bluuebunny/crossref_metadata_2025 huggingface dataset:
Differential androgen and estrogen substrates specificity in the mouse and primates type 12 17β-hydroxysteroid dehydrogenase
Authors: Blanchard Pierre-Gilles , Luu-The Van
Published: July 2007

Recently, we have shown that human and monkey type 12 17β-hydroxysteroid dehydrogenases (17β-HSD12) are estrogen-specific enzymes catalyzing the transformation of estrone (E1) into estradiol (E2). To further characterize this novel steroidogenic enzyme in an animal model, we have isolated a cDNA fragment encoding mouse 17β-HSD12 and characterized its enzymatic activity. Using human embryonic kidney cells (HEK)-293 cells stably expressing mouse 17β-HSD12, we found that in contrast with the human and monkey enzymes, which are specific for the transformation of E1 to E2, mouse 17β-HSD12 also catalyzes the transformation of 4-androstenedione into testosterone (T), dehydroepiandroster-one (DHEA) into 5-androstene-3β,17β-diol (5-diol), as well as androsterone into 5α-androstane-3α,17β-diol (3α-diol). Previously, we have shown that the specificity of human and monkey 17β-HSD12s for C18-steroid is due to the presence of a bulky phenylalanine (F) at position 234 creating steric hindrance, preventing the entrance of C19-steroids into the active site. To determine whether the smaller size of the corresponding leucine (L) in the mouse sequence is responsible for the entrance of androgenic substrates, we performed site-directed mutagenesis to substitute Leu 234 for Phe in the mouse enzyme. In agreement with our hypothesis, the mutated enzyme has a highly reduced ability to metabolize androgens. mRNA quantification in several mouse tissues using real-time PCR shows that mouse 17β-HSD12 mRNA is highly expressed in the female clitoral gland, male preputial gland, as well as in retroperitoneal fat and adrenal of both sexes. The differential androgenic/estrogenic substrate specificity of type 12 17β-HSD in the mouse and primates seems to agree with the observation that androgen and estrogen in the mouse are provided almost exclusively by gonads, while in primates an important part of these steroid hormones are produced locally from adrenal precursors.
Relationships between Soil and Runoff Phosphorus in Small Alberta Watersheds
Authors: Little Joanne L. , Nolan Sheilah C. , Casson Janna P. , Olson Barry M.
Published: July 2007

Field‐scale relationships between soil test phosphorus (STP) and flow‐weighted mean concentrations (FWMCs) of dissolved reactive phosphorus (DRP) and total phosphorus (TP) in runoff are essential for modeling phosphorus losses, but are lacking. The objectives of this study were (i) to determine the relationships between soil phosphorus (STP and degree of phosphorus saturation (DPS)) and runoff phosphorus (TP and DRP) from field‐sized catchments under spring snowmelt and summer rainfall conditions, and (ii) to determine whether a variety of depths and spatial representations of STP improved the prediction of phosphorus losses. Runoff was monitored from eight field‐scale microwatersheds (2 to 248 ha) for 3 yr. Soil test phosphorus was determined for three layers (0 to 2.5 cm, 0 to 5 cm, and 0 to 15 cm) in spring and fall and the DPS was determined for the surface layer. Average STP (0 to 15 cm) ranged from 3 to 512 mg kg−1, and DPS (0 to 2.5 cm) ranged from 5 to 91%. Seasonal FWMCs ranged from 0.01 to 7.4 mg L−1 DRP and from 0.1 to 8.0 mg L−1 TP. Strong linear relationships (r2 = 0.87 to 0.89) were found between the site mean STP and the FWMCs of DRP and TP. The relationships had similar extraction coefficients, intercepts, and predictive power among all three soil layers. Extraction coefficients (0.013 to 0.014) were similar to those reported for other Alberta studies, but were greater than those reported for rainfall simulation studies. The curvilinear DPS relationship showed similar predictive ability to STP. The field‐scale STP relationships derived from natural conditions in this study should provide the basis for modeling phosphorus in Alberta.
Interaction and Influence of Two Creeks on Escherichia coli Concentrations of Nearby Beaches: Exploration of Predictability and Mechanisms
Authors: Nevers Meredith B. , Whitman Richard L. , Frick Walter E. , Ge Zhongfu
Published: July 2007

The impact of river outfalls on beach water quality depends on numerous interacting factors. The delivery of contaminants by multiple creeks greatly complicates understanding of the source contributions, especially when pollution might originate up‐ or down‐coast of beaches. We studied two beaches along Lake Michigan that are located between two creek outfalls to determine the hydrometeorologic factors influencing near‐shore microbiologic water quality and the relative impact of the creeks. The creeks continuously delivered water with high concentrations of Escherichia coli to Lake Michigan, and the direction of transport of these bacteria was affected by current direction. Current direction reversals were associated with elevated E. coli concentrations at Central Avenue beach. Rainfall, barometric pressure, wave height, wave period, and creek specific conductance were significantly related to E. coli concentration at the beaches and were the parameters used in predictive models that best described E. coli variation at the two beaches. Multiple inputs to numerous beaches complicates the analysis and understanding of the relative relationship of sources but affords opportunities for showing how these complex creek inputs might interact to yield collective or individual effects on beach water quality.
Manoeuvring and vibration reduction of a flexible spacecraft integrating optimal sliding mode controller and distributed piezoelectric sensors/actuators
Authors: Hu Qinglei , Ma Guangfu
Published: July 2007

After publication, it was determined that this paper contained an error where Equation (36) cannot be solved because it is constrained by the inequality of Equation (30). To overcome this, we here change the mistake into a static output feedback problem.

Equation (29) can be rewritten in a first‐order state‐space form

where

and C̃ = [0 0 Λ 0].

