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Sample records for photoinduced wolff rearrangement

  1. QM/MM nonadiabatic dynamics simulations on photoinduced Wolff rearrangements of 1,2,3-thiadiazole

    NASA Astrophysics Data System (ADS)

    Liu, Xiang-Yang; Fang, Ye-Guang; Xie, Bin-Bin; Fang, Wei-Hai; Cui, Ganglong

    2017-06-01

    The photoinduced rearrangement reaction mechanism of 1,2,3-thiadiazole remains experimentally elusive. Two possible mechanisms have been proposed to date. The first is a stepwise mechanism via a thiocarbene intermediate; the second is an excited-state concerted rearrangement mechanism. Herein we have adopted both the electronic structure calculations and nonadiabatic dynamics simulations to study the photoinduced rearrangement reactions of 1,2,3-thiadiazole in the S2, S1, and S0 states in solution. On the basis of QM(CASPT2)/MM [quantum mechanics(complete active space self-consistent field second-order perturbation theory)/molecular mechanics] calculations, we have found that (1) the thiocarbene intermediate is not stable; thus, the stepwise mechanism should be unfavorable; (2) the excited-state decay from the S2 via S1 to S0 state is ultrafast and completed within ca. 200 fs; therefore, both the S2 and S1 states should not have a long enough time for the excited-state rearrangements. Instead, we have computationally proposed a modified photoinduced rearrangement mechanism. Upon irradiation, the S2 state is first populated (114.0 kcal/mol), followed by an ultrafast S2 → S1 → S0 excited-state decay along the S-N bond fission, which eventually leads to a very "hot" intermediate with the S-N bond broken (18.3 kcal/mol). Then, thermal rearrangements to thioketene, thiirene, and ethynethiol occur in a concerted asynchronous way. This mechanistic scenario has been verified by full-dimensional trajectory-based nonadiabatic dynamics simulations at the QM(CASPT2)/MM level. Finally, our present computational work provides experimentally interesting mechanistic insights into the photoinduced rearrangement reactions of cyclic and acyclic diazo compounds.

  2. Evidence for Nonstatistical Dynamics in the Wolff Rearrangement of a Carbene

    PubMed Central

    2008-01-01

    Two 13C-labeled isomers of the formal Diels−Alder adduct of acetylmethyloxirene to tetramethyl 1,2,4,5-benzenetetracarboxylate have been synthesized. Flash vacuum thermolysis of these adducts leads to various isotopic isomers of acetylmethylketene, the ratios of which have been determined by NMR. The surprising finding that the principal product comes from methylpyruvoyl carbene rather than its more stable isomer diacetylcarbene is explained by MPWB1K density functional calculations, which show that the reactant probably undergoes a unimolecular rearrangement to a norcaradiene derivative prior to its fragmentation. Coupled-cluster calculations on the methylpyruvoyl carbene show that it is capable of undergoing three unimolecular isomerizations. The fastest is 1,2-acetyl migration to give acetylmethylketene directly. The next is rearrangement via acetylmethyloxirene to diacetylcarbene and thence by Wolff rearrangement to acetylmethylketene. The least-favorable reaction is degenerate rearrangement via 1,3-dimethyl-2-oxabicyclo[1.1.0]butan-4-one (the epoxide of dimethylcyclopropenone). The combined experimental and computational results indicate that Wolff rearrangement of the diacetylcarbene occurs with a 2.5:1 ratio of the methyl groups despite the fact that they are related by a twofold axis of symmetry in the carbene. Preliminary molecular dynamics simulations are consistent with this conclusion. Taken together, the results suggest that the Wolff rearrangement is subject to the same kind of nonstatistical dynamical effects detected for other kinds of thermally generated reactive intermediates. PMID:18700757

  3. Photo-Wolff Rearrangement of 2-Diazo-1,2-naphthoquinone: Stern-Volmer Analysis of the Stepwise Reaction Pathway.

    PubMed

    Ladinig, Manfred; Ramseier, Markus; Wirz, Jakob

    2015-01-01

    2-Diazo-1,2-naphthoquinone (1) and its derivatives are the photoactive components in Novolak photoresists. A femtosecond infrared study has established that the photoreaction of 1 proceeds largely by a concerted Wolff rearrangement yielding the ketene 1H-inden-1-ylidene-methanone (3) within 300 fs after excitation, but earlier trapping studies gave evidence for a minor reaction path via a carbene intermediate 1-oxo-2(1H)-naphthalenylidene (2) with a lifetime of about 10 ps. Here, we provide a quantitative assessment of the stepwise pathway by Stern-Volmer analysis of the trapping of 2 by methanol to yield 2-methoxy-1-naphthol (4). We conclude that the lifetime of the carbene 2 is at least 200 ps. Moreover, [3 + 2]cycloaddition of 2 and acetonitrile yielding 2-methylnaphth[2,1-d]oxazole (5) was observed. A comparison of the yields of 5 formed upon photolysis and upon thermolysis of 1 in acetonitrile provides evidence that a substantial part of the hot nascent carbene 2 formed photolytically rearranges to the ketene 3 during its vibrational relaxation (hot ground-state reaction). © 2014 The American Society of Photobiology.

  4. Unusual reactions of diazocarbonyl compounds with α,β-unsaturated δ-amino esters: Rh(II)-catalyzed Wolff rearrangement and oxidative cleavage of N–H-insertion products

    PubMed Central

    Medvedev, Jury J; Galkina, Olesia S; Azarova, Ksenia V

    2016-01-01

    Summary Rh(II)-сatalyzed reactions of aroyldiazomethanes, diazoketoesters and diazodiketones with α,β-unsaturated δ-aminoesters, in contrast to reactions of diazomalonates and other diazoesters, give rise to the Wolff rearrangement and/or oxidative cleavage of the initially formed N–H-insertion products. These oxidation processes are mediated by Rh(II) catalysts possessing perfluorinated ligands. The formation of pyrrolidine structures, characteristic for catalytic reactions of diazoesters, was not observed in these processes at all. PMID:27829897

  5. Parallel Wolff Cluster Algorithms

    NASA Astrophysics Data System (ADS)

    Bae, S.; Ko, S. H.; Coddington, P. D.

    The Wolff single-cluster algorithm is the most efficient method known for Monte Carlo simulation of many spin models. Due to the irregular size, shape and position of the Wolff clusters, this method does not easily lend itself to efficient parallel implementation, so that simulations using this method have thus far been confined to workstations and vector machines. Here we present two parallel implementations of this algorithm, and show that one gives fairly good performance on a MIMD parallel computer.

  6. EPR studies of amine radical cations. Part 2. Thermal and photo-induced rearrangements of propargylamine and allylamine radical cations in low-temperature freon matrices.

    PubMed

    Knolle, Wolfgang; Janovský, Igor; Naumov, Sergej; Williams, Ffrancon

    2006-12-28

    Matrix EPR studies and quantum chemical calculations have been used to characterize the consecutive H-atom shifts undergone by the nitrogen-centered parent radical cations of propargylamine (1b*+) and allylamine (5*+) on thermal or photoinduced activation. The radical cation rearrangements of these unsaturated parent amines occur initially by a 1,2 H-atom shift from C1 to C2 with pi-bond formation at the positively charged nitrogen; this is followed by a consecutive reaction involving a second H-atom shift from C2 to C3. Thus, exposure to red light (lambda > 650 nm) converts 1b*+ to the vinyl-type distonic radical cation 2*+ which in turn is transformed on further photolysis with blue-green light (lambda approximately 400-600 nm) to the allene-type heteroallylic radical cation 3*+. Calculations show that the energy ordering is 1b*+ > 2*+ > 3*+, so that the consecutive H-atom shifts are driven by the formation of more stable isomers. Similarly, the parent radical cation of allylamine 5*+ undergoes a spontaneous 1,2-hydrogen atom shift from C1 to C2 at 77 K with a t1/2 of approximately 1 h to yield the distonic alkyl-type iminopropyl radical cation 6*+; this thermal reaction is attributed largely to quantum tunneling, and the rate is enhanced on concomitant photobleaching with visible light. Subsequent exposure to UV light (lambda approximately 350-400 nm) converts 6*+ by a 2,3 H-shift to the 1-aminopropene radical cation 7*+, which is confirmed to be the lowest-energy isomer derived from the ionization of either allylamine or cyclopropylamine. Although the parent radical cations of N, N-dimethylallylamine (9*+) and N-methylallylamine (11*+) are both stabilized by the electron-donating character of the methyl group(s), the photobleaching of 9*+ leads to the remarkable formation of the cyclic 1-methylpyrrolidine radical cation 10*+. The first step of this transformation now involves the migration of a hydrogen atom to C2 of the allyl group from one of the methyl

  7. Scaling law of Wolff cluster surface energy

    NASA Astrophysics Data System (ADS)

    Hsiao, Pai-Yi; Monceau, Pascal

    2003-05-01

    We study the scaling properties of the clusters grown by the Wolff algorithm on seven different Sierpinski-type fractals of Hausdorff dimension 1Wolff cluster follows a power law with respect to the lattice size. Moreover, we investigate the probability density distribution of the surface energy of the Wolff cluster and are able to establish a different scaling relation. It enables us to introduce an exponent that is associated to the surface energy of the Wolff cluster. Finally, this exponent is linked to a dynamical exponent via an inequality.

  8. On the mechanism of photoinduced refractive index changes in phosphosilicate glass

    SciTech Connect

    Larionov, Yu V; Sokolov, V O; Plotnichenko, V G

    2010-05-26

    The photoinduced growth of the refractive index of phosphosilicate glass during Bragg grating inscription and the thermal decay of the grating have a number of unusual features. The observed index variations are interpreted in terms of a new model for photoinduced glass network rearrangement. The model assumes the formation of photoinduced voids (nanopores) in the glass network near point defects. The nanopores may migrate through the network via bond switching when the network is in a 'soft' state. The photoinduced variations in network density lead to index variations. (fibres)

  9. History of Wolff-Parkinson-White syndrome.

    PubMed

    Scheinman, Melvin M

    2005-02-01

    While Drs. Wolff, Parkinson, and White fully described the syndrome that bears their names in 1930, prior case reports had already described the essentials. Over the ensuing century this syndrome has captivated the interest of anatomists, clinical cardiologists, and cardiac surgeons. Stanley Kent described lateral muscular connections over the atrioventricular (AV) groove, which he felt were the normal AV connections. The normal AV connections were, however, clearly described by His and Tawara. True right-sided AV connections were initially described by Wood et al., while Ohnell first described left free wall pathways. David Scherf is thought to be the first to describe our current understanding of the pathogenesis of the Wolff-Parkinson-White (WPW) syndrome in terms of a reentrant circuit involving both the AV node--His axis as well as the accessory pathway. This hypothesis was not universally accepted and many theories were applied to explain the clinical findings. The basics of our understandings were established by the brilliant work of Pick, Langendorf, and Katz who by using careful deductive analysis of ECGs were able to define the basic pathophysiological processes. Subsequently, Wellens and Durrer applied invasive electrical stimulation to the heart in order to confirm the pathophysiological processes. Sealy and his colleagues at Duke University Medical Center were the first to successfully surgically divide an accessory pathway and ushered in the modern area for curative therapy for these patients. Morady and Scheinman were the first to successfully ablate an accessory pathway (posteroseptal) using high-energy direct-current shocks. Subsequently, Jackman, Kuck, Morady, and a number of groups proved the remarkable safety and efficiency of catheter ablation for pathways in all locations using radiofrequency energy. More recently, Gallob et al. first described the gene responsible for a familial form of WPW. The current ability to cure patients with WPW is

  10. [Wolff-Parkinson-White syndrome and cardiopathies].

    PubMed

    Soria, R; Fernandez, F; Heller, J; Brétille, J; Cherif, F; Barrillon, A; Gerbaux, A; Gay, J

    1984-12-01

    Forty-nine cases of Wolff-Parkinson-White syndrome (WPW) were diagnosed out of 10 750 patients with cardiac disease (0.45 p. 100), 24 cases out of 3 761 congenital malformations and 25 cases in the 6 989 patients with acquired heart disease. Right ventricular pre-excitation was recorded in 31 cases; 13 in the lateral zone, 12 in the posterior paraseptal zone and 6 in the anterior paraseptal zone. Left ventricular pre-excitation was recorded in 18 cases: 8 in the lateral zone, 5 in the anterior paraseptal and 5 in the posterior paraseptal zones. WPW and congenital heart disease: Out of 20 cases of Ebstein's anomaly, 5 cases of WPW were observed: 4 right posterior and 1 right lateral pre-excitations. Out of 218 cases of hypertrophic obstructive cardiomyopathy, 7 cases of WPW were observed, 4 of which were congenital. Three cases of WPW were recorded in 699 patients with ventricular septal defects. Out of 1 348 cases of atrial septal defect, 5 cases of pre-excitation were recorded, including 3 right posterior pre-excitations associated with an ostium primum defect. Pre-excitation was also observed in isolated cases of corrected transposition of the great arteries, supravalvular aortic stenosis, aortic incompetence and patent ductus arteriosus. Pre-excitation and acquired heart disease: Five cases of pre-excitation were recorded out of 305 cases of dilated cardiomyopathy (1.62 p. 100). Eleven cases of pre-excitation were recorded in a total of 3 471 cases of valvular heart disease (0.31 p. 100): 9 in rheumatic valve disease and 2 in mitral valve prolapse. Nine cases of pre-excitation were observed in 2 850 cases of coronary artery disease. Intermittent Wolff-Parkinson-White syndrome: Ventricular pre-excitation masks the ECG changes of complete right bundle branch block in Ebstein's anomaly, complete left bundle branch block in aortic incompetence and dilated cardiomyopathy, and the in-complete right bundle branch block often seen in mitral valve prolapse. The

  11. Charlotte Wolff and lesbian history: reconfiguring liminality in exile.

    PubMed

    Brennan, Toni; Hegarty, Peter

    2010-01-01

    This article considers the "liminality" of the psychologist Charlotte Wolff, MD (1897-1986). Always living openly as a lesbian since her school days in Danzig, Wolff trained as a doctor-also pursuing a parallel interest in poetry and in philosophy. As a Jewish person, she was forced to leave the Berlin Health Service and flee Germany when the Nazi regime came to power. Having moved to Great Britain in 1936 after three years in France, Wolff reconfigured "exile" beyond the literal experience of emigration and immigration, as a form of "marginality" or "liminality" always involved in artistic and scientific endeavors. In her life and work she negotiated several liminal areas-from her gender presentation to her standing in the academic and scientific community (she was a Fellow of the British Psychological Society, to which she bequeathed her papers and the copyright to her work, but at the same time she was not an eminent psychologist), to her membership of sexual minority organizations (she conducted pioneering research on lesbianism and bisexuality, but some resented her connection with the psy-professions). In the spirit of Wolff's "liminality" as a strategy and creative zone, and along the lines indicated by Morawski (1994) as regards the transformative possibilities of feminist psychology as a liminal science, we argue for a reappraisal of Wolff's life and work that, in negotiating the borderlands between lesbian history and history of psychology, could enrich both disciplines.

  12. [From Wolff law, Ilizarov technology to natural reconstruction theory].

    PubMed

    Zang, Jian-cheng; Qin, Si-He

    2013-04-01

    Wolff law was an adaptable principle of bone, Tension-Stress Principle was equal to Distraction Osteogenesis or Distraction Tissue Regeneration, The Natural Reconstruction theory was a new orthopedic perspective proposed by Prof. QIN after deformity correction using Ilizarov technology. The thought about their relationship originated from a social phenomena, that the crowds and the confusion about export choice in Beijing's subway. Ilizarov technology and Wolff law were one concept related to Mechanics, and the former is completely in line with the latter. In other words, Ilizarov technology is an extension of Wolff law, is a repeated process of micro-trauma and continuous repair of bone trabecular initiated by moden engineering, just trabecular formed along the tension-stress direction. With adjustment of mechanical force,doctor can control the process of fracture healing and bone remolding to a certain extent. Natural Reconstruction theory enlarged the defined range of Wolff law obviously. Not only guided orthopedics clinical and basic research,but also related to the dialectical thinking of the doctor-patient relationship in sociology. There was an inevitable connection among Wolff law, Ilizarov technology and Natural Reconstruction theory. The history of discovery and understanding was a continuous process of thinking,practice and integration.

  13. Photoinduced Multicomponent Reactions.

    PubMed

    Garbarino, Silvia; Ravelli, Davide; Protti, Stefano; Basso, Andrea

    2016-12-12

    The combination of multicomponent approaches with light-driven processes opens up new scenarios in the area of synthetic organic chemistry, where the need for sustainable, atom- and energy-efficient reactions is increasingly urgent. Photoinduced multicomponent reactions are still in their infancy, but significant developments in this area are expected in the near future.

  14. Caring for the Student with Wolff-Parkinson-White Syndrome

    ERIC Educational Resources Information Center

    Prenni, Patricia G.

    2009-01-01

    Wolff-Parkinson-White syndrome is a cardiac condition in which an extra electrical pathway within the heart causes an abnormal increase in heart rate. It affects one to three people of every 1,000 people worldwide, occurring more often in males. Diagnosis usually occurs during young adulthood, so it is important for school nurses to be familiar…

  15. Caring for the Student with Wolff-Parkinson-White Syndrome

    ERIC Educational Resources Information Center

    Prenni, Patricia G.

    2009-01-01

    Wolff-Parkinson-White syndrome is a cardiac condition in which an extra electrical pathway within the heart causes an abnormal increase in heart rate. It affects one to three people of every 1,000 people worldwide, occurring more often in males. Diagnosis usually occurs during young adulthood, so it is important for school nurses to be familiar…

  16. Photoinduced diffusion molecular transport

    NASA Astrophysics Data System (ADS)

    Rozenbaum, Viktor M.; Dekhtyar, Marina L.; Lin, Sheng Hsien; Trakhtenberg, Leonid I.

    2016-08-01

    We consider a Brownian photomotor, namely, the directed motion of a nanoparticle in an asymmetric periodic potential under the action of periodic rectangular resonant laser pulses which cause charge redistribution in the particle. Based on the kinetics for the photoinduced electron redistribution between two or three energy levels of the particle, the time dependence of its potential energy is derived and the average directed velocity is calculated in the high-temperature approximation (when the spatial amplitude of potential energy fluctuations is small relative to the thermal energy). The thus developed theory of photoinduced molecular transport appears applicable not only to conventional dichotomous Brownian motors (with only two possible potential profiles) but also to a much wider variety of molecular nanomachines. The distinction between the realistic time dependence of the potential energy and that for a dichotomous process (a step function) is represented in terms of relaxation times (they can differ on the time intervals of the dichotomous process). As shown, a Brownian photomotor has the maximum average directed velocity at (i) large laser pulse intensities (resulting in short relaxation times on laser-on intervals) and (ii) excited state lifetimes long enough to permit efficient photoexcitation but still much shorter than laser-off intervals. A Brownian photomotor with optimized parameters is exemplified by a cylindrically shaped semiconductor nanocluster which moves directly along a polar substrate due to periodically photoinduced dipole moment (caused by the repetitive excited electron transitions to a non-resonant level of the nanocylinder surface impurity).

  17. The Bee Sting Related Wolff-Parkinson-White Syndrome

    PubMed Central

    Santhosh M., Shanmuga Ravi; Viswanathan, Stalin; Kumar, Shanthi

    2012-01-01

    Hymenoptera stings are common reasons for emergency visits. The admissions for the hymenoptera stings occur for systemic or unusual reactions. We are reporting a man with multiple bee stings, who presented with dizziness and palpitations and was found to have ECG findings of the Wolff-Parkinson-White syndrome. He had no worsening of symptoms or new ECG changes during his hospitalization. The hymenoptera related cardiac effects have also been reviewed and summarized. PMID:23285451

  18. Photo-induced structural changes in Ge-Sb-Se films

    NASA Astrophysics Data System (ADS)

    Lin, Li; Wang, Guoxiang; Shen, Xiang; Dai, Shixun; Xu, Tiefeng; Nie, Qiuhua

    2017-03-01

    Amorphous Ge-Sb-Se thin films have been prepared by the radio-frequency (RF) magnetron co-sputtering deposition technique, and their intrinsic photosensitivity and photo-induced structural changes have been investigated. The results show a crossover from photodarkening (PD) to photobleaching (PB) in the films when the film compositions change from Se-deficient to rich. Further Raman analysis on these as-prepared thin films irradiated with a laser of wavelength 655 nm in every five minutes provides direct evidence of photo-induced structure rearrangements.

  19. Critical Dynamics Behavior of the Wolff Algorithm in the Site-Bond-Correlated Ising Model

    NASA Astrophysics Data System (ADS)

    Campos, P. R. A.; Onody, R. N.

    Here we apply the Wolff single-cluster algorithm to the site-bond-correlated Ising model and study its critical dynamical behavior. We have verified that the autocorrelation time diminishes in the presence of dilution and correlation, showing that the Wolff algorithm performs even better in such situations. The critical dynamical exponents are also estimated.

  20. Asymptomatic Wolff-Parkinson-White Syndrome: Who Should Be Treated?

    PubMed

    Obeyesekere, Manoj N; Leong-Sit, Peter; Krahn, Andrew D; Gula, Lorne J; Yee, Raymond; Skanes, Allan C; Klein, George J

    2012-09-01

    This article discusses the merits of electrophysiology study (EPS) and/or ablation for asymptomatic preexcitation Wolff-Parkinson-White (WPW) ECG pattern. Sudden deaths in asymptomatic patients are too few to merit broad screening and aggressive intervention. It also discusses the risks of ablation and the low predictive accuracy of EPS. When WPW is an incidental finding, the decision to proceed with investigation and ablation can be made considering patients' situations and preferences. An invasive strategy is targeted at patients concerned about the low risk of life-threatening arrhythmia as a first presentation after a discussion of the risks and benefits.

  1. Wolff-Parkinson-White syndrome: lessons learnt and lessons remaining.

    PubMed

    Benson, D Woodrow; Cohen, Mitchell I

    2017-01-01

    The Wolff-Parkinson-White pattern refers to the electrocardiographic appearance in sinus rhythm, wherein an accessory atrioventricular pathway abbreviates the P-R interval and causes a slurring of the QRS upslope - the "delta wave". It may be asymptomatic or it may be associated with orthodromic reciprocating tachycardia; however, rarely, even in children, it is associated with sudden death due to ventricular fibrillation resulting from a rapid response by the accessory pathway to atrial fibrillation, which itself seems to result from orthodromic reciprocating tachycardia. Historically, patients at risk for sudden death were characterised by the presence of symptoms and a shortest pre- excited R-R interval during induced atrial fibrillation <250 ms. Owing to the relatively high prevalence of asymptomatic Wolff-Parkinson-White pattern and availability of catheter ablation, there has been a need to identify risk among asymptomatic patients. Recent guidelines recommend invasive evaluation for such patients where pre-excitation clearly does not disappear during exercise testing. This strategy has a high negative predictive value only. The accuracy of this approach is under continued investigation, especially in light of other considerations: Patients having intermittent pre-excitation, once thought to be at minimal risk may not be, and the role of isoproterenol in risk assessment.

  2. Relevance of collagen piezoelectricity to "Wolff's Law": a critical review.

    PubMed

    Ahn, Andrew C; Grodzinsky, Alan J

    2009-09-01

    According to "Wolff's Law", bone is deposited and reinforced at areas of greatest stress. From a clinical perspective, this "law" is supported by the strong association between bone density and physical activity. From a mechanistic standpoint, however, the law presents a challenge to scientists seeking to understand how osteocytes and osteoblasts sense the mechanical load. In the 1960s, collagen piezoelectricity was invoked as a potential mechanism by which osteocytes could detect areas of greater stress but piezoelectricity diminished in importance as more compelling mechanisms, such as streaming potential, were identified. In addition, accumulating evidence for the role of fluid-related shear stress in osteocyte's mechanosensory function has made piezoelectricity seemingly more obsolete in bone physiology. This review critically evaluates the role of collagen piezoelectricity (if any) in Wolff's Law--specifically, the evidence regarding its involvement in strain-generated potentials, existing alternate mechanisms, the present understanding of bone mechanosensation, and whether piezoelectricity serves an influential role within the context of this newly proposed mechanism. In addition to reviewing the literature, this review generates several hypotheses and proposes future research to fully address the relevance of piezoelectricity in bone physiology.

  3. Degradations and Rearrangement Reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Jianbo

    This section deals with recent reports concerning degradation and rearrangement reactions of free sugars as well as some glycosides. The transformations are classified in chemical and enzymatic ways. In addition, the Maillard reaction will be discussed as an example of degradation and rearrangement transformation and its application in current research in the fields of chemistry and biology.

  4. [Unusual supraventricular tachycardias in Wolff-Parkinson-White syndrome].

    PubMed

    Belhassen, B; Laniado, S

    1983-01-01

    Two unusual types of narrow-QRS tachycardias were initiated during electrophysiological investigation of a patient with the Wolff-Parkinson-White syndrome. In the first type, the QRS complexes were preceded by atrial activation, the chronological sequence of depolarisation of which was similar to the sinus rhythm, suggesting the mechanism of sino-atrial reentry. The narrow QRS complex during tachycardia was related to the fact that the refractory period of the accessory pathway was longer than the tachycardia cycle. The second type of tachycardia was associated with I/I retrograde atrial activation within the QRS complex, suggesting the mechanism of intranodal reentry. The main point of interest of this case is that the accessory pathway, which only conducted in the anterograde direction, did not participate in the mechanism of either of these tachycardias.

  5. [Sudden death in intermittent Wolff Parkinson White syndrome].

    PubMed

    Medeiros, A; Iturralde, P; Guevara, M; Mendoza, C; Colín, L

    2001-01-01

    Sudden death is a rare condition in asymptomatic patients with asymptomatic intermittent Wolff Parkinson syndrome (WPW); for this reason it is believed that these patients should not undergo to radiofrequency ablation. We report an asymptomatic 44 year old man who developed ventricular fibrillation with a pre-excited RR interval less than 200 msec during atrial fibrillation, as a first manifestation of WPW syndrome. The Holter monitoring showed intermittent pre-excitation at low heart rate (70 bpm). During the electrophysiological study a successfully radiofrequency catheter ablation of a right posteroseptal accessory pathway was performed. We concluded that intermittent pre-excitation may not be used to identify patients who are at risk of sudden death. Radiofrequency catheter ablation should be recommended in those patients with a very high success rate, and a low incidence of serious complications.

  6. Asymptomatic Wolff-Parkinson-White Pattern ECG in USAF Aviators.

    PubMed

    Davenport, Eddie D; Rupp, Karen A N; Palileo, Edwin; Haynes, Jared

    2017-01-01

    Wolff-Parkinson-White (WPW) pattern is occasionally found in asymptomatic aviators during routine ECGs. Aeromedical concerns regarding WPW pattern include risk of dysrhythmia or sudden cardiac death (SCD), thus affecting the safety of flight. The purpose of this study was to determine the prevalence and outcomes of aviators with asymptomatic WPW pattern and assess for risk factors that contribute to progression to dysrhythmia or symptoms. The U.S. Air Force (USAF) ECG library database containing over 1.2 million ECGs collected over the past 68 yr was used to identify 638 individual aviators with WPW pattern. Demographic, medical history, and outcome data were obtained by medical record review. Aviators who developed high risk features defined as symptoms, arrhythmia, or ablation of a high risk pathway, were compared to those who remained asymptomatic. Prevalence of WPW pattern was 0.30% among all USAF aviators. Of the 638 individuals, 64 (10%) progressed to the combined endpoint of SCD, arrhythmia, and/or ablation of a high risk pathway over 6868 patient years, with average follow-up of 10.5 yr. There were two sudden cardiac deaths (0.3%). Annual risk of possible sudden incapacitation was 0.95% and of SCD 0.03%. Those that progressed to high risk were significantly younger, had lower diastolic blood pressure, lower total cholesterol, and better physical fitness testing scores. WPW pattern on ECG found in asymptomatic aviators confers < 1% annual risk of arrhythmia or incapacitating events with the highest risk in the younger, healthier, and most fit populations.Davenport ED, Rupp KAN, Palileo E, Haynes J. Asymptomatic Wolff-Parkinson-White pattern ECG in USAF aviators. Aerosp Med Hum Perform. 2017; 88(1):56-60.

  7. Conversion of atrial fibrillation with ajmaline in a pregnant woman with Wolff-Parkinson-White syndrome.

    PubMed

    Mozo de Rosales, F; Moreno, J; Bodegas, A; Melchor, J C; Fernández LLebrez, L; Aranguren, G

    1994-07-01

    Pregnancy is related to an increased frequency of arrhythmias in asymptomatic patients with Wolff-Parkinson-White syndrome, which might lead to sudden death. A 40-year-old woman, with Wolff-Parkinson-White syndrome which was not diagnosed until pregnancy, presented in the 34th week with an atrial fibrillation, with high risk criteria for ventricular fibrillation. Intravenous ajmaline was given to convert the tachyarrhythmia to sinus rhythm. We obtained an excellent maternal control with no maternal or fetal adverse effects.

  8. Acceleration of ventricular rate by fibrillation associated with the Wolff-Parkinson-White syndrome.

    PubMed

    Sheinman, B D; Evans, T

    1982-10-09

    Amiodarone has proved to be a valuable drug in atrial fibrillation associated with the Wolff-Parkinson-White syndrome. When it was administered to a patient with this syndrome in atrial fibrillation, who had previously suffered an inferior myocardial infarction, the ventricular rate accelerated from 170 to 230 beats/minute.This unusual case emphasises the need for full electrophysiological assessment of patients with the Wolff-Parkinson-White syndrome for whom amiodarone treatment is being considered.

  9. Nature and mechanism of the photoinduced spin transition in [Fe(PM-BiA )2 (NCS )2

    NASA Astrophysics Data System (ADS)

    Ichiyanagi, K.; Hebert, J.; Toupet, L.; Cailleau, H.; Guionneau, P.; Létard, J.-F.; Collet, E.

    2006-02-01

    We report the investigation of a prototype cooperative photoinduced spin transition in [Fe(PM-BiA)2(NCS)2] by x-ray diffraction. The structural rearrangement accompanying the change of an electronic state between the low spin and the photoinduced out-of-equilibrium high spin phases is similar to the one occurring around the phase transition at thermal equilibrium. The cooperative behavior of the light-induced optical hysteresis and light-induced thermal hysteresis phenomena investigated here show a strong similarity with thermal hysteresis around first-order phase transitions, since they are driven by a domain nucleation process.

  10. Wolff-Parkinson-White Syndrome--current views.

    PubMed

    Chung, E K

    1977-02-01

    The Wolff-Parkinson-White (WPW) syndrome is an important clinical entity because of frequent recurrences of very rapid tachyarrhythmias. The electrocardiographic finding of the WPW syndrome often mimicks pseudo diaphragmatic (inferior) myocardial infarction which should not be misinterpreted. The most important diagnostic criterion is recognition of a delta wave; the short P-R interval or broad QRS complex may not be present in every case. The mechanism for the tachycardia is considered to be a reentry phenomenon via anomalous and normal atrioventricllar (A-V) pathways. The drug of choice for the treatment of regular supraventricular (reciprocating) tachycardia with narrow QRS complexes, which is the most common arrhythmia in the WPW syndrome, is propranolol. Digitalis is almost equally effective in this case. For tachyarrhythmias, particularly atrial fibrillation or flutter with anomalous conduction, intravenously-administered lidocaine is considered to be the drug of choice. Procainamide or quinidine is also frequently used under this circumstance with excellent therapeutic result. Many patients with the WPW syndrome require long-term maintenance drug therapy (propranolol, digitalis or quinidine in most cases). In urgent clinical situations, direct current (DC) shock should be applied immediately. In selected patients with refractory tachyarrhythmias, the use of an artificial pacemaker or surgical approach may be considered.

  11. [Outcome of 195 patients with Wolff-Parkinson-White syndrome].

