bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemistry/mass spectrometry as a tool in the investigation of the potent skin sensitizer p‐phenylenediamine and its reactivity toward nucleophiles
Authors: Jahn Sandra , Faber Helene , Zazzeroni Raniero , Karst Uwe 
Published: May 2012

RATIONALEAlthough para‐phenylenediamine (PPD) is known to cause severe allergic contact dermatitis in consequence of autoxidation and/or skin metabolism pathways, it is commonly utilized as an ingredient in permanent hair dyes. The aim of this work was to simultaneously accelerate the autoxidation process and to simulate the metabolic activation of PPD using a purely instrumental system.METHODSElectrochemistry (EC) in combination with electrospray ionization mass spectrometry (ESI‐MS) was used in this study to assess the skin‐sensitizing potential of PPD. Online and offline coupled EC/ESI‐MS experiments were carried out and the emerging oxidation products were investigated. In a second approach, these primary species were allowed to react with the nucleophiles glutathione (GSH), cysteine (Cys), potassium cyanide (KCN) and lysine (Lys) in order to evaluate their reactivity.RESULTSThe reactive p‐phenylene quinone diimine (PPQD), which can form upon autoxidation and/or skin metabolism of PPD, was effectively generated in a simple EC cell next to further oxidation products, including the trimeric product Bandrowski's Base (BB). Conjugation with GSH and Cys was successfully proven, but no adducts with KCN or Lys were observed. Furthermore, the application of different concentration ratios between PPD and nucleophile was shown to play a crucial role concerning the type of oxidation products and adducts being formed.CONCLUSIONSIt was found that EC/MS is a well‐suited approach for the targeted generation of reactive haptens such as PPQD while avoiding detection problems due to the complexity of matrices encountered when conducting conventional in vitro or in vivo experiments. Copyright © 2012 John Wiley & Sons, Ltd.
Predictive control: a historical perspective
Authors: Goodwin G.C. , Carrasco D.S. , Seron M.M. 
Published: May 2012

SUMMARYPredictive control is one of the major success stories in modern industrial control. It has been successfully used in hundreds of real‐world applications, and there is a rich associated theory. The goal of this paper is to provide a historical perspective of predictive control. In view of the breadth of predictive control, we will restrict the discussion to certain specific aspects. In particular, we give emphasis to the seminal work of David Clarke. Copyright © 2012 John Wiley & Sons, Ltd.
Fully parameterized tube model predictive control
Authors: Raković Saša V. , Kouvaritakis Basil , Cannon Mark , Panos Christos 
Published: May 2012

SUMMARYThe recently proposed parameterized tube model predictive control (MPC) exploited linearity to separate the treatment of future disturbances in robust model predictive control, thereby gaining significant computational advantages while superseding the state‐of‐the‐art closed‐loop strategies. The approach used an upper triangular parameterized tube prediction structure and a linear cost. The current paper proposes an extension of the tube prediction structure, which is fully parameterized and allows for the use of more general cost functions. The introduced parameterization generalizes the one associated with parameterized tube MPC (PTMPC), while it shares its strong system theoretic properties as well as its computational tractability. Copyright © 2012 John Wiley & Sons, Ltd.
On parameterized dissipation inequalities and receding horizon robust control
Authors: Lazar M. , Gielen R. H. 
Published: May 2012