The following cost function is to be minimized by the feedback gains Ḡ:

From the above Equation (31), the cost function designed in Equation (32) becomes

where

The optimization problem can be restated as follows:

subject to

where

Note that this kind of constraint optimization problem is a standard static output feedback problem, which may be solved by using the efficient software package LMI Control Toolbox for MATLAB. For space limitation, the details of the derivative process are omitted here.
Natural history of aging in Cornelia de Lange syndrome
Authors: Kline Antonie D. , Grados Marco , Sponseller Paul , Levy Howard P. , Blagowidow Natalie , Schoedel Christianne , Rampolla Joni , Clemens Douglas K. , Krantz Ian , Kimball Amy , Pichard Carmen , Tuchman David
Published: July 2007

Observations about the natural history of aging in Cornelia de Lange syndrome (CdLS) are made, based on 49 patients from a multidisciplinary clinic for adolescents and adults. The mean age was 17 years. Although most patients remain small, obesity may develop. Gastroesophageal reflux persists or worsens, and there are early long‐term sequelae, including Barrett esophagus in 10%; other gastrointestinal findings include risk for volvulus, rumination, and chronic constipation. Submucous cleft palate was found in 14%, most undetected before our evaluation. Chronic sinusitis was noted in 39%, often with nasal polyps. Blepharitis improves with age; cataracts and detached retina may occur. Decreased bone density is observed, with occasional fractures. One quarter have leg length discrepancy and 39% scoliosis. Most females have delayed or irregular menses but normal gynecologic exams and pap smears. Benign prostatic hypertrophy occurred in one male prior to 40 years. The phenotype is variable, but there is a distinct pattern of facial changes with aging. Premature gray hair is frequent; two patients had cutis verticis gyrata. Behavioral issues and specific psychiatric diagnoses, including self‐injury, anxiety, attention‐deficit disorder, autistic features, depression, and obsessive‐compulsive behavior, often worsen with age. This work presents some evidence for accelerated aging in CdLS. Of 53% with mutation analysis, 55% demonstrate a detectable mutation in NIPBL or SMC1A. Although no specific genotype–phenotype correlations have been firmly established, individuals with missense mutations in NIPBL and SMC1A appear milder than those with other mutations. Based on these observations, recommendations for clinical management of adults with CdLS are made. © 2007 Wiley‐Liss, Inc.
Challenges of diagnosis in fetal alcohol syndrome and fetal alcohol spectrum disorder in the adult
Authors: Chudley Albert E. , Kilgour Andrea R. , Cranston Meghan , Edwards Michelle
Published: July 2007

Adults with fetal alcohol syndrome (FAS) and the subsets of individuals with attenuated phenotype subsumed under the umbrella term of fetal alcohol spectrum disorder (FASD) provide clinicians with a challenge. Compounding this, FASD is different from most genetic syndromes since a specific diagnostic biological test is not available. The diagnosis first needs to be suspected and confirmation requires a diagnostic assessment that is best carried out in the context of a multi‐disciplinary team approach. There is surprisingly little research published on the prevalence, natural history, medical, and social complications relevant to adults with FASD. The evidence that is emerging suggests that this disorder is common, and that services to diagnose and treat these individuals are limited. Adults with FASD have a higher incidence of impairments in social adaptive and executive function, and a higher degree of psychopathology when compared to the general population. The impact of FASD has significant and serious effects on those affected with FASD, their families, and our communities. There is a need for improved access to diagnosis, and more research and evaluation of interventions currently in use. In this paper, we describe the current diagnostic criteria, the differential diagnosis, the prevalence, natural history, the behavioral and mental health consequences, medical and social management issues, and interventions for adults affected with this disorder. © 2007 Wiley‐Liss, Inc.
Sustainable Concepts in Olefin Metathesis
Authors: Clavier Hervé , Grela Karol , Kirschning Andreas , Mauduit Marc , Nolan Steven P.
Published: July 2007

Ruthenium‐catalyzed olefin metathesis reactions represent an attractive and powerful transformation for the formation of new carbon–carbon double bonds. This area is now quite familiar to most chemists as numerous catalysts are available that enable a plethora of olefin metathesis reactions. Nevertheless, with the exception of uses in polymerization reactions, only a limited number of industrial processes use olefin metathesis. This is mainly due to difficulties associated with removing ruthenium from the final products. In this context, a number of studies have been carried out to develop procedures for the removal of the catalyst or the products of catalyst decomposition, however, none are universally attractive so far. This situation has resulted in tremendous activity in the area dealing with supported or tagged versions of homogeneous catalysts. This Review summarizes the numerous studies focused on developing cleaner ruthenium‐catalyzed metathesis processes.
DNA–Metal Base Pairs
Authors: Clever Guido H. , Kaul Corinna , Carell Thomas
Published: July 2007

Recent developments show encouraging results for the use of DNA as a construction material for nanometer‐sized objects. Today, however, DNA‐based molecular nanoarchitectures are constructed with mainly unmodified or at best end‐modified oligonucleotides, thus shifting the development of functionalized DNA structures into the limelight. One of most recent developments in this direction is the substitution of the canonical Watson–Crick base pairs by metal complexes. In this way “metal–base pairs” are created, which could potentially impart magnetic or conductive properties to DNA‐based nanostructures. This review summarizes research which started almost 45 years ago with the investigation of how metal ions interact with unmodified DNA and which recently culminated in the development of artificial ligand‐like nucleobases so far able to coordinate up to ten metal ions inside a single DNA duplex in a programmable fashion.
Reply to “Recently Reported Crystalline Isothiazole Carbenes: Myth or Reality”
Authors: Wolf Janine , Böhlmann Winfried , Findeisen Matthias , Gelbrich Thomas , Hofmann Hans‐Jörg , Schulze Bärbel
Published: July 2007

In light of the results of Bertrand and co‐workers, the isothiazole carbenes previously reported by us cannot be considered to be stable. Evidently they are intermediates, which rapidly isomerize to the 2‐imino‐2H‐thiete isomers. Nevertheless, it is possible to obtain their dimers and to postulate their contribution in the formation of morpholino or piperidino derivatives.
A query language for discovering semantic associations, Part II: sample queries and query evaluation
Authors: Niemi Timo , Jämsen Janne
Published: July 2007