    PubMed

    Brembilla-Perrot, B; Aliot, E; Louis, P; Terrier de la Chaise, A; Khalife, K; Marçon, F; Cherrier, F; Gilgenkrantz, J M; Pernot, C

    1987-03-01

    Between 1974 and 1984, 207 patients with Wolff-Parkinson-White syndrome (WPW) were admitted to our hospital department; 195 of them were followed up for periods ranging from 1 to 12 years (6 years in children, 3 years and 9 months in adults on average); 160 had undergone electrophysiological exploration. Fifty-seven patients were less than 16 years old: 7 died, including 6 with associated congenital heart disease; an asymptomatic 12-year old girl died suddenly while taking part in a sporting event. The signs of WPW disappeared in 5 out of 10 children under 1 year of age. One hundred and thirty-eight patients were older than 15: 15 of them died, but only 3 deaths were related to WPW: one was consecutive to surgery for WPW and one to fulguration; the third patient died of WPW tachyarrhythmia; the refractory period of his Kent's bundle was short, but his compliance with treatment was irregular. We found no correlation between changes in functional symptoms and Kent's bundle refractory period values; paradoxically, the frequency of attacks and resistance to treatment was higher in cases with long refractory period. On the whole, this series confirms that WPW usually is a benign disease. However, the risk of sudden death, of which it offers an example, indicates that all patients with WPW should be evaluated with at least an exercise test and, depending on its results or on the socio-professional context, an electrophysiological exploration.

  12. Parallelization of the Wolff single-cluster algorithm

    NASA Astrophysics Data System (ADS)

    Kaupužs, J.; Rimšāns, J.; Melnik, R. V. N.

    2010-02-01

    A parallel [open multiprocessing (OpenMP)] implementation of the Wolff single-cluster algorithm has been developed and tested for the three-dimensional (3D) Ising model. The developed procedure is generalizable to other lattice spin models and its effectiveness depends on the specific application at hand. The applicability of the developed methodology is discussed in the context of the applications, where a sophisticated shuffling scheme is used to generate pseudorandom numbers of high quality, and an iterative method is applied to find the critical temperature of the 3D Ising model with a great accuracy. For the lattice with linear size L=1024 , we have reached the speedup about 1.79 times on two processors and about 2.67 times on four processors, as compared to the serial code. According to our estimation, the speedup about three times on four processors is reachable for the O(n) models with n≥2 . Furthermore, the application of the developed OpenMP code allows us to simulate larger lattices due to greater operative (shared) memory available.

  13. Parallelization of the Wolff single-cluster algorithm.

    PubMed

    Kaupuzs, J; Rimsāns, J; Melnik, R V N

    2010-02-01

    A parallel [open multiprocessing (OpenMP)] implementation of the Wolff single-cluster algorithm has been developed and tested for the three-dimensional (3D) Ising model. The developed procedure is generalizable to other lattice spin models and its effectiveness depends on the specific application at hand. The applicability of the developed methodology is discussed in the context of the applications, where a sophisticated shuffling scheme is used to generate pseudorandom numbers of high quality, and an iterative method is applied to find the critical temperature of the 3D Ising model with a great accuracy. For the lattice with linear size L=1024, we have reached the speedup about 1.79 times on two processors and about 2.67 times on four processors, as compared to the serial code. According to our estimation, the speedup about three times on four processors is reachable for the O(n) models with n> or =2. Furthermore, the application of the developed OpenMP code allows us to simulate larger lattices due to greater operative (shared) memory available.

  14. Photoinduced and thermal stress in silicon microcantilevers

    NASA Astrophysics Data System (ADS)

    Datskos, Panos G.; Rajic, Slobodan; Datskou, Irene

    1998-10-01

    The photogeneration of free charge carriers in a semiconductor gives rise to mechanical strain. We measured the deflection of silicon microcantilevers resulting from photoinduced stress. The excess charge carriers responsible for the photoinduced stress, were produced via photon irradiation from a diode laser with wavelength λ=780 nm. For Si microcantilevers, the photoinduced stress is of opposite direction and about four times larger than the stress resulting from only thermal excitation. In this letter we report on our study of the photoinduced stress in silicon microcantilevers and discuss their temporal and photometric response.

  15. The cubyl cation rearrangements.

    PubMed

    Jalife, Said; Mondal, Sukanta; Cabellos, Jose Luis; Martinez-Guajardo, Gerardo; Fernandez-Herrera, Maria A; Merino, Gabriel

    2016-02-25

    Born-Oppenheimer molecular dynamics simulations and high-level ab initio computations predict that the cage-opening rearrangement of the cubyl cation to the 7H(+)-pentalenyl cation is feasible in the gas phase. The rate-determining step is the formation of the cuneyl cation with an activation barrier of 25.3 kcal mol(-1) at the CCSD(T)/def2-TZVP//MP2/def2-TZVP level. Thus, the cubyl cation is kinetically stable enough to be formed and trapped at moderate temperatures, but it may be rearranged at higher temperatures.

  16. The history of the wolff-Parkinson-white syndrome.

    PubMed

    Scheinman, Melvin M

    2012-07-01

    While Drs Wolff, Parkinson, and White fully described the syndrome in 1930, prior case reports had described the essentials. Over the ensuing century this syndrome has captivated the interest of anatomists, clinical cardiologists, and cardiac surgeons. Stanley Kent described lateral muscular connections over the atrioventricular (AV) groove which he felt were the normal AV connections. The normal AV connections were, however, clearly described by His and Tawara. True right-sided AV connections were initially described by Wood et al., while Öhnell first described left free wall pathways. David Scherf is thought to be the first to describe our current understanding of the pathogenesis of the WPW syndrome in terms of a re-entrant circuit involving both the AV node-His axis as well as the accessory pathway. This hypothesis was not universally accepted, and many theories were applied to explain the clinical findings. The basics of our understanding were established by the brilliant work of Pick, Langendorf, and Katz who by using careful deductive analysis of ECGs were able to define the basic pathophysiological processes. Subsequently, Wellens and Durrer applied invasive electrical stimulation to the heart in order to confirm the pathophysiological processes. Sealy and his colleagues at Duke University Medical Center were the first to successfully surgically divide an accessory pathway and ushered in the modern era of therapy for these patients. Morady and Scheinman were the first to successfully ablate an accessory pathway (posteroseptal) using high-energy direct-current shocks. Subsequently Jackman, Kuck, Morady, and a number of groups proved the remarkable safety and efficiency of catheter ablation for pathways in all locations using radiofrequency energy. More recently, Gollob et al. first described the gene responsible for a familial form of WPW. The current ability to cure patients with WPW is due to the splendid contributions of individuals from diverse

  17. [Electrophysiological characteristics of asymptomatic Wolff-Parkinson-White syndromes].

    PubMed

    Brembilla-Perrot, B; Ghawi, R; Dechaux, J P

    1991-11-01

    The management of the Wolff-Parkinson-White syndrome (WPW) is controversial especially when the patient is asymptomatic. The aim of this study was to evaluate the electrophysiological characteristics of such patients. Thirty two asymptomatic subjects with overt WPW on the surface ECG aged 14 to 68 years (average 36 +/- 15 years) underwent endocavitary or oesophageal electrophysiological study with the following protocol: programmed atrial stimulation using 1 or 2 extrastimuli over 3 cycles to evaluate the induction of paroxysmal junctional tachycardia and atrial fibrillation; atrial pacing at increasing frequencies to assess the shortest cycle conducted by the bundle of Kent. This protocol was repeated during intravenous infusion of 20 to 30 mg of Isoproterenol. Four electrophysiological characteristics were identified: the incidence of induction of junctional tachycardia was very low (2 cases, 6%); the incidence of induction of atrial fibrillation or tachycardia was similar to that of symptomatic WPW (9 cases 30%); the incidence of rapid conduction via the bundle of Kent (cycle conducted by the Kent less than 250 ms under basal conditions less than 200 ms with Isoproterenol) was 19% (6 cases); the incidence of potentially serious forms of WPW with rapid conduction in the bundle of Kent and atrial vulnerability (induction of atrial fibrillation at a frequency less than the Wenckebach point by programmed atrial stimulation) was similar to that in symptomatic WPW, 3 cases (10%). In conclusion, the asymptomatic character of the WPW is very probably due to the absence of junctional tachycardias. Nevertheless, these patients are at risk of atrial fibrillation with an incidence of potentially serious forms of 10%.(ABSTRACT TRUNCATED AT 250 WORDS)

  18. [Oral propranolol in Wolff-Parkinson-White syndrome. Electrophysiological data].

    PubMed

    Dolla, E; Levy, S; Cointe, R; Moyal, C; Bru, P; Rossi, P; Gérard, R

    1991-07-01

    The effects of oral propranolol were studied in 24 patients with the WPW syndrome. The average daily dose of propranolol was 130 +/- 24 mg administered in 3 doses over a period of 48 to 72 hours. Endocavitary electrophysiological study was performed 2 to 4 hours after the last dose. The effective anterograde refractory periods (EARP) of the accessory and normal pathways were measured before and after propranolol (and, in both studies, before and after isoproterenol). The EARP of the accessory pathway was not affected by the propranolol. However, in the 9 patients in whom its value was less than 270 ms, it increased significantly (p = 0.01). The EARP of the accessory pathway measured after administration of isoproterenol increased significantly in all patients with oral propranolol (p = 0.001). Sustained reciprocating tachycardia could be induced in 19 patients and non-sustained reciprocating tachycardia in 5 other patients during base line electrophysiological study. Oral propranolol prevented the induction of the tachycardias in 18 patients (75%), even after isoproterenol. The shortest R-R interval between two pre-excited complexes in atrial fibrillation increased after propranolol (283 +/- 45 to 343 +/- 95 ms). These results show that oral propranolol increases the EARP of the accessory pathway and the shortest R-R interval between two pre-excited complexes in atrial fibrillation in patients with short anterograde refractory periods of their accessory pathways, and is effective in preventing reciprocating tachycardia. Oral propranolol may be useful and can be used safely in patients with the Wolff-Parkinson-White syndrome.

  19. [Ventricular fibrillation in Wolff-Parkinson-White syndrome. Predictive factors].

    PubMed

    Attoyan, C; Haissaguerre, M; Dartigues, J F; Le Métayer, P; Warin, J F; Clémenty, J

    1994-07-01

    The incidence of sudden death in the Wolff-Parkinson-White (WPW) syndrome is not well documented and probably underestimated. This retrospective study concerned 28 consecutive patients presenting with ventricular fibrillation either spontaneously (20) or during electrophysiological investigation (8) but whose characteristics allowed them to be assimilated into a single group. Their clinical and electrophysiological characteristics were compared with those of 60 consecutive patients with the WPW syndrome who had documented atrial fibrillation (and even reciprocating tachycardia) but never ventricular fibrillation. There were no significant differences between the two groups with respect to the following clinical parameters: sex, duration of symptoms, the type of tachycardia previously recorded, history of syncope and presence of underlying cardiac disease. With respect to the electrophysiological data, there were no differences in the point of anterograde block, the effective anterograde refractory period of the accessory pathway, the effective and functional refractory periods of the right atrium and atrial vulnerability. On the other hand, a significant difference was observed in the age of patients with ventricular fibrillation (29 +/- 13 years vs 36 +/- 12 years; p < 0.02), the prevalence of multiple accessory pathways (25% vs 7%; p < 0.04) with a dominant localisation in the postero-septal region (75% vs 47%, p < 0.026), preexcitation during exercise stress testing and under antiarrhythmic therapy (95% vs 68%, p < 0.037). The most discriminating parameter was the shorter RR interval during atrial fibrillation (172 +/- 23 ms vs 230 +/- 50 ms, p < 0.008). Multivariate analysis only showed one independent predictive factor: the minimum preexcited RR interval.(ABSTRACT TRUNCATED AT 250 WORDS)

  20. Photo-induced Defects in Semiconductors

    NASA Astrophysics Data System (ADS)

    Redfield, David; Bube, Richard H.

    2006-03-01

    1. Introduction: metastable defects; 2. III-V compounds: DX2 and EL2 centers; 3. Other crystalline materials; 4. Hydrogenated amorphous silicon: properties of defects; 5. Hydrogenated amorphous silicon: photo-induced defect kinetics and processes; 6. Other amorphous semiconductors; 7. Photo-induced defect effects in devices; References; Index.

  1. Wolff algorithm and anisotropic continuous-spin models: An application to the spin-van der Waals model

    NASA Astrophysics Data System (ADS)

    D'onorio de Meo, Marco; Oh, Suhk Kun

    1992-07-01

    The problem of applying Wolff's cluster algorithm to anisotropic classical spin models is resolved by modifying a part of the Wolff algorithm. To test the effectiveness of our modified algorithm, the spin-van der Waals model is investigated in detail. Our estimate of the dynamical exponent of the model is z=0.19+/-0.04.

  2. [Surgical atrioventricular disconnection in Wolff-Parkinson-White syndrome].

    PubMed

    Pavie, A; Mesnildrey, P; Gandjbakhch, I; Cabrol, C; Fontaine, G; Franck, R; Grosgogeat, Y; Slama, R

    1984-06-01

    Surgical atrioventricular disconnection is a possible means of treating patients with severe paroxysmal arrhythmias resistant to medical treatment due to the Wolff-Parkinson-White syndrome. Between 1971 and April 1982 we operated 50 patients (38 men and 12 women) with the WPW syndrome. Thirty seven patients were operated for arrhythmias (paroxysmal tachycardia) resistant to medical therapy or with a high risk of sudden death. Thirteen patients had associated cardiac disease with less severe arrhythmias (aortic valve disease: 6 cases; mitral and aortic valve disease: 3 cases; mitral valve disease: 3 cases, and atrial septal defect: 1 case). The causes of paroxysmal tachycardia were atrial fibrillation (13 cases), atrial flutter (2 cases), orthodromic reciprocating tachycardia (30 cases), with associated atrial fibrillation in 9 cases, and with associated atrial flutter in 4 cases. Antidromic reciprocating tachycardia was present in 2 cases. In 3 cases, the preexcitation was a chance finding. Electrophysiological studies performed before and after antiarrhythmic drug administration showed type A WPW (LV preexcitation) in 23 cases, and type B WPW (RV preexcitation) in 20 cases. The ECG was normal in the horizontal plane in 7 cases. The atrioventricular accessory pathway was permeable in both directions in 39 cases; in 9 cases the pathway was permeable only in the retrograde direction and in 2 cases it was permeable only in the anterograde direction. In 7 patients an atrio-hisian short circuit was demonstrated. The site of the accessory conduction pathway was located by epicardial mapping, the first surgical stage, in the left lateral region of the atrioventricular junction (28 cases), in the right lateral region (6 cases), in the posterior septal region (15 cases) (right sided in 4 cases, left sided in 11 cases), and in the anterior septal region (1 case). The accessory pathway (so-called Bundle of Kent) was interrupted by atrioventricular disconnection. Six patients

  3. Phosphonate–Phosphinate Rearrangement

    PubMed Central

    2014-01-01

    LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH3O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH3O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate. PMID:25525945

  4. A Hydrazine-Free Wolff-Kishner Reaction Suitable for an Undergraduate Laboratory

    ERIC Educational Resources Information Center

    Cranwell, Philippa B.; Russell, Andrew T.

    2016-01-01

    A Wolff-Kishner reaction that does not require hydrazine has been developed. The reaction sequence has two steps: formation of a carbomethoxyhydrazone from methyl hydrazinocarboxylate and acetophenone, then decomposition of this intermediate by treatment with potassium hydroxide in triethylene glycol. Purification is by filtration through a plug…

  5. Alternating Wolff-Parkinson-White syndrome associated with attack of angina

    SciTech Connect

    Mangiafico, R.A.; Petralito, A.; Grimaldi, D.R. )

    1990-07-01

    In a patient with Wolff-Parkinson-White syndrome and an inferior-posterior bypass tract, transient restoration of normal conduction occurred during an attack of angina. The ECG pattern of inferior posterior ischemia was present when the conduction was normal. Thallium scintigraphy showed a reversible posterolateral perfusion defect. The possible mechanisms for production of intermittent preexcitation are discussed.

  6. Atrial flutter with 1:1 conduction in undiagnosed Wolff-Parkinson-White syndrome.

    PubMed

    Nelson, Jessie G; Zhu, Dennis W

    2014-05-01

    Atrial flutter with 1:1 atrioventricular conduction via an accessory pathway is an uncommon presentation of Wolff-Parkinson-White syndrome not previously reported in the emergency medicine literature. Wolff-Parkinson-White syndrome, a form of ventricular preexcitation sometimes initially seen and diagnosed in the emergency department (ED), can present with varied tachydysrhythmias for which certain treatments are contraindicated. For instance, atrial fibrillation with preexcited conduction needs specific consideration of medication choice to avoid potential degeneration into ventricular fibrillation. We describe an adult female presenting with a very rapid, regular wide complex tachycardia successfully cardioverted in the ED followed by a normal electrocardiogram (ECG). Electrophysiology study confirmed atrial flutter with 1:1 conduction and revealed an accessory pathway consistent with Wolff-Parkinson-White syndrome, despite lack of ECG findings of preexcitation during sinus rhythm. Why should an emergency physician be aware of this? Ventricular tachycardia must be the first consideration in patients with regular wide complex tachycardia. However, clinicians should consider atrial flutter with 1:1 conduction related to an accessory pathway when treating patients with the triad of very rapid rate (>250 beats/min), wide QRS complex, and regular rhythm, especially when considering pharmacologic treatment. Emergency physicians also should be aware of electrocardiographically concealed accessory pathways, and that lack of delta waves does not rule out preexcitation syndromes such as Wolff-Parkinson-White syndrome. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. Wolff-Michael Roth's passibility: at the limits of the constructivist metaphor: a book review

    NASA Astrophysics Data System (ADS)

    Brendel, Michelle

    2014-12-01

    Wolff-Michael Roth deconstructs the preeminent role conceded to constructivism in Science Education and demonstrates how we learn and know through pain, suffering, love or passion. This review explores his book "Passibility: At the Limits of the Constructivist Metaphor" through the eyes of an outsider to the world of science education.

  8. [Significance of tachycardia induced by atrial stimulation in Wolff-Parkinson-White syndrome].

    PubMed

    Brembilla-Perrot, B

    1992-04-01

    Increased atrial vulnerability is one of the criteria of malignant Wolff-Parkinson-White syndrome. The aim of this study was to try to define the methods of induction of atrial tachycardias (tachycardia, flutter, fibrillation) by endocavitary and oesophageal stimulation characterising an increased vulnerability. The incidence of induced sustained tachycardia by fixed atrial stimulation at incremental rates until the Wenckebach point is attained and programmed atrial stimulation using 1 and 2 extrastimuli under basal conditions and then with isoproterenol was compared in subjects without cardiac disease, Wolff-Parkinson-White or spontaneous tachycardia (Group I) and patients with Wolff-Parkinson-White and spontaneous tachycardias (Group II). Atrial stimulation only induced tachycardia in 2.5% of normal subjects under basal conditions or with isoproterenol, by the endocavitary or oesophageal approaches. Programmed stimulation induced tachycardia in 15% of normal subjects under basal conditions or with isoproterenol by the endocavitary approach alone. In Group II, tachycardia was reproduced under basal conditions or with isoproterenol by atrial stimulation or programmed stimulation in all patients. In conclusion, the induction of a tachyarrhythmia by incremental atrial stimulation up to the Wenckebach point is always pathological even with isoproterenol. Programmed atrial stimulation is less specific except by the oesophageal approach. The use of bursts of very rapid stimuli in the Wolff-Parkinson-White syndrome is of no value as tachycardia can be induced by classical methods in all subjects at risk.

  9. [Wolff-Parkinson-White syndrome in a case of acute rejection of cardiac transplantation].

    PubMed

    Ollitrault, J; Daubert, J C; Ramée, M P; Ritter, P; Mabo, P; Leguerrier, A; Rioux, C; Logeais, Y

    1990-09-01

    A Wolff-Parkinson-White syndrome was observed during acute rejection in a patient who had undergone orthotopic cardiac transplantation. The sometimes intermittent nature of this syndrome could explain its postoperative appearance in this patient; the relationship with the episode of rejection is discussed.

  10. Normalization of reverse redistribution of thallium-201 with procainamide pretreatment in Wolff-Parkinson-White syndrome

    SciTech Connect

    Nii, T.; Nakashima, Y.; Nomoto, J.; Hiroki, T.; Ohshima, F.; Arakawa, K. )

    1991-03-01

    Stress thallium-201 myocardial perfusion imaging was performed in a patient with Wolff-Parkinson-White syndrome. Reverse redistribution phenomenon was observed in the absence of coronary artery disease. This seems to be the first report of normalization of this phenomenon in association with reversion of accessory pathway to normal atrioventricular conduction after pretreatment with procainamide.

  11. A Hydrazine-Free Wolff-Kishner Reaction Suitable for an Undergraduate Laboratory

    ERIC Educational Resources Information Center

    Cranwell, Philippa B.; Russell, Andrew T.

    2016-01-01

    A Wolff-Kishner reaction that does not require hydrazine has been developed. The reaction sequence has two steps: formation of a carbomethoxyhydrazone from methyl hydrazinocarboxylate and acetophenone, then decomposition of this intermediate by treatment with potassium hydroxide in triethylene glycol. Purification is by filtration through a plug…

  12. Subjectivity and Cultural Adjustment in Mathematics Education: A Response to Wolff-Michael Roth

    ERIC Educational Resources Information Center

    Brown, Tony

    2012-01-01

    In this volume, Wolff-Michael Roth provides a critical but partial reading of Tony Brown's book "Mathematics Education and Subjectivity". The reading contrasts Brown's approach with Roth's own conception of subjectivity as derived from the work of Vygotsky, in which Roth aims to "reunite" psychology and sociology. Brown's book, however, focuses on…

  13. Photoinduced Intramolecular Cyclopentanation vs Photoprotolytic Oxametathesis in Polycyclic Alkenes Outfitted with Conformationally Constrained Aroylmethyl Chromophores‡

    PubMed Central

    Valiulin, Roman A.; Arisco, Teresa M.; Kutateladze, Andrei G.

    2012-01-01

    Intramolecular photoinduced cyclizations are investigated in photoprecursors assembled in a modular fashion via a Diels-Alder reaction of acetylenic dienophiles with subsequent Michael additions of aromatic ketones to install a chromophore capable of initiating Paternò-Büchi cycloadditions or radical cyclization cascades. The protolytic oxametathesis in these systems allows for rapid access to novel polycyclic scaffolds decorated by formyl groups and carboxylates suitable for subsequent modifications. In conformationally constrained photoprecursors a radical rearrangement takes place resulting in intramolecular 1,3-diradical cyclopentanation of the double bond. PMID:23106813

  14. Multifractal analysis of photoinduced cooperative phenomena

    NASA Astrophysics Data System (ADS)

    Ishida, Kunio; Nasu, Keiichiro

    2008-01-01

    We study the multifractal properties of the geometrical patterns which appear in the initial processes of photoinduced structural change. Employing a model of localized electrons coupled with a single-phonon mode, we calculate the Lipschitz-Hölder exponent α and singularity spectrum f(α) on the distribution of excited electronic states and molecular distortion by using the box-counting method, and discuss the temporal behavior of photoinduced domains.

  15. Acceleration of ventricular rate by amiodarone in atrial fibrillation associated with the Wolff-Parkinson-White syndrome

    PubMed Central

    Sheinman, Bryan D; Evans, Tom

    1982-01-01

    Amiodarone has proved to be a valuable drug in atrial fibrillation associated with the Wolff-Parkinson-White syndrome. When it was administered to a patient with this syndrome in atrial fibrillation, who had previously suffered an inferior myocardial infarction, the ventricular rate accelerated from 170 to 230 beats/minute. This unusual case emphasises the need for full electrophysiological assessment of patients with the Wolff-Parkinson-White syndrome for whom amiodarone treatment is being considered. Imagesp1000-a PMID:6812745

  16. Capturing ultrafast photoinduced local structural distortions of BiFeO3

    DOE PAGES

    Wen, Haidan; Sassi, Michel JPC; Luo, Zhenlin; ...

    2015-10-14

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by themore » in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This uniaxial elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated nonequilibrium processes in polar materials.« less

  17. Capturing ultrafast photoinduced local structural distortions of BiFeO3

    NASA Astrophysics Data System (ADS)

    Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell G.; Rosso, Kevin M.; Zhang, Xiaoyi

    2015-10-01

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This anisotropic elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated non-equilibrium processes in polar materials.

  18. Capturing ultrafast photoinduced local structural distortion of BiFeO3

    SciTech Connect

    Wen, Haidan; Sassi, Michel; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell G.; Rosso, Kevin M.; Zhang, Xiaoyi

    2015-10-14

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This anisotropic elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated non-equilibrium processes in polar materials.

  19. Capturing ultrafast photoinduced local structural distortions of BiFeO3

    SciTech Connect

    Wen, Haidan; Sassi, Michel JPC; Luo, Zhenlin; Adamo, Carolina; Schlom, Darrell; Rosso, Kevin M.; Zhang, Xiaoyi

    2015-10-14

    The interaction of light with materials is an intensively studied research forefront, in which the coupling of radiation energy to selective degrees of freedom offers contact-free tuning of functionalities on ultrafast time scales. Capturing the fundamental processes and understanding the mechanism of photoinduced structural rearrangement are essential to applications such as photo-active actuators and efficient photovoltaic devices. Using ultrafast x-ray absorption spectroscopy aided by density functional theory calculations, we reveal the local structural arrangement around the transition metal atom in a unit cell of the photoferroelectric archetype BiFeO3 film. The out-of-plane elongation of the unit cell is accompanied by the in-plane shrinkage with minimal change of interaxial lattice angles upon photoexcitation. This uniaxial elastic deformation of the unit cell is driven by localized electric field as a result of photoinduced charge separation, in contrast to a global lattice constant increase and lattice angle variations as a result of heating. The finding of a photoinduced elastic unit cell deformation elucidates a microscopic picture of photocarrier-mediated nonequilibrium processes in polar materials.

  20. [Radiofrequency catheter ablation in children with Wolff-Parkinson-White syndrome and sudden cardiac death who had been resuscitated].

    PubMed

    Benito Bartolomé, F; Sánchez Fernández-Bernal, C

    2001-04-01

    Sudden death may be the first manifestation of the Wolff-Parkinson-White syndrome, especially in children and adolescents. The aim of this study was to evaluate the usefulness of radiofrequency catheter ablation in children with Wolff-Parkinson-White syndrome with aborted sudden death. We report four patients with Wolff-Parkinson-White syndrome who survived cardiac arrest. The patients were aged from 2.5 months to 16 years. The two first patients were lactating infants; in the first sudden death occurred during digoxin treatment for supraventricular tachycardia secondary to Wolff-Parkinson-White syndrome and in the second the syndrome was diagnosed after an episode of sudden death. In these patients a free wall accessory pathway (left posterior and left lateral, respectively) was successfully ablated using a transseptal approach. The third patient was diagnosed with asymptomatic Wolff-Parkinson-White syndrome; sudden death occurred during exercise. In the fourth patient, sudden death occurred after intravenous therapy with adenosine triphosphate and amiodarone for rapid atrial fibrillation. In both patients, one accessory pathway, located in right posteroseptal and right anterior free wall, respectively, was ablated. After a mean follow-up of 43.5 26.4 months, no recurrence of sudden death had occurred and electrocardiogram showed sinus rhythm without delta wave. The third patient presented severe sequelae of hypoxemic encephalopathy, which persisted during the follow-up. Radiofrequency catheter ablation is the treatment of choice in Wolff-Parkinson-White syndrome with episodes of aborted sudden death.

  1. Photoinduced toxicity of engineered nanomaterials

    NASA Astrophysics Data System (ADS)

    Jones, Philip Scott

    Engineered nanomaterials including metal, metal oxide and carbon based nanomaterials are extensively used in a wide variety of applications to the extent that their presence in the environment is expected to increase dramatically over the next century. These nanomaterials may be photodegraded by solar radiation and thereby release metal ions into the environment that can produce cytotoxic and genotoxic effects. Photoinduced toxicity experiments are performed exposing human lung epithelial carcinoma cells [H1650] to engineered semiconductor nanoparticles such as CdSe quantum dots and ZnO nanoparticles after exposure to 3, 6, and 9 hours of solar simulated radiation. Cytotoxicity and genotoxicity of the metal ions are evaluated using ZnSO4 and CdCl2 solutions for the MTT assay and Comet assay respectively. The objective of the dissertation is to obtain quantitative information about the environmental transformation of engineered nanomaterials and their mechanism of toxicity. This information is critical for addressing the environmental health and safety risks of engineered nanomaterials to workers, consumers and the environment.

  2. Photoinduced magnetic force between nanostructures

    NASA Astrophysics Data System (ADS)

    Guclu, Caner; Tamma, Venkata Ananth; Wickramasinghe, Hemantha Kumar; Capolino, Filippo

    2015-12-01

    Photoinduced magnetic force between nanostructures, at optical frequencies, is investigated theoretically. Till now optical magnetic effects were not used in scanning probe microscopy because of the vanishing natural magnetism with increasing frequency. On the other hand, artificial magnetism in engineered nanostructures led to the development of measurable optical magnetism. Here two examples of nanoprobes that are able to generate strong magnetic dipolar fields at optical frequency are investigated: first, an ideal magnetically polarizable nanosphere and then a circular cluster of silver nanospheres that has a looplike collective plasmonic resonance equivalent to a magnetic dipole. Magnetic forces are evaluated based on nanostructure polarizabilities, i.e., induced magnetic dipoles, and magnetic-near field evaluations. As an initial assessment on the possibility of a magnetic nanoprobe to detect magnetic forces, we consider two identical magnetically polarizable nanoprobes and observe magnetic forces on the order of piconewtons, thereby bringing it within detection limits of conventional atomic force microscopes at ambient pressure and temperature. The detection of magnetic force is a promising method in studying optical magnetic transitions that can be the basis of innovative spectroscopy applications.

  3. [Electrophysiological effects of chloroacetyl ajmaline in Wolff-Parkinson-White syndrome].

    PubMed

    Touboul, P; Gressard, A; Atallah, G; Chatelain, M T; Delahaye, J P

    1978-07-01

    The electrophysiological effects of chloro-acetyl-ajmaline in the Wolff-Parkinson-White syndrome have been studied in 7 patients after an intravenous dose of 1.5 mg/kg of the drug. Preexcitation was abolished in 3 cases, while 3 other subjects showed a slight increase in effective refractory period of the abnormal route of excitation (a mean of 13 ms). The possibility of bringing about a reciprocal rhythm was removed in one case out of two. During tachycardia, chloro-acetyl-ajmaline produced significant lengthening of the ventriculo-atrial conduction time (p less than 0.05). These results show the usefulness of chloro-acetyl-ajmaline in the control of the arrhythmias associated with the Wolff-Parkinson-White syndrome.

  4. Suppression of refractory arrhythmias by aprindine in patients with the Wolff-Parkinson-White syndrome.

    PubMed Central

    Reid, P R; Greene, H L; Varghese, P J

    1977-01-01

    Four patients with supraventricular tachycardia associated with the Wolff-Parkinson-White syndrome were refractory to conventional pharmacological therapy and received aprindine hydrochloride intravenously and orally. Electrophysiological studies disclosed that intravenous aprindine caused increased refractoriness and slowed conduction in the atria, atrioventricular node, ventricles, and accessory pathway. The ability to induce supraventricular tachycardia with timed atrial and ventricular premature stimuli was totally abolished in all 4 patients after intravenous aprindine. Oral aprindine therapy, twice daily thereafter, provided symptomatic relief of the supraventricular tachycardia without significant side effects. Aprindine is useful in the management of supraventricular tachycardia associated with Wolff-Parkinson-White and may offer significant advantages over currently available therapy. Images PMID:603737

  5. [Atrioventricular and ventriculoatrial conduction in patients operated on for the Wolff-Parkinson-White syndrome].

    PubMed

    Colín, L; Dorado, M; Iturralde, P; Romero, L; Kershenovich, S; de Micheli, A; Barragán, R; Ramírez, S; González-Hermosillo, J A

    1992-01-01

    Over the last decade the surgical treatment of the Wolff-Parkinson-White syndrome has been well accepted. It is important to make an early diagnosis for surgical success. For this purpose we utilized programmed electrical stimulation to assess the functional characteristics of atrioventricular and ventriculoatrial conduction in our post-operative patients. In 55% of the cases we found accelerated nodal conduction. Programmed electrical stimulation correctly identified 90% of successfully treated patients. We did not found any false positive curve, therefore, this method has a high specificity. We concluded that in post-operative patients with the Wolff-Parkinson-White syndrome: 1- There is a high incidence of accelerated nodal conduction and 2- programmed electrical stimulation can correctly identify most of the patients who were successfully treated.