SUMMARYThis paper considers the standard input‐to‐state stability (ISS) inequality for discrete‐time nonlinear systems, which involves a candidate Lyapunov function and a supply function that dictates the ISS gain of the system. In order to reduce conservatism, a set of parameters is assigned to both the Lyapunov and the supply function, respectively. A set‐valued map, which generates admissible sets of parameters for each state and input, is defined such that the corresponding parameterized Lyapunov and supply functions enjoy the standard ISS inequality. It is demonstrated that the so‐obtained parameterized ISS inequality offers nonconservative analysis conditions, even when Lyapunov functions with a particular structure, such as quadratic forms, are considered. For bounded inputs, it is then shown how parameterized ISS inequalities can be used to synthesize a closed‐loop system with an optimized envelope of trajectories. An implementation method based on receding horizon optimization is proposed, along with a recursive feasibility and complexity analysis. The effectiveness of the proposed synthesis methodology is illustrated for a benchmark test case for model predictive control, that is, a continuous stirred tank reactor.Copyright © 2012 John Wiley & Sons, Ltd.
Robust characterizations of k‐wise independence over product spaces and related testing results
Authors: Rubinfeld Ronitt , Xie Ning 
Published: May 2012

AbstractA discrete distribution D over Σ1 ×··· ×Σn is called (non‐uniform) k ‐wise independent if for any subset of k indices {i1,…,ik} and for any z1∈Σ,…,zk∈Σ, PrX∼D[X···X = z1···zk] = PrX∼D[X = z1]···PrX∼D[X = zk]. We study the problem of testing (non‐uniform) k ‐wise independent distributions over product spaces. For the uniform case we show an upper bound on the distance between a distribution D from k ‐wise independent distributions in terms of the sum of Fourier coefficients of D at vectors of weight at most k. Such a bound was previously known only when the underlying domain is {0,1}n. For the non‐uniform case, we give a new characterization of distributions being k ‐wise independent and further show that such a characterization is robust based on our results for the uniform case. These results greatly generalize those of Alon et al. (STOC'07, pp. 496–505) on uniform k ‐wise independence over the Boolean cubes to non‐uniform k ‐wise independence over product spaces. Our results yield natural testing algorithms for k ‐wise independence with time and sample complexity sublinear in terms of the support size of the distribution when k is a constant. The main technical tools employed include discrete Fourier transform and the theory of linear systems of congruences.© 2012 Wiley Periodicals, Inc. Random Struct. Alg., 2013
Maximum matchings in random bipartite graphs and the space utilization of Cuckoo Hash tables
Authors: Frieze Alan , Melsted Páll 
Published: May 2012

AbstractWe study the the following question in Random Graphs. We are given two disjoint sets L,R with |L| = n and |R| = m. We construct a random graph G by allowing each x∈L to choose d random neighbours in R. The question discussed is as to the size μ(G) of the largest matching in G. When considered in the context of Cuckoo Hashing, one key question is as to when is μ(G) = n whp? We answer this question exactly when d is at least three. © 2012 Wiley Periodicals, Inc. Random Struct. Alg., 2012
Preparation of high‐substituted cationic starch in presence of organic bases
Authors: Bendoraitienė Joana , Klimaviciute Rima , Zemaitaitis Algirdas 
Published: May 2012

AbstractCross‐linked N‐(hydroxypropyl)–N,N,N–trimethylammonium starch chlorides (CQS) with preserved microgranules, degree of substitution (DS) from 0.18 to 1.05 are prepared by reaction of starch with glycidyltrimethylammonium chloride (GTAC) accelerated by benzyltrimethylammonium hydroxide (BTMAOH) or tertiary amines–triethylamine (TEA) and dimethylbenzylamine (DMBA). When BTMAOH instead of NaOH is used as a catalyst, the reaction of cross‐linked starch (CS) with GTAC proceeds slightly slower and with a lower efficiency (RE). DMBA unexpectedly showed similar catalyst efficiency as BTMAOH. It is suggested that the reason for such phenomena is the reaction of GTAC with tertiary amines and the formation of strong bases – quaternary ammonium hydroxides. They actually catalyse starch cationization. DMBA is more active in this reaction in comparison with TEA. It is shown that, due to a higher amount of quaternary ammonium hydroxides in the liquid phase of the reaction mixture, the yield of starch cationization decreases. Cationization in the presence of organic bases provides higher sorption capabilities to the modified polysaccharide.
Maternal hemodynamics at 11–13 weeks' gestation and risk of pre‐eclampsia
Authors: Khalil A. , Akolekar R. , Syngelaki A. , Elkhouli M. , Nicolaides K. H. 
Published: May 2012