In our query language introduced in Part I (Niemi & Jämsen, in press) the user can formulate queries to find out (possibly complex) semantic relationships among entities. In this article we demonstrate the usage of our query language and discuss the new applications that it supports. We categorize several query types and give sample queries. The query types are categorized based on whether the entities specified in a query are known or unknown to the user in advance, and whether text information in documents is utilized. Natural language is used to represent the results of queries in order to facilitate correct interpretation by the user. We discuss briefly the issues related to the prototype implementation of the query language and show that an independent operation like Rho (Sheth et al., 2005; Anyanwu & Sheth, 2002, 2003), which presupposes entities of interest to be known in advance, is exceedingly inefficient in emulating the behavior of our query language. The discussion also covers potential problems, and challenges for future work.
Synthesis of Optically Active P‐Chiral and Optically Inactive Oligophosphines
Authors: Morisaki Yasuhiro , Ouchi Yuko , Naka Kensuke , Chujo Yoshiki
Published: July 2007

A series of optically active P‐chiral oligophosphines (S,R,R,S)‐2, (S,R,S,S,R,S)‐3, (S,R,S,R,R,S,R,S)‐4, and (S,R,S,R,S,R,R,S,R,S,R,S)‐5 with four, six, eight, and 12 chiral phosphorus atoms, respectively, were successfully synthesized by a step‐by‐step oxidative‐coupling reaction from (S,S)‐1. The corresponding optically inactive oligophosphines 1′–5′ were also prepared. Their properties were characterized by DSC, XRD, and optical‐rotation analyses. While optically active bisphosphine (S,S)‐1 and tetraphosphine (S,R,R,S)‐2 behaved as small molecules, octaphosphine (S,R,S,R,R,S,R,S)‐4 and dodecaphosphine (S,R,S,R,S,R,R,S,R,S,R,S)‐5 exhibited the features of a polymer. Furthermore, DSC and XRD analyses showed that hexaphosphine (S,R,S,S,R,S)‐3 is an intermediate between a small molecule and a polymer. Comparison of optically active oligophosphines 1–5 with the corresponding optically inactive oligophosphines 1′–5′ revealed that the optically active phosphines have higher crystallinity than the optically inactive counterparts. It is considered that the properties of oligophosphines depend on the enantiomeric purity as well as the oligomer chain length.
exo‐Selective Asymmetric Diels–Alder Reaction Catalyzed by Diamine Salts as Organocatalysts
Authors: Kano Taichi , Tanaka Youhei , Maruoka Keiji
Published: July 2007

An organocatalyst formed from a binaphthyl‐substituted diamine and trifluoromethanesulfonic acid exhibited unprecedented levels of exo selectivity in the Diels–Alder reaction of α,β‐unsaturated aldehydes with cyclopentadiene. A novel axially chiral diamine was also designed as an organocatalyst for an asymmetric variant of this reaction, in which the desired cycloadducts were formed with high diastereo‐ and enantioselectivities. The highest diastereoselectivity observed was greater than 20:1 in favor of the exo cycloadduct in the asymmetric Diels–Alder reaction of crotonaldehyde with cyclopentadiene.
Ludwig: Moratorium okay? no way!
Authors: Stone Edward J.
Published: July 2007

Ludwig, never a shrinking violet, is clearly against a freeze on bank insurance powers.
Leach leads uproar over Magna Bank ruling
Authors: Stone Edward J.
Published: July 2007

In a blistering speech, Leach accused the Comptroller of blatantly ignoring the law.
OCC reveals thinking on key issues
Authors: Stone Edward J.
Published: July 2007

A new advisory letter reveals the OCC's thinking on several key issues.
Illinois surprise is another win for bankers
Authors: Stone Edward J.
Published: July 2007

In a surprising turn of events, the Illinois legislature has crafted an insurance powers law that makes bankers happy.
Fate of “modernization” hangs on commerce committee action
Authors: Stone Edward J.
Published: July 2007

The House Commerce Committee will decide the fate offinancial modernization legislation by September 15th.
Contradictory Massachusetts bill would turn back clock
Authors: Stone Edward J.
Published: July 2007

The new bill is a maze of conflicting regulations.
Critics say thumbs down on October 7th “compromise”
Authors: Stone Edward J.
Published: July 2007

Critics urged bankers to reject the latest version of the financial modernization bill.
House bill would ban new title insurance sales; fragile compromise is crumbling
Authors: Stone Edward J.
Published: July 2007

Bankers' fragile support for H.R. 10 is crumbling because of two controversial amendments.
The Lewis Acidic Ruthenium‐Complex‐Catalyzed Addition of β‐Diketones to Alcohols and Styrenes Is in Fact Brønsted Acid Catalyzed
Authors: Liu Pei Nian , Zhou Zhong Yuan , Lau Chak Po
Published: July 2007

The perchlorate salt of the dicationic bipy–ruthenium complex cis‐[Ru(6,6′‐Cl2bipy)2(H2O)2]2+ effectively catalyzes addition of β‐diketones to secondary alcohols and styrenes to yield the α‐alkylated β‐diketones. In a catalytic addition reaction of acetylacetone to 1‐phenylethanol, the κ2‐acetylacetonate complex [Ru(6,6′‐Cl2bipy)2(κ2‐acac)]ClO4 was isolated after the catalysis; this complex is readily synthesized by reacting cis‐[Ru(6,6′‐Cl2bipy)2(H2O)2](ClO4)2 with acetylacetone. [Ru(6,6′‐Cl2bipy)2(κ2‐acac)]ClO4 is unreactive toward 1‐phenylethanol in the presence of HClO4; it also fails to catalyze the addition of acetylacetone to 1‐phenylethanol. On the basis of these observations, it is proposed and confirmed by independent experiments that the catalytic addition of β‐diketones to the secondary alcohols is in fact catalyzed by the Brønsted acid HClO4, which is generated by the reaction of cis‐[Ru(6,6′‐Cl2bipy)2(H2O)2](ClO4)2 with the β‐diketone.
Molecular recognition of sugars by lanthanide (III) complexes of a conjugate of N, N‐bis[2‐[bis[2‐(1, 1‐dimethylethoxy)‐2‐oxoethyl]amino]ethyl]glycine and phenylboronic acid
Authors: Battistini Elisa , Mortillaro Armando , Aime Silvio , Peters Joop A.
Published: July 2007