  6. [Does patient age influence the indications for investigating asympatomatic Wolff-Parkinson-White syndrome?].

    PubMed

    Brembilla-Perrot, B; Holban, I; Houriez, P; Beurrier, D; Claudon, O; Vançon, A C

    2000-12-01

    Sudden death may be the presenting symptom of a Wolff-Parkinson-White syndrome. Electrophysiological investigation is the best method of identifying high risk cases. The aim of this study was to determine whether this investigation should be proposed to all patients, irrespective of age. Transoesophageal stimulation was performed in 85 asymptomatic patients with the Wolff-Parkinson-White syndrome. Of the 85 subjects, 13 were under 20 years of age, 30 under 30 years, 15 under 40 years, 16 under 50 years and 11 between 50 and 69 years of age. A protocol of incremental stimulation until 2nd degree AVB was attained and programmed atrial stimulation with one or two extrastimuli delivered on 2 paced cycles (600 and 400 ms) was used under basal conditions and with Isoprenaline. A malignant form of the condition was defined as the demonstration of two abnormalities: rapid conduction in the bundle of Kent (over 240/min) under basal conditions or over 300/min after Isoprenaline, and if it induced sustained atrial fibrillation (> 1 min). The results were: [table: see text] In conclusion, the number of malignant forms of the Wolff-Parkinson-White syndrome is exactly the same, irrespective of age. Elderly patients remain at risk of malignant WPW syndrome because of the increased incidence of atrial fibrillation. Therefore, the authors recommend systematic evaluation of this syndrome if the patient has an active life-style especially with regard to sporting activities.

  7. Computational study of Wolff's law with trabecular architecture in the human proximal femur using topology optimization.

    PubMed

    Jang, In Gwun; Kim, Il Yong

    2008-08-07

    In the field of bone adaptation, it is believed that the morphology of bone is affected by its mechanical loads, and bone has self-optimizing capability; this phenomenon is well known as Wolff's law of the transformation of bone. In this paper, we simulated trabecular bone adaptation in the human proximal femur using topology optimization and quantitatively investigated the validity of Wolff's law. Topology optimization iteratively distributes material in a design domain producing optimal layout or configuration, and it has been widely and successfully used in many engineering fields. We used a two-dimensional micro-FE model with 50 microm pixel resolution to represent the full trabecular architecture in the proximal femur, and performed topology optimization to study the trabecular morphological changes under three loading cases in daily activities. The simulation results were compared to the actual trabecular architecture in previous experimental studies. We discovered that there are strong similarities in trabecular patterns between the computational results and observed data in the literature. The results showed that the strain energy distribution of the trabecular architecture became more uniform during the optimization; from the viewpoint of structural topology optimization, this bone morphology may be considered as an optimal structure. We also showed that the non-orthogonal intersections were constructed to support daily activity loadings in the sense of optimization, as opposed to Wolff's drawing.

  8. Comparative effects of ajmaline on intermittent bundle branch block and the Wolff-Parkinson-White syndrome.

    PubMed

    Chiale, P A; Przybylski, J; Halpern, M S; Lazzari, J O; Elizari, M V; Rosenbaum, M B

    1977-05-04

    Phase 4 or phase 3 block or both occurred in the His bundle branch system of 11 patients with intermittent bundle branch block and in the anomalous bundle of 6 of 46 patients with the Wolff-Parkinson-White syndrome (13%). Administration of a single dose of ajmaline (50 mg intravenously) in these patients caused a similar response: expansion of the range of phase 3 and phase 4 block at the expense of the intermediate normal conduction range and total interruption of conduction in the affected fascicle when the effect of the drug was maximal. The great similarity in physiologic behavior and pharmacologic response in these groups of patients suggests that the anomalous bundle was probably diseased or abnormal in the six patients with Wolff-Parkinson-White conduction. In addition, ajmaline caused the first appearance of phase 4 or phase 3 block, or both, but not total interruption of conduction in 26 of the 46 patients with Wolff-Parkinson-White conduction (56.5%). Ajmaline does not cause fascicular block in normal subjects; thus this finding suggests either that the anomalous bundle is diseased or that the safety margin for conduction in the anomalous bundle is much narrower than in the bundle branch system. The conduction-depressing action of ajmaline may be greater at relatively rapid or relatively slow rates of stimulation, and smaller or absent at intermediate rates.

  9. [MLL rearrangements in acute leukemias].

    PubMed

    Urioste, M; Arranz, E; Martínez-Delgado, B; Soto, C; Román, A; Pérez, I; Mayayo, M; Pérez-Pons, C; Barroso, A; Benítez, J

    1999-12-01

    In present study we have studied MLL rearrangements in a serie of acute myeloid, lymphoblastic and biphenotypic leukaemias. We analyzed a total of 11 cases: 9 acute myeloid leukaemias (M4 and M5 subtypes in FAB classification), 1 lymphoid leukaemia, and 1 acute biphenotypic leukaemia. We studied bone marrow samples from all patients by using conventional cytogenetic techniques and fluorescence in situ hybridization (FISH) with an MLL probe. We also analyzed the correlation between clinical features and genetic results. Cells from 6 patients showed to contain MLL rearrangements and these arose in all types of leukaemias included in this study. Some MLL rearrangements were detected by FISH in kariotypically normal cases or without cytogenetic evidence of 11q23 aberration. MLL gene duplication has been observed in two cases with M4 and biphenotypic leukaemia, respectively. The presence of MLL gene rearrangements does not shape a group of patients with a common clinical pattern. MLL rearrangements occurs in a wide variety of leukemias. These rearrangements should be screened by FISH techniques, taking into account that gene duplications could arise in cases with normal karyotype. MLL rearrangements appear to have a considerable clinicopathologic heterogeneity.

  10. Dearomatising rearrangements of lithiated thiophenecarboxamides.

    PubMed

    Clayden, Jonathan; Turnbull, Rachel; Helliwell, Madeleine; Pinto, Ivan

    2004-11-07

    Thiophene-3-carboxamides bearing allyl or benzyl substituents at nitrogen undergo dearomatising cyclisation on treatment with LDA. Rearrangements transform the dearomatised products into pyrrolinones, azepinones or partially saturated azepinothiophenes.

  11. Claisen thermally rearranged (CTR) polymers.

    PubMed

    Tena, Alberto; Rangou, Sofia; Shishatskiy, Sergey; Filiz, Volkan; Abetz, Volker

    2016-07-01

    Thermally rearranged (TR) polymers, which are considered the next-generation of membrane materials because of their excellent transport properties and high thermal and chemical stability, are proven to have significant drawbacks because of the high temperature required for the rearrangement and low degree of conversion during this process. We demonstrate that using a [3,3]-sigmatropic rearrangement, the temperature required for the rearrangement of a solid glassy polymer was reduced by 200°C. Conversions of functionalized polyimide to polybenzoxazole of more than 97% were achieved. These highly mechanically stable polymers were almost five times more permeable and had more than two times higher degrees of conversion than the reference polymer treated under the same conditions. Properties of these second-generation TR polymers provide the possibility of preparing efficient polymer membranes in a form of, for example, thin-film composite membranes for various gas and liquid membrane separation applications.

  12. Claisen thermally rearranged (CTR) polymers

    PubMed Central

    Tena, Alberto; Rangou, Sofia; Shishatskiy, Sergey; Filiz, Volkan; Abetz, Volker

    2016-01-01

    Thermally rearranged (TR) polymers, which are considered the next-generation of membrane materials because of their excellent transport properties and high thermal and chemical stability, are proven to have significant drawbacks because of the high temperature required for the rearrangement and low degree of conversion during this process. We demonstrate that using a [3,3]-sigmatropic rearrangement, the temperature required for the rearrangement of a solid glassy polymer was reduced by 200°C. Conversions of functionalized polyimide to polybenzoxazole of more than 97% were achieved. These highly mechanically stable polymers were almost five times more permeable and had more than two times higher degrees of conversion than the reference polymer treated under the same conditions. Properties of these second-generation TR polymers provide the possibility of preparing efficient polymer membranes in a form of, for example, thin-film composite membranes for various gas and liquid membrane separation applications. PMID:27482538

  13. Immunoglobulin λ Gene Rearrangement Can Precede κ Gene Rearrangement

    DOE PAGES

    Berg, Jörg; Mcdowell, Mindy; Jäck, Hans-Martin; ...

    1990-01-01

    Imore » mmunoglobulin genes are generated during differentiation of B lymphocytes by joining gene segments. A mouse pre-B cell contains a functional immunoglobulin heavy-chain gene, but no light-chain gene. Although there is only one heavy-chain locus, there are two lightchain loci: κ and λ .It has been reported that κ loci in the germ-line configuration are never (in man) or very rarely (in the mouse) present in cells with functionally rearranged λ -chain genes. Two explanations have been proposed to explain this: (a) the ordered rearrangement theory, which postulates that light-chain gene rearrangement in the pre-B cell is first attempted at the κ locus, and that only upon failure to produce a functional κ chain is there an attempt to rearrange the λ locus; and (b) the stochastic theory, which postulates that rearrangement at the λ locus proceeds at a rate that is intrinsically much slower than that at the κ locus. We show here that λ -chain genes are generated whether or not the κ locus has lost its germ-line arrangement, a result that is compatible only with the stochastic theory.« less

  14. [Caspar Friedrich Wolff (1734-1794). The concept of epigenesis and the problem of spontaneous generation].

    PubMed

    Bednarczyk, Andrzej

    2005-01-01

    The link between the notion of epigenesis and that of spontaneous generation does not seem complicated when it is viewed in theoretical terms or when it is approached in a pure model form. However, once any of its particular manifestations in the history of biology is analysed, the interrelationship between the two notions ceases to be unequivocal. One example of that comes with the first fully-fledged concept of epigenesis, based on careful observation of embryonic development, presented by Caspar Friedrich Wolff in the 18th century. The process of development that an act of spontaneous generation has given rise to cannot, of course, be anything else but one of epigenesis. In this sense, epigenesis constitutes a necessary condition for spontaneous generation, but is not a sufficient condition, i.e. not every process of development through epigenesis has at its source an act of spontaneous generation. Evidence that Wolff was inclined towards the concept of spontaneous generation comes from the presence in his works of a notion described by the Latin term ortus (emergence). That notion--together with that of an organic body--is subject to detailed analysis in the current paper. If the process of spontaneous generation is understood as a process of emergence in nature of what is animate and organic, from what is inanimate and non-organic, and as a process in which living beings are not involved, but a living being is its outcome, then the notion of ortus is close in meaning to the notion of spontaneous generation. However, the deistic and theological philosophical foundation of Wolff's concept of epigenesis is in conflict with the notion of spontaneous generation. It seems that Wolff's notion of ortus can be interpreted in two ways. Firstly, it can be interpreted as as result of the theoretical extrapolation in time applied by Wolff to the usual way in which organic bodies emerge (the process is always given rise to by a nonorganic body, supplied by another organic

  15. A Wolff in sheep's clothing: trabecular bone adaptation in response to changes in joint loading orientation.

    PubMed

    Barak, Meir M; Lieberman, Daniel E; Hublin, Jean-Jacques

    2011-12-01

    This study tests Wolff's law of trabecular bone adaptation by examining if induced changes in joint loading orientation cause corresponding adjustments in trabecular orientation. Two groups of sheep were exercised at a trot, 15 min/day for 34 days on an inclined (7°) or level (0°) treadmills. Incline trotting caused the sheep to extend their tarsal joints by 3-4.5° during peak loading (P<0.01) but has no effect on carpal joint angle (P=0.984). Additionally, tarsal joint angle in the incline group sheep were maintained more extended throughout the day using elevated platform shoes on their forelimbs. A third "sedentary group" group did not run but wore platform shoes throughout the day. As predicted by Wolff's law, trabecular orientation in the distal tibia (tarsal joint) were more obtuse by 2.7 to 4.3° in the incline group compared to the level group; trabecular orientation was not significantly different in the sedentary and level groups. In addition, trabecular orientations in the distal radius (carpal joint) of the sedentary, level and incline groups did not differ between groups, and were aligned almost parallel to the radius long axis, corresponding to the almost straight carpal joint angle at peak loading. Measurements of other trabecular bone parameters revealed additional responses to loading, including significantly higher bone volume fraction (BV/TV), Trabecular number (Tb.N) and trabecular thickness (Tb.Th), lower trabecular spacing (Tb.Sp), and less rod-shaped trabeculae (higher structure model index, SMI) in the exercised than sedentary sheep. Overall, these results demonstrate that trabecular bone dynamically adjusts and realigns itself in very precise relation to changes in peak loading direction, indicating that Wolff's law is not only accurate but also highly sensitive.

  16. Asymptotic behavior and Denjoy-Wolff theorems for Hilbert metric nonexpansive maps

    NASA Astrophysics Data System (ADS)

    Lins, Brian C.

    We study the asymptotic behavior of fixed point free Hilbert metric nonexpansive maps on bounded convex domains. For such maps, we prove that the omega limit sets are contained in a convex subset of the boundary when the domain is either polyhedral or two dimensional. Similar results are obtained for several classes of positive operators defined on closed cones, including linear maps, affine linear maps, max-min operators, and reproduction-decimation operators. We discuss the relationship between these results and other Denjoy-Wolff type theorems. In particular, we investigate the interaction of nonexpansive maps with the horofunction boundary in the Hilbert geometry and in finite dimensional normed spaces.

  17. A fetal Wolff-Parkinson-White syndrome diagnosed prenatally by magnetocardiography.

    PubMed

    Hosono, T; Chiba, Y; Shinto, M; Kandori, A; Tsukada, K

    2001-01-01

    We report a case of fetal Wolff-Parkinson-White (WPW) syndrome diagnosed prenatally by magnetocardiography (MCG). At 32 weeks' gestation, the fetus was diagnosed to have a paroxysmal supraventricular tachycardia by ultrasonography and direct fetal electrocardiogram (ECG). Transplacental fetal therapy by maternal oral administration of propranolol resolved the fetal tachyarrhythmia. Although the wave forms of the fetal MCG at 32 weeks' gestation were normal, the fetal MCG at 35 weeks' gestation showed a short PR interval and a long QRS complex duration with a delta wave, indicating WPW syndrome. The findings of the fetal MCG were confirmed by the postnatal ECG. MCG made the prenatal diagnosis of WPW syndrome possible.

  18. Spinal Anaesthesia is Safe in a Patient with Wolff-Parkinson-White Syndrome Undergoing Evacuation of Molar Pregnancy

    PubMed Central

    Pujari, Vinayak S

    2016-01-01

    Wolff-Parkinson-White (WPW) syndrome is an uncommon cardiac condition where there is an abnormal band of atrial tissue connecting atria and ventricles which can electrically bypass atrioventricular node. The anaesthetic management in these patients is challenging as life threatening complications can occur perioperatively like paroxysmal supraventricular tachycardia and atrial fibrillation. Also, regional anaesthetic technique like subarachnoid block is a safe and cost effective alternative to general anaesthesia as it avoids polypharmacy. We report the successful anaesthetic management of Wolff Parkinson White syndrome in a primi with hydatiform mole posted for suction and evacuation. PMID:27042562

  19. [Treatment of junctional paroxysmal tachycardia, without patent Wolff-Parkinson-White syndrome, by sectioning an accessory Kent-His bundle].

    PubMed

    Slama, R; Attuel, P; Flammang, D; Coumel, P; Guiraudon, G

    1976-11-01

    The authors report the case of a patient suffering from a Bouveret's tachycardia without syndrome of Wolff-Parkinson-White. The analysis of the tachycardic spells however showed that during a reciprocal crisis, the circuit went through a left accessory ventriculo-atrial bundle, functioning only in the reverse direction. This accessory bundle was successfully cut by the surgeon, following the procedure of wide atrioventricular desinsertion as described by the authors of Duke University for the surgical treatment of the Wolff-Parkinson-White syndrome.

  20. Photoinduced mass transport in azo compounds

    NASA Astrophysics Data System (ADS)

    Klismeta, K.; Teteris, J.; Aleksejeva, J.

    2013-12-01

    The photoinduced changes of optical properties in azobenzene containing compound thin films were studied under influence of polarized and non-polarized 532 nm laser light. Under influence of light azo compounds experience trans-cis isomerisation process, that can be observed in the absorbance spectrum of the sample. If the light is linearly polarized, molecules align perpendicularly to the electric field vector and as a result photoinduced dichroism and birefringence is obtained. If a known lateral polarization modulation of the light beam is present, mass transport of the azobenzene containing compound occurs. By measuring the surface relief with a profilometer the direction of mass transport can be determined. The studies of this work show that direct holographic recording of surface relief gratings can be used in optoelectronics, telecommunications and data storage.

  1. [Fitness for sports of patients with Wolff-Parkinson-White syndrome].

    PubMed

    Montgermont, P; Adams, C; Heulin, A; Vacheron, A

    1987-06-01

    The fitness of patients with Wolff-Parkinson-White syndrome to indulge in sporting activities is a practical cardiology problem. The major risk is sudden death due to atrial fibrillation deteriorating to ventricular fibrillation. This risk is small or even theoretical, but signing a fitness certificate engages the clinician's responsibility. Non invasive complementary examinations are useful. Echocardiography may detect a heart disease that would preclude any sport. Exercise tests explore the behaviour of the accessory pathway and rarely trigger off arrhythmias. Holter recordings mainly investigate disorders of the atrial rhythm. The decision concerning fitness may be based on clinical symptoms. Exercise-induced tachycardia is a classical contra-indication to competitive sports. In patients whose tachycardia is unrelated to exercise, fitness may be discussed according to the results of exercise tests and of the electrophysiological study. A refractory period which would be considered as rather prolonged at rest does not protect against fast ventricular rate during passage to atrial fibrillation. If pre-excitation disappears during the exercise test in an asymptomatic patient, then competitive sports can be authorized without limitations. If not, only surgical excision or fulguration would provide full protection against a potentially dangerous fibrillation. It is concluded that Wolff-Parkinson-White syndrome contra-indicates competitive sports in most cases. Games played outside competitions remain possible in the absence of symptoms or when arrhythmias are well controlled by medical treatment.

  2. The aging of Wolff's "law": ontogeny and responses to mechanical loading in cortical bone.

    PubMed

    Pearson, Osbjorn M; Lieberman, Daniel E

    2004-01-01

    The premise that bones grow and remodel throughout life to adapt to their mechanical environment is often called Wolff's law. Wolff's law, however, is not always true, and in fact comprises a variety of different processes that are best considered separately. Here we review the molecular and physiological mechanisms by which bone senses, transduces, and responds to mechanical loads, and the effects of aging processes on the relationship (if any) between cortical bone form and mechanical function. Experimental and comparative evidence suggests that cortical bone is primarily responsive to strain prior to sexual maturity, both in terms of the rate of new bone growth (modeling) as well as rates of turnover (Haversian remodeling). Rates of modeling and Haversian remodeling, however, vary greatly at different skeletal sites. In addition, there is no simple relationship between the orientation of loads in long bone diaphyses and their cross-sectional geometry. In combination, these data caution against assuming without testing adaptationist views about form-function relationships in order to infer adult activity patterns from skeletal features such as cross-sectional geometry, cortical bones density, and musculo-skeletal stress markers. Efforts to infer function from shape in the human skeleton should be based on biomechanical and developmental models that are experimentally tested and validated.

  3. Quantum pattern formation dynamics of photoinduced nucleation

    NASA Astrophysics Data System (ADS)

    Ishida, Kunio; Nasu, Keiichiro

    2008-06-01

    We study the dynamics of quantum pattern formation processes in molecular crystals which is concomitant with photoinduced nucleation. Since the nucleation process in coherent regime is driven by the nonadiabatic transition in each molecule followed by the propagation of phonons, it is necessary to take into account the quantum nature of both electrons and phonons in order to pursue the dynamics of the system. Therefore, we employ a model of localized electrons coupled with a quantized phonon mode and solve the time-dependent Schrödinger equation numerically. We found that there is a minimal size of clusters of excited molecules which triggers the photoinduced nucleation process; i.e., nucleation does not take place unless sufficient photoexcitation energy is concentrated within a narrow area of the system. We show that this result means that the spatial distribution of photoexcited molecules plays an important role in the nonlinearity of the dynamics and also in the optical properties observed in experiments. We calculate the conversion ratio, the rate of cluster formation, and correlation functions to reveal the dynamical properties of the pattern formation process; the initial dynamics of the photoinduced structural change is discussed from the viewpoint of pattern formation.

  4. Genome rearrangements: mother knows best!

    PubMed

    Chalker, Douglas L

    2005-10-25

    In Paramecium, developmentally programmed genome rearrangements can be altered by the presence of homologous sequences within the maternal somatic nucleus. Newly identified RNA-binding proteins appear to mediate the transfer of homologous sequence information from the maternal to the developing somatic nucleus, facilitating epigenetic regulation of this large-scale genome reorganization.

  5. Coumarin-Induced DNA Ligation, Rearrangement to DNA Interstrand Crosslinks, and Photorelease of Coumarin Moiety.

    PubMed

    Sun, Huabing; Fan, Heli; Eom, Hyeyoung; Peng, Xiaohua

    2016-11-03

    Coumarin moieties react with thymine and cytosine in DNA by photoinduced [2+2] cycloaddition, which allows quantitative DNA interstrand crosslink (ICL) formation. Here, we report the application of coumarin analogues for DNA photoligation and the rearrangement of coumarin-induced ligation to ICL products. Both DNA sequences and the linker units at position 4 of the coumarin moieties affected coumarin-induced DNA photoligation. A flexible linker unit favored DNA ICL formation but led to inefficient photoligation, whereas coumarins without linker units greatly increased DNA photoligation efficiency. DNA photoligation induced by the coumarin moiety was photoswitchable. Ligation products were formed between coumarin and dT or dC upon 350 nm irradiation but reverted to the original single-stranded oligodeoxyribonucleotides (ODNs) upon 254 nm irradiation. Rearrangement of ligated ODNs into ICL products occurred during the switchable (350 nm/254 nm) processes. Additionally, photoinduced cleavage of coumarin 3 occurred with dC-3 cycloadducts upon 254 nm irradiation, which was confirmed by mass spectrometry analysis.

  6. Sensitivity as a Privileged Predictor of Attachment: A Second Perspective of De Wolff and van IJzendoorn's Meta-Analysis

    ERIC Educational Resources Information Center

    Nievar, M. Angela; Becker, Betsy Jane

    2004-01-01

    This secondary analysis of De Wolff and van IJzendoorn's (1997) meta-analysis of maternal behavior and attachment reexamined their conclusion that sensitivity was not a preferred predictor of attachment security. The meta-analysis included 66 studies with 123 effect sizes sorted through a combination of personal choice and homogeneity analysis…

  7. [Is the transesophageal approach preferable to endocavitary approach in the evaluation of Wolff-Parkinson-White syndrome?].

    PubMed

    Brembilla-Perrot, B; Beurrier, D

    1995-03-01

    Now that the radical treatment of the Wolff-Parkinson-White syndrome is established, it is essential to evaluate the prognosis of this condition accurately. Initiation of atrial fibrillation is one of the factors which influence the prognosis. The aim of this study was to compare the results of electrophysiological studies performed by the endocavitary and transoesophageal approaches in the measurement of the initiation of atrial fibrillation. Twenty-six patients with a patent Wolff-Parkinson-White syndrome were studied by the two methods with a similar protocol: incremental atrial pacing to the Wenckebach point, programmed atrial stimulation using up to two extrastimuli, repeated with an infusion of 20 to 30 ug of isoproterenol. Sixteen patients had reciprocating nodal tachycardia or were asymptomatic (group I) and the other 10 had spontaneous atrial fibrillation (group II). In group I, atrial fibrillation was induced in 9 cases (56%) by the endocavitary and in two cases (12.5%) by the transoesophageal method. In group II, spontaneous atrial fibrillation was reproduced in all cases by the endocavitary and transoesophageal protocols. None of the patients in group I developed atrial fibrillation during follow-up (average 2 years +/- 9 months). The authors observe that all spontaneous atrial fibrillation of the Wolff-Parkinson-White syndrome can be triggered by oesophageal stimulation. The prevalence of atrial fibrillation was overestimated by endocavitary studies in asymptomatic or paucisymptomatic patients. The assessment of atrial vulnerability of a Wolff-Parkinson-White syndrome may therefore be performed by transoesophageal electro-physiological studies.

  8. [Wolff-Parkinson-White syndrome after 50 yars of age. Clinical and electrophysiological data].

    PubMed

    Lévy, S; Borde, C; Dupon, J; Bémurat, M; Gérard, R; Bricaud, H

    1980-07-01

    The Wolff-Parkinson-White syndrome is usually observed in young people and is much rarer in patients over 50 years old. This fact may be explained by the demise of a certain number of patients before the age of 50 and/or a change in the clinical features of the syndrome with age and/or of the electrophysiological properties of the normal and accessory conduction pathways. To test the latter hypothesis, the clinical and electrophysiological data of 15 patients over 50 years old with the Wolff-Parkinson-White syndrome (Group I) were compared with that of 10 patients under 30 years old with the same syndrome (Group II). The same protocol of electrophysiological investigation was used in both groups of patients. The results showed a significant difference (p < 0.001) between the two groups in the incidence of associated cardiac disease. This was more common in Group I (1 4 out of 15 patients) than in Group II (2 out of 10 patients). The cardiothoracic ratio was significantly higher in Group I (p < 0.01). The two groups also differed in the age at which tachycardia first occured. 9 out of 11 patients in Group I only had symptoms after thirty years. On the other hand, there was no significant difference in the types of tachycardia and the frequency of attacks. There was no significant difference in QRS, PR, AH, HV intervals, in the ventriculo-atrial conduction time and the effective refractory periods of the atrium, right ventricle or atrio-ventricular node. There was no significant difference in the anterograde and retrograde refractory periods of the accessory pathways between the two groups. Reciprocating tachycardia, initiated by electrical stimulation in 7 patients in Group I and 6 patients in Group II, was conducted anterogradely to the ventricles through the normal pathway and retrogradely to the atria through the the accessory pathway. This study suggest that age-related changes in the electrophysiological properties of the accessory are not an important

  9. The cytogenetics of mammalian autosomal rearrangements

    SciTech Connect

    Daniel, A.

    1988-01-01

    Combining data from animal and clinical studies with classical cytogenetic observations, the volume provides information on various aspects of mammalian autosomal rearrangements. Topics range from the reproductive consequences to carriers of autosomal rearrangements to the application of structural rearrangements and DNA probes to gene mapping. In addition, the book presents an overview of new perspectives and future directions for research.

  10. Photo-induced defects and photoconductivity in amorphous silicon

    NASA Astrophysics Data System (ADS)

    Okamoto, H.; Kida, H.; Hamakawa, Y.

    1984-02-01

    An essential connection between photo-induced defects and photoconductivity in amorphous silicon is discussed within the framework of Street's defect creation model. The excitation intensity dependence and doping level dependence of the photo-induced defect density and photoconductivity are derived on the basis of simple rate equation analysis, and compared with experimental data.

  11. Wolff-type embedding algorithms for general nonlinear σ-models

    NASA Astrophysics Data System (ADS)

    Caracciolo, Sergio; Edwards, Robert G.; Pelissetto, Andrea; Sokal, Alan D.

    1993-08-01

    We study a class of Monte Carlo algorithms for the nonlinear σ-model, based on A Wolff-type embedding of Ising spins into the target manifold M. We argue heuristically that, at least for an asymptotically free model, such an algorithm can have a dynamic critical exponent z « 2 only if the embedding is based on an (involutive) isometry of M whose fixed-point manifold has codimension 1. Such an isometry exist only if the manifold is a discrete quotient of a product of spheres. Numerical simulations of the idealized codimension-2 algorithm for the two-dimensional O(4)-symmetric σ-model yield z int, M2 = 1.5±0.5 (sujective 68% confidence interval), in agreement with our heuristic argument.

  12. [Polymorphic atrial tachycardia and Wolff-Parkinson-White syndrome in a newborn infant].

    PubMed

    Chantepie, A; Ramponi, N; Vaillant, M C; Laugier, J; Raynaud, P; Fauchier, J P

    1986-08-01

    The authors report a case of polymorphic supraventricular tachycardia in a premature neonate born at 33 weeks by caesarean section because of foeto-placental insufficiency and hydramnios due to foetal tachycardia diagnosed in utero. This arrhythmia was of interest because of the association of chaotic atrial tachycardia and the Wolff-Parkinson-White syndrome (WPW), which has rarely been described in the neonate. The mechanism of atrial tachycardia in the WPW syndrome is variable. In our case, there was retrograde atrial activation by the accessory pathway with atrial desynchronisation aided by left atrial dilatation. Digoxin, an effective anti arrhythmic agent in neonatal tachycardia, should not be used in cases of atrial tachycardia associated with ventricular preexcitation because of the risk of dangerous ventricular tachycardia.

  13. [Current treatment of Wolff-Parkinson-White syndrome and ventricular tachycardia: surgical ablation versus catheter ablation?].

    PubMed

    Misaki, T; Watanabe, G; Iwa, T; Watanabe, Y

    1992-09-01

    From November 1973, 454 patients with Wolff-Parkinson-White syndrome underwent surgical ablation of accessory pathways. Overall curative rate was 94% in our series including 65 cases of simultaneous surgical repair for combined heart diseases. In recent months, radiofrequency catheter ablation was applied in 7 cases. There has been 2 failures, which have taken more than 2 hours of radiation exposure and have required surgery. There has been 47 patients who underwent surgical ablation for non-ischemic ventricular tachycardia. Forty cases (85%) had a successful outcome of surgical ablation and another 2 cases required DC catheter ablation postoperatively to eliminate ventricular tachycardias. In conclusion, radiofrequency ablation of WPW syndrome in patients without combined heart disease or multiple accessory pathways is feasible. Surgical ablation is effective and safe technique compared with catheter ablation in patients with ventricular tachycardia.

  14. [Wolff-Parkinson-White syndrome and longitudinal dissociation of the atrioventricular node. Anatomical and electrophysiological correlates].

    PubMed

    Brechenmacher, C; Fauchier, J P; James, T N

    1981-07-01

    A 58 year old man who died of metastatic carcinoma had undergone electrophysiological investigation 4 years previously for a Wolff-Parkinson-White syndrome (Rosenbaum Type A, Frank and Boineau Type IV) associated with supraventricular tachycardia (SVT) at 180/mn, atrial fibrillation and flutter and slow junctional (or low atrial) rhythm at 70-80/mn. Atrial extrasystoles or appropriate atrial stimulation not only induced and terminated the SVT but also the junctional rhythm and allowed passage from one arrhythmia to another. These studies showed the presence of a left lateral Kent bundle responsible for orthodromic SVT with retrograde conduction through the accessory pathway, and suggested that the junctional rhythm might be due to longitudinal dissociation of the AV node. Autopsy findings confirmed the presence of the left posterolateral Kent bundle in an almost horizontal position, parallel to the mitral annulus (it might therefore have escaped eventual surgical section) and the longitudinal dissociation of the AV node.

  15. Biomagnetic noninvasive localization of accessory pathways in Wolff-Parkinson-White syndrome.

    PubMed

    Weismüller, P; Abraham-Fuchs, K; Schneider, S; Richter, P; Kochs, M; Edrich, J; Hombach, V

    1991-11-01

    It was our purpose to assess the clinical relevance of noninvasive magnetocardiographic localization of accessory pathways. Nine patients with Wolff-Parkinson-White (WPW) syndrome were studied. For all of them the site of the accessory pathway was known from invasive catheter mapping. A 37-SQUID (superconducting quantum interference device) sensor multichannel system (KRENIKON) was used, allowing synchronous registration with all channels. The site of the electrophysiological activity at the beginning of the delta wave was determined. Magnetic resonance images of the heart were obtained to correlate the biomagnetically localized activity with the anatomy. Magnetocardiographic localization of the bypass tract corresponded with catheter mapping with a spatial difference of 0-5 cm, 1.8 cm on the average, compared to the results obtained by catheter mapping. Thus, magnetocardiography is a promising new method for noninvasive localization of accessory pathways in WPW patients. This may streamline further invasive procedures.