AbstractObjectiveWomen who develop pre‐eclampsia are at increased risk of cardiovascular disease and stroke in the subsequent decades. Individuals with cardiovascular disorders have increased central aortic systolic blood pressure (SBPAo) and arterial stiffness, as assessed by pulse wave velocity (PWV) and augmentation index (AIx). The aim of this study was to examine the potential value of assessment of SBPAo, PWV and AIx at 11–13 weeks' gestation in identifying women who subsequently develop pre‐eclampsia.MethodsThis was a screening study for pre‐eclampsia in singleton pregnancies at 11 + 0 to 13 + 6 weeks' gestation. Maternal history and characteristics were recorded and PWV, AIx (adjusted to a heart rate of 75 beats per min (AIx‐75)) and SBPAo measured. We compared these parameters in women who developed pre‐eclampsia (n = 181) with those in unaffected controls (n = 6766) and examined their performance in screening for pre‐eclampsia.ResultsIn the pre‐eclampsia group, compared to unaffected controls, there was an increase in AIx‐75 (1.13 vs. 1.00 multiples of the median (MoM); P < 0.0001), PWV (1.06 vs. 1.00 MoM; P < 0.0001) and SBPAo (1.09 vs. 1.00 MoM; P < 0.0001). In screening for pre‐eclampsia by a combination of maternal variables and log10AIx‐75 MoM, log10PWV MoM and log10SBPAo MoM, the estimated detection rate was 56.9% at a false‐positive rate of 10%.ConclusionCompared with women who remain normotensive, women who develop pre‐eclampsia have higher SBPAo and arterial stiffness, which is apparent from the first trimester of pregnancy. Copyright © 2012 ISUOG. Published by John Wiley & Sons, Ltd.
How and to what extent are free radicals involved in the nonoxidative thermal dehydrochlorination of poly(vinyl chloride)?
Authors: Starnes William H. 
Published: May 2012

AbstractKinetic analyses based on the resonance delocalization energies of polyenes and polyenyl radicals are used to rule out the free‐radical mechanisms of Arlman and of Winkler and Stromberg for the growth of conjugated polyenes during the thermolysis of poly(vinyl chloride) under nonoxidizing conditions. Possible sources of radicals during the thermolysis are described, and the radicals that cause the greatest reduction in thermal stability are identified as those that result from the reaction of polyenes with HCl. The way in which these radicals accelerate dehydrochlorination is discussed. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers
Language and music: sound, structure, and meaning
Authors: Slevc L. Robert 
Published: May 2012

AbstractLanguage and music are the most impressive examples of humans' capacity to process complex sound and structure. Though interest in the relationship between these two abilities has a long history, only recently has cognitive and neuroscientific research started to illuminate both what is shared and what is distinct between linguistic and musical processing. This review considers evidence for a link between language and music at three levels of analysis: sound, structure, and meaning. These links not only inform our understanding of language and music, but also add to a more basic understanding of our processing of complex auditory stimuli, structure, meaning, and emotion. WIREs Cogn Sci 2012, 3:483–492. doi: 10.1002/wcs.1186This article is categorized under:

Linguistics > Language in Mind and Brain
Protein–RNA footprinting: an evolving tool
Authors: Fourmy Dominique , Yoshizawa Satoko 
Published: May 2012