A novel conjugate of phenylboronic acid and an Ln(DTPA) derivative, in which the central acetate pendant arm was replaced by the methylamide of L‐lysine, was synthesized and characterized. The results of a fit of variable 17O NMR data and a 1H NMRD profile show that the water residence lifetime of the Gd(III) complex (150 ns) is shorter than that of the parent compound Gd(DTPA)2− (303 ns). Furthermore, the data suggest that several water molecules in the second coordination sphere of Gd(III) contribute to the relaxivity of the conjugate. The Ln(III) complexes of this conjugate are highly suitable for molecular recognition of sugars. The interaction with various sugars was investigated by 11B NMR spectroscopy. Thanks to the thiourea function that links the phenylboronic acid targeting vector with the DTPA derivative, the interactions are stronger than that of phenylboronic acid itself. In particular, the interaction with N‐propylfructosamine, a model for the glucose residue in glycated human serum albumin (HSA), is very strong. Unfortunately, the complex also shows a rather strong interaction with hexose‐free HSA (KA = 705 ± 300). Copyright © 2007 John Wiley & Sons, Ltd.
Morphological characterization of spinal cord dorsal horn lamina I neurons projecting to the parabrachial nucleus in the rat
Authors: Almarestani L. , Waters S.M. , Krause J.E. , Bennett G.J. , Ribeiro‐da‐Silva A.
Published: July 2007

Many Rexed's lamina I neurons are nociceptive and project to the brain. Lamina I projection neurons can be classified as multipolar, fusiform, or pyramidal, based on cell body shape and characteristics of their proximal dendrites in the horizontal plane. There is also evidence that both multipolar and fusiform cells are nociceptive and pyramidal neurons nonnociceptive. In this investigation we identified which types of lamina I neurons belong to the spinoparabrachial tract in the rat and characterized them regarding the presence or absence of neurokinin‐1 receptor (NK‐1r) immunoreactivity. For this, cholera toxin subunit B (CTb), conjugated to a fluorescent marker was injected unilaterally into the parabrachial nucleus. Sections were additionally stained for the detection of NK‐1r immunoreactivity and were examined using fluorescence and confocal microscopy. Serial confocal optical sections and 3D reconstructions were obtained for a considerable number of neurons per animal. Using immunofluorescence, we assessed the proportion of lamina I neurons belonging to the spinoparabrachial (SPB) tract and/or expressing NK‐1r. The relative distribution of neurons belonging to the SPB tract was: 38.7% multipolar, 36.8% fusiform, 22.7% pyramidal, and 1.9% unclassified. Most of the SPB neurons expressing NK‐1r were either multipolar or fusiform. Pyramidal SPB neurons were seldom immunoreactive for NK‐1r, an observation that provides further support to the concept that most lamina I projection neurons of the pyramidal type are nonnociceptive. In addition, our study provides further evidence that these distinct morphological types of neurons differ in their phenotypic properties, but not in their projection patterns. J. Comp. Neurol. 504:287–297, 2007. © 2007 Wiley‐Liss, Inc.
Acute and chronic changes in dorsal horn innervation by primary afferents and descending supraspinal pathways after spinal cord injury
Authors: Kalous Adrianna , Osborne Peregrine B. , Keast Janet R.
Published: July 2007

Sprouting of peptidergic nociceptive and descending supraspinal projections to the dorsal horn following spinal cord injury (SCI) has been proposed as a mechanism of neuropathic pain. To identify structural changes that could initiate or maintain SCI pain, we used a complete transection model in rats to examine how structural remodeling in the dorsal horn rostral to the lesion relates to distance from injury, laminar region, and duration of injury. The major classes of C‐fiber primary afferents differed greatly in their susceptibility to structural and chemical changes and their ability to undergo plasticity. Peptidergic primary afferents showed a widespread loss throughout the dorsal horn of segments approaching the injury site. Some of this loss may have been due to decreased neuropeptide expression. The reduction in peptidergic fibers was transient, indicating compensatory sprouting and perhaps also increased neuropeptide expression within the cord. Nonpeptidergic afferents expressing GFRα1 were largely unaffected by SCI. In contrast, in GFRα2‐expressing nonpeptidergic afferents SCI caused a permanent loss of dorsal horn innervation. Unexpectedly, GFRα2 was transiently induced throughout deeper laminae but this was not due to upregulation of GFRα2 in dorsal root ganglia. We also observed permanent sprouting of catecholamine terminals of supraspinal origin. This was restricted to the superficial laminae. Our results show that SCI caused a loss of sensory input as well as structural remodeling such that the balance of nociceptive inputs and descending modulation was permanently altered. These changes may contribute to mechanisms rostral to the site of SCI that trigger and maintain neuropathic pain. J. Comp. Neurol. 504:238–253, 2007. © 2007 Wiley‐Liss, Inc.
AP180 and CALM in the developing hippocampus: Expression at the nascent synapse and localization to trafficking organelles
Authors: Petralia Ronald S. , Yao Pamela J.
Published: July 2007

Genetic and biochemical evidence has established that clathrin assembly protein AP180 is required for the proper assembly of synaptic vesicles via clathrin‐mediated endocytosis. The assembly protein CALM, the ubiquitously expressed homolog of AP180, also regulates the formation of clathrin‐coated vesicles. In this study we found high expression levels of AP180 and CALM in hippocampal tissues as early as embryonic day 18, before the expression of synaptophysin. We also used immunoelectron microscopy to establish the distribution of AP180 and CALM in the developing hippocampal synapses. We found AP180 and CALM in synapses at all developmental stages and in nonsynaptic growing processes. In addition to localization on the plasma membrane and clathrin‐coated vesicles that originated from the plasma membrane, we also report the presence of AP180 and CALM on other types of membrane structures. Our observations link AP180 and CALM to multiple vesicular organelles and raise the possibility that these proteins may play additional roles in developing neurons. J. Comp. Neurol. 504:314–327, 2007. Published 2007 Wiley‐Liss, Inc.
The Synthesis and Characterisation of Ferromagnetic CaMn2O4 Nanowires
Authors: Arnold Donna C. , Kazakova Olga , Audoit Guillaume , Tobin Joseph M. , Kulkarni Jaideep S. , Nikitenko Sergey , Morris Michael A. , Holmes Justin D.
Published: July 2007