  16. Effect of exercise on ventricular response to atrial fibrillation in Wolff-Parkinson-White syndrome.

    PubMed Central

    Crick, J C; Davies, D W; Holt, P; Curry, P V; Sowton, E

    1985-01-01

    Ten patients with Wolff-Parkinson-White syndrome underwent cardiac electrophysiological study extended to include the induction of atrial fibrillation at maximum exercise in the upright position. This was performed using a new temporary bipolar lead with a helical active fixation tip for atrial pacing. The highest rate of atrioventricular conduction via the accessory pathway was greater during exercise than at rest in all 10 patients (mean increase 28%). In three cases the resulting ventricular rate exceeded 300 beats/min, but no patient had severe symptoms or ventricular arrhythmias. The exercise induced enhancement of accessory pathway conduction may significantly but unpredictably affect the risk from spontaneous atrial fibrillation especially in patients with coronary artery disease or in those taking antiarrhythmic drugs. The test procedure was sufficiently simple and well tolerated to be included in our routine electrophysiological investigation. PMID:4015920

  17. Programmed Genome Rearrangements in Tetrahymena.

    PubMed

    Yao, Meng-Chao; Chao, Ju-Lan; Cheng, Chao-Yin

    2014-12-01

    Ciliates are champions in programmed genome rearrangements. They carry out extensive restructuring during differentiation to drastically alter the complexity, relative copy number, and arrangement of sequences in the somatic genome. This chapter focuses on the model ciliate Tetrahymena, perhaps the simplest and best-understood ciliate studied. It summarizes past studies on various genome rearrangement processes and describes in detail the remarkable progress made in the past decade on the understanding of DNA deletion and other processes. The process occurs at thousands of specific sites to remove defined DNA segments that comprise roughly one-third of the genome including all transposons. Interestingly, this DNA rearranging process is a special form of RNA interference. It involves the production of double-stranded RNA and small RNA that guides the formation of heterochromatin. A domesticated piggyBac transposase is believed to cut off the marked chromatin, and the retained sequences are joined together through nonhomologous end-joining processes. Many of the proteins and DNA players involved have been analyzed and are described. This link provides possible explanations for the evolution, mechanism, and functional roles of the process. The article also discusses the interactions between parental and progeny somatic nuclei that affect the selection of sequences for deletion, and how the specific deletion boundaries are determined after heterochromatin marking.

  18. Photoinduced heterostructure in a vanadium dioxide film

    NASA Astrophysics Data System (ADS)

    Semenov, A. L.

    2017-02-01

    A photoinduced semiconductor-metal phase transition that occurs in a surface layer of vanadium dioxide film on an aluminum substrate within the time Δ t < 1 ps has been studied theoretically. A nonthermal mechanism of the development of instability has been considered. It has been shown that a heterophase structure containing metallic and semiconductor layers is formed in the VO2 film. The phase transition time τ has been calculated as a function of the distance z from the film surface. Comparison with the experiment has been carried out.

  19. Kinetics of a photoinduced NH tautomerism of free-base porphyrins in crystalline matrices at low temperatures: Computer simulations and experiment

    NASA Astrophysics Data System (ADS)

    Stanishevsky, I. V.; Solovyov, K. N.

    2004-03-01

    Photoinduced NH tautomerism, along with the reaction pathways of phototautomerization in tetrabenzoporphin and porphin free bases in n-octane polycrystalline matrices at 77 K, is studied by simulation of kinetic processes and their experimental observation. The simulation of the processes is performed by the numerical solution of the system of kinetic equations describing the populations of electronic levels and transitions between them. Kinetic dependences are obtained by measuring the perturbation of stationary fluorescence of one component of the 0-0 doublet origin upon pulsed selective photoexcitation of the other component. For two tautomeric forms related by the reversibility of the photochemical reaction, under the assumption of synchronism of the NH rearrangement, (i) analytical solutions governing the reaction rate are found, (ii) a method of measuring the rate constants of the proton rearrangement is suggested and the constants themselves are estimated, and (iii) direct evidence of the participation of T 1 levels in the photochemical reaction is obtained. With the aid of numerical simulations, the specific features of kinetic manifestation of an asynchronous mechanism of the photoinduced NH rearrangement are studied.

  20. Nanoscale chemical imaging by photoinduced force microscopy

    PubMed Central

    Nowak, Derek; Morrison, William; Wickramasinghe, H. Kumar; Jahng, Junghoon; Potma, Eric; Wan, Lei; Ruiz, Ricardo; Albrecht, Thomas R.; Schmidt, Kristin; Frommer, Jane; Sanders, Daniel P.; Park, Sung

    2016-01-01

    Correlating spatial chemical information with the morphology of closely packed nanostructures remains a challenge for the scientific community. For example, supramolecular self-assembly, which provides a powerful and low-cost way to create nanoscale patterns and engineered nanostructures, is not easily interrogated in real space via existing nondestructive techniques based on optics or electrons. A novel scanning probe technique called infrared photoinduced force microscopy (IR PiFM) directly measures the photoinduced polarizability of the sample in the near field by detecting the time-integrated force between the tip and the sample. By imaging at multiple IR wavelengths corresponding to absorption peaks of different chemical species, PiFM has demonstrated the ability to spatially map nm-scale patterns of the individual chemical components of two different types of self-assembled block copolymer films. With chemical-specific nanometer-scale imaging, PiFM provides a powerful new analytical method for deepening our understanding of nanomaterials. PMID:27051870

  1. Photoinduced Force Mapping of Plasmonic Nanostructures.

    PubMed

    Tumkur, Thejaswi U; Yang, Xiao; Cerjan, Benjamin; Halas, Naomi J; Nordlander, Peter; Thomann, Isabell

    2016-12-14

    The ability to image the optical near-fields of nanoscale structures, map their morphology, and concurrently obtain spectroscopic information, all with high spatiotemporal resolution, is a highly sought-after technique in nanophotonics. As a step toward this goal, we demonstrate the mapping of electromagnetic forces between a nanoscale tip and an optically excited sample consisting of plasmonic nanostructures with an imaging platform based on atomic force microscopy. We present the first detailed joint experimental-theoretical study of this type of photoinduced force microscopy. We show that the enhancement of near-field optical forces in gold disk dimers and nanorods follows the expected plasmonic field enhancements with strong polarization sensitivity. We then introduce a new way to evaluate optically induced tip-sample forces by simulating realistic geometries of the tip and sample. We decompose the calculated forces into in-plane and out-of-plane components and compare the calculated and measured force enhancements in the fabricated plasmonic structures. Finally, we show the usefulness of photoinduced force mapping for characterizing the heterogeneity of near-field enhancements in precisely e-beam fabricated nominally alike nanostructures - a capability of widespread interest for precise nanomanufacturing, SERS, and photocatalysis applications.

  2. DNA Rearrangements through Spatial Graphs

    NASA Astrophysics Data System (ADS)

    Jonoska, Nataša; Saito, Masahico

    The paper is a short overview of a recent model of homologous DNA recombination events guided by RNA templates that have been observed in certain species of ciliates. This model uses spatial graphs to describe DNA rearrangements and show how gene recombination can be modeled as topological braiding of the DNA. We show that a graph structure, which we refer to as an assembly graph, containing only 1- and 4-valent rigid vertices can provide a physical representation of the DNA at the time of recombination. With this representation, 4-valent vertices correspond to the alignment of the recombination sites, and we model the actual recombination event as smoothing of these vertices.

  3. Noninvasive Localization of Accessory Pathways in Wolff-Parkinson-White Syndrome by Three-Dimensional Speckle Tracking Echocardiography.

    PubMed

    Ishizu, Tomoko; Seo, Yoshihiro; Igarashi, Miyako; Sekiguchi, Yukio; Machino-Ohtsuka, Tomoko; Ogawa, Kojiro; Kuroki, Kenji; Yamamoto, Masahiro; Nogami, Akihiko; Kawakami, Yasushi; Aonuma, Kazutaka

    2016-06-01

    We have developed a noninvasive isochrone activation imaging (AI) system with 3-dimensional (3D) speckle tracking echocardiography (STE), which allows visualization of the wavefront image of mechanical propagation of the accessory pathway (ACP) in Wolff-Parkinson-White syndrome. Patients with manifest Wolff-Parkinson-White syndrome were imaged in 3D-STE AI mode, which quantified the time from QRS onset to regional endocardial deformation. In 2 patients with left- and right-side ACP, we confirmed that intraoperative contact endocardial electric mapping and the 3D-STE AI system showed comparable images pre- and postablation. In normal heart assessment by 3D-echo AI, the earliest activation sites were found at the attachment of the papillary muscles in the left ventricle and midseptum in the right ventricle, and none showed earliest activation at the peri-atrioventricular valve annuli. An analyzer who was unaware of the clinical information assessed 39 ACP locations in 38 Wolff-Parkinson-White syndrome patients using 3D-STE. All showed abnormal perimitral or tricuspid annular activations, and the location of 34 ACP (87%) showed agreement with the successful ablation sites within a 2-o'clock range. Especially for left free wall ACP, 17/18 (94%) showed consistency with the ablation site within a 2 o'clock range. Among 15 ACP at the ventricular septum, 9 (60%) showed early local activation in both right and left sides of the septum. Isochrone AI with 3D-STE may be a promising noninvasive imaging tool to assess cardiac synchronized activation in normal hearts and detect abnormal breakthrough of mechanical activation from both atrioventricular annuli in Wolff-Parkinson-White syndrome. © 2016 American Heart Association, Inc.

  4. Wolff-Parkinson-White syndrome in the era of catheter ablation: insights from a registry study of 2169 patients.

    PubMed

    Pappone, Carlo; Vicedomini, Gabriele; Manguso, Francesco; Saviano, Massimo; Baldi, Mario; Pappone, Alessia; Ciaccio, Cristiano; Giannelli, Luigi; Ionescu, Bogdan; Petretta, Andrea; Vitale, Raffaele; Cuko, Amarild; Calovic, Zarko; Fundaliotis, Angelica; Moscatiello, Mario; Tavazzi, Luigi; Santinelli, Vincenzo

    2014-09-02

    The management of Wolff-Parkinson-White is based on the distinction between asymptomatic and symptomatic presentations, but evidence is limited in the asymptomatic population. The Wolff-Parkinson-White registry was an 8-year prospective study of either symptomatic or asymptomatic Wolff-Parkinson-White patients referred to our Arrhythmology Department for evaluation or ablation. Inclusion criteria were a baseline electrophysiological testing with or without radiofrequency catheter ablation (RFA). Primary end points were the percentage of patients who experienced ventricular fibrillation (VF) or potentially malignant arrhythmias and risk factors. Among 2169 enrolled patients, 1001 (550 asymptomatic) did not undergo RFA (no-RFA group) and 1168 (206 asymptomatic) underwent ablation (RFA group). There were no differences in clinical and electrophysiological characteristics between the 2 groups except for symptoms. In the no-RFA group, VF occurred in 1.5% of patients, virtually exclusively (13 of 15) in children (median age, 11 years), and was associated with a short accessory pathway antegrade refractory period (P<0.001) and atrioventricular reentrant tachycardia initiating atrial fibrillation (P<0.001) but not symptoms. In the RFA group, ablation was successful in 98.5%, and after RFA, no patients developed malignant arrhythmias or VF over the 8-year follow-up. Untreated patients were more likely to experience malignant arrhythmias and VF (log-rank P<0.001). Time-dependent receiver-operating characteristic curves for predicting VF identified an optimal anterograde effective refractory period of the accessory pathway cutoff of 240 milliseconds. The prognosis of the Wolff-Parkinson-White syndrome essentially depends on intrinsic electrophysiological properties of AP rather than on symptoms. RFA performed during the same procedure after electrophysiological testing is of benefit in improving the long-term outcomes. © 2014 American Heart Association, Inc.

  5. [Association of Wolff-Parkinson-White syndrome with isolated non-compaction of the left ventricle: a case report].

    PubMed

    Brembilla-Perrot, B; Codreanu, A; Marie, P Y; Beurrier, D; Husson, J L; Hutin, O; Pruna, A; Yangni N'Da, O; Ernst, Y; Bosser, G

    2006-06-01

    The Wolff-Parkinson-White syndrome (WPW) may be associated with a number of cardiac pathologies, especially congenital disease, in 7.5 to 17% of cases. The authors report a rare association of the WPW syndrome with two Kent bundles, right and left septal, with non-compaction of the left ventricle in a 52 year old man. This was a chance finding during systematic echocardiography after ablation, and confirmed by cardiac MRI. The patient was asymptomatic.

  6. Optimal Arrangement of Components Via Pairwise Rearrangements.

    DTIC Science & Technology

    1987-10-01

    reliability function under component pairwise rearrangement. They use this property to find the optimal component arrangement. Worked examples illustrate the methods proposed. Keywords: Optimization; Permutations; Nodes.

  7. Photo-induced electron transfer method

    DOEpatents

    Wohlgemuth, Roland; Calvin, Melvin

    1984-01-01

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospho-lipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transfering electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  8. Photoinduced Fusion of Lipid Bilayer Membranes.

    PubMed

    Suzuki, Yui; Nagai, Ken H; Zinchenko, Anatoly; Hamada, Tsutomu

    2017-03-14

    We have developed a novel system for photocontrol of the fusion of lipid vesicles through the use of a photosensitive surfactant containing an azobenzene moiety (AzoTAB). Real-time microscopic observations clarified a change in both the surface area and internal volume of vesicles during fusion. We also determined the optimal cholesterol concentrations and temperature for inducing fusion. The mechanism of fusion can be attributed to a change in membrane tension, which is caused by the solubilization of lipids through the isomerization of AzoTAB. We used a micropipet technique to estimate membrane tension and discuss the mechanism of fusion in terms of membrane elastic energy. The obtained results regarding this novel photoinduced fusion could lead to a better understanding of the mechanism of membrane fusion in living cells and may also see wider applications, such as in drug delivery and biomimetic material design.

  9. Photo-induced electron transfer method

    DOEpatents

    Wohlgemuth, R.; Calvin, M.

    1984-01-24

    The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospholipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transferring electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

  10. Photoinduced decomposition of trichloroethylene in soil components

    SciTech Connect

    Tao, T.; Yang, J.J.; Maciel, G.E.

    1999-01-01

    The photoinduced decomposition of trichloroethylene adsorbed on Ca-montmorillonite by long-wavelength UV irradiation has been studied in a quartz tube open to air or through which air or oxygen is passed. Solid-sample and liquid-solution NMR techniques were used to identify apparent products or intermediates of the photodecomposition. Dichloroacetic acid was identified as a major organic product/intermediate; substantial amounts of pentachloroethane and trichloroacetic acid were also identified. The formation of CO{sub 2} was characterized quantitatively by wet chemical analysis. About 40% and 57%, respectively, of the total carbon of trichloroethylene was converted to carbon dioxide in air and O{sub 2} environments over a period of 16 days. Phosgene and HCl were also detected. The photodecomposition of trichloroethylene adsorbed on whole soil, on Zn{sup 2+}-exchanged and Cu{sup 2+}-exchanged montmorillonites, on kaolinite, and on silica gel was also examined in less detail; qualitatively, the conversion of trichloroethylene to dichloroacetic acid in a 48-h period occurred with the following order of decreasing efficiencies: Zn{sup 2+}-montmorillonite > silica gel > kaolinite > Ca{sup 2+}-montmorillonite > whole soil > Cu{sup 2+}-montmorillonite. These results show that the photoinduced decomposition of adsorbed trichloroethylene occurs on a variety of adsorbents, generating products and intermediates that are similar to what have been reported previously for TiO{sub 2}-based photodecomposition but with much longer time scales. These conversions can, therefore, be expected to occur in sunlight at the air-soil interface.

  11. A novel planarization method based on photoinduced confined chemical etching.

    PubMed

    Fang, Qiuyan; Zhou, Jian-Zhang; Zhan, Dongping; Shi, Kang; Tian, Zhao-Wu; Tian, Zhong-Qun

    2013-07-21

    A photoinduced confined chemical etching system based on TiO2 nanotube arrays is developed for the planarization of the copper surface, which is proved to be a prospective stress-free chemical planarization method for metals and semiconductors.

  12. Review of the photo-induced toxicity of environmental contaminants.

    PubMed

    Roberts, Aaron P; Alloy, Matthew M; Oris, James T

    2017-01-01

    Solar radiation is a vital component of ecosystem function. However, sunlight can also interact with certain xenobiotic compounds in a phenomenon known as photo-induced, photo-enhanced, photo-activated, or photo-toxicity. This phenomenon broadly refers to an interaction between a chemical and sunlight resulting in increased toxicity. Because most aquatic ecosystems receive some amount of sunlight, co-exposure to xenobiotic chemicals and solar radiation is likely to occur in the environment, and photo-induced toxicity may be an important factor impacting aquatic ecosystems. However, photo-induced toxicity is not likely to be relevant in all aquatic systems or exposure scenarios due to variation in important ecological factors as well as physiological adaptations of the species that reside there. Here, we provide an updated review of the state of the science of photo-induced toxicity in aquatic ecosystems.

  13. Photoinduced nanocomposites—creation, modification, linear and nonlinear optical properties

    NASA Astrophysics Data System (ADS)

    Bityurin, N.; Alexandrov, A.; Afanasiev, A.; Agareva, N.; Pikulin, A.; Sapogova, N.; Soustov, L.; Salomatina, E.; Gorshkova, E.; Tsverova, N.; Smirnova, L.

    2013-07-01

    UV irradiation of materials consisting of a polymer matrix that possesses precursors of noble metals followed by annealing results in creation of metal nanoparticles within the irradiated domains. Such photoinduced nanocomposites are promising for photonics applications due to the strong alteration of their optical properties compared to initial nonirradiated materials. We report our results on the synthesis and investigation of two kinds of these materials: (a) Photoinduced Au nanocomposites based on PMMA matrices, including bulk materials prepared by means of the polymerization technique;

  14. Trabecular bone of precocials at birth; Are they prepared to run for the wolf(f)?

    PubMed Central

    Wolschrijn, Claudia F.; van Vilsteren, Anouk A.M.; van Rietbergen, Bert; van Weeren, P. René

    2016-01-01

    ABSTRACT Bone is a dynamic tissue adapting to loading according to “Wolff's law of bone adaptation.” During very early life, however, such a mechanism may not be adequate enough to adapt to the dramatic change in environmental challenges in precocial species. Their neonates are required to stand and walk within hours after birth, in contrast to altricial animals that have much more time to adapt from the intrauterine environment to the outside world. In this study, trabecular bone parameters of the talus and sagittal ridge of the tibia from stillborn but full‐term precocials (calves and foals) were analyzed by micro‐CT imaging in order to identify possible anticipatory mechanisms to loading. Calculated average bone volume fraction in the Shetland pony (49–74%) was significantly higher compared to Warmblood foals (28–51%). Bovine trabecular bone was characterized by a low average bone volume fraction (22–28%), however, more directional anisotropy was found. It is concluded that anticipatory strategies in skeletal development exist in precocial species, which differ per species and are most likely related to anatomical differences in joint geometry and related loading patterns. The underlying regulatory mechanisms are still unknown, but they may be based on a genetic blueprint for the development of bone. More knowledge, both about a possible blueprint and its regulation, will be helpful in understanding developmental bone and joint diseases. J. Morphol. 277:948–956, 2016. © 2016 Wiley Periodicals, Inc. PMID:27098190

  15. Existence of automaticity in anomalous bundle of Wolff-Parkinson-White syndrome.

    PubMed Central

    Przybylski, J; Chiale, P A; Halpern, M S; Lázzari, J O; Elizari, M V; Rosenbaum, M B

    1978-01-01

    Escape beats probably arising from the anomalous bundle were documented in 2 patients with the Wolff-Parkinson-White (WPW) syndrome. A third patient, in whom complete AV block developed both in the anomalous bundle and the normal pathway, showed the occurrence of escape beats (an escape-bigeminy pattern), as well as a regular idioventricular rhythm arising from the anomalous bundle. Phase 4 block in the anomalous bundle occurred in 7 other patients, in 4 of them spontaneously and in 3 only after the administration of ajmaline or amiodarone. Only 4 of 14 fully investigated patients (out of a total number of 23) showed absence of both escape beats and phase 4 block. The escape beats were considered as direct evidence, and the phase 4 block as indirect evidence, for the existence of automaticity in the anomalous bundle. Such evidence supports the view that the anomalous bundle, like the His bundle-branch system, may be composed of specialised tissue endowed with the property of automaticity. PMID:656241

  16. [Genesis of auricular fibrillation in the Wolff-Parkinson-White syndrome].

    PubMed

    Gressard, A; Atallah, G; Chatelain, M T; Touboul, P

    1981-11-01

    Atrial fibrillation seems to be more common in the absence of associated cardiac disease in the Wolff-Parkinson-White syndrome (WPW) than in subjects of the same age without this condition. The aim of this study was to analyse the electrophysiological mechanism of AF and to establish its relationship to the accessory pathway. The series comprises 14 out of 51 patients with WPW undergoing classical endocavitary investigation associating the recording of cardiac potentials from the His bundle, right atrium (RA), left atrium (LA) via the coronary sinus and atrial and ventricular stimulation techniques. Three mechanisms of inducing AF were analysed : - AF triggered by RA stimulation : either by a premature extra stimulus or overdrive atrial pacing. In all cases, the accessory pathway was right sides. - AF triggered by overdrive ventricular pacing : three cases were left sided accessory pathways in which atrial desynchronisation was localised in the LA. - Conversion of reciprocating tachycardia to AF (9 cases). In 2 cases, this was preceded by a progressive acceleration of the heart rate. Of 3 left sided accessory pathways, the atrial desynchronisation was located in the LA in 2 cases. The factors which facilitate AF in THE WPW syndrome are discussed : increased atrial vulnerability, the role of the rapid return of ventricular excitation to the atria through the accessory pathway. Our observations suggest that the accessory pathway plays a role in the genesis of AF in the WPW syndrome.

  17. [The double ventricular response phenomenon in 2 cases of Wolff-Parkinson-White syndrome].

    PubMed

    Guize, L; Meilhac, B; Cabanis, C; Di Mattéo, J; Maurice, P

    1978-02-01

    The authors report two cases of "true" consecutive double ventricular response caused by a single premature atrial stimulation; both were young men with Wolff-Parkinson-White syndrome. In both cases, the presence of a bundle of Kent was confirmed. The phenomenon of double ventricular response arising successively from the bundle of Kent and node-His pathway is rare, being mentioned in only two cases in the literature. It is only found when there is the combination of a good bundle of Kent, fair forward conduction, and a relative ventricle-His retrograde block. Amongst the other mechanisms for double ventricular repsonse, re-entry from branch to branch presents the most difficult differential diagnosis. From our observations, the forward characteristics of the spread through the bundle of His which always procedes the bundle of His which always precedes the second ventricular complex have been confirmed, especially in view of the freat variation in the position of this potential which can easily be explained by variations in intra-nodal conduction. In one of these cases, the atriogram, taken after the second ventriculogram, was provided by retrograde activity in the bundle of Kent.

  18. [Prognosis of Wolff-Parkinson-White syndrome in infants. Apropos of 31 cases].

    PubMed

    Becquart, J; Vaksmann, G; Becquart, V; Dupuis, C

    1988-05-01

    The fate of 31 children (18 boys, 13 girls) whose Wolff-Parkinson-White syndrome (WPW) had been diagnosed before they were 2 years' old (mean 3.4 months) was investigated. The circumstances in which WPW was discovered were: evaluation of a heart disease in 9 cases, attack of orthodromic tachycardia in 16 cases (including one with cardiopathy), and routine electrocardiography in 6 cases. Type A WPW was the most frequent, being found in 20 patients of whom only 3 had a heart disease; type B WPW was present in 11 patients, and 7 of these had a heart disease. Mean follow-up was 5.9 years; 3 children died of other causes than WPW. In patients followed up for more than one year WPW disappeared in 65 p. 100 of the cases (11/17) in the absence of cardiopathy, and in only 14 p. 100 of the cases (1/7) in the presence of cardiopathy. In children who had suffered attacks of tachycardia WPW disappeared in 64 p. 100 of the cases (9/14). When WPW disappeared it was before the age of 1 year in 8 out of 12 cases. Only one child whose WPW had disappeared had further attacks of tachycardia (11 p. 100), while 3 children whose WPW persisted had short and widely spaced attacks (60 p. 100). This study confirms the high rate of spontaneous disappearance of WPW and the excellent prognosis of this syndrome in the absence of heart disease.

  19. Atrial pacing at multiple sites in the Wolff-Parkinson-White syndrome.

    PubMed Central

    Denes, P; Wyndham, C R; Amat-y-Leon, F; Wu, D; Dhingra, R C; Miller, R H; Rosen, K M

    1977-01-01

    Atrial pacing at multiple sites was used in an attempt to predict the site of pre-excitation in 5 patients with Wolff-Parkinson-White syndrome with 5 different anomalous pathway locations (right anterior, right posterior, septal, left posterior, and left lateral). At least 3 atrial pacing sites were tested in each patient. Pacing sites tested included high right atrium, low lateral right atrium, low septal right atrium, proximal coronary sinus, and distal coronary sinus. Atrial stimulation sites with shortest and longest stimulus-delta intervals could be identified in each patient, the shortest stimulus-delta interval in each case ranging from 60 to 80 ms. The difference between the shortest and longest stimulus-delta interval in each case ranged from 60 to 110 ms. It was suggested that the site with the shortest stimulus-delta interval corresponded to a site close to the atrial insertion of the anomalous pathway. This hypothesis was confirmed in all cases (3 with epicardial mapping and 2 with retrograde atrial activation data). In conclusion, atrial pacing at multiple sites is helpful in predicting the site of anterogradely conducting anomalous pathways, and appears particularly useful for differentiation of right posterior, left posterior, and septal pre-excitation. Images PMID:861093

  20. Photoinduced electro-optics measurements of biosilica transformation to cristobalite

    SciTech Connect

    Fuchs, Ido; Aluma, Yaniv; Ilan, Micha; Kityk, Iwan; Mastai, Yitzhak

    2015-03-15

    In this paper we studied the photoinduced electro optics effects in the thermal transformation process of biosilica to cristobalite, at a relatively low temperature and ambient pressure. This process was characterized by a variety of standards techniques with emphasis on linear electro optic effect measurements. Overall we demonstrated that photoinduced electro optics measurements are very sensitive to the transformation from amorphous structure of silica in the natural sponge samples to laminar string morphology of cristobalite. With this technique we could probe the change in the samples chirality from achiral bio silica to chiral cristobalite structure. Furthermore it is shown that natural biosilica have photoinduced linear electro optics respond indicating the chiral natural of biosilica. - Graphical abstract: The phase transformation of biosilica from marine sponges to Cristobalite under thermal treatment was investigated using photoinduced electro optics measurements. The figure shows the changes of the electro-optic coefficient of cristobalite and biosilica. - Highlights: • We examine phase transformation of biosilica. • We report transition from amorphous biosilica to crystalline Cristobalite. • Biosilica transformation to Cristobalite at temperature of 850 °C. • Biosilica transformation is studied with photoinduced measurements. • We examine changes in the photoinduced linear electro optics properties.

  1. Multiple genome rearrangement by reversals.

    PubMed

    Wu, Shiquan; Gu, Xun

    2002-01-01

    In this paper, we discuss a multiple genome rearrangement problem: Given a collection of genomes represented by permutations, we generate the collection from some fixed genome, e.g., the identity permutation, in a minimum number of signed reversals. It is NP-hard, so efficient heuristics is important for finding its optimal solution. We at first discuss how to generate two and three genomes from a fixed genome by polynomial algorithms for some special cases. Then based on the polynomial algorithms, we obtain some approximation algorithms for generating two and three genomes in general, respectively. Finally, we apply these approximation algorithms to design a new approximation algorithm for generating more genomes. We also show by some experimental examples that the algorithms are efficient.

  2. Integrin activation and structural rearrangement.

    PubMed

    Takagi, Junichi; Springer, Timothy A

    2002-08-01

    Among adhesion receptor families, integrins are particularly important in biological processes that require rapid modulation of adhesion and de-adhesion. Activation on a timescale of < 1 s of beta2 integrins on leukocytes and beta3 integrins on platelets enables deposition of these cells at sites of inflammation or vessel wall injury. Recent crystal, nuclear magnetic resonance (NMR), and electron microscope (EM) structures of integrins and their domains lead to a unifying mechanism of activation for both integrins that contain and those that lack an inserted (I) domain. The I domain adopts two alternative conformations, termed open and closed. In striking similarity to signaling G-proteins, rearrangement of a Mg2+-binding site is linked to large conformational movements in distant backbone regions. Mutations that stabilize a particular conformation show that the open conformation has high affinity for ligand, whereas the closed conformation has low affinity. Movement of the C-terminal alpha-helix 10 A down the side of the domain in the open conformation is sufficient to increase affinity at the distal ligand-binding site 9,000-fold. This C-terminal "bell-rope" provides a mechanism for linkage to conformational movements in other domains. Recent structures and functional studies reveal interactions between beta-propeller, I, and I-like domains in the integrin headpiece, and a critical role for integrin epidermal growth factor (EGF) domains in the stalk region. The headpiece of the integrin faces down towards the membrane in the inactive conformation, and extends upward in a "switchblade"-like opening upon activation. These long-range structural rearrangements of the entire integrin molecule involving interdomain contacts appear closely linked to conformational changes within the I and I-like domains, which result in increased affinity and competence for ligand binding.

  3. Rearrangement of sulfonamidyl radicals with hydrogen migration

    SciTech Connect

    Troyanskii, E.I.; Lazareva, M.I.; Nikishin, G.I.

    1987-01-20

    One-step outlying oxidative chlorination of alkanesulfonamides by the action of the Na/sub 2/S/sub 2/O/sub 8/-CuCl/sub 2/ system via intermediate sulfonamidyl radicals gives 3- and 4-chloroalkanesulfonamides. Rearrangements of sulfonamidyl radicals with H atom migration from the sulfonyl segment predominates over rearrangement with H atom migration from the amide segment.

  4. Microwave accelerated aza-Claisen rearrangement.

    PubMed

    Gajdosíková, Eva; Martinková, Miroslava; Gonda, Jozef; Conka, Patrik

    2008-11-14

    A study of microwave-induced and standard thermal Overman rearrangement of selected allylic trichloroacetimidates 1a-1f, 6-8 to the corresponding acetamides 2a-2f, 9-11 is reported. The microwave-assisted rearrangement of trifluoroacetimidate 13 is also described. Using this methodology, an efficient access to versatile allylic trihaloacetamides building synthons was established.

  5. Rearrangements of organic peroxides and related processes

    PubMed Central

    Yaremenko, Ivan A; Vil’, Vera A; Demchuk, Dmitry V

    2016-01-01

    Summary This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O–O-bond cleavage. Detailed information about the Baeyer−Villiger, Criegee, Hock, Kornblum−DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately. PMID:27559418

  6. Rearrangements of organic peroxides and related processes.

    PubMed

    Yaremenko, Ivan A; Vil', Vera A; Demchuk, Dmitry V; Terent'ev, Alexander O

    2016-01-01

    This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O-O-bond cleavage. Detailed information about the Baeyer-Villiger, Criegee, Hock, Kornblum-DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.