AbstractAs more RNA molecules with important cellular functions are discovered, there is a strong need to characterize their structures, functions, and interactions. Chemical and enzymatic footprinting methods are used to map RNA secondary and tertiary structure, to monitor ligand interactions and conformational changes, and in the study of protein–RNA interactions. These methods provide data at single‐nucleotide resolution that nicely complements the structural information available from X‐ray diffraction, nuclear magnetic resonance spectroscopy (NMR), or cryo‐electron microscopy. Footprinting methods also complement the dynamic information derived from single‐molecule Förster resonance energy transfer. RNA footprinting tools have been used for decades, but we have recently seen spectacular advances, for instance, the use in combination with massive parallel sequencing techniques. Large libraries of RNA molecules (small or large in size) can now be probed in high‐throughput manner when RNA footprinting methods are combined with fluorescent probe technologies and automation. In this article, after a brief historical overview, we summarize recent advances in RNA–protein footprinting methodologies that now integrate tools for massive parallel analysis. WIREs RNA 2011, 3:557–566. doi: 10.1002/wrna.1119This article is categorized under:

RNA Interactions with Proteins and Other Molecules > Protein–RNA Recognition
RNA Interactions with Proteins and Other Molecules > RNA–Protein Complexes
RNA Methods > RNA Analyses In Vitro and In Silico
Potential pitfalls in microRNA profiling
Authors: Chugh Pauline , Dittmer Dirk P. 
Published: May 2012

AbstractMicroRNAs (miRNAs) are small, noncoding RNAs that post‐transcriptionally influence a wide range of cellular processes such as the host response to viral infection, innate immunity, cell cycle progression, migration, and apoptosis through the inhibition of target mRNA translation. Owing to the growing number of miRNAs and identification of their functional roles, miRNA profiling of many different sample types has become more expansive, especially with relevance to disease signatures. In this review, we address some of the advantages and potential pitfalls of the currently available methods for miRNA expression profiling. Some of the topics discussed include isomiRNAs, comparison of different profiling platforms, normalization strategies, and issues with regard to sample preparation and experimental analyses. WIREs RNA 2011 DOI: 10.1002/wrna.1120This article is categorized under:

Regulatory RNAs/RNAi/Riboswitches > Biogenesis of Effector Small RNAs
Regulatory RNAs/RNAi/Riboswitches > Regulatory RNAs
RNA in Disease and Development > RNA in Disease
Economical Oxygenation of Olefins and Sulfides Catalyzed by New Molybdenum(VI) Tridentate Schiff Base Complexes: Synthesis and Crystal Structure
Authors: Rezaeifard Abdolreza , Jafarpour Maasoumeh , Raissi Heidar , Alipour Mahboubeh , Stoeckli‐Evans Helen 
Published: May 2012

AbstractAbstract. New cis‐dioxomolybdenum(VI) complexes (MoO2YxCH3OH) were synthesized using MoO2(acac)2 and 2[(1‐hydroxy‐2‐methylpropane‐2‐ylimino)methyl]phenol derivatives as tridentate ONO donor Schiff base ligands (H2Yx). MoY1 was crystallized in orthorhombic space group Pbca. The epoxidation of olefins using tert‐butyl hydroperoxide and oxidation of sulfides to the sulfoxides by hydrogen peroxide were efficiently enhanced by the catalytic activity of title MoVI complexes with excellent selectivity. The high efficiency and relative stability of the catalysts was observed by turnover number and UV/Vis investigations. The electron‐rich and bulky ligands promoted the effectiveness of the catalysts.
Structural Aspects of Copper‐Mediated Atom Transfer Radical Polymerization with a Novel Tetradentate Bisguanidine Ligand
Authors: Bienemann Olga , Froin Ann‐Kathrin , dos Santos Vieira Ines , Wortmann Ramona , Hoffmann Alexander , Herres‐Pawlis Sonja 
Published: May 2012