The synthesis of marokite CaMn2O4 nanowires using a hydrothermal method is reported. Transmission electron microscopy and electron diffraction measurements show that the nanowires are polycrystalline in nature with diameters between 10 and 20 nm and lengths ranging from approximately 100 to 500 nm. Most interestingly, in contrast with the bulk material, magnetization measurements show that these nanowires exhibit ferromagnetic ordering with a Curie temperature (TC) of approximately 40 K.
The Structure of the First Supramolecular α‐Cyclodextrin Complex with an Aliphatic Monofunctional Carboxylic Acid
Authors: Rodríquez‐Llamazares Saddys , Yutronic Nicolás , Jara Paul , Englert Ulli , Noyong Michael , Simon Ulrich
Published: July 2007

The crystal structure of the supramolecular complex between α‐cyclodextrin and decanoic acid was determined: The aliphatic chain of the carboxylic acid is threaded through a head‐to‐head dimer of two cyclodextrin residues, resulting in a 1:2 stoichiometry. Head‐to‐head orientation is also observed between neighboring complexes. The overall degree of hydration with 25 water molecules per supramolecular complex is remarkably high. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Implementation of chemometric methodology in ACE: Predictive investigation of protein–ligand binding
Authors: Hanrahan Grady , Montes Ruth E. , Pao Amaris , Johnson Amos , Gomez Frank A.
Published: July 2007

An ACE predictive investigation of protein–ligand binding using a highly effective chemometric response surface design technique is presented. Here, Kd was estimated using one noninteracting standard which relates to changes in the electrophoretic mobility of carbonic anhydrase B (CAB, EC 4.2.1.1) on complexation with the ligand 4‐carboxybenzenesulfonamide (CBSA) present in the electrophoresis buffer. Experimental factors including injection time, capillary length, and applied voltage were selected and tested at three levels in a Box–Behnken design. Statistical analysis results were used to create a mathematical model for response surface prediction via contour and surface plots at a given target response (Kd = 1.19×10−6 M). As expected, there were a number of predicted solutions that reached our target response based on the significance of each factor at appropriate levels. The adequacy of the model was validated by experimental runs with the predicted model solution (capillary length = 47 cm, voltage = 11 kV, injection time = 0.01 min) presented in detail as an example.
Fabrication of a monolithic sampling probe system for automated and continuous sample introduction in microchip‐based CE
Authors: He Qiao‐Hong , Fang Qun , Du Wen‐Bin , Fang Zhao‐Lun
Published: July 2007

A fabrication process for producing monolithic sampling probes on glass chips, with tip diameters of a few hundred micrometers was developed, using simple tools including a glass cutter and a bench drill. Microfluidic chips with probes fabricated by this approach were coupled to a linearly moving slotted‐vial array sample presentation system for performing continuous sample introduction in the chip‐based CE system. On‐chip horizontal tubular reservoirs containing working electrolyte and waste were used to maintain a stable hydrostatic pressure in the chip channels during prolonged working periods. The performance of the system was demonstrated in the separation of FITC‐labeled amino acids with LIF detection, by continuously introducing a train of different samples without interruption. Throughputs of 30–60/h were achieved with <1.0% carry‐over and reproducibilities in peak height of 3.6, 3.3, and 3.5% RSD for arginine, FITC, and phenylalanine, respectively (n = 11). Continuous analysis of a mixture of FITC‐labeled amino acids for 2 h, involving 60 analytical cycles, yielded an RSD of 7.5 and 6.8% for arginine and FITC (n = 60), respectively. An extremely low sample consumption of 30 nL for each analysis was obtained. Separation efficiencies in plate numbers were in the range of 0.8–2×105/m. In addition to the application in sample introduction, the sample/reagent introduction system was also used to produce working electrolyte gradients during a CE separation to improve the separation efficiency. Comparing with isocratic electrophoresis separation, gradient CE demonstrated better separation efficiencies for a mixture of FITC‐labeled amino acids.
Use of multiplex PCR and CE for gene dosage quantification and its biomedical applications for SMN, PMP22, and α‐globin genes
Authors: Hung Chia‐Cheng , Chien Shu‐Chin , Lin Chia‐Yun , Chang Chien‐Hui , Chang Yin‐Fei , Jong Yuh‐Jyh , Hsieh Sung‐Tsang , Hsieh Wu‐Shiun , Liu Ming S. , Lin Win‐Li , Lee Chien‐Nan , Su Yi‐Ning
Published: July 2007

Many genetic diseases are caused by the presence of point mutations, small insertions, and deletions in respective genes, and the number of diseases known to be caused by deletions and duplications involving large DNA genomes is increasing. These changes lead to underexpression or overexpression of the gene, according to changes in gene dosage. The methods for the detection of point mutations, small insertions, and deletions are well established, but the detection of larger genomic deletions or duplications is more difficult. Due to the lack of efficient and technically feasible protocols for gene dosage quantification, we describe a diagnostic protocol employing a combination of available methods. The efficient and accurate gene dosage quantification platform is combined with multiplex PCR and CE, and applied to detect dosages of several genes, including SMN, PMP22, and α‐globin genes. The reliability of this novel methodology shows that it is a relatively speedy and low‐cost procedure and a significant tool for genetic diagnosis. Its sensitivity and specificity for identifying deletion and duplication genotypes approach 100%. Moreover, once we establish this powerful system, we will further apply this technique to the rapid detection of trisomy syndromes and microdeletion syndromes, including trisomy 13, Down syndrome, DiGeorge syndrome, and others.
IPG with electrodic plateaus (and other unusual procedures for 2‐DE)
Authors: Gianazza Elisabetta , Rocco Alessandro Guerini , Marchetto Andrea , Vergani Lodovica
Published: July 2007

We describe some simple changes to the geometry of the IPG strips that make them suitable to the loading of very large sample volumes and of high‐salt solutions. Of special relevance is the possibility of using strips with immobilized plateau(s) to either side of the gradient, or to both, also in connection with in‐gel rehydration protocols and focusing in stock trays. The only requirement to achieve this is to leave the all‐ready‐made attitude and go back to custom polymerization of the IPGs in one's laboratory.
Generalized Birnbaum‐Saunders distributions applied to air pollutant concentration
Authors: Leiva Víctor , Barros Michelli , Paula Gilberto A. , Sanhueza Antonio
Published: July 2007