  7. Diverse mutational mechanisms cause pathogenic subtelomeric rearrangements

    PubMed Central

    Luo, Yue; Hermetz, Karen E.; Jackson, Jodi M.; Mulle, Jennifer G.; Dodd, Anne; Tsuchiya, Karen D.; Ballif, Blake C.; Shaffer, Lisa G.; Cody, Jannine D.; Ledbetter, David H.; Martin, Christa L.; Rudd, M. Katharine

    2011-01-01

    Chromosome rearrangements are a significant cause of intellectual disability and birth defects. Subtelomeric rearrangements, including deletions, duplications and translocations of chromosome ends, were first discovered over 40 years ago and are now recognized as being responsible for several genetic syndromes. Unlike the deletions and duplications that cause some genomic disorders, subtelomeric rearrangements do not typically have recurrent breakpoints and involve many different chromosome ends. To capture the molecular mechanisms responsible for this heterogeneous class of chromosome abnormality, we coupled high-resolution array CGH with breakpoint junction sequencing of a diverse collection of subtelomeric rearrangements. We analyzed 102 breakpoints corresponding to 78 rearrangements involving 28 chromosome ends. Sequencing 21 breakpoint junctions revealed signatures of non-homologous end-joining, non-allelic homologous recombination between interspersed repeats and DNA replication processes. Thus, subtelomeric rearrangements arise from diverse mutational mechanisms. In addition, we find hotspots of subtelomeric breakage at the end of chromosomes 9q and 22q; these sites may correspond to genomic regions that are particularly susceptible to double-strand breaks. Finally, fine-mapping the smallest subtelomeric rearrangements has narrowed the critical regions for some chromosomal disorders. PMID:21729882

  8. Reversibility of cell surface label rearrangement

    PubMed Central

    1976-01-01

    Cell surface labeling can cause rearrangements of randomly distributed membrane components. Removal of the label bound to the cell surface allows the membrane components to return to their original random distribution, demonstrating that label is necessary to maintain as well as to induce rearrangements. With scanning electron microscopy, the rearrangement of concanavalin A (con A) and ricin binding sites on LA-9 cells has been followed by means of hemocyanin, a visual label. The removal of con A from its binding sites at the cell surface with alpha- methyl mannoside, and the return of these sites to their original distribution are also followed in this manner. There are labeling differences with con A and ricin. Under some conditions, however, the same rearrangements are seen with both lectins. The disappearance of labeled sites from areas of ruffling activity is a major feature of the rearrangements seen. Both this ruffling activity and the rearrangement of label are sensitive to cytochalasin B, and ruffling activity, perhaps along with other cytochalasin-sensitive structure, may play a role in the rearrangements of labeled sites. PMID:1025154

  9. "Effects of networking on career success: A longitudinal study": Correction to Wolff and Moser (2009).

    PubMed

    2017-02-01

    Reports an error in "Effects of networking on career success: A longitudinal study" by Hans-Georg Wolff and Klaus Moser (Journal of Applied Psychology, 2009[Jan], Vol 94[1], 196-206). In the article, results from a confirmatory factor analysis on subjective career success in the Measures section contained an error in the reported Chi-square (i.e., χ² (5, N = 257) = 9.17). This error does not alter any conclusions or substantive statements in the original article. The correct fit indices are " χ²(5, N = 257) 9.67, p = .08, RMSEA = 0.059, CFI = 1.00." (The following abstract of the original article appeared in record 2009-00697-007.) Previous research has reported effects of networking, defined as building, maintaining, and using relationships, on career success. However, empirical studies have relied exclusively on concurrent or retrospective designs that rest upon strong assumptions about the causal direction of this relation and depict a static snapshot of the relation at a given point in time. This study provides a dynamic perspective on the effects of networking on career success and reports results of a longitudinal study. Networking was assessed with 6 subscales that resulted from combining measures of the facets of (a) internal versus external networking and (b) building versus maintaining versus using contacts. Objective (salary) and subjective (career satisfaction) measures of career success were obtained for 3 consecutive years. Multilevel analyses showed that networking is related to concurrent salary and that it is related to the growth rate of salary over time. Networking is also related to concurrent career satisfaction. As satisfaction remained stable over time, no effects of networking on the growth of career satisfaction were found. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  10. Intermittent versus Persistent Wolff-Parkinson-White Syndrome in Children: Electrophysiologic Properties and Clinical Outcomes.

    PubMed

    Kiger, Michelle E; McCanta, Anthony C; Tong, Suhong; Schaffer, Michael; Runciman, Martin; Collins, Kathryn K

    2016-01-01

    Intermittent Wolff-Parkinson-White (WPW) syndrome is considered to have a lower risk of sudden death. Fewer data exist regarding electrophysiologic (EP) characteristics and the natural history of intermittent WPW in children. All patients with WPW age 1-18 years at a single institution (1996-2013) were reviewed. Patients with intermittent preexcitation were compared to those with loss of preexcitation on Holter/exercise testing and those with persistent preexcitation. High-risk accessory pathway (AP) was defined as AP effective refractory period (APERP), block cycle length, or shortest preexcited RR interval during atrial fibrillation ≤250 ms. A total of 295 patients were included: 226 (76.6%) persistent, 39 (13.2%) intermittent, and 30 (10.2%) loss of preexcitation Holter/exercise. There were no differences in symptoms between groups. Median interquartile range APERP was significantly longer in intermittent WPW (380 [320, 488] ms vs 320 [300, 350] ms persistent, 310 [290, 330] ms loss of preexcitation Holter/exercise; P = 0.0008). At baseline, there was no difference between groups in frequency of high-risk pathways. However, when isoproterenol values were included, high-risk pathways were more frequent among patients with loss of preexcitation on Holter/exercise (54% vs 16% persistent, 11% intermittent; P = 0.005). There was one death in a patient with loss of preexcitation on exercise testing, no EP study, and prior drug use. A second patient with persistent WPW and APERP 270 ms required resuscitation following a methadone overdose. Intermittent preexcitation in children does not connote a lower risk AP by EP criteria or reduced symptoms. The low number of pediatric WPW patients who develop preexcited atrial fibrillation or sudden death warrants larger studies to investigate these outcomes. ©2015 Wiley Periodicals, Inc.

  11. A 2003 update of bone physiology and Wolff's Law for clinicians.

    PubMed

    Frost, Harold M

    2004-02-01

    By 1892, Julius Wolff and others realized that mechanical loads can affect bone architecture in living beings, but the mechanisms responsible for this effect were unknown, and it had no known clinical applications. In 2003 we know how this effect occurs and some of its applications. Our load-bearing bones (LBBs) include tibias, femurs, humeri, vertebrae, radii, mandibles, maxillae, wrists, hips, etc (so LBBs are not limited to weight-bearing ones). The strength of such bones and their trabeculae would represent their most important physiologic feature but in the special sense of relative to the size of the typical peak voluntary loads on them. The biologic "machinery" that determines whole-bone strength forms a tissue-level negative feedback system called the mechanostat. Two thresholds make a bone's strains determine its strength by switching on and off the biologic mechanisms that increase or decrease its strength. Equally, two thermostats can determine a room's temperature by switching on and off the room's heating and cooling systems. General features show that the largest voluntary loads on LBBs determine most of their strength after birth. These loads come from muscle forces so muscle strength strongly influences the strength of our LBBs. This process affects, in part, the healing of fractures, bone grafts, osteotomies, and arthrodeses; the bone's ability to endure load-bearing joint and dental endoprostheses; why healthy bones are stronger than the minimum needed to keep voluntary loads from breaking them suddenly or from fatigue; some general functions and disorders of bone modeling and basic multicellular unit-based bone remodeling; some limitations of in vitro data and of pharmaceutical actions; and the fact that many bone-active humoral and local agents have permissive roles in a bone's adaptations and healing, instead of forcing them to occur.

  12. [Should the Isuprel test be performed systematically in Wolff-Parkinson-White syndrome?].

    PubMed

    Brembilla-Perrot, B; Terrier de la Chaise, A; Marçon, F; Cherrier, F; Pernot, C

    1988-10-01

    The isoprenaline (Is) test was designed by Wellens et al. in 1982 to evaluate the effect of catecholamines on the effective refractory period (ERP) of Kent's bundle (K). The purpose of our study was to assess the value of this test in the prognosis of Wolff-Parkinson-White syndrome (WPW), to define its criteria of severity and to determine the usefulness of the test. Out of 33 patients with WPW syndrome, 10 (group I) had a clinical history of severe arrhythmia and 23 (group II) were asymptomatic or had paroxysmal nodal tachycardia. The prognosis of WPW syndrome was evaluated by measuring Kent's bundle ERP under coupled atrial stimulation (S1 S2) and the shortest cycle conducted by K during induced atrial fibrillation (AF) and atrial pacing (AP) both in the basal state (B) and under a 20-30 micrograms Is infusion. (table; see text). Analysis of the results showed constant shortening of ERP in group I and reproduction of the clinical tachycardia in 6 cases. In group II patients isoprenaline unmasked the WPW syndrome in 3 cases and reproduced the clinical tachycardia in 5 cases. The ERP of Kent's bundle evaluated by S1 S2 became smaller or equal to 220 ms in 70 p. 100 of the cases, and this shortening was not specific. The shortest cycle in AF or AP became inferior of equal to 220 ms in only 6 cases, the history being concordant with clinical findings in 4 of them. Altogether, the most reliable and simplest way of evaluating the severity of WPW syndrome is the highest frequency conducted by Kent's bundle in atrial pacing during the Is test which should be performed in all patients in view of its specificity, simplicity and safety.

  13. Native vs photoinduced chemiluminescence in dimethoate determination.

    PubMed

    Catalá-Icardo, M; López-Paz, J L; Choves-Barón, C; Peña-Bádena, A

    2012-01-13

    The determination of dimethoate using either its native chemiluminescent (CL) properties or its photoinduced chemiluminescence obtained by irradiation with a 15 W low-pressure mercury lamp was studied. Thereby, two flow injection systems (FIA) with and without irradiation were exhaustively optimized and their analytical characteristics studied. Better sensitivity and selectivity was found in absence of irradiation, due to the enhancing effect of hexadecylpyridinium chloride (HPC), which acted as a sensitizer. In the developed FIA-CL system, the alkaline hydrolysis of dimethoate with NaOH was performed on-line in presence of HPC. The oxidation of the product of hydrolysis with Ce(IV) in hydrochloric medium induced chemiluminescence. The method provided a limit of detection of only 0.05 ng mL(-1) without any pre-treatment. However, the combination with solid phase extraction allowed the removal of some potential interferents as well as the preconcentration of the pesticide. Finally, the developed method was successfully applied to natural waters with recoveries between 95 and 108%.

  14. Photoinduced electron transfer in ordered polymers

    SciTech Connect

    Jones, G. II.

    1991-12-01

    Long range photoinduced electron transfer between electron donor and acceptor groups is of considerable current interest in terms of strategies for artificial photosynthesis and studies regarding the redox properties of proteins. As part of an extensive study of long range electron transfer involving biopolymers, we have carried out this year investigations of the assembly of electron transfer agents in a system of model short peptides. Also studied is a polyelectrolyte that can adopt a helical conformation when electrostatically complexed with organic dye counter-ions. The principal interest in these systems has to do with the well ordered secondary structures adopted by peptide polymers, and the capabilities for synthetic modification of peptide side chains and end groups with chromophores or electroactive substituents. The present report gives a brief account of the following elements of work related to photochemical electron transfer themes: (1) the synthesis and photochemical characterization of chromophore-bound peptides and amino acid model compounds based on the amino acids, tryptophan and the spacer residue, alanine (Ala); (2) the study of binding of the cationic organic dye to a peptide electrolyte, for which cooperative dye loading and helix formation is important; and (3) completion of the synthesis of a new series of acridinium chromophores that have rod-like'' arrangements of inked aryl rings for assembly of electron donor-acceptor systems that will exhibit especially long lived charge separation.

  15. Photoinduced formation of thiols in human hair.

    PubMed

    Fedorkova, M V; Brandt, N N; Chikishev, A Yu; Smolina, N V; Balabushevich, N G; Gusev, S A; Lipatova, V A; Botchey, V M; Dobretsov, G E; Mikhalchik, E V

    2016-11-01

    Raman, scanning electron, and optical microscopy of hair and spectrophotometry of soluble hair proteins are used to study the effect of UV-vis radiation on white hair. The samples of a healthy subject are irradiated using a mercury lamp and compared with non-irradiated (control) hair. The cuticle damage with partial exfoliation is revealed with the aid of SEM and optical microscopy of semifine sections. Gel filtration chromatography shows that the molecular weight of soluble proteins ranges from 5 to 7kDa. Absorption spectroscopy proves an increase in amount of thiols in a heavier fraction of the soluble proteins of irradiated samples under study. Raman data indicate a decrease in the amount of SS and CS bonds in cystines and an increase in the amount of SH bonds due to irradiation. Such changes are more pronounced in peripheral regions of hair. Conformational changes of hair keratins presumably related to the cleavage of disulfide bonds, follow from variations in amide I and low-frequency Raman bands. An increase in the content of thiols in proteins revealed by both photometric data on soluble proteins and Raman microspectroscopy of hair cuts can be used to develop a protocol of the analysis of photoinduced hair modification.

  16. Photoinduced chemiluminescence determination of carbamate pesticides.

    PubMed

    Catalá-Icardo, M; Meseguer-Lloret, S; Torres-Cartas, S

    2016-05-11

    A liquid chromatography method with post-column photoinduced chemiluminescence (PICL) detection is proposed for the simultaneous determination of eight carbamate pesticides, namely aldicarb, butocarboxim, ethiofencarb, methomyl, methiocarb, thiodicarb, thiofanox and thiophanate-methyl. After chromatographic separation, quinine (sensitizer) was incorporated and the flow passed through an UV lamp (67 s of irradiation time) to obtain the photoproducts, which reacted with acidic Ce(iv) and provided a CL emission. The PICL method showed great selectivity for carbamate pesticides containing sulphur in their chemical structure. A solid-phase extraction process increased sensitivity (LODs ranging from 0.06 to 0.27 ng mL(-1)) and allowed the carbamate pesticides in surface and ground water samples to be determined, with recoveries in the range 87-110% (except for thiophanate-methyl, whose recoveries were between 60 and 75%). The intra- and inter-day precision was evaluated, with RSD ranging from 1.1 to 7.5% and from 2.6 to 12.3%, respectively. A discussion about the PICL mechanism is also included.

  17. Inactivation of tyrosinase photoinduced by pterin

    SciTech Connect

    Laura Dantola, M.; Gojanovich, Aldana D.; Thomas, Andres H.

    2012-08-03

    Highlights: Black-Right-Pointing-Pointer Under UV-A radiation, tirosinase is photoinactivated by pterin. Black-Right-Pointing-Pointer The mechanism involves an electron transfer-initiated process. Black-Right-Pointing-Pointer The photochemical process affects both activities of tyrosinase. -- Abstract: Tyrosinase catalyzes in mammals the first and rate-limiting step in the biosynthesis of the melanin, the main pigment of the skin. Pterins, heterocyclic compounds able to photoinduce oxidation of DNA and its components, accumulate in the skin of patients suffering from vitiligo, a chronic depigmentation disorder in which the protection against UV radiation fails due to the lack of melanin. Aqueous solutions of tyrosinase were exposed to UV-A irradiation (350 nm) in the presence of pterin, the parent compound of oxidized pterins, under different experimental conditions. The enzyme activity in the irradiated solutions was determined by spectrophotometry and HPLC. In this work, we present data that demonstrate unequivocally that the enzyme is photoinactivated by pterin. The mechanism of the photosensitized process involves an electron transfer from tyrosinase to the triplet excited state of pterin, formed after UV-A excitation of pterin. The biological implications of the results are discussed.

  18. Lateral gene transfer, rearrangement, reconciliation

    PubMed Central

    2013-01-01

    Background Models of ancestral gene order reconstruction have progressively integrated different evolutionary patterns and processes such as unequal gene content, gene duplications, and implicitly sequence evolution via reconciled gene trees. These models have so far ignored lateral gene transfer, even though in unicellular organisms it can have an important confounding effect, and can be a rich source of information on the function of genes through the detection of transfers of clusters of genes. Result We report an algorithm together with its implementation, DeCoLT, that reconstructs ancestral genome organization based on reconciled gene trees which summarize information on sequence evolution, gene origination, duplication, loss, and lateral transfer. DeCoLT optimizes in polynomial time on the number of rearrangements, computed as the number of gains and breakages of adjacencies between pairs of genes. We apply DeCoLT to 1099 gene families from 36 cyanobacteria genomes. Conclusion DeCoLT is able to reconstruct adjacencies in 35 ancestral bacterial genomes with a thousand gene families in a few hours, and detects clusters of co-transferred genes. DeCoLT may also be used with any relationship between genes instead of adjacencies, to reconstruct ancestral interactions, functions or complexes. Availability http://pbil.univ-lyon1.fr/software/DeCoLT/ PMID:24564205

  19. String Rearrangement Metrics: A Survey

    NASA Astrophysics Data System (ADS)

    Amir, Amihood; Levy, Avivit

    A basic assumption in traditional pattern matching is that the order of the elements in the given input strings is correct, while the description of the content, i.e. the description of the elements, may be erroneous. Motivated by questions that arise in Text Editing, Computational Biology, Bit Torrent and Video on Demand, and Computer Architecture, a new pattern matching paradigm was recently proposed by [2]. In this model, the pattern content remains intact, but the relative positions may change. Several papers followed the initial definition of the new paradigm. Each paper revealed new aspects in the world of string rearrangement metrics. This new unified view has already proven itself by enabling the solution of an open problem of the mathematician Cayley from 1849. It also gave better insight to problems that were already studied in different and limited situations, such as the behavior of different cost functions, and enabled deriving results for cost functions that were not yet sufficiently analyzed by previous research. At this stage, a general understanding of this new model is beginning to coalesce. The aim of this survey is to present an overview of this recent new direction of research, the problems, the methodologies, and the state-of-the-art.

  20. Utility of Exercise Testing and Adenosine Response for Risk Assessment in Children with Wolff-Parkinson-White Syndrome.

    PubMed

    Ergul, Yakup; Ozturk, Erkut; Ozyilmaz, Isa; Unsal, Serkan; Carus, Hayat; Tola, Hasan Tahsin; Tanidir, Ibrahim Cansaran; Guzeltas, Alper

    2015-01-01

    We aimed to determine the correlation between noninvasive testing (exercise stress testing [EST] and adenosine responsiveness of accessory pathway [AP] ) and invasive electrophysiology study (EPS) for assessment antegrade conduction of the AP in Wolff-Parkinson-White syndrome. This prospective, observational study enrolled 40 children (58% male children, median age of 13 years, and median weight of 47.5 kg) with Wolff-Parkinson-White syndrome. Conduction through the AP to a cycle length of ≤250 ms was considered rapid or high-risk; otherwise, patients were nonrapid or low-risk. The sudden disappearance of the delta-wave was seen in 10 cases (25%) during EST. Accessory pathway was found to be high-risk in 13 cases (13/40, 32.5%) while the accessory path was identified as low-risk in 27 cases; however, six patients (15%) had blocked AP conduction with adenosine during EPS. Low-risk classification by EST alone to identify patients with nonrapid conduction in baseline EPS had a specificity of 93% and a positive predictive value of 90% (accuracy 54%). Blocked AP conduction with adenosine as a marker of nonrapid baseline AP conduction had a specificity of 93% and a positive predictive value of 84%. Finally, AP was adenosine nonresponsive in the majority of patients (28/30, 93%) with persistent delta-waves, 40% of those who had a sudden disappearance of delta-waves had an adenosine-responsive AP (P value: .028). Abrupt loss of preexcitation during EST and blocked AP conduction with adenosine had high specificity and positive predictive value for nonrapid and low-risk antegrade conduction during baseline invasive EPS. Successful risk stratification of pediatric patients with Wolff-Parkinson-White is possible through the use of EST and the adenosine responsiveness of AP. © 2015 Wiley Periodicals, Inc.

  1. A randomized study of prophylactic catheter ablation in asymptomatic patients with the Wolff-Parkinson-White syndrome.

    PubMed

    Pappone, Carlo; Santinelli, Vincenzo; Manguso, Francesco; Augello, Giuseppe; Santinelli, Ornella; Vicedomini, Gabriele; Gulletta, Simone; Mazzone, Patrizio; Tortoriello, Valter; Pappone, Alessia; Dicandia, Cosimo; Rosanio, Salvatore

    2003-11-06

    Young age and inducibility of atrioventricular reciprocating tachycardia or atrial fibrillation during invasive electrophysiological testing identify asymptomatic patients with a Wolff-Parkinson-White pattern on the electrocardiogram as being at high risk for arrhythmic events. We tested the hypothesis that prophylactic catheter ablation of accessory pathways would provide meaningful and durable benefits as compared with no treatment in such patients. From 1997 to 2002, among 224 eligible asymptomatic patients with the Wolff-Parkinson-White syndrome, patients at high risk for arrhythmias were randomly assigned to radio-frequency catheter ablation of accessory pathways (37 patients) or no treatment (35 patients). The end point was the occurrence of arrhythmic events over a five-year follow-up period. Patients assigned to ablation had base-line characteristics that were similar to those of the controls. Two patients in the ablation group (5 percent) and 21 in the control group (60 percent) had arrhythmic events. One control patient had ventricular fibrillation as the presenting arrhythmia. The five-year Kaplan-Meier estimates of the incidence of arrhythmic events were 7 percent among patients who underwent ablation and 77 percent among the controls (P<0.001 by the log-rank test); the risk reduction with ablation was 92 percent (relative risk, 0.08; 95 percent confidence interval, 0.02 to 0.33; P<0.001). Prophylactic accessory-pathway ablation markedly reduces the frequency of arrhythmic events in asymptomatic patients with the Wolff-Parkinson-White syndrome who are at high risk for such events. Copyright 2003 Massachusetts Medical Society

  2. A study of dynamic finite size scaling behavior of the scaling functions—calculation of dynamic critical index of Wolff algorithm

    NASA Astrophysics Data System (ADS)

    Gündüç, Semra; Dilaver, Mehmet; Aydın, Meral; Gündüç, Yiğit

    2005-02-01

    In this work we have studied the dynamic scaling behavior of two scaling functions and we have shown that scaling functions obey the dynamic finite size scaling rules. Dynamic finite size scaling of scaling functions opens possibilities for a wide range of applications. As an application we have calculated the dynamic critical exponent (z) of Wolff's cluster algorithm for 2-, 3- and 4-dimensional Ising models. Configurations with vanishing initial magnetization are chosen in order to avoid complications due to initial magnetization. The observed dynamic finite size scaling behavior during early stages of the Monte Carlo simulation yields z for Wolff's cluster algorithm for 2-, 3- and 4-dimensional Ising models with vanishing values which are consistent with the values obtained from the autocorrelations. Especially, the vanishing dynamic critical exponent we obtained for d=3 implies that the Wolff algorithm is more efficient in eliminating critical slowing down in Monte Carlo simulations than previously reported.

  3. Spontaneous Transition of Double Tachycardias with Atrial Fusion in a Patient with Wolff-Parkinson-White Syndrome

    PubMed Central

    Kim, Dongmin

    2016-01-01

    Among patients with Wolff-Parkinson-White syndrome, atrioventricular reciprocating tachycardia (AVRT) and atrioventricular nodal reentrant tachycardia (AVNRT) can coexist in a single patient. Direct transition of both tachycardias is rare; however, it can occur after premature atrial or ventricular activity if the cycle lengths of the two tachycardias are similar. Furthermore, persistent atrial activation by an accessory pathway (AP) located outside of the AV node during ongoing AVNRT is also rare. This article describes a case of uncommon atrial activation by an AP during AVNRT and gradual transition of the two supraventricular tachycardias without any preceding atrial or ventricular activity in a patient with preexcitation syndrome. PMID:27482269

  4. [Obvious or inapparent Wolff-Parkinson-White syndrome associated with duality of nodal conduction. Apropos of 4 cases].

    PubMed

    Motté, G; Belhassen, B; Bodereau, P

    1979-03-01

    In a series of 48 patients undergoing electrophysiological investigation for attacks of reciprocating tachycardia related to concealed or overt Wolff-Parkinson-White syndrome in sinus rhythm, 4 patients were found to have duality of nodal conduction. This association was responsible for several tachycardia circuits: in 2 patients the activation passed constantly retrogradely through the accessory pathway and then either through the slow nodal pathway or the rapid nodal pathway in the anterograde direction. In the other two patients, in addition to classical orthodromic tachycardia, purely intranodal reciprocating rhythms giving rise to sustained tachycardia in one case and to simple echos in the other, were observed.

  5. Ventricular fibrillation development following atrial fibrillation after the ingestion of sildenaphil in a patient with Wolff-Parkinson-White syndrome

    PubMed Central

    Inci, Sinan; Izgu, Ibrahim; Aktas, Halil; Dogan, Pinar; Dogan, Ali

    2015-01-01

    Summary Complications in the accessory pathway in Wolff-Parkinson-White (WPW) syndrome could cause different clinical conditions by inducing different arrhythmias. Atrial fibrillation (AF) is one of these arrhythmias and is important as it causes life-threatening arrhythmias. It is known that some drugs, underlying cardiac diseases, and the number of accessory pathways, cause a predisposition to this condition. In the current report, we presented a patient with WPW who was admitted to the emergency department with AF, wide QRS and a rapid ventricular response that progressed to ventricular fibrillation. PMID:26361569

  6. The cytogenetics of mammalian autosomal rearrangements

    SciTech Connect

    Daniel, A. )

    1988-01-01

    This book is covered under the following topics: Ascertainment and risks of recombinant progeny; Infertility, gametic selection, and fetal loss; origin of chromosome rearrangements; and Some implications of chromosome breakpoints.

  7. Glycolytic regulation of cell rearrangement in angiogenesis

    PubMed Central

    Cruys, Bert; Wong, Brian W.; Kuchnio, Anna; Verdegem, Dries; Cantelmo, Anna Rita; Conradi, Lena-Christin; Vandekeere, Saar; Bouché, Ann; Cornelissen, Ivo; Vinckier, Stefan; Merks, Roeland M. H.; Dejana, Elisabetta; Gerhardt, Holger; Dewerchin, Mieke; Bentley, Katie; Carmeliet, Peter

    2016-01-01

    During vessel sprouting, endothelial cells (ECs) dynamically rearrange positions in the sprout to compete for the tip position. We recently identified a key role for the glycolytic activator PFKFB3 in vessel sprouting by regulating cytoskeleton remodelling, migration and tip cell competitiveness. It is, however, unknown how glycolysis regulates EC rearrangement during vessel sprouting. Here we report that computational simulations, validated by experimentation, predict that glycolytic production of ATP drives EC rearrangement by promoting filopodia formation and reducing intercellular adhesion. Notably, the simulations correctly predicted that blocking PFKFB3 normalizes the disturbed EC rearrangement in high VEGF conditions, as occurs during pathological angiogenesis. This interdisciplinary study integrates EC metabolism in vessel sprouting, yielding mechanistic insight in the control of vessel sprouting by glycolysis, and suggesting anti-glycolytic therapy for vessel normalization in cancer and non-malignant diseases. PMID:27436424

  8. Photo-induced foveal injury after viewing a solar eclipse.

    PubMed

    Källmark, Fredrik P; Ygge, Jan

    2005-10-01

    To study the injury to and possible recovery of the visual function and foveal morphology in patients with photo-induced foveal injury due to watching the solar eclipse of August 11th, 1999 in Stockholm, Sweden. Fifteen patients, all of whom viewed the solar eclipse, were followed for 1 year, during which their visual symptoms were recorded and visual acuity (VA) was tested, and ophthalmoscopy and scanning laser ophthalmoscopy were performed. Photo-induced foveal injury gave rise to subjective visual disturbances, reduced VA and morphological changes in the fovea. Central scotomas could still be seen in all patients 1 year after the foveal injury. Photo-induced foveal injury gave rise to subjective visual disturbances, reduced VA and morphological changes in the fovea. Scanning laser ophthalmoscopy offers the possibility of detailed examination of small retinal lesions, which can sometimes be difficult to localize with ophthalmoscopy.

  9. Photoinduced electro-optics measurements of biosilica transformation to cristobalite

    NASA Astrophysics Data System (ADS)

    Fuchs, Ido; Aluma, Yaniv; Ilan, Micha; Kityk, Iwan; Mastai, Yitzhak

    2015-03-01

    In this paper we studied the photoinduced electro optics effects in the thermal transformation process of biosilica to cristobalite, at a relatively low temperature and ambient pressure. This process was characterized by a variety of standards techniques with emphasis on linear electro optic effect measurements. Overall we demonstrated that photoinduced electro optics measurements are very sensitive to the transformation from amorphous structure of silica in the natural sponge samples to laminar string morphology of cristobalite. With this technique we could probe the change in the samples chirality from achiral bio silica to chiral cristobalite structure. Furthermore it is shown that natural biosilica have photoinduced linear electro optics respond indicating the chiral natural of biosilica.

  10. Photoinduced structural changes to protein kinase A

    NASA Astrophysics Data System (ADS)

    Rozinek, Sarah C.; Thomas, Robert J.; Brancaleon, Lorenzo

    2014-03-01

    The importance of porphyrins in organisms is underscored by the ubiquitous biological and biochemical functions that are mediated by these compounds and by their potential biomedical and biotechnological applications. Protoporphyrin IX (PPIX) is the precursor to heme and has biomedical applications such as its use as a photosensitizer in phototherapy and photodetection of cancer. Among other applications, our group has demonstrated that low-irradiance exposure to laser irradiation of PPIX, Fe-PPIX, or meso-tetrakis (4-sulfonatophenyl) porphyrin (TSPP) non-covalently docked to a protein causes conformational changes in the polypeptide. Such approach can have remarkable consequences in the study of protein structure/function relationship and can be used to prompt non-native protein properties. Therefore we have investigated protein kinase A (PKA), a more relevant protein model towards the photo-treatment of cancer. PKA's enzymatic functions are regulated by the presence of cyclic adenosine monophosphate for intracellular signal transduction involved in, among other things, stimulation of transcription, tumorigenesis in Carney complex and migration of breast carcinoma cells. Since phosphorylation is a necessary step in some cancers and inflammatory diseases, inhibiting the protein kinase, and therefore phosphorylation, may serve to treat these diseases. Changes in absorption, steady-state fluorescence, and fluorescence lifetime indicate: 1) both TSPP and PPIX non-covalently bind to PKA where they maintain photoreactivity; 2) absorptive photoproduct formation occurs only when PKA is bound to TSPP and irradiated; and 3) PKA undergoes secondary structural changes after irradiation with either porphyrin bound. These photoinduced changes could affect the protein's enzymatic and signaling capabilities.

  11. Photoinduced charge separation by polymer-bound chromophores

    SciTech Connect

    Rodgers, M.A.J.

    1991-09-01

    This project has examined the photodynamic behavior of water-soluble polymers that have covalently linked hydrophobic chromophores spaced along the chains. These polymeric systems have been examined for photoinduced charge separation with electron-accepting ions having different total charge. Focus has been on the excited singlet (S{sub 1}) state formed by laser flash absorption. The effects of pH and ionic strength -- factors that govern the conformational nature of the polymer in solution -- have been studied. A second major effort has been to study photoinduced redox processes involving excited states of water-soluble variants of anthracene and acridine. 27 refs., 16 figs., 2 tabs.

  12. Quantitative analysis of sideband coupling in photoinduced force microscopy

    NASA Astrophysics Data System (ADS)

    Jahng, Junghoon; Kim, Bongsu; Lee, Eun Seong; Potma, Eric Olaf

    2016-11-01

    We present a theoretical and experimental analysis of the cantilever motions detected in photoinduced force microscopy (PiFM) using the sideband coupling detection scheme. In sideband coupling, the cantilever dynamics are probed at a combination frequency of a fundamental mechanical eigenmode and the modulation frequency of the laser beam. Using this detection mode, we develop a method for reconstructing the modulated photoinduced force gradient from experimental parameters in a quantitative manner. We show evidence, both theoretically and experimentally, that the sideband coupling detection mode provides PiFM images with superior contrast compared to images obtained when detecting the cantilever motions directly at the laser modulation frequency.

  13. Photo-induced chaos in the Briggs-Rauscher reaction

    NASA Astrophysics Data System (ADS)

    Okazaki, Noriaki; Hanazaki, Ichiro

    1998-07-01

    Discovery of the photo-induced chaos in the Briggs-Rauscher system is reported. The chaotic oscillations were observed between the large- and the small-amplitude simple oscillatory states existent in low and high light intensity regions, respectively. Period-doubling sequence from the large-amplitude oscillations to the chaos was observed. Deterministic nature of the chaos was confirmed by the next-amplitude return map. The stretching and folding mechanism of the trajectories was revealed through the three-dimensional attractor reconstructed via the singular value decomposition method. The chemical origin of the photoinduced chaos is discussed based on the photoautocatalysis of HIO2.

  14. [Prevalence and electrocardiographic forms of the Wolff-Parkinson-White syndrome].