AbstractThis contribution reports the synthesis of the novel tetradentate bisguanidine ligand 2′,2′‐[ethane‐1, 2‐diylbis(methylazanediyl)]bis(ethane‐2, 1‐diyl)bis(1, 1, 3, 3‐tetramethylguanidine) (L1, TMG2dmtrien), which combines two weak amine and two strong guanidine donor functions. Two new copper(II) complexes were isolated and structurally characterized as complexes [Cu(TMG2dmtrien)][Br]2·3MeCN (C1[Br]2·3MeCN) and [Cu(TMG2dmtrien)][Cl]2·3MeCN (C2[Cl]2·3MeCN). The cations C1 and C2 [Cu(TMG2dmtrien)]2+ show a square‐planar coordination environment and are chiral with both enantiomers being observed in the unit cell. We investigated the application of L1 in copper‐mediated styrene ATRP. L1 shows with CuBr and PEBr as initiator a high polymerization activity according to the polymerization rate. First order kinetics confirm the living character of the polymerization. However, the deviation of molecular weights from theoretical molecular weights and the broad molecular weight distributions hint for a low controlled ATRP. The ATRP with further copper(I) salts {CuCl, [Cu(MeCN)4]BF4 and [Cu(MeCN)4]PF6} and PECl and PEBr as initiators were investigated as well. Herein the use of [Cu(MeCN)4]PF6 with PECl led to promising results.
Cyclopentadienyl Dicarbonyl Iron‐Bismuth Compounds – Synthesis, Structure, and Reactivity
Authors: Wójcik Katarzyna , Ecorchard Petra , Schaarschmidt Dieter , Rüffer Tobias , Lang Heinrich , Mehring Michael 
Published: May 2012

AbstractAbstract. The cyclopentadienyl‐substituted iron‐bismuth complexes [{Cp(CO)2Fe}BiCl2] (1), [{Cp(CO)2Fe}BiBr2] (2), [{Cp′′(CO)2Fe}BiBr2] (3) and [{Cp*(CO)2Fe}BiBr2] (4) were prepared with high yields starting from [Cpx(CO)2Fe]2 [Cpx = C5H5 (Cp), C5H3‐1, 3‐tBu2 (Cp′′), C5Me5 (Cp*)] and the corresponding bismuth halides. The single crystal X‐ray structure analyses of compounds 2–4 are reported. Comparison of their solubility demonstrates that the steric hindrance in this type of compounds is only slightly higher for compound 3 compared with compound 2 but significantly lower compared with the Cp* derivative 4. Compounds 1–4 react with nucleophililic reagents such as KOtBu, NaOCH2CH2OCH3, and NaOSiMe3 as well as with water in the presence of an amine to give a mixture of [{Cpx(CO)2Fe}BiX] (X = Cl, Br) and [{Cpx(CO)2Fe}3Bi]. In case of a reaction with nBu4NCl and DMAP (dimethylaminopyridine) no such dismutation is observed. Instead the complexes [{Cp(CO)2Fe}BiBr2(DMAP)2] (5), [NnBu4]2[{{Cp(CO)2Fe}BiBr3}2] (6) and [NnBu4]2[{{Cp(CO)2Fe}BiCl3}2] (7) were isolated and characterized by single‐crystal X‐ray diffraction.
Synthesis, Spectroscopic Characterization, DFT Calculations, and Dynamic Behavior of Mononuclear Macrocyclic Diorganotin(IV) Bis‐Dithiocarbamate Complexes
Authors: Tlahuext‐Aca Adrian , Höpfl Herbert , Medrano‐Valenzuela Felipe , Guerrero‐Alvarez Jorge , Tlahuext Hugo , Ochoa Lara Karen , Reyes‐Márquez Viviana , Tlahuextl Margarita 
Published: May 2012

AbstractNine mononuclear diorganotin(IV) dithiocarbamate complexes 1–9 with 19‐, 20‐ and 21‐membered macrocyclic structures were synthesized from dimethyl, di‐n‐butyl, and diphenyltin(IV) dichloride and three bis‐dithiocarbamate ligands derived from secondary bis‐amines having aromatic spacer groups. All compounds were characterized by elemental analysis, mass spectrometry, and spectroscopic methods (IR and 1H, 13C, and 119Sn NMR). Additionally, quantum chemical DFT calculations were performed for the dimethyltin(IV) derivatives in order to model the molecular structures. For one compound series the NMR spectra showed a concentration‐dependent behavior in solution, which was analyzed in detail and permitted to postulate the existence of an equilibrium with the corresponding [2+2] macrocycles.
Primary carnitine deficiency and pivalic acid exposure causing encephalopathy and fatal cardiac events
Authors: Rasmussen Jan , Nielsen Olav W. , Lund Allan M. , Køber Lars , Djurhuus Høgni 
Published: May 2012