The generalized Birnbaum‐Saunders (GBS) distribution is a new class of positively skewed models with lighter and heavier tails than the traditional Birnbaum‐Saunders (BS) distribution, which is largely applied to study lifetimes. However, the theoretical argument and the interesting properties of the GBS model have made its application possible beyond the lifetime analysis. The aim of this paper is to present the GBS distribution as a useful model for describing pollution data and deriving its positive and negative moments. Based on these moments, we develop estimation and goodness‐of‐fit methods. Also, some properties of the proposed estimators useful for developing asymptotic inference are presented. Finally, an application with real data from Environmental Sciences is given to illustrate the methodology developed. This example shows that the empirical fit of the GBS distribution to the data is very good. Thus, the GBS model is appropriate for describing air pollutant concentration data, which produces better results than the lognormal model when the administrative target is determined for abating air pollution. Copyright © 2007 John Wiley & Sons, Ltd.
A systematic evaluation of the ataxia telangiectasia mutated gene does not show an association with non‐Hodgkin lymphoma
Authors: Sipahimalani Payal , Spinelli John J. , MacArthur Amy C. , Lai Agnes , Leach Stephen R. , Janoo‐Gilani Rozmin T. , Palmquist Diana L. , Connors Joseph M. , Gascoyne Randy D. , Gallagher Richard P. , Brooks‐Wilson Angela R.
Published: July 2007

The ataxia telangiectasia mutated (ATM) gene is critical for the detection and repair of DNA double‐stranded breaks. Mutations in this gene cause the autosomal recessive syndrome ataxia telangiectasia (AT), an attribute of which is an increased risk of cancer, particularly lymphoma. We have undertaken a population‐based case/control study to assess the influence of genetic variation in ATM on the risk of non‐Hodgkin lymphoma (NHL). A number of the subtypes that constitute NHL have in common the occurrence of specific somatic translocations that contribute to lymphomagenesis. We hypothesize that ATM function is slightly attenuated by some variants, which could reduce double‐stranded break repair capacity, contributing to the occurrence of translocations and subsequent lymphomas. We sequenced the promoter and all exons of ATM in the germline DNA of 86 NHL patients and identified 79 variants. Eighteen of these variants correspond to nonsynonymous amino acid differences, 6 of which were predicted to be deleterious to protein function; these variants were all rare. Eleven common variants make up 10 haplotypes that are specified by 7 tagSNPs. Linkage disequilibrium across the ATM gene is high but incomplete. TagSNPs and the 6 putatively deleterious variants were genotyped in 798 NHL cases and 793 controls. Our results indicate that common variants of ATM do not significantly contribute to the risk of NHL in the general population. However, some rare, functionally deleterious variants may contribute to an increased risk of development of rare subtypes of the disease. © 2007 Wiley‐Liss, Inc.
Polymorphisms in PTGS1, PTGS2 and IL‐10 do not influence colorectal adenoma recurrence in the context of a randomized aspirin intervention trial
Authors: Hubner Richard A. , Muir Kenneth R. , Liu Jo‐Fen , Logan Richard F.A. , Grainge Matthew J. , Houlston Richard S. ,   Members of the UKCAP Consortium
Published: July 2007

Regular use of aspirin and other nonsteroidal antiinflammatory drugs reduces both the development of colorectal neoplasia and recurrence of colorectal adenoma (CRA). Modulation of the effects of aspirin by genetic factors has been reported, potentially allowing targeting of treatment to individuals most likely to gain benefit. Prostaglandin H synthase 1 (PTGS1) and PTGS2 are key enzymes in prostaglandin synthesis and are inhibited by aspirin, whilst interleukin‐10 (IL‐10) is an important antiinflammatory cytokine. We investigated whether functional genetic polymorphisms in the PTGS1, PTGS2 and IL‐10 genes influence CRA recurrence in individuals participating in a randomized aspirin intervention trial. DNA was available for genotyping from 546 patients who received aspirin (300 mg daily) or placebo for a mean 41‐months' duration. Homozygote carriers of variant alleles for the PTGS1 50C>T, PTGS2 −765G>C and IL‐10 −592C>A polymorphisms did not have a significantly altered risk of CRA recurrence (relative risk [RR] = 0.91; 95% confidence interval [CI]: 0.14–6.07, RR = 1.32; 95%CI: 0.66–2.62 and RR = 1.24; 95% CI: 0.74–2.07, respectively). There were also no significant interactions between aspirin intervention and genotype in determining recurrence risk. These data indicate that these polymorphisms are unlikely to influence CRA recurrence and cannot be used to identify individuals who derive benefit from aspirin intervention. © 2007 Wiley‐Liss, Inc.
The renal effects of alginates isolated from brown seaweed Sargassum vulgare
Authors: Sousa Alessandra de Paula Alves , Barbosa Paulo Sergio Ferreira , Torres Márcia Rocha , Martins Alice Maria Costa , Martins René Duarte , Alves Renata de Sousa , Sousa Daniel Freire de , Alves Claudênio Diógenes , Costa‐Lotufo Letícia Veras , Monteiro Helena Serra Azul
Published: July 2007

Alginates isolated from Sargassum vulgare, present a strong antitumor activity, associated with kidney reversible damage, as analysed by histopathology of treated animals. In the present study, the renal alteration mechanisms of S. vulgare alginates were investigated using the isolated perfused rat kidney and the isolated perfused rat mesenteric blood vessel methods. The results showed that the effects of Sargassum vulgare low viscosity (SVLV) alginate were more potent than those of Sargassum vulgare high viscosity (SVHV) alginate in the isolated rat kidney. The SVLV alginate caused considerable changes in renal physiology, as shown by an increase in parameters such as perfusion pressure, renal vascular resistance, glomerular filtration rate, urinary flow and sodium, potassium and chloride excretion and by reduction of chloride tubular transport. The effects of SVHV were weaker than those of SVLV. The effects of SVLV on kidney could be related to direct vascular action as demonstrated with SVLV alginate on mesenteric blood vessels. In conclusion, the Sargassum vulgare alginate altered the renal function parameters evaluated. S. vulgare low viscosity alginate renal effects were more potent than S. vulgare high viscosity alginate. It is suggested that physicochemical differences between SVHV and SVLV could explain the differences found in the results. Copyright © 2007 John Wiley & Sons, Ltd.
Bortrihalogenid‐Addukte von α‐Carbonyl‐diazoverbindungen
Authors: Fahr Egon , Dieter Hörmann Wolf
Published: July 2007

