , Remaud‐Simeon Magali , Monsan Pierre , Puzo Germain
Published: March 2004

Complex gluco‐oligosaccharide mixtures of two regioisomer series were successfully separated by CE. The gluco‐oligosaccharide series were synthesized, employing a dextransucrase from Leuconostoc mesenteroides NRRL B‐512F, by successive glucopyranosyl transfers from sucrose to the acceptor glucose or maltose. The glucosyl transfer to both acceptors, occurring through the formation of α1→6 linkages, differed for the two series only in the glucosidic bond to the reducing end namely α1→6 or α1→4 bond for glucose or maltose acceptor, respectively. Thus, the combination of the two series results in mixed pairs of gluco‐oligosaccharide regioisomers with different degrees of polymerization (DP). These regioisomer series were first derivatized by reductive amination with 9‐aminopyrene‐1,4,6‐trisulfonate (APTS). Under acidic conditions using triethyl ammonium acetate as electrolyte, the APTS‐gluco‐oligosaccharides of each series were separated enabling unambiguous size determination by coupling CE to electrospray‐mass spectrometry. However, neither these acidic conditions nor alkaline buffer systems could be adapted for the separation of the gluco‐oligosaccharide regioisomers arising from the two combined series. By contrast, increased resolution was observed in an alkaline borate buffer, using differential complexation of the regioisomers with the borate anions. Such conditions were also successfully applied to the separation of glucodisaccharide regioisomers composed of α1→2, α1→3, α1→4, and α1→6 linkages commonly synthesized by glucansucrase enzymes.
Mixed cationic/anionic surfactants for semipermanent wall coatings in capillary electrophoresis
Authors: Wang Chuanzhong , Lucy Charles A.
Published: March 2004

Mixtures of the cationic surfactant cetyltrimethylammonium bromide (CTAB) with the anionic surfactant sodium dodecyl sulfate (SDS) form more stable coatings in fused‐silica capillaries than CTAB alone. The reversed electroosmotic flow (EOF) generated by CTAB/SDS mixtures remains stable for over 80 min after removal of the surfactants from the buffer. Enhanced stability (relative to CTAB alone) was found even when the ratio of SDS to CTAB was as low as 1%. This greater coating stability is attributed to the structural transition from adsorbed micelle to bilayer, which is induced by addition of SDS. Separation of a mixture of basic proteins yielded efficiencies of 364 000–562 000 plates/m and recoveries ranging from 85% to 98%. Migration time reproducibility was less than 0.9% relative standard deviation (RSD) from run to run and less than 2.6% RSD from day to day.
Determination of the DNA methylation level in tumor cells by capillary electrophoresis and laser‐ induced fluorescence detection
Authors: Wirtz Michaela , Stach Dirk , Kliem Hans‐Christian , Wiessler Manfred , Schmitz Oliver J.
Published: March 2004

An analytical method to determine the genome‐wide DNA methylation in only 100 ng DNA is presented. The analysis is based on DNA isolation and hydrolysis followed by derivatization of the 2'‐desoxyribonucleoside‐3'‐monophosphates with a fluorescence dye (4,4‐difluoro‐5,7‐dimethyl‐4‐bora‐3a,4a‐diaza‐s‐indacene‐3‐propionyl ethylene diamine hydrochloride, Bodipy FL EDA). The separation of the derivatives was carried out by micellar electrokinetic chromatography, and laser‐induced fluorescence was used for detection. To calculate the methylation level, the derivatization factor and the quantum yields of the Bodipy conjugates of 2'‐desoxycytidine‐3'‐monophosphate (dCMP) and 2'‐desoxy‐5‐methylcytidine‐3'‐monophosphate (5m‐dCMP) were determined by measurement of methylated Lambda DNA. The assignment was made by cochromatography with the synthesized and characterized standard compound 5m‐dCMP. After optimization of the method it was possible to determine the methylation level in 100‐ng DNA samples with a standard deviation of less than 5%.
Search for serum protein‐binding disaccharides and disaccharide‐binding serum proteins by affinity capillary electrophoresis
Authors: Taga Atsushi , Yamamoto Yuka , Maruyama Rie , Honda Susumu
Published: March 2004

The potential use of affinity capillary electrophoresis in a microscale search for mutually interacting substances in biological fluid is demonstrated. Some disaccharides, especially gentiobiose (Gen), derivatized with 1‐phenyl‐3‐methyl‐5‐pyrazolone, caused peak retardation when electrophoresed in a neutral running buffer, containing human serum. Gen, the most significantly retarded disaccharide, was converted to its negatively charged bis‐mercaptoethanesulfonate derivative (MerESGen), and a serum sample was analyzed in a neutral buffer containing the derivatized disaccharide. Two peaks, belonging to the β‐globulin fraction, were found to be remarkably retarded in the buffer containing MerES‐Gen in a concentration‐dependent way. These findings prove an interaction between disaccharides and serum proteins.
Ultraviolet sealing and poly(dimethylacrylamide) modification for poly(dimethylsiloxane)/glass microchips
Authors: Chen Lin , Ren Jicun , Bi Rui , Chen Di
Published: March 2004