AbstractBackgroundSeveral episodes of sudden death among young Faroese individuals have been associated with primary carnitine deficiency (PCD). Patients suffering from PCD have low carnitine levels and can present with metabolic and/or cardiac complications. Pivalic acid exposure decreases carnitine levels. The purpose of this study was to investigate and describe the association and pathophysiology of exposure to antibiotics containing pivalic acid and severe neurological and cardiac complications in six identified subjects suffering from PCD.Methods and materialsSix cases of PCD were identified and studied through medical records and family interview. Stored biomaterial was analyzed for mutations causing PCD.ResultsFive patients (two children, three adults) died suddenly while one adult patient survived sudden cardiac arrest. Lethal cardiac arrhythmia was documented in five patients, while one patient was not monitored at time of death, but had signs of cardiac arrhythmia a few days earlier. All patients suffered encephalopathy before cardiac arrhythmia. Autopsy showed severe hepatic steatosis and signs of cerebral edema in four out of five. One subject had a dilated heart. All patients were homozygous for the c.95A>G (p.N32S) mutation in SLC22A5 causing PCD. All patients had been treated with antibiotics containing pivalic acid prior to the episode.ConclusionExposure to antibiotics containing pivalic acid was associated with encephalopathy and progression to lethal cardiac arrhythmia in patients suffering from PCD.
Transient lymphocyte decrease due to adhesion and migration following catumaxomab (anti-EpCAM x anti-CD3) treatment in vivo
Authors: Dettmar Kirsten , Seitz-Merwald Isabell , Lindemann Carsten , Schroeder Petra , Seimetz Diane , Atz Judith 
Published: May 2012

AbstractIntroductionIn patients, a transient decrease in peripheral blood lymphocyte counts was observed following intraperitoneal administration of the trifunctional monoclonal antibody catumaxomab (anti-human EpCAM x anti-human CD3). The aim of this study was to clarify the observed effect in a preclinical mouse model and to analyse the related mechanism of actionin vitro.Materials and methodsA related antibody, BiLu (antihuman EpCAM x anti-mouse CD3), was administered to mice and blood leukocytes were analysed.In vitrostudies measured activation and cytokine secretion from human peripheral blood mononuclear cells (PBMC). For the analysis of T cell adhesion, PBMC were preincubated with catumaxomab and then co-cultured with human endothelial cells (HUVEC); T cell adhesion was assessed in the presence or absence of endothelial cell preactivation by TNFα. Adherent T cells were determined by flow cytometry.ResultsTreatment of mice with BiLu resulted in a dosedependent transient decrease in CD3+ T cells (both CD4+ and CD8+) that returned to the normal range within 48 h. Catumaxomab physiologically activated T cellsin vitro(increased CD69 expression) and induced cytokine release (TNFα, IFNγ). TNFα increased expression of adhesion molecules CD54 and CD62E on endothelial cells. Furthermore, catumaxomab dose-dependently enhanced adhesion of T cells to endothelial cells. Adhesion was further increased when endothelial cells were preactivated with TNFα.ConclusionsCatumaxomab increases adhesion of T cells to endothelial cells due to antibody-mediated activation of T cells and production of T cell cytokines that up-regulate endothelial cell adhesion molecules. These results provide a mechanistic rationale for the transient, reversible decrease in lymphocyte counts observed following catumaxomab administration in patients, which is likely to be due to redistribution of lymphocytes.