α.α′‐Dicarbonyl‐diazoverbindungen geben mit Bortrifluorid oder Bortrichlorid kristalline, farblose bis schwachgelbe Addukte. Diese enthalten 2 Moleküle Bortrihalogenid auf 1 Molekül der α.α′‐Dicarbonyl‐diazoverbindung. Auf chemischem und IR‐spektroskopischem Wege konnte gezeigt werden, daß das Bortrihalogenid koordinativ an die Carbonylgruppen gebunden wird. Wie die – verglichen mit den α.α′‐Dicarbonyl‐diazoverbindungen – ins Kürzerwellige verschobenen Diazo‐Valenzschwingungsbanden zeigen, weisen die Addukte einen Bindungszustand der CN2‐Gruppierung auf, der demjenigen aromatischer Diazoniumsalze entspricht. – Diazoketone bilden mit Bortrifluorid gleichfalls Addukte, die jedoch so unbeständig sind, daß sie nur in einigen Fällen bei Raumtemperatur in Substanz erhalten werden konnten.
Monoacetylierte Dimere des 2‐Phenyl‐4‐hydroxy‐thiazols
Authors: Behringer Hans , Weber Dieter
Published: July 2007

2‐Phenyl‐thiazolon‐(4) (Ia bzw. Ib) liefert mit Acetanhydrid, je nach den Bedingungen, entweder die O‐Acetylverbindung des Autokondensationsprodukts II (R = C6H5) oder ein labiles N‐Acetylderivat IIIa, das als Anlagerungsprodukt von 2‐Phenyl‐4‐hydroxy‐thiazol (Ib) an die CN‐Doppelbindung seines Tautomeren Ia formuliert wird. Letzteres wandelt sich beim Erhitzen in äthanol/Wasser in das isomere 2‐Phenyl‐4‐acetoxy‐5‐[4‐oxo‐2‐phenyl‐thiazolidinyl‐(2)]‐thiazol (VIIIa) um.
Über Orceinfarbstoffe, XXIII1). Die Autoxydation des 4.6‐Di‐tert.‐butyl‐resorcins
Authors: Musso Hans , Maaßen Dieter
Published: July 2007

Bei der Autoxydation des 4.6‐Di‐tert.‐butyl‐resorcins (13) in Alkali wird zunächst das Chinolhydroperoxyd 14 gebildet, das sich bei —20° in 96‐proz. Ausbeute isolieren läßt. Bei 20° erhält man dagegen das daraus entstandene Chinol 16 als Hauptprodukt neben wenig 5‐Hydroxy‐2‐tert.‐butyl‐chinon (23) und 6‐tert.‐Butoxy‐4‐tert.‐butyl‐resorcin (18). Das Peroxyd 14 wandelt sich über das Chinol 16 in den tert.‐Butyl‐äther 18 um. Beim trocknen Erhitzen zerfällt das Peroxyd in das Hydroxy‐chinon 23 und Isobutylen sowie andere Produkte. In heißer konzentrierter Lauge entsteht aus Peroxyd und Chinol 4‐Hydroxy‐1.2‐di‐tert.‐butyl‐cyclohexen‐(4)‐dion‐(3.6) (21). Die Konstitutionsermittlung der Produkte erfolgt vorwiegend spektroskopisch und wird z. T. durch Synthesen bestätigt.
Asymmetrische Induktionen, I. Konfigurationsspezifische Reduktionen von (±)‐α‐Dicarbonsäureimido‐und (±)‐α‐Acylamino‐propiophenonen
Authors: KarlMüller Horst , Werchan Hans‐Georg
Published: July 2007

Es wurde der sterische Verlauf der Reduktion von Acylderivaten des (±)‐α‐Amino‐propiophenons untersucht. Beim Vergleich des sterisch dirigierenden Einflusses von Dicarbonsäure‐imidogruppen mit dem bestimmter Dicarbonsäureamide ergaben sich weitere Hinweise auf die Beziehungen, die zwischen der Konstitution der substituierten Aminogruppen in den Ausgangsketonen und der Konfiguration der Reduktionsprodukte bestehen. Aus einem substituierten Phthalamidsäureester entstand im alkoholischen Medium das zugehörige Phthalimidoderivat.
Asymmetrische Induktionen, II. Konfigurationsspezifische Reduktionen von (±)‐α‐Dialkylamino‐propiophenonen
Authors: KarlMüller Horst , Müller Editha
Published: July 2007

Racemische α‐Dialkylamino‐propiophenone, in denen die Dialkylaminogruppen Methyl‐, Äthyl‐, Propyl‐ und Isopropylreste in verschiedenen Kombinationen enthalten, werden zu erythro‐Epimeren der zugehörigen Aminoalkohole reduziert.
Derivate des Methylendioxybenzols, XIII. Reaktionen der Schwefel‐ und Selenabkömmlinge des Methylendioxybenzols
Authors: Dallacker Franz , Eschelbach Friedrich‐Erhard , Zegers Herman
Published: July 2007

Es wird über Alkylierungs‐, Acylierungs‐ und Oxydationsreaktionen am 3.4‐Methylendioxy‐thiophenol und ‐selenophenol berichtet.
Derivate des Methylendioxybenzols, XIV. Zur Darstellung von Alkylmercapto‐3.4‐methylendioxy‐benzaldehyden. Ein Beitrag zur Aldehydsynthese nach Vilsmeier‐Haak
Authors: Dallacker Franz , Eschelbach Friedrich‐Erhard
Published: July 2007