    PubMed

    Soria, R; Guize, L; Fernandez, F; Chaouat, J C; Chrétien, J M

    1982-12-01

    In a routine electrocardiographic study of 133929 subjects aged from 20 to 73, 136 cases of the Wolff-Parkinson-White syndrome were detected, 6 with intermittent pre-excitation. In this study, the prevelance of WPW was about 1 in a 1000, the highest incidence being in the 20-40 year age group with an equal sex ratio. The ECG analysis of the 136 cases consisted in determining the orientation of the delta wave in the precordial leads to establish the right or left ventricular origin of the pre-excitation, calculating the direction of the delta wave vector in the frontal plane to find out the anterior, lateral or posterior origin of the pre-excitation and analyse the position of the QRS axis to assess the appearances of the latest ventricular activity. The 136 ECGs were then classified according to electrophysiological criteria and the results of mapping: 1. Left ventricular pre-excitation; 74 cases characterised by a dominant delta wave in the right precordial leads. These cases were subdivided into: - 30 cases with posterior paraseptal pre-excitation, axis of the delta wave deviated superiorly and to the left, between -30 degrees and -60 degrees; - 20 cases of lateral pre-excitation with the vector of the delta wave deviated inferiorly and to the right between +100 degrees and +120 degrees; - 24 cases of anterior paraseptal pre-excitation with high amplitude delta and QRS deflections in all precordial leads and a delta wave axis between +50 degrees and +80 degrees. 2. Right ventricular pre-excitation; 62 cases characterised by a negative or isoelectric delta wave in the right precordial leads, including: - 14 posterior paraseptal pre-excitation with significant delta wave axis deviation between -30 degrees and -60 degrees; - 33 lateral pre-excitation with the delta and QRS axis pointing directly to the left at about 0 degrees; - 15 cases of anterior paraseptal pre-excitation with the delta wave axis between +50 degrees and +80 degrees. The cases with terminal forces

  15. The nature and role of bridged carbonyl intermediates in theultrafast photo-induced rearrangement of Ru3(CO)12.

    SciTech Connect

    Glascoe, Elizabeth A.; Kling, Matthias F.; Shanoski, Jennifer E.; Harris, Charles B.

    2005-09-18

    The photochemistry of the trimetal cluster,Ru(3)(CO)12, was investigated on the ultrafast timescale using UV-vis pump, infrared probe spectroscopy in order to study the transient intermediates formed upon photoexcitation.

  16. Measurements of Photo-induced Changes in Conjugated Polymers

    DOE R&D Accomplishments Database

    Seager, C. H.; Sinclair, M. B.; Mc Branch, D.; Heeger, A. J.; Baker, G. L.

    1991-01-01

    We have used the highly sensitive technique of Photothermal Deflection Spectroscopy (PDS) to measure changes in the infrared absorption spectra of MEHPPV, P3HT and Polydiacetylene-4BCMU induced by pumping these polymers with light above the {pi} - {pi}* transition energy. In contrast to previous chopped light transmission measurements of these effects, the PDS technique can directly measure the buildup or decay of the absorption coefficient, {alpha}, on the time scale of second to days. In the case of MEHPPV we observe that the time scale of seconds to days. In the case of MEHPPV we observe that above-gap light causes the appearance of a broad infrared peak in {alpha}, which continues to grow-in hours after the pump light is first applied. For this polymer the general shape of the absorption spectra in the unpumped state mimics the photo-induced changes, suggesting that remnant photo-induced states determine the maximum transparency observed under normal experimental conditions. For P3HT and to a lesser extent, MEHPPV, we also observe irreversible photo-induced absorption components which we tentatively identify with photo-induced oxidation of the polymer matrix.

  17. Linewidths of photoinduced L x rays of uranium

    NASA Astrophysics Data System (ADS)

    Hoszowska, J.; Dousse, J.-Cl.; Rhême, Ch.

    1994-07-01

    High-resolution measurements of the photoinduced L x-ray spectrum of metallic uranium were performed with a transmission-type bent-crystal spectrometer. Linewidths of 32 L x-ray emission lines were extracted. Nonlifetime broadening effects, such as multiple-vacancy configuration states and multiplet splitting, that influence the line profiles are discussed.

  18. Linewidths of photoinduced [ital L] x rays of uranium

    SciTech Connect

    Hoszowska, J.; Dousse, J.; Rheme, C. )

    1994-07-01

    High-resolution measurements of the photoinduced [ital L] x-ray spectrum of metallic uranium were performed with a transmission-type bent-crystal spectrometer. Linewidths of 32 [ital L] x-ray emission lines were extracted. Nonlifetime broadening effects, such as multiple-vacancy configuration states and multiplet splitting, that influence the line profiles are discussed.

  19. Molecular mechanisms of chromosomal rearrangement in fungi.

    PubMed

    Fierro, F; Martín, J F

    1999-01-01

    Both sexual and asexual fungi undergo chromosomal rearrangements, which are the main cause of karyotype variability among the populations. Different recombination processes can produce chromosomal reorganizations, both during mitosis and meiosis, but other mechanisms operate to limit the extent of the rearrangements; some of these mechanisms, such as the RIP (repeat-induced point mutations) of Neurospora crassa, have been well established for sexual fungi. In laboratory strains, treatments such as mutation and transformation enhance the appearance of chromosomal rearrangements. Different DNA sequences present in fungal genomes are able to promote these reorganizations; some of these sequences are involved in well-regulated processes (e.g., site-specific recombination) but most of them act simply as substrates for recombination events leading to DNA rearrangements. In Penicillium chrysogenum we have found that short specific DNA sequences are involved in tandem reiterations leading to amplification of the cluster of the penicillin biosynthesis genes. In some cases, specific chromosomal rearrangements have been associated with particular phenotypes (as occurs in adaptive-like mutants of Candida albicans and Candida stellatoidea), and they may play a role in genetic variability for environmental adaptation.

  20. Cortical microtubule rearrangements and cell wall patterning

    PubMed Central

    Oda, Yoshihisa

    2015-01-01

    Plant cortical microtubules, which form a highly ordered array beneath the plasma membrane, play essential roles in determining cell shape and function by directing the arrangement of cellulosic and non-cellulosic compounds on the cell surface. Interphase transverse arrays of cortical microtubules self-organize through their dynamic instability and inter-microtubule interactions, and by branch-form microtubule nucleation and severing. Recent studies revealed that distinct spatial signals including ROP GTPase, cellular geometry, and mechanical stress regulate the behavior of cortical microtubules at the subcellular and supercellular levels, giving rise to dramatic rearrangements in the cortical microtubule array in response to internal and external cues. Increasing evidence indicates that negative regulators of microtubules also contribute to the rearrangement of the cortical microtubule array. In this review, I summarize recent insights into how the rearrangement of the cortical microtubule array leads to proper, flexible cell wall patterning. PMID:25904930

  1. Facile Oxidative Rearrangements Using Hypervalent Iodine Reagents

    PubMed Central

    Singh, Fateh V; Rehbein, Julia; Wirth, Thomas

    2012-01-01

    Aromatic substituents migrate in a novel oxidative cyclization mediated by iodine(III) reagents. 4-Arylbut-3-enoic acids are cyclized and rearranged to 4-arylfuran-2(5H)-ones by hypervalent iodine compounds in good to excellent yields under mild reaction conditions. Other ring sizes are also accessible. The mechanism of the reaction is described in detail, and calculations highlight the cationic nature of the intermediates in the rearrangement. The fast access to heavily substituted furanones is used for the synthesis of biologically active derivatives. PMID:24551514

  2. New anticancer antibiotic acts through diradical rearrangement

    SciTech Connect

    Stinson, S. )

    1990-05-28

    This paper reports that chemists have found and characterized an anticancer antibiotic, dynemicin A, that may be the fouth of a series of antibiotics that act by metabolic rearrangement to a diradical. If true, diradical precursors may represent an antibiotic strategy that evolved widely in nature. And, there may be many more anticancer antibiotics awaiting discovery. Also, the unique internal trigger that seems to set off the dynemicin rearrangement gives chemists a new understanding of how these compounds work. If, indeed, the anthraquinone nucleus in dynemicin A binds by intercalation between strands of DNA as is now thought, chemists will learn more about how to deliver drugs to specific sites.

  3. Electrophysiology testing and catheter ablation are helpful when evaluating asymptomatic patients with Wolff-Parkinson-White pattern: the con perspective.

    PubMed

    Skanes, Allan C; Obeyesekere, Manoj; Klein, George J

    2015-09-01

    The association between asymptomatic Wolff-Parkinson-White (WPW) syndrome and sudden cardiac death (SCD) has been well documented. The inherent properties of the accessory pathway determine the risk of SCD in WPW, and catheter ablation essentially eliminates this risk. An approach to WPW syndrome is needed that incorporates the patient's individualized considerations into the decision making. Patients must understand that there is a trade-off of a small immediate risk of an invasive approach for elimination of a small lifetime risk of the natural history of asymptomatic WPW. Clinicians can minimize the invasive risk by only performing ablation for patients with at-risk pathways. Copyright © 2015 Elsevier Inc. All rights reserved.

  4. Wolff-Parkinson-White syndrome type B and left bundle-branch block: electrophysiologic and radionuclide study

    SciTech Connect

    Rakovec, P.; Kranjec, I.; Fettich, J.J.; Jakopin, J.; Fidler, V.; Turk, J.

    1985-01-01

    Coinciding left bundle-branch block and Wolff-Parkinson-White syndrome type B, a very rare electrocardiographic occurrence, was found in a patient with dilated cardiomyopathy. Electrophysiologic study revealed eccentric retrograde atrial activation during ventricular pacing, suggesting right-sided accessory pathway. At programmed atrial pacing, effective refractory period of the accessory pathway was 310 ms; at shorter pacing coupling intervals, normal atrioventricular conduction with left bundle-branch block was seen. Left bundle-branch block was seen also with His bundle pacing. Radionuclide phase imaging demonstrated right ventricular phase advance and left ventricular phase delay; both right and left ventricular phase images revealed broad phase distribution histograms. Combined electrophysiologic and radionuclide investigations are useful to disclose complex conduction abnormalities and their mechanical correlates.

  5. Rearrangement Reactions of 1,1-Divinyl-2-phenylcyclopropanes

    PubMed Central

    2015-01-01

    1,1-Divinyl-2-phenylcyclopropanes are entry points to a rich area of rearrangement chemistry. With N,N-diallyl amide substrates, tandem radical cyclizations can be initiated at room temperature. Warming provides products of pure thermal rearrangements with acids, ester, and amides. These isomerizations give vinylcyclopentenes resulting from divinylcyclopropane rearrangements and more deeply rearranged tricyclic spirolactams resulting from aromatic Cope rearrangements followed by ene reactions. Conversion of the carbonyl group to an alcohol or ether opens retro-ene pathways followed by either tautomerization or Claisen rearrangement. PMID:25530073

  6. Comparison of the accuracy of three algorithms in predicting accessory pathways among adult Wolff-Parkinson-White syndrome patients.

    PubMed

    Maden, Orhan; Balci, Kevser Gülcihan; Selcuk, Mehmet Timur; Balci, Mustafa Mücahit; Açar, Burak; Unal, Sefa; Kara, Meryem; Selcuk, Hatice

    2015-12-01

    The aim of this study was to investigate the accuracy of three algorithms in predicting accessory pathway locations in adult patients with Wolff-Parkinson-White syndrome in Turkish population. A total of 207 adult patients with Wolff-Parkinson-White syndrome were retrospectively analyzed. The most preexcited 12-lead electrocardiogram in sinus rhythm was used for analysis. Two investigators blinded to the patient data used three algorithms for prediction of accessory pathway location. Among all locations, 48.5% were left-sided, 44% were right-sided, and 7.5% were located in the midseptum or anteroseptum. When only exact locations were accepted as match, predictive accuracy for Chiang was 71.5%, 72.4% for d'Avila, and 71.5% for Arruda. The percentage of predictive accuracy of all algorithms did not differ between the algorithms (p = 1.000; p = 0.875; p = 0.885, respectively). The best algorithm for prediction of right-sided, left-sided, and anteroseptal and midseptal accessory pathways was Arruda (p < 0.001). Arruda was significantly better than d'Avila in predicting adjacent sites (p = 0.035) and the percent of the contralateral site prediction was higher with d'Avila than Arruda (p = 0.013). All algorithms were similar in predicting accessory pathway location and the predicted accuracy was lower than previously reported by their authors. However, according to the accessory pathway site, the algorithm designed by Arruda et al. showed better predictions than the other algorithms and using this algorithm may provide advantages before a planned ablation.

  7. [The natural history of 270 cases of Wolff-Parkinson-White syndrome in a survey of the general population].

    PubMed

    Soria, R; Guize, L; Chretien, J M; Le Heuzey, J Y; Lavergne, T; Desnos, M; Hagege, A; Guerre, Y

    1989-03-01

    Among 226,464 ambulatory subjects who underwent medical check-ups over a 15-year period, 270 were found to have Wolff-Parkinson-White syndrome (1.2 case in 1,000). The syndrome was more frequent in men (181 cases, 1.4 p. 1,000) than in women (89 cases, 0.9 p. 1,000). 222 subjects were aged from 20 to 49 years (1.4 p. 1,000) and only 48 were between 50 and 80 years of age (0.7 p. 1,000). 197 subjects were re-evaluated: 119 (60.4 p. 100) complained of palpitations and 78 (39.6 p. 100) were asymptomatic. Palpitations began at all ages, even after 50 years, and usually proceeded in short attacks lasting a few seconds or minutes, with a mean recurrence rate of 5 attacks per annum (76.4 p. 100). This constant pattern sometimes was interrupted for months or years. Conversely, in a minority of cases (23.5 p. 100) an unexpected accentuation occurred which lasted for hours or days. As years went by, palpitations tented to decrease and disappear. The pre-excitation area and its degree of fusion with the normal ventricular activation had no influence on the origin and frequency of palpitations. In contrast, sustained tachycardia seemed to be more frequent in cases with lateral and posterior left pre-excitation. Among 270 subjects with pre-excitation syndrome, 7 died including 4 whose death was not due to a cardiac disease, 2 who died suddenly and 1 who succumbed to ventricular tachycardia after a road accident. None of these patients had an associated heart disease. These last 3 cases might contribute to alter the usually favourable prognosis of Wolff-Parkinson-White syndrome.

  8. Photo-orientation of azobenzene-containing liquid-crystalline materials by means of domain structure rearrangement.

    PubMed

    Bogdanov, Alexey V; Vorobiev, Andrey Kh

    2013-11-07

    A novel mechanism of photo-orientation of azobenzene-containing liquid-crystalline materials is proposed. This mechanism is based on the notion of photochemically induced domain rearrangement driven by destabilization of liquid-crystalline phase in light absorbing domains due to photochemical formation of non-mesogenic cis-azobenzene moieties. The experimental evidence of photoinduced movement of a domain boundary is presented, and the velocity of this movement is measured. A mathematical model for photo-orientation of a polydomain azobenzene-containing material is formulated. The values of model parameters for a liquid-crystalline azopolymer have been measured in separate experiments. Theoretical predictions demonstrate quantitative agreement with the experimental observations.

  9. Photoinduced "stick-slip" on superhydrophilic semiconductor surfaces.

    PubMed

    Denison, Kieth R; Boxall, Colin

    2007-04-10

    Transparent mesoporous TiO2 (M-TiO2) thin films were prepared on quartz via a reverse micelle, sol-gel, spin-coating technique. Films were characterized by atomic force microscopy (AFM) and Raman and UV-vis spectroscopies and were found to be mostly anatase with low surface roughness (Rt approximately 5 nm). The time dependence of film photoinduced superhydrophilicity (PISH) was measured by observation of the spreading of a sessile water drop using a new, continuous measurement technique wherein the drop was first applied to the semiconductor surface and then was filmed while it and the underlying substrate were illuminated by 315 nm ultraband gap light. Results obtained at 100% relative humidity (RH) at 293 K showed that drops on M-TiO2 surfaces exhibited a photoinduced "stick-slip" behavior, the first time such an effect has been observed. The thermodynamic driving force for this photoinduced stick-slip was the departure of the system from capillary equilibrium as, with increasing illumination time, the concentration of surface Ti-OH groups increased and the equilibrium contact angle of the drop, theta0, decreased. A simple theoretical description of photoinduced stick-slip is derived and is used to calculate a value of the potential energy barrier associated with surface inhomogeneities that oppose onset of movement of the triple line, U = 6.63 x 10(-6) J m(-1). This is the first time that U has been quantified for a surface with photoinduced superhydrophilicity. Triple line retreat measurements on an evaporating drop on M-TiO2 in the dark, RH = 60%, T = 293 K, gave a value of U = 9.4 x 10(-6) J m(-1), indicating that U decreases upon UV illumination and that U in the light is primarily associated with inhomogeneities that are unaffected by an increase in the surface Ti-OH population, such as the physical roughness of the surface. In the dark evaporation experiment, the drop was found to retreat with an areal velocity of 1.48 x 10(-8) m2 s(-1). However, under UV

  10. Facility rearrangement scoping study: Draft letter report

    SciTech Connect

    Not Available

    1987-04-17

    We assessed the feasibility of designing the salt repository layouts so that shafts, surface structures and facilities would be totally within the north-east (NE) and center-east (CE) (one square mile) sections of the 9 square mile Deaf Smith site. With the latest version of the SCP-Conceptual Design as the basis, rearrangement analyses were conducted for the surface and subsurface layouts. For the rearranged layouts that were workable, impact assessments, relative to the SCP-Conceptual Design, were performed. This study concluded that, on a qualitative basis, the salt repository surface facilities can be relocated to within the north-east and center-east sections of the site. A suitable subsurface layout can be designed to accommodate this rearrangement. The resultant surface rearrangement is depicted. The two study sections (NE and CE) are emphasized on this figure. For reference, the location of the surface facilities in the SCP-Conceptual Design is also shown. 11 refs., 1 tab.

  11. Genomic rearrangements at rrn operons in Salmonella.

    PubMed

    Helm, R Allen; Lee, Alison G; Christman, Harry D; Maloy, Stanley

    2003-11-01

    Most Salmonella serovars are general pathogens that infect a variety of hosts. These "generalist" serovars cause disease in many animals from reptiles to mammals. In contrast, a few serovars cause disease only in a specific host. Host-specific serovars can cause a systemic, often fatal disease in one species yet remain avirulent in other species. Host-specific Salmonella frequently have large genomic rearrangements due to recombination at the ribosomal RNA (rrn) operons while the generalists consistently have a conserved chromosomal arrangement. To determine whether this is the result of an intrinsic difference in recombination frequency or a consequence of lifestyle difference between generalist and host-specific Salmonella, we determined the frequency of rearrangements in vitro. Using lacZ genes as portable regions of homology for inversion analysis, we found that both generalist and host-specific serovars of Salmonella have similar tolerances to chromosomal rearrangements in vitro. Using PCR and genetic selection, we found that generalist and host-specific serovars also undergo rearrangements at rrn operons at similar frequencies in vitro. These observations indicate that the observed difference in genomic stability between generalist and host-specific serovars is a consequence of their distinct lifestyles, not intrinsic differences in recombination frequencies.

  12. Light chain replacement: a new model for antibody gene rearrangement

    PubMed Central

    1995-01-01

    A functional B cell antigen receptor is thought to regulate antibody gene rearrangement either by stopping further rearrangement (exclusion) or by promoting additional rearrangement (editing). We have developed a new model to study the regulation of antibody gene rearrangement. In this model, we used gene targeting to replace the J kappa region with a functional V kappa-J kappa light chain gene. Two different strains of mice were created; one, V kappa 4R, has a V kappa 4-J kappa 4 rearrangement followed by a downstream J kappa 5 segment, while the other, V kappa 8R, has a V kappa 8-J kappa 5 light chain. Here, we analyze the influence of these functional light chains on light chain rearrangement. We show that some V kappa 4R and V kappa 8R B cells only have the V kappa R light chain rearrangement, whereas others undergo additional rearrangements. Additional rearrangement can occur not only at the other kappa allele or isotype (lambda), but also at the targeted locus in both V kappa 4R and V kappa 8R. Rearrangement to the downstream J kappa 5 segment is observed in V kappa 4R, as is deletion of the targeted locus in both V kappa 4R and V kappa 8R. The V kappa R models illustrate that a productively rearranged light chain can either terminate further rearrangement or allow further rearrangement. We attribute the latter to editing of autoantibodies and to corrections of dysfunctional receptors. PMID:7629511

  13. Rearrangement moves on rooted phylogenetic networks.

    PubMed

    Gambette, Philippe; van Iersel, Leo; Jones, Mark; Lafond, Manuel; Pardi, Fabio; Scornavacca, Celine

    2017-08-01

    Phylogenetic tree reconstruction is usually done by local search heuristics that explore the space of the possible tree topologies via simple rearrangements of their structure. Tree rearrangement heuristics have been used in combination with practically all optimization criteria in use, from maximum likelihood and parsimony to distance-based principles, and in a Bayesian context. Their basic components are rearrangement moves that specify all possible ways of generating alternative phylogenies from a given one, and whose fundamental property is to be able to transform, by repeated application, any phylogeny into any other phylogeny. Despite their long tradition in tree-based phylogenetics, very little research has gone into studying similar rearrangement operations for phylogenetic network-that is, phylogenies explicitly representing scenarios that include reticulate events such as hybridization, horizontal gene transfer, population admixture, and recombination. To fill this gap, we propose "horizontal" moves that ensure that every network of a certain complexity can be reached from any other network of the same complexity, and "vertical" moves that ensure reachability between networks of different complexities. When applied to phylogenetic trees, our horizontal moves-named rNNI and rSPR-reduce to the best-known moves on rooted phylogenetic trees, nearest-neighbor interchange and rooted subtree pruning and regrafting. Besides a number of reachability results-separating the contributions of horizontal and vertical moves-we prove that rNNI moves are local versions of rSPR moves, and provide bounds on the sizes of the rNNI neighborhoods. The paper focuses on the most biologically meaningful versions of phylogenetic networks, where edges are oriented and reticulation events clearly identified. Moreover, our rearrangement moves are robust to the fact that networks with higher complexity usually allow a better fit with the data. Our goal is to provide a solid basis for

  14. Dynamics of genome rearrangement in bacterial populations.

    PubMed

    Darling, Aaron E; Miklós, István; Ragan, Mark A

    2008-07-18

    Genome structure variation has profound impacts on phenotype in organisms ranging from microbes to humans, yet little is known about how natural selection acts on genome arrangement. Pathogenic bacteria such as Yersinia pestis, which causes bubonic and pneumonic plague, often exhibit a high degree of genomic rearrangement. The recent availability of several Yersinia genomes offers an unprecedented opportunity to study the evolution of genome structure and arrangement. We introduce a set of statistical methods to study patterns of rearrangement in circular chromosomes and apply them to the Yersinia. We constructed a multiple alignment of eight Yersinia genomes using Mauve software to identify 78 conserved segments that are internally free from genome rearrangement. Based on the alignment, we applied Bayesian statistical methods to infer the phylogenetic inversion history of Yersinia. The sampling of genome arrangement reconstructions contains seven parsimonious tree topologies, each having different histories of 79 inversions. Topologies with a greater number of inversions also exist, but were sampled less frequently. The inversion phylogenies agree with results suggested by SNP patterns. We then analyzed reconstructed inversion histories to identify patterns of rearrangement. We confirm an over-representation of "symmetric inversions"-inversions with endpoints that are equally distant from the origin of chromosomal replication. Ancestral genome arrangements demonstrate moderate preference for replichore balance in Yersinia. We found that all inversions are shorter than expected under a neutral model, whereas inversions acting within a single replichore are much shorter than expected. We also found evidence for a canonical configuration of the origin and terminus of replication. Finally, breakpoint reuse analysis reveals that inversions with endpoints proximal to the origin of DNA replication are nearly three times more frequent. Our findings represent the first

  15. Deep cytoplasmic rearrangements in ventralized Xenopus embryos

    NASA Technical Reports Server (NTRS)

    Brown, E. E.; Denegre, J. M.; Danilchik, M. V.

    1993-01-01

    Following fertilization in Xenopus, dramatic rearrangements of the egg cytoplasm relocalize maternally synthesized egg components. During the first cell cycle the vegetal yolk mass rotates relative to the egg surface, toward the sperm entry point (SEP) (J. P. Vincent, G. F. Oster, and J. C. Gerhart, 1986, Dev. Biol. 113, 484-500), while concomitant deep cytoplasmic rearrangements occur in the animal hemisphere (M. V. Danilchik and J. M. Denegre, 1991, Development 111, 845-856). In this paper we examine the role of vegetal yolk mass rotation in producing the animal cytoplasmic rearrangements. We inhibited rotation by uv-irradiating embryos during the first cell cycle, a treatment that yields an extremely ventralized phenotype. Both uv-irradiated embryos and unirradiated control embryos show cytoplasmic rearrangements in the animal hemisphere during the first cell cycle. Cytoplasmic rearrangements on the SEP side of the embryo associated with the path of the sperm pronucleus, plus a swirl on the anti-SEP (dorsal) side, are seen, whether or not yolk mass rotation has occurred. This result suggests a role for the expanding sperm aster in directing animal hemisphere cytoplasmic movements. In unirradiated control embryos the anti-SEP (dorsal) swirl is larger than that in uv-irradiated embryos and often extends into the vegetal hemisphere, consistent with the animal cytoplasm having been pulled dorsally and vegetally by the sliding vegetal yolk mass. Thus the yolk mass rotation may normally enhance the dorsalward cytoplasmic movement, begun by the sperm aster, enough to induce normal axis formation. We extended our observations of unirradiated control and uv-irradiated embryos through early cleavages. The vegetal extent of the anti-SEP (dorsal) swirl pattern seen in control embryos persists through the early cleavage period, such that labeled animal cytoplasm extends deep into dorsal third-tier blastomeres at the 32-cell stage. Significantly, in uv-irradiated embryos

  16. Deep cytoplasmic rearrangements in ventralized Xenopus embryos

    NASA Technical Reports Server (NTRS)

    Brown, E. E.; Denegre, J. M.; Danilchik, M. V.

    1993-01-01

    Following fertilization in Xenopus, dramatic rearrangements of the egg cytoplasm relocalize maternally synthesized egg components. During the first cell cycle the vegetal yolk mass rotates relative to the egg surface, toward the sperm entry point (SEP) (J. P. Vincent, G. F. Oster, and J. C. Gerhart, 1986, Dev. Biol. 113, 484-500), while concomitant deep cytoplasmic rearrangements occur in the animal hemisphere (M. V. Danilchik and J. M. Denegre, 1991, Development 111, 845-856). In this paper we examine the role of vegetal yolk mass rotation in producing the animal cytoplasmic rearrangements. We inhibited rotation by uv-irradiating embryos during the first cell cycle, a treatment that yields an extremely ventralized phenotype. Both uv-irradiated embryos and unirradiated control embryos show cytoplasmic rearrangements in the animal hemisphere during the first cell cycle. Cytoplasmic rearrangements on the SEP side of the embryo associated with the path of the sperm pronucleus, plus a swirl on the anti-SEP (dorsal) side, are seen, whether or not yolk mass rotation has occurred. This result suggests a role for the expanding sperm aster in directing animal hemisphere cytoplasmic movements. In unirradiated control embryos the anti-SEP (dorsal) swirl is larger than that in uv-irradiated embryos and often extends into the vegetal hemisphere, consistent with the animal cytoplasm having been pulled dorsally and vegetally by the sliding vegetal yolk mass. Thus the yolk mass rotation may normally enhance the dorsalward cytoplasmic movement, begun by the sperm aster, enough to induce normal axis formation. We extended our observations of unirradiated control and uv-irradiated embryos through early cleavages. The vegetal extent of the anti-SEP (dorsal) swirl pattern seen in control embryos persists through the early cleavage period, such that labeled animal cytoplasm extends deep into dorsal third-tier blastomeres at the 32-cell stage. Significantly, in uv-irradiated embryos

  17. Afrobatrachian mitochondrial genomes: genome reorganization, gene rearrangement mechanisms, and evolutionary trends of duplicated and rearranged genes

    PubMed Central

    2013-01-01

    Background Mitochondrial genomic (mitogenomic) reorganizations are rarely found in closely-related animals, yet drastic reorganizations have been found in the Ranoides frogs. The phylogenetic relationships of the three major ranoid taxa (Natatanura, Microhylidae, and Afrobatrachia) have been problematic, and mitogenomic information for afrobatrachians has not been available. Several molecular models for mitochondrial (mt) gene rearrangements have been proposed, but observational evidence has been insufficient to evaluate them. Furthermore, evolutionary trends in rearranged mt genes have not been well understood. To gain molecular and phylogenetic insights into these issues, we analyzed the mt genomes of four afrobatrachian species (Breviceps adspersus, Hemisus marmoratus, Hyperolius marmoratus, and Trichobatrachus robustus) and performed molecular phylogenetic analyses. Furthermore we searched for two evolutionary patterns expected in the rearranged mt genes of ranoids. Results Extensively reorganized mt genomes having many duplicated and rearranged genes were found in three of the four afrobatrachians analyzed. In fact, Breviceps has the largest known mt genome among vertebrates. Although the kinds of duplicated and rearranged genes differed among these species, a remarkable gene rearrangement pattern of non-tandemly copied genes situated within tandemly-copied regions was commonly found. Furthermore, the existence of concerted evolution was observed between non-neighboring copies of triplicated 12S and 16S ribosomal RNA regions. Conclusions Phylogenetic analyses based on mitogenomic data support a close relationship between Afrobatrachia and Microhylidae, with their estimated divergence 100 million years ago consistent with present-day endemism of afrobatrachians on the African continent. The afrobatrachian mt data supported the first tandem and second non-tandem duplication model for mt gene rearrangements and the recombination-based model for concerted

  18. The time of a photoinduced spin-Peierls phase transition

    SciTech Connect

    Semenov, A. L.

    2015-02-15

    The time τ of the spin-Peierls phase transition is analyzed theoretically as a function of the duration τ{sub p} of the exciting light pulse and the average number x{sub 0} of absorbed photons per magnetic ion after the transmission of the pulse. It is shown that the phase transition occurs at x{sub 0} > x{sub c}. The critical value x{sub c} is determined as a function of the duration τ{sub p} of the light pulse. A photoinduced variation in the optical reflection coefficient R is calculated as a function of time t. The results of calculation are compared with experimental data on ultrafast photoinduced melting of the low-temperature spin-Peierls phase into potassium tetracyanoquinodimethan (K-TCNQ)

  19. Dynamical properties of nucleus boundaries in photoinduced structural change

    NASA Astrophysics Data System (ADS)

    Ishida, Kunio; Nasu, Keiichiro

    2014-01-01

    Dynamics of the boundaries of photoinduced nuclei in electron-phonon systems is theoretically studied. By regarding the spatial distribution of the excited electronic state population as a geometric pattern, we applied the multifractal analysis to it and calculated the temporal behavior of the fractal dimension f(α) as a function of the Lipschitz-Hölder exponent α, which is an appropriate method for understanding the cooperative relaxation process of photoexcited states. We found that the incubation period observed in various types of photoinduced cooperative phenomena corresponds to the formation of embryonic nuclei which is driven by nonadiabatic/adiabatic transition between electronic states during the relaxation of the Franck-Condon state.

  20. [Photo-induced processes and reaction dynamics in bacteriorhodopsin].

    PubMed

    Terpugov, E L; Degtyareva, O V

    2015-01-01

    In this review we have focused on the advances madein observing the photo-induced response in bacteriorhodopsin and understanding the mechanisms of retinal-protein interactions which are still obscure. We discuss our recent data obtained on the wild type of bacteriorhodopsin and model compounds. This paper presents our new spectroscopic data on amino acids obtained using FT-IR emission spectroscopy. Based on the characteristics of the structure and optical properties of glycine and L-lysine that simulate a photo-induced behaviour of an opsin under natural conditions we tried to find an answer to one of the most important questions concerning the role of protein in the primary processes in bacteriorhodopsin.

  1. Photo-induced electron-transfer reactions in heterogeneous media

    NASA Astrophysics Data System (ADS)

    Yang, J. M.

    1981-11-01

    The conversion of solar energy into chemical energy was pursued by two approaches. One is the photo-induced electron transfer reactions in heterogeneous media, and the other is the photo-decomposition of water with liquid-junction solar cells. Photo-induced electron-transfer reactions in heterogeneous media with colloidal silica or poly-acrylate were studied by flash photolysis. In an effort to illustrate that small band-gap semiconductors can be protected from photo-corrosion through surface modification, the surface of polycrystalline ZnO was chemically coated with zinc phthalocyanine and the electron-transfer process across the coated ZnO-electrolyte interface was studied by photo-electrochemical techniques.