Simple sealing methods for poly(dimethylsiloxane) (PDMS)/glass‐based capillary electrophoresis (CE) microchips by UV irradiation are described. Further, we examined the possibility to modify the inner surface of separation channels, using polymethylacrylamide (PDMA) as a dynamic coating reagent. The surface properties of native PDMS, UV‐irradiated PDMS, and PDMA‐coated PDMS were systematically studied by atomic force microscopy (AFM), infrared absorption by attenuated total reflection infrared (ATR‐IR) spectroscopy, and contact angle measurement. We found that PDMA forms a stable coating on PDMS and glass surfaces, eliminating the nonhomogeneous electroosmotic flow (EOF) in channels on PDMS/glass microchips, and improving the hydrophilicity of PDMS surfaces. Mixtures of flavin mononucleotide (FMN), flavin adenine dinucleotide (FAD), and fluorescein were separated in 35 s using PDMA‐coated PDMS/glass microchips. A high efficiency of theoretical plates with at least 1365 (105 000 N/m) and a good reproducibility with relative standard deviations (RSD) below 4% in five successive separations were achieved.
Plasma thiols redox status by laser‐induced fluorescence capillary electrophoresis
Authors: Carru Ciriaco , Deiana Luca , Sotgia Salvatore , Pes Giovanni Mario , Zinellu Angelo
Published: March 2004

High concentrations of total plasma thiols such as cysteine and homocysteine are important risk factors for atherosclerosis and cardiovascular diseases. We have recently described a new laser‐induced fluorescence capillary electrophoresis (CE‐LIF) method to measure total plasma thiols, in which the baseline separation of cysteinylglycine, homocysteine, cysteine, and glutathione was achieved by adding the organic base N‐methyl‐D‐glucamine to the run buffer. However, because the active fractions of homocysteine and cysteine responsible for vascular injuries are still unknown, research calls for a set up of methods able to analyze different forms of plasma thiols. In this paper, we present an improvement of our previous method that allows the measurement of different thiol forms. Total, reduced, and free thiols were measured by varying the order of disulfide reduction with tributylphosphine and proteins precipitation with 5‐sulfosalicylic acid. After derivatization with 5‐iodoacetamidofluorescein, samples were separated and measured by CE‐LIF using a phosphate/borate buffer in the presence of 75 mmol/L N‐methyl‐D‐glucamine. Oxidized thiols and protein bound thiols were calculated by difference, free minus reduced and total minus free form, respectively. Linearity, reproducibility, analytical recovery, and sensitivity were evaluated. The assay was used to measure the thiols redox status in 15 plasma samples from healthy volunteers.
Rapid analysis of genetically modified organisms by in‐house developed capillary electrophoresis chip and laser‐induced fluorescence system
Authors: Obeid Pierre J. , Christopoulos Theodore K. , Ioannou Penelope C.
Published: March 2004

A microfabricated, inexpensive, reusable glass capillary electrophoresis chip and a laser‐induced fluorescence system were developed in‐house for the rapid DNA‐based analysis of genetically modified organisms (GMOs). The 35S promoter sequence of cauliflower mosaic virus and the terminator of the nopaline synthase (NOS) gene from Agrobacterium tumefaciens were both detected since they are present in most genetically modified organisms. The detection of genetically modified soybean in the presence of unaltered soybean was chosen as a model. Lectin, a plant‐specific gene, was also detected for confirmation of the integrity of extracted DNA. The chip was composed of two glass plates, each 25×76 mm, thermally bonded together to form a closed structure. Photomasks with cross‐topology were prepared rapidly by using polymeric material instead of chrome plates. The widths of the injection and separation channels were 30 and 70 μm, respectively, the effective separation length 4.5 cm. The glass slide was etched to a depth of 30 μm for both the injection and separation channel. The cost of the chip was less than 1 $ and required 2 days for photomask preparation and microfabrication. The separation and detection of polymerase chain reaction‐amplified NOS, 35S, and lectin sequences (180, 195, and 181 bp, respectively) was completed in less than 60 s. As low as 0.1% GMO content was detectable by the proposed system after 35 and 40 amplification cycles for 35S and NOS, respectively, using 25 ng of extracted DNA as starting material. This corresponds to only 20 genome copies of genetically modified soybean.
SPICKER: A clustering approach to identify near‐native protein folds
Authors: Zhang Yang , Skolnick Jeffrey
Published: March 2004

We have developed SPICKER, a simple and efficient strategy to identify near‐native folds by clustering protein structures generated during computer simulations. In general, the most populated clusters tend to be closer to the native conformation than the lowest energy structures. To assess the generality of the approach, we applied SPICKER to 1489 representative benchmark proteins ≤200 residues that cover the PDB at the level of 35% sequence identity; each contains up to 280,000 structure decoys generated using the recently developed TASSER (Threading ASSembly Refinement) algorithm. The best of the top five identified folds has a root‐mean‐square deviation from native (RMSD) in the top 1.4% of all decoys. For 78% of the proteins, the difference in RMSD from native to the identified models and RMSD from native to the absolutely best individual decoy is below 1 Å; the majority belong to the targets with converged conformational distributions. Although native fold identification from divergent decoy structures remains a challenge, our overall results show significant improvement over our previous clustering algorithms. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 865–871, 2004