Die Formylierung von Alkylmercapto‐3.4‐methylendioxy‐benzolen mit verschiedenartig substituierten N‐Methyl‐formanilid/POCl3‐Komplexen wird untersucht.
Zur Chemie des Benzolglykols, XIII1). Synthese von Desoxyinosadiaminen
Authors: Nakajima Minoru , Hasegawa Akira , Kurokawa Takashi
Published: July 2007

Aus vier stereoisomeren Tetraacetyl‐konduraminen2) (Trihydroxyaminocyclohexen‐tetraacetaten) wurden über die Bromhydrine durch katalytische Entbromierung Tetraacetyl‐desoxyinosamine dargestellt. Deren Oxydation lieferte vier stereoisomere Desoxyinosaminosen. Drei davon wurden über ihre Oxime in die Desoxyinosadiamine übergeführt. Die Konfigurationen wurden aufgrund der NMR‐Spektren festgelegt.
Einfluß der Photooxydation auf Histidingehalt und Aktivität von Insulin
Authors: Weitzel Günther , Schaeg Werner , Boden Günther , Willms Berend
Published: July 2007

Bei der Photooxydation des Insulins mit molekularem Sauerstoff in Gegenwart von Methylenblau werden bevorzugt Histidylreste angegriffen. Tyrosylreste werden in erheblich geringerem Maße, Disulfidbrücken praktisch nicht oxydiert. — Photooxydierte Insuline zeigen im Vergleich zu Normalinsulin eine Verschiebung des isoelektrischen Fällungsbereiches nach der sauren Seite sowie beträchtliche Minderung des Zinkbindungsvermögens. — Mit zunehmender Bestrahlungsdauer sinken Histidingehalt und biologische Aktivität des Insulins parallel ab (Tab. 5). Daraus folgt, daß die Imidazolzerstörung den Wirkungsverlust bedingt.
Untersuchungen an Cyclopropanverbindungen, VIII1). Solvolysereaktionen acyclischer Homoallyl‐Verbindungen
Authors: Hanack Michael , Kang Sungzong , Häffner Jürgen , Görler Klaus
Published: July 2007

Homoallylhalogenide sowie ‐tosylate der Struktur 1 werden in verschiedenen Lösungsmitteln solvolysiert und die dabei entstehenden Reaktionsprodukte (Tabb. 1—3) ermittelt. Die Solvolysegeschwindigkeiten von substituierten Homoallyl‐β‐naphthylsulfonaten in absol. Äthanol und in Eisessig werden gemessen (Tab. 4).
Ubichinone und verwandte Substanzen, IX1). Umsetzung von Ubichinon(35) mit Lithiumalanat und Natriumborhydrid
Authors: Morimoto Hiroshi , Imada Isuke , Sasaki Marekichi
Published: July 2007

Bei der Reaktion von Ubichinon(35) (1a), seinem Hydrochinon (2a) und dessen Diacetat (3a) mit LiAlH4 bildet sich ein Gemisch der Desmethyl‐Verbindungen 4a—5a. Diese Hydroxy‐Homologen von 1a entstehen auch aus 1a mit NaBH4. Methylierung des Gemisches von 4a + 5a ergibt 1a zurück; Äthylierungführt zum Gemisch der Äthyläther 6a—7a, Acetylierung zu den Acetylverbindungen 8a + 9a. Reduktion der Äthyläther 6a + 7a mit anschließender Methylierung ergibt ein Gemisch der Dimethyläther 10a + 11a, die sich von den zugrundeliegenden Hydrochinonen ableiten. Die Oxydation von 10a + 11a mit KMnO4 liefert die bekannten Phenylessigsäure‐Derivate 16 + 17 (IR‐spektroskopischer Vergleich).
Stereoisomere Formen des Äthyl‐hemiacetals von aldehydo‐D‐Galaktosepentaacetat
Authors: Wolfrom Melville L. , Decker William H.
Published: July 2007

Es wird bewiesen, daß das Äthyl‐hemiacetal von aldehydo‐D‐Galaktosepentaacetat in zwei stereoisomeren Formen existiert, deren Mutarotationseigenschaften in Chloroform (Abb. 1) verglichen werden.
Messung der Elektronenspinresonanz an Semidehydroascorbinsäure
Authors: Foerster GüNther V. , Weis Willi , Staudinger HansjüRgen
Published: July 2007

Durch Elektronenspinresonanz‐Messungen wird die Struktur der Semidehydroascorbinsäure (2) aufgeklärt. Die Massenwirkungskonstante für ihre Entstehung aus Ascorbinsäure und Dehydroascorbinsäure sowie deren pH‐Abhängigkeit werden bestimmt.
Untersuchungen über die Plastein‐Reaktion, IX1). Prolin‐haltige Monomere und ihre enzymatischen Umwandlungsprodukte
Authors: Determann Helmut , Köhler Rudolf
Published: July 2007

Von den beiden synthetisierten Pentapeptiden läßt sich L‐Tyrosyl‐L‐leucyl‐L‐prolyl‐L‐glutamyl‐L‐phenylalanin (1) unter der Einwirkung von Pepsin kondensieren, während L‐Alanyl‐L‐leucyl‐L‐prolyl‐L‐glutamyl‐L‐phenylalanin (2), das in Wasser besonders gut löslich ist, kein Plastein bildet. Aus 2 entstehen lediglich niedermolekulare Spalt‐ und Transpeptidierungsprodukte; das Plastein aus 1 setzt sich aus oligomeren Homologen (bis n = 5) zusammen.
Untersuchungen in der Cyclobutanreihe, XV1). Diels‐Alder Synthesen des cis‐3.4‐Dichlor‐cyclobutens mit 9.10‐Dimethyl‐ und 9.10‐Dibrom‐anthracen
Authors: Avram Margarete , Dinulescu Ilie G. , Nenitzescu Costin D.
Published: July 2007

Diels‐Alder Addukte des cis‐3.4‐Dichlor‐cyclobutens (2) mit 9.10‐Dimethyl‐anthracen und mit 9.10‐Dibrom‐anthracen sowie die durch Eliminierung des Halogens aus diesen Verbindungen erhaltenen Kohlenwasserstoffe werden beschrieben.