  2. Photoinduced translational molecular mobility in solid nanostructured azo dye films

    SciTech Connect

    Ezhov, A A; Kozenkov, V M; Magnitskii, Sergey A; Nagorskii, Nikolay M; Panov, Vladimir I

    2011-11-30

    A new mechanism controlling the molecular motion in thin azo-containing films during a photoinduced change in the surface nanorelief is found. It is shown experimentally that exposure of a solid AD-1 azo dye, deposited on a glass substrate, to incoherent linearly polarised light leads to formation of nanostructures with a characteristic size of 200 nm, which are similar to droplets of melt of this dye on the same substrate. It is shown that photoinduced mass transport in a solid AD-1 azo dye film can be explained by the mobility of molecules related to their trans-cis-photoisomerisation, which leads to film softening with subsequent formation of spherical protrusions under surface tension forces.

  3. Heterodyne technique in photoinduced force microscopy with photothermal effect

    NASA Astrophysics Data System (ADS)

    Yamanishi, J.; Naitoh, Y.; Li, Y. J.; Sugawara, Y.

    2017-03-01

    The heterodyne technique is used to detect short-range forces. Using the heterodyne technique, we demonstrate photoinduced force microscopy (PiFM) imaging and z-spectroscopy without the artifact of photothermal vibration. The rejection ratio was at least 99.975% under a high-scattering condition. In addition, the heterodyne technique employs the optimal amplitude at the first resonance frequency of the cantilever to detect the photoinduced force sensitively. According to our calculation, the optimal ratio of the amplitude to the distance between the dipole of the tip and that of the sample is 0.4448. The heterodyne technique can be employed to perform PiFM without the artifact by using the optimal amplitude.

  4. Modeling photoinduced fluorescence enhancement in semiconductor nanocrystal arrays

    NASA Astrophysics Data System (ADS)

    Maenosono, Shinya

    2003-07-01

    Photoinduced fluorescence enhancement (PFE) in semiconductor nanocrystal (NC) arrays is modeled based on the rate equations for ground-state, excited-state and photoionized NCs in the array. The photoionization process is broken down into fast and slow ionization processes, which are expected to relate to blinking and darkening phenomena, respectively. Consequently, PFE behavior is found to change drastically, as it depends on both the intrinsic properties of NCs, and on external conditions, such as surface-capping molecules and atmosphere.

  5. Photoinduced changes in the Raman spectra of germanosilicate optical fibres

    SciTech Connect

    Vasil'ev, Sergei A; Dianov, Evgenii M; Koltashev, V V; Mashinsky, V M; Medvedkov, O I; Plotnichenko, V G; Pyrkov, Yu N; Sazhin, O D; Frolov, A A; Marchenko, V M

    1998-04-30

    An investigation was made of changes in the Raman spectra of germanosilicate optical fibres as a result of UV irradiation. The photoinduced changes in the spectra were of the same nature for all types of irradiation used. These changes increased with increase in the radiation dose and in the GeO{sub 2} concentration in the fibre core and were evidence of a structural modification of glass. (nonlinear optical phenomena and devices)

  6. Vicinal Difluoroalkylation and Aminosulfonylation of Alkynes under Photoinduced Conditions.

    PubMed

    Xiang, Yuanchao; Li, Yuewen; Kuang, Yunyan; Wu, Jie

    2017-01-23

    A photoinduced vicinal difluoroalkylation and aminosulfonylation of alkynes under photocatalysis was realized. The combination of ethyl 2-bromo-2,2-difluoroacetate, alkynes, and DABCO⋅(SO2 )2 with hydrazines, catalyzed by 9-mes-10-methyl acridinium perchlorate in the presence of visible light, afforded (E)-ethyl 2,2-difluoro-4-aryl-4-sulfamoylbut-3-enoates in good yields with high stereoselectivity. This four-component reaction proceeds through radical addition with the insertion of sulfur dioxide.

  7. Plasmonic, excitonic and exciton-plasmonic photoinduced nanocomposites

    NASA Astrophysics Data System (ADS)

    Bityurin, N.; Ermolaev, N.; Smirnov, A. A.; Afanasiev, A.; Agareva, N.; Koryukina, T.; Bredikhin, V.; Kamensky, V.; Pikulin, A.; Sapogova, N.

    2016-03-01

    UV irradiation of materials consisting of a polymer matrix that possesses precursors of different kinds can result in creation of nanoparticles within the irradiated domains. Such photoinduced nanocomposites are promising for photonic applications due to the strong alteration of their optical properties compared to initial non-irradiated materials. We report our results on the synthesis and investigation of plasmonic, excitonic and exciton-plasmonic photoinduced nanocomposites. Plasmonic nanocomposites contain metal nanoparticles of noble metals with a pronounced plasmon resonance. Excitonic nanocomposites possess semiconductor nanoclusters (quantum dots). We consider the CdS-Au pair because the luminescent band of CdS nanoparticles enters the plasmon resonance band of gold nanoparticles. The obtaining of such particles within the same composite materials is promising for the creation of media with exciton-plasmon resonance. We demonstrate that it is possible to choose appropriate precursor species to obtain the initially transparent poly(methyl methacrylate) (PMMA) films containing both types of these molecules either separately or together. Proper irradiation of these materials by a light-emitting diode operating at the wavelength of 365 nm provides material alteration demonstrating light-induced optical absorption and photoluminescent properties typical for the corresponding nanoparticles. Thus, an exciton-plasmonic photoinduced nanocomposite is obtained. It is important that here we use the precursors that are different from those usually employed.

  8. PAFc, a key player in MLL-rearranged leukemogenesis.

    PubMed

    Tan, Jiaying; Muntean, Andrew G; Hess, Jay L

    2010-10-01

    Recent studies identified an interaction between the Polymerase Associated Factor complex (PAFc) and Mixed Lineage Leukemia (MLL), including MLL-rearranged oncoproteins. This interaction is critical for MLL transcriptional activity and MLL-rearranged leukemogenesis. Here, we discuss the potential molecular role of the PAFc in transcriptional dysregulation of MLL target genes and the interplay between PAFc and MLL-rearranged oncoproteins in leukemogenesis.

  9. [Wolff-Parkinson-White syndrome with orthodromic supraventricular tachycardia associated with a "hyper-conductor" atrio-ventricular node. A therapeutic challenge].

    PubMed

    Hernández González, D; Iturralde Torres, P; Romero, L; Colín, L; Villarreal, A; González Hermosillo, J A

    1990-01-01

    One case of Wolff-Parkinson-White Syndrome with paroxysmal supraventricular tachycardia related to orthodromic atrioventricular reentry using an accessory pathway for retrograde conduction an a rapidly conducting AV node for anterograde conduction is present. The pharmacological therapy with Digoxin, Propranolol, Quinidine, Disopyramide and Propafenone was not effective. An electrophysiologic study showed a reciprocating tachycardia induced by spontaneous ventricular beats. Both the effective refractory period of the AV node and the anterograde effective refractory period of the accessory pathway were minor or equal to 220 msec which made the control of the arrhythmia difficult. Amiodarone was able to suppress the premature ventricular beats, depress conduction and prolong refractoriness in both, the AV node and accessory pathway to prevent recurrences of atrioventricular reentry. In this patient a false positive test with ajmaline was documented. The electrophysiologic study showed the association of Wolff-Parkinson-White Syndrome with an enhanced atrioventricular nodal-conduction and allowed the selection of an appropriate antiarrhythmic agent.

  10. Catalytic synthesis of amides via aldoximes rearrangement.

    PubMed

    Crochet, Pascale; Cadierno, Victorio

    2015-02-14

    Amide bond formation reactions are among the most important transformations in organic chemistry because of the widespread occurrence of amides in pharmaceuticals, natural products and biologically active compounds. The Beckmann rearrangement is a well-known method to generate secondary amides from ketoximes. However, under the acidic conditions commonly employed, aldoximes RHC=NOH rarely rearrange into the corresponding primary amides RC(=O)NH2. In recent years, it was demonstrated that this atom-economical transformation can be carried out efficiently and selectively with the help of metal catalysts. Several homogeneous and heterogenous systems have been described. In addition, protocols offering the option to generate the aldoximes in situ from the corresponding aldehydes and hydroxylamine, or even from alcohols, have also been developed, as well as a series of tandem processes allowing the access to N-substituted amide products. In this Feature article a comprehensive overview of the advances achieved in this particular research area is presented.

  11. Three-dimensional micro-level computational study of Wolff's law via trabecular bone remodeling in the human proximal femur using design space topology optimization.

    PubMed

    Boyle, Christopher; Kim, Il Yong

    2011-03-15

    The law of bone remodeling, commonly referred to as Wolff's Law, asserts that the internal trabecular bone adapts to external loadings, reorienting with the principal stress trajectories to maximize mechanical efficiency creating a naturally optimum structure. The goal of the current study was to utilize an advanced structural optimization algorithm, called design space optimization (DSO), to perform a micro-level three-dimensional finite element bone remodeling simulation on the human proximal femur and analyse the results to determine the validity of Wolff's hypothesis. DSO optimizes the layout of material by iteratively distributing it into the areas of highest loading, while simultaneously changing the design domain to increase computational efficiency. The result is a "fully stressed" structure with minimized compliance and increased stiffness. The large-scale computational simulation utilized a 175 μm mesh resolution and the routine daily loading activities of walking and stair climbing. The resulting anisotropic trabecular architecture was compared to both Wolff's trajectory hypothesis and natural femur samples from literature using a variety of visualization techniques, including radiography and computed tomography (CT). The results qualitatively revealed several anisotropic trabecular regions, that were comparable to the natural human femurs. Quantitatively, the various regional bone volume fractions from the computational results were consistent with quantitative CT analyses. The global strain energy proceeded to become more uniform during optimization; implying increased mechanical efficiency was achieved. The realistic simulated trabecular geometry suggests that the DSO method can accurately predict bone adaptation due to mechanical loading and that the proximal femur is an optimum structure as the Wolff hypothesized. Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.

  12. Polyyne synthesis using carbene/carbenoid rearrangements.

    PubMed

    Chalifoux, Wesley A; Tykwinski, Rik R

    2006-01-01

    Rearrangement of a carbene/carbenoid intermediate to form an acetylene moiety, known as the Fritsch-Buttenberg-Wiechell (FBW) rearrangement, was developed for the formation of polyynes and polyyne frameworks within highly conjugated organic materials. Necessary precursors can be prepared through formation of an alkynyl ketone, followed by dibromoolefination under Corey-Fuchs conditions. The carbenoid rearrangement is brought about by treatment of the dibromoolefin with BuLi under mild conditions. The success of these FBW reactions is quite solvent-dependent, and nonpolar hydrocarbon solvents (e.g., hexanes, toluene, benzene) work quite well, while use of ethereal solvents such as diethyl ether and tetrahydrofuran (THF) does not provide the desired polyyne product. This protocol was successfully applied to the formation of silyl, alkyl, alkenyl, and aryl polyynes, including di-, tri-, and tetrayne products, as well as the construction of two-dimensional carbon-rich molecules. A one-pot variant of this procedure is being developed and is particularly applicable toward the synthesis of polyyne natural products. Formation of a series of triisopropylsilyl end-capped polyynes, from the triyne to decayne, was achieved. Third-order nonlinear optical properties of these polyynes were evaluated. This study shows that the molecular second hyperpolarizabilities for the polyynes as a function of length increase at a rate that is higher than all other nonaromatic organic oligomers.

  13. The radical cation of anti-tricyclooctadiene and its rearrangement products

    PubMed

    Bally; Bernhard; Matzinger; Truttmann; Zhu; Roulin; Marcinek; Gebicki; Williams; Chen; Roth; Herbertz

    2000-03-03

    The anti dimer of cyclobutadiene (anti-tricyclo[4.2.0.0(2.5)]octa-3,7-diene, TOD) is subjected to ionization by gamma-irradiation in Freon matrices, pulse radiolysis in hydrocarbon matrices, and photoinduced electron transfer in solution. The resulting species are probed by optical and ESR spectroscopy (solid phase) as well as by CIDNP spectroscopy (solution). Thereby it is found that ionization of anti-TOD invariably leads to spontaneous decay to two products, that is bicyclo[4.2.0]octa-2,4,7-triene (BOT) and 1,4-dihydropentalene (1,4-DHP), whose relative yield strongly depends on the conditions of the experiment. Exploration of the C8H8*+ potential energy surface by the B3LYP/6-31G* density functional method leads to a mechanistic hypothesis for the observed rearrangements which involves a bifurcation between a pathway leading to the simple valence isomer, BOT*+, and another one leading to an unprecedented other valence isomer, the anti form of the bicyclo[3.3.0]octa-2,6-diene-4,8-diyl radical cation (anti-BOD*+). The latter product undergoes a very facile H-shift to yield the radical cation of 1,3a-dihydropentalene (1,3a-DHP*+) which ultimately rearrranges by a further H-shift to the observed product, 1,4-DHP*+.

  14. Photoinduced surface reactions on TiO{sub 2} and SrTiO{sub 3} films: Photocatalytic oxidation and photoinduced hydrophilicity

    SciTech Connect

    Miyauchi, Masahiro; Nakajima, Akira; Fujishima, Akira; Hashimoto, Kazuhito; Watanabe, Toshiya

    2000-01-01

    In the present study, the authors have evaluated photocatalytic activities and photoinduced wettabilities for TiO{sub 2} and SrTiO{sub 3} films. Although both types of films had almost the same photocatalytic oxidation activity, photoinduced wettabilities of these films showed different phenomena. The photoinduced hydrophilicity peculiar to TiO{sub 2} is not caused by the photocatalytic oxidation of organic compounds adsorbed on the surface. The highly hydrophilic surface of TiO{sub 2} is ascribed to photogenerated Ti{sup 3+} defect sites that are favorable for dissociative water absorption. The yield of this photoinduced hydrophilic reaction is not clear at the present time. It is noted that this reaction involves a surface structural change, which should not require a high quantum efficiency as compared to conventional photocatalytic oxidation.

  15. Accuracy of the Electrocardiogram in Localizing the Accessory Pathway in Patients with Wolff-Parkinson-White Pattern

    PubMed Central

    Teixeira, Carlos Manuel; Pereira, Telmo António; Lebreiro, Ana Margarida; Carvalho, Sérgio Alexandre

    2016-01-01

    Background There are currently several electrocardiographic algorithms to locate the accessory pathway (AP) in patients with Wolff-Parkinson-White (WPW) syndrome. Objective To compare the ability of electrocardiographic algorithms in identifying the location of the AP in patients with WPW pattern referred for ablation. Methods Observational, cross-sectional, retrospective study with 111 patients with WPW syndrome referred for AP ablation. The electrocardiogram (ECG) obtained prior to the ablation was analyzed by an experienced observer who consecutively applied seven algorithms to identify non-invasively the AP. We then compared the location estimated with this assessment with that obtained in the electrophysiological study and calculated the agreement rates. Results Among the APs, 59 (53.15%) were distributed around the mitral annulus and the remaining 52 (46.85%) were located around the tricuspid annulus. The overall absolute accuracy of the algorithms evaluated varied between 27% and 47%, increasing to between 40% and 76% when we included adjacent locations. The absolute agreement rate by AP location was 2.00-52.20% for septal APs (n = 51), increasing to 5.90-90.20% when considering adjacent locations; 7.70-69.20% for right APs (n = 13), increasing to 42.90-100% when considering adjacent locations; and 21.70-54.50% for left APs (n = 47), increasing to 50-87% when considering adjacent locations. Conclusion The agreement rates observed for the analyzed scores indicated a low discriminative ability of the ECG in locating the AP in patients with WPW. PMID:27627222

  16. Overexpression of G100S mutation in PRKAG2 causes Wolff-Parkinson-White syndrome in zebrafish.

    PubMed

    Zhang, B L; Ye, Z; Xu, R L; You, X H; Qin, Y W; Wu, H; Cao, J; Zhang, J L; Zheng, X; Zhao, X X

    2014-09-01

    The Wolff-Parkinson-White (WPW) syndrome was believed to be associated with PRKAG2 gene mutations. In this study, we verified the pathopoiesis of G100S mutation, a novel mutation only discovered in Chinese patients with WPW, in cardiac disorder. Similar to R302Q, when overexpressed PRKAG2 G100S mutant in zebrafish, we observed a thicker heart wall, detected a decreased AMPK enzymatic activity by tissue AMPK kinase activity colorimetric technique, as well as examined an increased glycogen storage in heart wall using the method for periodic acid-Schiff staining, in comparison with the zebrafish without exogenous PRKAG2 (mock) or with wild-type PRKAG2 (WT). Taken together, we concluded PRKAG2 G100S mutation might contribute to impair the AMP-activated protein kinase function, which resulted in increased cardiac glycogen storage, serving as a pathogenesis for WPW syndrome in Chinese. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  17. Parametric imaging of experimentally simulated Wolff-Parkinson-White syndrome conduction abnormalities in dogs: a concise communication

    SciTech Connect

    Weismueller, P.H.; Henze, E.; Adam, W.E.; Roth, J.; Bitter, F.; Stauch, M.

    1986-01-01

    In order to test the diagnostic potential of phase analysis of radionuclide ventriculography (RNV) for localizing accessory bundles in Wolff-Parkinson-White (WPW) syndrome, 24 experimental runs were performed in three open chest instrumented dogs. After a baseline study, WPW syndrome was simulated by stimulation at seven different sites around the base of the ventricles, and RNV's were obtained. Subsequent data processing including Fourier transformation allowed the localization of the site of the first inward motion of the ventricles by an isophasic wave display. In sinus rhythm, the septum contracted first. During ectopic premature ventricular stimulation by triggering the atrial signal, the phase scan was altered only when the stimulus was applied earlier than 20 ms before the expected QRS complex during sinus rhythm. During stimulation with fixed frequency, only the left lateral positions of the premature stimulation were detected by phase analysis with a sensitivity of 86%. Neither the antero- or posteroseptal nor the right ventricular premature contraction pattern could be exactly localized.

  18. [Influence of exercise on the permeability of accessory pathways and supraventricular arrhythmia in Wolff-Parkinson-White syndrome].

    PubMed

    Mabo, P; Kermarrec, A; Gras, D; Paillard, F; Bédossa, M; Daubert, C

    1992-10-01

    The influence of adrenergic stimulation on the effective anterograde refractory period of the accessory pathways and on supraventricular arrhythmias, was studied in 20 patients (average age 38 +/- 16 years) with an untreated permanent Wolff-Parkinson-White syndrome and a resting anterograde refractory period < or = 400ms. Repeated electrophysiological studies with a single endocavity catheter positioned near the atrial pole of the accessory pathway were performed under basal conditions and during a standardised exercise test on a bicycle ergometer. The effective anterograde refractory period of the accessory pathway, the length of the tachycardia cycle during reciprocating orthodromic tachycardia, the average heart rate, the percentage of preexcited QRS complexes during induced atrial fibrillation, were measured in all patients under basal conditions and at the peak of exercise. Exercise significantly reduced the anterograde refractory period of the accessory pathway (287 +/- 49 ms at rest versus 238 +/- 24 ms on exercise: p < 0.001), the cycle of orthodromic tachycardia (302 +/- 32 vs 260 +/- 22 ms p < 0.001), the minimal R-R interval (270 +/- 65 vs 227 +/- 46 ms: p < 0.05) and % of preexcited QRS complexes (75 +/- 33 vs 51 +/- 39: p < 0.05) in atrial fibrillation whilst increasing the average heart rate (165 +/- 42 vs 202 +/- 39 bpm: p < 0.02). Adrenergic stimulation significantly improves anterograde conduction in the accessory pathway. The reduction in the % of preexcited QRS complexes in atrial fibrillation could indicate a preferential action of catecholamines on the nodo-hisian pathway.(ABSTRACT TRUNCATED AT 250 WORDS)

  19. [Wolff-Parkinson-White syndrome. Outcome of patients treated with anti-arrhythmia agents from data of electrophysiological examinations].

    PubMed

    Cointe, R; Lévy, S; Metge, M; Bru, P; Bricaud, H; Gérard, R

    1988-02-01

    Seventy-two consecutive patients with electrocardiographic evidence of Wolff-Parkinson-White syndrome underwent electrophysiological study (EPS). Fifty-five of these patients (76 p. 100) had episodes of tachycardia, 11 experienced palpitations or syncopes and 6 were asymptomatic. The decision to prescribe an antiarrhythmic agent was reached on the basis of the patients' symptoms and EPS data. One patient was treated by surgery before the medical treatment was tried; 17 patients were discharged without treatment, 4 were discharged with an episodic and 50 with a preventive antiarrhythmic treatment. Among these 50 patients, 46 (92 p. 100) could be followed up for a mean period of 45.7 +/- 28 months. One died of lung cancer; 43 presented with spontaneous episodes of tachycardia, 4 were able to discontinue treatment at the end of the follow-up period since they had very few symptoms and 2 were lost sight of. Among the 37 patients under antiarrhythmic treatment followed up, 29 (78 p. 100) are well controlled, while 8 (22 p. 100) still present with episodes of tachycardia. A tachycardia-reducing pacemaker was implanted in 5 of these 8 patients. It therefore appears that 78 p. 100 of patients presenting with spontaneous episodes of tachycardia associated with WPW syndrome can be controlled with an antiarrhythmic treatment. This result was obtained after trying at least two types of antiarrhythmic agents in 86 p. 100 of the cases.(ABSTRACT TRUNCATED AT 250 WORDS)

  20. [Difficulties of persistent repolarization following normalization of the QRS wave in the Wolff-Parkinson-White syndrome].

    PubMed

    Laham, J; Frank, R; Fontaine, G; Artigou, Y; Heller, J; Gerbaux, A; Grosgogeat, Y

    1982-06-01

    The normalisation of the ventricular complex in the Wolff-Parkinson-White syndrome is often accompanied by changes in the repolarisation phase with a deep, symmetric and pointed T wave suggestive of coronary artery disease. In order to study this phenomenon we examined 29 cases of intermittent WPW, 13 of which had abnormalities of the normalised complex. Normalisation occurred spontaneously on 10 occasions, twice on exercise and once after Ajmaline. In the majority of cases (9/13) the preexcitation was a right (4 cases) or left (5 cases) posterior pathway and the T waves were abnormal in the posterior leads (II, III and AVF). In left lateral preexcitation the T waves were negative in lead 1 and AVL. The T wave changes seem to be related to the topography of the preexcitation pathway. They gradually disappeared in the 3 cases in which preexcitation had not recurred. The age of the patients (11 to 45 years, average 31 years) or normal coronary angiography, performed in 3 cases, excluded coronary pathology as did the close relationship between the topography of the preexcitation and the T wave changes and the gradual disappearance of the abnormalities in the cases where preexcitation did not recur. This phenomenon, related to abnormal ventricular activation, seems to be comparable to the changes in ventricular repolarisation observed on termination of ventricular pacing, on the regression of certain intermittent left bundle branch blocks and perhaps, in some cases, of the post-ventricular tachycardia syndrome.

  1. [Influence of age on the presumed cause of syncope in patients with the Wolff-Parkinson-White syndrome].

    PubMed

    Chometon, F; Brembilla-Perrot, B

    2007-01-01

    The aim of this study was to assess the causes of syncope in patients with the Wolff-Parkinson-White syndrome (WPW) and to determine whether the age of the patients was a significant factor. Forty-seven patients with a WPW, aged 11 to 72 years, underwent electrophysiological study by the oesophageal approach because of an unexplained syncope. Nineteen patients were under 20 years of age (16 +/- 3 years: group I) and 28 were over 20 years of age (40 +/- 13 years: group II). Junctional tachycardia was induced in 8 patients of group I (42%) and in 13 of group II (46%) (NS); atrial fibrillation was induced in 8 patients of group I (42%) and in 9 of group II (35%) (NS). A potentially malignant form of WPW was identified in 8 patients of group I (42%) and in 11 of group II (39%) (NS); Syncope was directly attributed to the WPW in 14 patients of group I (74%) and in 19 of group II (78%), either after identification of a serious form or induction of junctional tachycardia (6 patients of group I and 8 of group II). The rest of the syncopal episodes had various causes. There were no deaths. The authors conclude that oesophageal electrophysiological investigations enable rapid identification of a high incidence of tachycardias probably responsible for syncope in WPW. The causes of syncope and incidence of potentially severe forms of WPW were not significantly influenced by the age of the patients.

  2. Phase analysis in the Wolff-Parkinson-White syndrome with surgically proven accessory conduction pathways: concise communication

    SciTech Connect

    Nakajima, K.; Bunko, H.; Tada, A.; Taki, J.; Tonami, N.; Hisada, K.; Misaki, T.; Iwa, T.

    1984-01-01

    Twenty-one patients with the Wolff-Parkinson-White (WPW) syndrome who underwent surgical division of the accessory conduction pathway (ACP) were studied by gated blood-pool scintigraphy. In each case, a functional image of the phase was generated, based on the fundamental frequency of the Fourier transform. The location of the ACP was confirmed by electrophysiologic study, epicardial mapping, and surgery. Phase analysis identified the side of preexcitation correctly in 16 out of 20 patients with WPW syndrome with a delta wave. All patients with right-cardiac type (N=9) had initial contraction in the right ventricle (RV). In patients with left-cardiac type (N=10), six had initial movement in the left ventricle (LV); but in the other four the ACPs in the anterior or lateral wall of the left ventricle (LV) could not be detected. In patients with multiple ACPs (N=2), one right-cardiac type had initial contraction in the RV, while in the other (with an intermittent WPW syndrome) the ACP was not detected. These observations indicate that abnormal wall motion is associated with the conduction anomalies of the WPW syndrome. We conclude that phase analysis can correctly identify the side of initial contraction in the WPW syndrome before and after surgery. However, as a method of preoperative study, it seems difficult to determine the precise site of the ACP by phase analysis alone.

  3. Photoinduced electron transfer across molecular bridges: electron- and hole-transfer superexchange pathways.

    PubMed

    Natali, Mirco; Campagna, Sebastiano; Scandola, Franco

    2014-06-21

    Photoinduced electron transfer plays key roles in many areas of chemistry. Superexchange is an effective model to rationalize photoinduced electron transfer, particularly when molecular bridges between donor and acceptor subunits are present. In this tutorial review we discuss, within a superexchange framework, the complex role played by the bridge, with an emphasis on differences between thermal and photoinduced electron transfer, oxidative and reductive photoinduced processes, charge separation and charge recombination. Modular bridges are also considered, with specific attention to the distance dependence of donor-acceptor electronic coupling and electron transfer rate constants. The possibility of transition, depending on the bridge energetics, from coherent donor-acceptor electron transfer to incoherent charge injection and hopping through the bridge is also discussed. Finally, conceptual analogies between bridge effects in photoinduced electron transfer and optical intervalence transfer are outlined. Selected experimental examples, instrumental to illustration of the principles, are discussed.

  4. Photo-Induced Assembly of a Luminescent Tetraruthenium Square.

    PubMed

    Laramée-Milette, Baptiste; Nastasi, Francesco; Puntoriero, Fausto; Campagna, Sebastiano; Hanan, Garry S

    2017-09-18

    Self-assembly is a powerful synthetic tool that has led to the development of one-, two- and three-dimensional architectures. From MOFs to molecular flasks, self-assembled materials have proven to be of great interest to the scientific community. Here we describe a strategy for the construction and de-construction of a supramolecular structure through unprecedented photo-induced assembly and dis-assembly. The combination of two approaches, a [n×1]-directional bonding strategy and a ligand photo-dissociation strategy, allows the photo-induced assembly of a polypyridyl Ru(II) precursor into a discrete molecular square. Diffusion-ordered NMR spectroscopy confirmed the synthesis of a higher volume species, while the identity of the species was established by high-resolution mass spectrometry and single-crystal X-ray diffraction studies. The self-assembled square is not obtained by classical thermal techniques in similar conditions, but is obtained only by light-irradiation. The tetraruthenium square has an excited-state lifetime (135 ns), 40 times that of its mononuclear precursor and its luminescence quantum yield (1.0 %) is three orders of magnitude higher. These remarkable luminescence properties are closely related to the relatively rigid square structure of the tetraruthenium assembly, as suggested by slow radiationless decay and transient absorption spectroscopy. The results described herein are a rare example of photo-induced assembly and dis-assembly processes, and can open the way to a new avenue in supramolecular chemistry, leading to the preparation of structurally organized supermolecules by photochemical techniques. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Photoinduced ordering and anchoring properties of azo-dye films.

    PubMed

    Kiselev, Alexei D; Chigrinov, Vladimir; Huang, Dan Ding

    2005-12-01

    We study both theoretically and experimentally the anchoring properties of photoaligning azo-dye films in contact with a nematic liquid crystal depending on the photoinduced ordering of azo-dye molecules. In the mean field approximation, we found that the bare surface anchoring energy depends linearly on the azo-dye order parameter and the azimuthal anchoring strength decays to zero in the limit of vanishing photoinduced ordering. From the absorption dichroism spectra measured in azo-dye films that are prepared from an azo-dye derivative with polymerizable terminal groups we obtain the dependence of the dichroic ratio on the irradiation dose. We also measure the polar and azimuthal anchoring strengths in nematic liquid crystal (NLC) cells aligned by the azo-dye films and derive the anchoring strengths as functions of the dichroic ratio, which is proportional to the photoinduced order parameter. Although linear fitting of the experimental data for both anchoring strengths gives reasonable results, it, predicts vanishing of the azimuthal anchoring strength at some nonzero value of the azo-dye order parameter, in contradiction with theory. By using a simple phenomenological model we show that this discrepancy can be attributed to the difference between the surface and bulk order parameters in the films. The measured polar anchoring energy is found to be an order of magnitude higher than the azimuthal strength. Our theory suggests that the quadrupole term of the spherical harmonics expansion for the azo-dye-NLC intermolecular potential might be of importance for the understanding of this difference.

  6. Structural analysis of a carcinogen-induced genomic rearrangement event

    SciTech Connect

    Barr, F.G.; Davis, R.J.; Eichenfield, L.; Emanuel, B.S. Univ. of Pennsylvania, Philadelphia )

    1992-02-01

    The authors have explored the mechanism of genomic rearrangement in a hamster fibroblast cell culture system in which rearrangements are induced 5{prime} to the endogenous thymidine kinase gene by chemical carcinogen treatment. The wild-type region around one rearrangement breakpoint was cloned and sequenced. With this sequence information, the carcinogen-induced rearrangement was cloned from the corresponding rearranged cell line by the inverse polymerase chain reaction. After the breakpoint fragment was sequenced, the wild-type rearrangement partner (RP15) was isolated by a second inverse polymerase chain reaction of unrearranged DNA. Comparison of the sequence of the rearrangement breakpoint with the wild-type RP15 and 5{prime} thymidine kinase gene regions revealed short repeats directly at the breakpoint, as well as nearby A+T-rich regions in rearrangement partner. Therefore, these studies reveal interesting sequence and chromatin features near the rearrangement breakpoints and suggest a role for nuclear organization in the mechanism of carcinogen-induced genomic rearrangement.

  7. Optical control of plasmonic grating transmission by photoinduced anisotropy

    NASA Astrophysics Data System (ADS)

    Palto, Sergey P.; Draginda, Yulia A.; Artemov, Vladimir V.; Gorkunov, Maxim V.

    2017-07-01

    Light transmission through subwavelength silver slit gratings coated with Langmuir-Blodgett films of an azo-dye compound was studied. While the coating was found to dramatically enhance the TM-polarized grating transmittance, it also enabled its low-intensity optical control: the photoinduced alignment of the azo-dye molecules yielded a significant (˜ 40 nm) shift of the extraordinary transmission peaks to shorter or longer wavelengths depending on the orientation of the induced optical axis with respect to the gratings.

  8. Distance dependence in photo-induced intramolecular electron transfer

    NASA Astrophysics Data System (ADS)

    Larsson, Sven; Volosov, Andrey

    1986-09-01

    The distance dependence of the rate of photo-induced electron transfer reactions is studied. A quantum mechanical method CNDO/S is applied to a series of molecules recently investigated by Hush et al. experimentally. The calculations show a large interaction through the saturated bridge which connects the two chromophores. The electronic matrix element HAB decreases a factor 10 in about 4 Å. There is also a decrease of the rate due to less exothermicity for the longer molecule. The results are in fair agreement with the experimental results.

  9. Photo-induced transmittance in copper selenide nanowires

    NASA Astrophysics Data System (ADS)

    Statkutė, G.; Mikulskas, I.; Jagminas, A.; Tomašiūnas, R.

    2008-01-01

    Photo-induced transmission was investigated in Cu 1.7Se nanowires electrochemically deposited in alumina matrix pores with a central channel of the diameters of 12, 15 and 60 nm by means of the degenerate picosecond pump-probe technique at 1.064 μm wavelength. Resonant excitation intensity dependencies were interpreted. Absorption saturation was ascertained as a result of the drain of acceptor shallow centers. The estimated absorption cross-section was 10 -12 cm 2, saturation intensity - was 1-10 mJ cm -2.

  10. Photoinduced electron transfer based ion sensing within an optical fiber.

    PubMed

    Englich, Florian V; Foo, Tze Cheung; Richardson, Andrew C; Ebendorff-Heidepriem, Heike; Sumby, Christopher J; Monro, Tanya M

    2011-01-01

    We combine suspended-core microstructured optical fibers with the photoinduced electron transfer (PET) effect to demonstrate a new type of fluorescent optical fiber-dip sensing platform for small volume ion detection. A sensor design based on a simple model PET-fluoroionophore system and small core microstructured optical fiber capable of detecting sodium ions is demonstrated. The performance of the dip sensor operating in a high sodium concentration regime (925 ppm Na(+)) and for lower sodium concentration environments (18.4 ppm Na(+)) is explored and future approaches to improving the sensor's signal stability, sensitivity and selectivity are discussed.

  11. Photoinduced absolute negative current in a symmetric molecular electronic bridge

    SciTech Connect

    Prociuk, Alexander; Dunietz, Barry D

    2010-09-28

    The study of current induced by photoradiating a molecular-based device under bias is of fundamental importance to the improvement of photoconductors and photovoltaics. In this technology, electron pumps generate an uphill current that opposes a potential drop and thereby recharges a fuel cell. While the modeled molecular electron pump is completely symmetric, the sign of the photocurrent is solely determined by the existing bias and the nature of photoinduced electronic excitations. The photoradiation induces nonequilibrium population of the electrode-coupled system. The dependence of the photocurrent on electrode coupling, photoradiation field strength, and applied bias are studied at a basic model level.

  12. Photoinduced underwater superoleophobicity of TiO2 thin films.

    PubMed

    Sawai, Yusuke; Nishimoto, Shunsuke; Kameshima, Yoshikazu; Fujii, Eiji; Miyake, Michihiro

    2013-06-11

    The photoinduced wettabilities of water, n-hexadecane, dodecane, and n-heptane on a flat TiO2 surface prepared by a sol-gel method-based coating were investigated. An amphiphilic surface produced by UV irradiation exhibited underwater superoleophobicity with an extremely high static oil contact angle (CA) of over 160°. The TiO2 surface almost completely repelled the oil droplet in water. A robust TiO2 surface with no fragile nanomicrostructure was fabricated on a Ti mesh with a pore size of approximately 150 μm. The fabricated mesh was found to be applicable as an oil/water separation filter.

  13. Photo-induced nonlinear absorption in carbon nanostructures

    NASA Astrophysics Data System (ADS)

    Zatrudina, Rimma Sh.; Gribkov, Vladislav Yu.

    2017-05-01

    Photoinduced nonlinear absorption of new carbon nanoparticles - astralenes and two types of carbon nanoclusters was investigated. The nonlinear absorption of aqueous suspensions of astralenes and solutions of carbon nanoclusters was studied by the method of z-scanning with Nd3+ -glass laser (wavelength λ = 1064 nm) in Q-switching regimes. A numerical model of the propagation of the laser pulse in a medium with reverse saturable absorption was created. Relaxation time of the first exited state and the ratio of absorption cross-sections of the first exited and ground states for the researched types of carbon nanoparticles were determined by the numerical simulation.

  14. Nonclassical 21-Homododecahedryl Cation Rearrangement Revisited.

    PubMed

    Jalife, Said; Mondal, Sukanta; Osorio, Edison; Cabellos, José Luis; Martínez-Guajardo, Gerardo; Fernández-Herrera, María A; Merino, Gabriel

    2016-03-04

    The degenerate rearrangement in the 21-homododecahedryl cation (1) has been studied via density functional theory computations and Born-Oppenheimer Molecular Dynamics simulations. Compound 1 can be described as a highly fluxional hyperconjugated carbocation. Complete scrambling of 1 can be achieved by the combination of two unveiled barrierless processes. The first one is a "rotation" of one of the six-membered rings via a 0.8 kcal·mol(-1) barrier, and the second one is a slower interconvertion between two hyperconjomers via an out-of-plane methine bending (ΔG(⧧) = 4.0 kcal·mol(-1)).

  15. Molecular Cytogenetic Analysis of Telomere Rearrangements

    PubMed Central

    Martin, Christa Lese; Ledbetter, David H.

    2015-01-01

    Genomic imbalances involving the telomeric regions of human chromosomes, which contain the highest gene concentration in the genome, are proposed to have severe phenotypic consequences. For this reason, it is important to identify telomere rearrangements and assess their contribution to human pathology. This unit describes the structure and function of human telomeres and outlines several FISH-based methodologies that can be employed to study these unique regions of human chromosomes. It is a revision of the original version of the unit published in 2000, now including an introductory section describing advances in the discipline that have taken place since the original publication. PMID:25599669

  16. Structures of Local Rearrangements in Soft Colloidal Glasses

    NASA Astrophysics Data System (ADS)

    Yang, Xiunan; Liu, Rui; Yang, Mingcheng; Wang, Wei-Hua; Chen, Ke

    2016-06-01

    We image local structural rearrangements in soft colloidal glasses under small periodic perturbations induced by thermal cycling. Local structural entropy S2 positively correlates with observed rearrangements in colloidal glasses. The high S2 values of the rearranging clusters in glasses indicate that fragile regions in glasses are structurally less correlated, similar to structural defects in crystalline solids. Slow-evolving high S2 spots are capable of predicting local rearrangements long before the relaxations occur, while fluctuation-created high S2 spots best correlate with local deformations right before the rearrangement events. Local free volumes are also found to correlate with particle rearrangements at extreme values, although the ability to identify relaxation sites is substantially lower than S2. Our experiments provide an efficient structural identifier for the fragile regions in glasses and highlight the important role of structural correlations in the physics of glasses.

  17. Maximum likelihood estimates of pairwise rearrangement distances.

    PubMed

    Serdoz, Stuart; Egri-Nagy, Attila; Sumner, Jeremy; Holland, Barbara R; Jarvis, Peter D; Tanaka, Mark M; Francis, Andrew R

    2017-06-21

    Accurate estimation of evolutionary distances between taxa is important for many phylogenetic reconstruction methods. Distances can be estimated using a range of different evolutionary models, from single nucleotide polymorphisms to large-scale genome rearrangements. Corresponding corrections for genome rearrangement distances fall into 3 categories: Empirical computational studies, Bayesian/MCMC approaches, and combinatorial approaches. Here, we introduce a maximum likelihood estimator for the inversion distance between a pair of genomes, using a group-theoretic approach to modelling inversions introduced recently. This MLE functions as a corrected distance: in particular, we show that because of the way sequences of inversions interact with each other, it is quite possible for minimal distance and MLE distance to differently order the distances of two genomes from a third. The second aspect tackles the problem of accounting for the symmetries of circular arrangements. While, generally, a frame of reference is locked, and all computation made accordingly, this work incorporates the action of the dihedral group so that distance estimates are free from any a priori frame of reference. The philosophy of accounting for symmetries can be applied to any existing correction method, for which examples are offered. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Exceptional Complex Chromosomal Rearrangements in Three Generations

    PubMed Central

    Kartapradja, Hannie; Marzuki, Nanis Sacharina; Pertile, Mark D.; Francis, David; Suciati, Lita Putri; Anggaratri, Helena Woro; Ambarwati, Debby Dwi; Idris, Firman Prathama; Lesmana, Harry; Trimarsanto, Hidayat; Paramayuda, Chrysantine; Harahap, Alida Roswita

    2015-01-01

    We report an exceptional complex chromosomal rearrangement (CCR) found in three individuals in a family that involves 4 chromosomes with 5 breakpoints. The CCR was ascertained in a phenotypically abnormal newborn with additional chromosomal material on the short arm of chromosome 4. Maternal karyotyping indicated that the mother carried an apparently balanced CCR involving chromosomes 4, 6, 11, and 18. Maternal transmission of the derivative chromosome 4 resulted in partial trisomy for chromosomes 6q and 18q and a partial monosomy of chromosome 4p in the proband. Further family studies found that the maternal grandmother carried the same apparently balanced CCR as the proband's mother, which was confirmed using the whole chromosome painting (WCP) FISH. High resolution whole genome microarray analysis of DNA from the proband's mother found no evidence for copy number imbalance in the vicinity of the CCR translocation breakpoints, or elsewhere in the genome, providing evidence that the mother's and grandmother's CCRs were balanced at a molecular level. This structural rearrangement can be categorized as an exceptional CCR due to its complexity and is a rare example of an exceptional CCR being transmitted in balanced and/or unbalanced form across three generations. PMID:25722897

  19. Molecular refinement of gibbon genome rearrangements.

    PubMed

    Roberto, Roberta; Capozzi, Oronzo; Wilson, Richard K; Mardis, Elaine R; Lomiento, Mariana; Tuzun, Eray; Cheng, Ze; Mootnick, Alan R; Archidiacono, Nicoletta; Rocchi, Mariano; Eichler, Evan E

    2007-02-01

    The gibbon karyotype is known to be extensively rearranged when compared to the human and to the ancestral primate karyotype. By combining a bioinformatics (paired-end sequence analysis) approach and a molecular cytogenetics approach, we have refined the synteny block arrangement of the white-cheeked gibbon (Nomascus leucogenys, NLE) with respect to the human genome. We provide the first detailed clone framework map of the gibbon genome and refine the location of 86 evolutionary breakpoints to <1 Mb resolution. An additional 12 breakpoints, mapping primarily to centromeric and telomeric regions, were mapped to approximately 5 Mb resolution. Our combined FISH and BES analysis indicates that we have effectively subcloned 49 of these breakpoints within NLE gibbon BAC clones, mapped to a median resolution of 79.7 kb. Interestingly, many of the intervals associated with translocations were gene-rich, including some genes associated with normal skeletal development. Comparisons of NLE breakpoints with those of other gibbon species reveal variability in the position, suggesting that chromosomal rearrangement has been a longstanding property of this particular ape lineage. Our data emphasize the synergistic effect of combining computational genomics and cytogenetics and provide a framework for ultimate sequence and assembly of the gibbon genome.

  20. Dynamic behavior of rearranging carbocations – implications for terpene biosynthesis

    PubMed Central

    Hare, Stephanie R

    2016-01-01

    Summary This review describes unexpected dynamical behaviors of rearranging carbocations and the modern computational methods used to elucidate these aspects of reaction mechanisms. Unique potential energy surface topologies associated with these rearrangements have been discovered in recent years that are not only of fundamental interest, but also provide insight into the way Nature manipulates chemical space to accomplish specific chemical transformations. Cautions for analyzing both experimental and theoretical data on carbocation rearrangements are included throughout. PMID:27340434

  1. Photo-induced oxidation of Sb(III) on goethite.

    PubMed

    Fan, Jian-Xin; Wang, Yu-Jun; Fan, Ting-Ting; Cui, Xiao-Dan; Zhou, Dong-Mei

    2014-01-01

    Goethite widely exists in soils and sediments, and plays a very important role in the environmental fate of toxic metal(loid)s. In the present study, photo-induced oxidation of antimonite [Sb(III)] on goethite was investigated with kinetic measurements and X-ray photoelectron spectroscopy (XPS) techniques. Effects of environmental factors including solution pH, the content of goethite as well as humic acid on the photo-induced oxidation of antimonite were tested. The results indicated that no oxidation of antimonite occurred in goethite suspension in the dark, but significant amounts of antimonite were transformed to antimonate when the suspension was exposed to light. Ferrous ions were found in the solution during the antimonite oxidation process, and its concentration decreased with increasing solution pH, which strongly affected the oxidation rate of antimonite. The initial solution pH has great impact on Sb oxidation. After 2h illumination, the highest oxidation rate was found at pH 3, while the initial oxidation rate was even higher at pH 9. In conclusion, the antimonite can be adsorbed and oxidized on goethite irradiated with light, which will greatly reduce its environmental risk. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Photoinduced Birefringence in Azo-Dye Doped Polyurethane

    NASA Astrophysics Data System (ADS)

    Aleksejeva, J.; Gerbreders, A.; Reinfelde, M.; Teteris, J.

    2011-01-01

    In this report we describe a photoinduced birefringence in disperse red (DR1) azo-dye doped polyurethane films. DR1 dye molecules in these films are chemically bound with the polyurethane polymer's main chain. Under laser radiation the DR1 molecules experience the isomerization process; as a result, the dipole moment of such a molecule changes and they align in the presence of electric field. Photo-birefringence was induced by linearly polarized laser radiation (532 nm, 448 nm, 375 nm and 632.8 nm) in the films with various concentrations of DR1 dye. The photo-induced birefringence (PIBR) Δn was measured at 634 nm wavelength, and its dependences on the pumping beam wavelength and intensity were evaluated. The Δn relaxation was studied both in the dark and under light illumi-nation. In DR1-doped polyurethane films the holographic recording was performed using laser light radiation (532 nm). The profile of surface relief grating (SRG) was studied using AFM. The relationship between SRG formation and PIBR is discussed.

  3. Photoinduced Kondo effect in CeZn3P3

    NASA Astrophysics Data System (ADS)

    Kitagawa, J.; Kitajima, D.; Shimokawa, K.; Takaki, H.

    2016-01-01

    The Kondo effect, which originates from the screening of a localized magnetic moment by a spin-spin interaction, is widely observed in nonartificial magnetic materials, artificial quantum dots, and carbon nanotubes. In devices based on quantum dots or carbon nanotubes that target quantum information applications, the Kondo effect can be tuned by a gate voltage, a magnetic field, or light. However, the manipulation of the Kondo effect in nonartificial materials has not been thoroughly studied; in particular, the artificial creation of the Kondo effect remains unexplored. Per this subject study, however, a route for the optical creation of the Kondo effect in the nonartificial material p -type semiconductor CeZn3P3 is presented. The Kondo effect emerges under visible-light illumination of the material by a continuous-wave laser diode and is ultimately revealed by photoinduced electrical resistivity, which clearly exhibits a logarithmic temperature dependency. By contrast, a La-based compound (LaZn3P3 ) displays only normal metallic behavior under similar illumination. The photoinduced Kondo effect, which occurs at higher temperatures when compared with the Kondo effect in artificial systems, provides a potential range of operation for not only quantum information/computation devices but also for operation of magneto-optic devices, thereby expanding the range of device applications based on the Kondo effect.

  4. Photoinduced Electron Transfer Process Visualized on Single Silver Nanoparticles.

    PubMed

    Lei, Gang; Gao, Peng Fei; Yang, Tong; Zhou, Jun; Zhang, Hong Zhi; Sun, Shan Shan; Gao, Ming Xuan; Huang, Cheng Zhi

    2017-02-28

    Understanding the photoinduced electron transfer (PET) mechanism is vital to improving the photoelectric conversion efficiency for solar energy materials and photosensitization systems. Herein, we visually demonstrate the PET process by real-time monitoring the photoinduced chemical transformation of p-aminothiophenol (p-ATP), an important SERS signal molecule, to 4,4'-dimercaptoazobenzene on single silver nanoparticles (AgNPs) with a localized surface plasmon resonance (LSPR) spectroscopy coupled dark-field microscopy. The bidirectional LSPR scattering spectral shifts bathochromically at first and hypsochromically then, which are caused by the electron transfer delay of p-ATP, disclose the PET path from p-ATP to O2 through AgNPs during the reaction, and enable us to digitalize the corresponding electron loss and gain on the surface of AgNP at different time periods. This visualized PET process could provide a simple and efficient approach to explore the nature of PET and help to interpret the SERS mechanism in terms of p-ATP.

  5. Imaging of photoinduced tautomerism in single porphyrin molecules

    NASA Astrophysics Data System (ADS)

    Jäger, Regina; Chizhik, Anna M.; Chizhik, Alexey I.; Mack, Hans-Georg; Lyubimtsev, Alexey; Hanack, Michael; Meixner, Alfred J.

    2011-10-01

    In this work we present our new experimental and theoretical results upon investigations of the photoinduced tautomerism processes of single metal-free porphyrin-type molecules. During tautomerization a molecule changes its structure, therefore the excitation transition dipole moment (TDM) of the molecule changes its orientation. Using confocal microscopy in combination with azimuthally and radially polarized laser beams we are able to determine the orientation of the TDM as well as the orientation of a single molecule itself. In the case of tautomerism we are able to visualize this process and even the involved isomers separately. The study first focuses on two symmetrical compounds: a phthalocyanine and a porphyrin. Additionally, differences of the single molecules embedded in a polymer matrix or just spin-coated on a glass cover slide and under nitrogen flow are investigated. In the latter case we observe a higher frequency of the change of the TDM orientation. The experimental studies are supplemented by quantum chemical calculations. Variations of the molecular substituents, the environment and excitation wavelength can give new insights into the excited-state tautomerism process of a single molecule. We also introduce some suggestions for future experiments to support the understanding of the photoinduced tautomerism.

  6. Overview of photo-induced therapy for ATP production

    NASA Astrophysics Data System (ADS)

    Abdalla, Mohamed; Nagy, A.; Ye, W. N.; Mussivand, T.

    2012-10-01

    The purpose of this report is to provide a review of the effects of low-power photo-induced therapy using lasers of different device parameters such as intensity, wavelength, lasing mechanism (i.e., pulsed or continuous) on the production of Adenosine triphosphate (ATP) in mammalian cells. This is a very important research topic as it is suggested in literature that there might be a relationship between the ATP levels and specific diseases. It has been shown that the ATP production was enhanced at wavelengths ranging between 600 nm and 1000 nm (also known as the optical window), in particular at 600nm, 632.8nm, 635nm, 650nm, and 904nm. However, certain experiments showed that the effectiveness of the photo-induced therapy was also dependent on the dosage and the duration of the supplied light. We present the research conclusions drawn from the experiments reported within the last decade, and provide a list of potential medical treatment(s) for patients using visible and near infrared (NIR) light.

  7. Photoinduced development of antibacterial materials derived from isosorbide moiety.

    PubMed

    Lorenzini, Cedric; Haider, Adnan; Kang, Inn-Kyu; Sangermano, Marco; Abbad-Andalloussi, Samir; Mazeran, Pierre-Emmanuel; Lalevée, Jacques; Renard, Estelle; Langlois, Valérie; Versace, Davy-Louis

    2015-03-09

    A straightforward method for immobilizing in situ generated silver nanoparticles on the surface of a photoactivable isosorbide-derived monomer is developed with the objective to design a functional material having antibacterial properties. The photoinduced thiol-ene mechanism involved in these syntheses is described by the electron spin resonance/spin trapping technique. The resulting materials with or without silver nanoparticles (Ag NPs) were used as films or as coatings on glass substrate. The surface of the synthesized materials was characterized by X-ray photoelectron spectroscopy and scanning electron microscopy, and their thermal and mechanical properties were evaluated by dynamic-mechanical thermal tests, differential scanning calorimetry, thermogravimetric analyses, along with pencil hardness, nanoindentation, and scratch resistance tests. The photoinduced formation of Ag NPs is also confirmed by UV spectrophotometry. Finally, a primary investigation demonstrates the antibacterial properties of the isosorbide-derived material against Staphylococcus aureus and Escherichia coli, as well as its cytocompatibility toward NIH 3T3 fibroblastic cells.

  8. Photo-induced reduction of flavin mononucleotide in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Song, S.-H.; Dick, B.; Penzkofer, A.

    2007-01-01

    The photo-induced reduction of flavin mononucleotide (FMN) in aqueous solutions is studied by absorption spectra measurement under aerobic and anaerobic conditions. Samples without exogenous reducing agent and with the exogenous reducing agents ethylene-diamine-tetraacetic acid (EDTA) and dithiothreitol (DTT) are investigated. Under anaerobic conditions the photo-induced reduction with and without reducing agents is irreversible. Under aerobic conditions the photo-reduction without added reducing agent is small compared to the photo-degradation, and the photo-reduction of FMN by the reducing agents is reversible (re-oxidation in the dark). During photo-excitation of FMN the dissolved oxygen is consumed by singlet oxygen formation and subsequent chemical reaction. After light switch-off slow re-oxidation (slow absorption recovery) occurs due to air in-diffusion from surface. EDTA degradation by FMN excitation leads to oxygen scavenging. The quantum efficiencies of photo-reduction under aerobic and anaerobic conditions are determined. The re-oxidation of reduced FMN under aerobic conditions and due to air injection is investigated.

  9. Model for photoinduced bending of slender molecular crystals.

    PubMed

    Nath, Naba K; Pejov, Ljupčo; Nichols, Shane M; Hu, Chunhua; Saleh, Na'il; Kahr, Bart; Naumov, Panče

    2014-02-19

    The growing realization that photoinduced bending of slender photoreactive single crystals is surprisingly common has inspired researchers to control crystal motility for actuation. However, new mechanically responsive crystals are reported at a greater rate than their quantitative photophysical characterization; a quantitative identification of measurable parameters and molecular-scale factors that determine the mechanical response has yet to be established. Herein, a simple mathematical description of the quasi-static and time-dependent photoinduced bending of macroscopic single crystals is provided. This kinetic model goes beyond the approximate treatment of a bending crystal as a simple composite bilayer. It includes alternative pathways for excited-state decay and provides a more accurate description of the bending by accounting for the spatial gradient in the product/reactant ratio. A new crystal form (space group P21/n) of the photoresponsive azo-dye Disperse Red 1 (DR1) is analyzed within the constraints of the aforementioned model. The crystal bending kinetics depends on intrinsic factors (crystal size) and external factors (excitation time, direction, and intensity).

  10. Photoinduced giant magnetic polarons in EuTe

    NASA Astrophysics Data System (ADS)

    Henriques, A. B.; Naupa, A. R.; Usachev, P. A.; Pavlov, V. V.; Rappl, P. H. O.; Abramof, E.

    2017-01-01

    Photoinduced magnetic polarons in EuTe, with a magnetic moment of several hundred Bohr magnetons, were investigated as a function of pump intensity and temperature by pump-probe Faraday rotation. The quantum efficiency for optical generation of magnetic polarons is found to be 0.09. The pump-intensity dependence of the photoinduced Faraday rotation shows a sublinear increase, from which we deduce that the population of photoexcited polarons is limited by a maximum value of 4.5 ×1015cm-3 . This is four orders of magnitude less than the concentration of polarons that would completely fill the crystal, which suggests that the photoexcited polarons are anchored by defects. In addition to the generation of polarons, at high pump densities the modulated pump light also causes a small alternating heating of the illuminated region. The temperature dependence of the polaron magnetic moment is well described by the Curie-Weiss law. Above 100 K, polarons are thermally quenched with an activation energy of 11 meV.

  11. Millisecond Photoinduced Absorption Studies of Pyridine-Based Copolymer Films

    NASA Astrophysics Data System (ADS)

    Coplin, K. A.; Clark, D. T.; Jessen, S. W.; Epstein, A. J.; Fu, D.-K.; Swager, T. M.

    1997-03-01

    We present a study of the photoexcited states in copolymers of poly(p-pyridyl vinylene) and poly(p-phenylene vinylene) (PPyVPR_iV) with sidegroups R_1=C_12H_25 or R_2=COOC_12H_25 attached at the 2 and 5 positions of the phenyl ring. Previous studies discussed the millisecond photoinduced absorption (ms PA) characteristics of PPyVPR_iV powders(S.W. Jessen et al.), Synth. Met., in press.. In particular, triplet-triplet (T-T) transitions were observed at 1.6 eV for both materials. Additional polaron signatures were also observed in both the electronic ( ~ 0.85 eV) and infrared (1100 - 1600 cm-1) regions of the photoinduced spectrum. We compare these powder results with ms PA features for film morphologies of both the copolymers. We observe a weaker ( ~ 10X) T-T^* transition for copolymer films cast from xylene solution indicating a reduction in triplet exciton production as compared to powder samples. These results are contrasted with the behavior we reported(S.W. Jessen et al.), to be published. earlier for film and powder samples of the parent polymer poly(p-pyridyl vinylene).

  12. Applications of the Wittig-Still rearrangement in organic synthesis.

    PubMed

    Rycek, Lukas; Hudlicky, Tomas

    2017-02-16

    This review traces the discovery of the Wittig-Still rearrangement and its applications in organic synthesis. Its relationship to Wittig rearrangements is discussed along with detailed analysis of E/Z- and diastereoselectivity. Modifications of the products arising from the Wittig-Still rearrangement are reviewed in the context of increased complexity in intermediates potentially useful in target oriented synthesis. Early applications of the Wittig-Still rearrangement to modifications of steroids are reviewed as are applications to various terpene and alkaloid natural product targets and miscellaneous compounds. To the best of our knowledge, the literature is covered through December 2016.

  13. Temperature Dependence of the Photoinduced Dynamics on the Cleaved Surface of BaV10O15

    NASA Astrophysics Data System (ADS)

    Nogami, Ayaka; Kanzaki, Tatsuya; Furuhashi, Asuka; Katsufuji, Takuro

    2013-03-01

    The temperature dependence of the photoinduced dynamics by the irradiation of a femtosecond laser pulse was studied for the cleaved surface of BaV10O15, which shows V trimerization with orbital ordering at Tc=123 K. For T>Tc, the photoinduced reflectivity change exhibits oscillation with time, indicating that a photoinduced state propagates with time in the crystal. For Tphotoinduced phase. The different photoinduced dynamics above and below Tc can be attributed to the absence or existence of V trimerization with orbital ordering. We also found that the absolute values of the photoinduced reflectivity change are several times larger on the cleaved surface than those on the polished surface, indicating that remnant stress on the polished surface affects the photoinduced dynamics.

  14. Kinetics of photoinduced anisotropy in bacteriorhodopsin film under two pumping beams.

    PubMed

    Han, Junhe; Yao, Baoli; Gao, Peng; Chen, Liju; Wang, Yingli; Lei, Ming

    2008-07-20

    Photoinduced anisotropy in bacteriorhodopsin (BR) film arises from the selective bleaching of BR molecules to linearly polarized light. The kinetics of photoinduced anisotropy excited by single and two pumping beams are investigated theoretically and experimentally. Compared with a single pumping beam (650 nm), which produces comparatively small photoinduced anisotropy, dual-wavelength linearly polarized pumping beams (650 and 405 nm) can obviously change the photoinduced anisotropy. When the polarization orientation of the 405 nm pumping beam is perpendicular to that of the 650 nm pumping beam, the peak and steady values of the photoinduced anisotropy kinetic curves are remarkably enhanced. But when the two pumping beams have parallel polarization orientation, the peak and steady values are restrained. At a fixed intensity of the 650 nm pumping beam, there exists an optimal intensity for the 405 nm pumping beam to maximize the value of the photoinduced anisotropy. The photoinduced transmittance of the polarizer-BR-analyzer system is modulated by the polarization angle of the 405 nm pumping beam in an approximate-cosine form.

  15. Phase mapping of radionuclide gated biventriculograms in patients with sustained ventricular tachycardia or Wolff-Parkinson-White syndrome

    SciTech Connect

    Le Guludec, D.; Bourguignon, M.; Sebag, C.; Valette, H.; Sirinelli, A.; Davy, J.M.; Syrota, A.; Motte, G.

    1987-01-01

    Accuracy of Fourier phase mapping of radionuclide gated biventriculograms in detecting the origin of abnormal ventricular activation was studied during ventricular tachycardia or preexcitation. Group I included six patients suffering from clinical recurrent VT; 3 gated blood pool studies were acquired for each patient: during sinus rhythm, right ventricular pacing, and induced sustained VT-Group II included seven patients with Wolff-Parkinson-White syndrome and recurrent paroxysmal tachycardia; 3 gated blood pool studies were acquired for each patient: during sinus rhythm, right atrial pacing and orthodromic reciprocating tachycardia. Each acquisition lasted 5 min, in 30 degrees-40 degrees left anterior oblique projection. In Group I, the Fourier phase mapping was consistent with QRS morphology and axis during VT (5/6), except in one patient with LV aneurysm and LBBB electrical pattern during VT. Origin of VT on phase mapping was located in the right ventricle (n = 2) or in left ventricle (n = 4), at the border of wall motion abnormalities each time they existed (5/6). In Group II, the phase advance correlated with the location of the accessory pathway determined by ECG and endocardial mapping (n = 6) and per-operative epicardial mapping (n = 1). Discrimination between anterior and posterior localization of paraseptal pathways and location of intermittent preexcitation was not possible. We conclude that Fourier phase mapping is an accurate method for locating the origin of VT and determining its etiology. It can help locate the site of ventricular preexcitation in patients with only one accessory pathway; its accuracy in locating multiple accessory pathways remains unknown.

  16. [An electrophysiologic and electropharmacological study of functional properties of the bundle of Kent in Wolff-Parkinson-White syndrome].

    PubMed

    Costantini, M; Chimienti, M; Zardini, M; Klersy, C; Guasti, L; Salerno, J A

    1989-04-01

    The aim of this report is to attempt a definition of functional properties of Kent bundle on the basis of electrophysiologic and electropharmacologic data obtained from 89 cases of Wolff-Parkinson-White syndrome selected among a total number of 114 consecutive cases of WPW syndrome that underwent electrophysiologic intracavitary study. In 36 cases anterograde (ant) and retrograde (retr) effective refractory period (ERP) of accessory pathway were evaluated with premature (atrial and ventricular) stimulation at the same driven cycle length. The ant-ERP was longer than retr-ERP in 28/36 patients, shorter in 5 and equal in 2. This strong discrepancy between ant- and retr- ERP suggests an important role of "impedance mismatch" in the activation of ventricular (or atrial) muscle through an anomalous muscular bundle. In 11 cases an intermittent pattern of ventricular preexcitation was observed; in all these patients an anterograde supernormal conduction through the accessory pathway was observed. This aspect could be related to the activation of ventricular muscle, beyond Kent bundle, in its supernormal phase of excitability, suggesting the critical role played by ventricular activation for the appearance of preexcitation. Isoproterenol, injected in 11 cases (1 among them with intermittent ventricular preexcitation in basal conditions), produced a reduction of ant-ERP in all these cases, in spite of its well known poor effect on refractoriness of myocardial fibers. Ajmaline, injected in 32 patients, was able to block ventricular preexcitation in 81% of the cases, in spite of its poor effect on refractoriness of normal tissues. It is very likely that the disappearance of ventricular preexcitation is in this instance expression of lack of ventricular excitation (distal to Kent bundle) consequent to a drug-induced reduction of membrane responsiveness of ventricular cells. In conclusion, all these aspects strongly suggest that the appearance of ventricular (or atrial

  17. Physiological Expression of AMPKγ2RG Mutation Causes Wolff-Parkinson-White Syndrome and Induces Kidney Injury in Mice.

    PubMed

    Yang, Xiaodong; Mudgett, John; Bou-About, Ghina; Champy, Marie-France; Jacobs, Hugues; Monassier, Laurent; Pavlovic, Guillaume; Sorg, Tania; Herault, Yann; Petit-Demoulière, Benoit; Lu, Ku; Feng, Wen; Wang, Hongwu; Ma, Li-Jun; Askew, Roger; Erion, Mark D; Kelley, David E; Myers, Robert W; Li, Cai; Guan, Hong-Ping

    2016-11-04

    Mutations of the AMP-activated kinase gamma 2 subunit (AMPKγ2), N488I (AMPKγ2(NI)) and R531G (AMPKγ2(RG)), are associated with Wolff-Parkinson-White (WPW) syndrome, a cardiac disorder characterized by ventricular pre-excitation in humans. Cardiac-specific transgenic overexpression of human AMPKγ2(NI) or AMPKγ2(RG) leads to constitutive AMPK activation and the WPW phenotype in mice. However, overexpression of these mutant proteins also caused profound, non-physiological increase in cardiac glycogen, which might abnormally alter the true phenotype. To investigate whether physiological levels of AMPKγ2(NI) or AMPKγ2(RG) mutation cause WPW syndrome and metabolic changes in other organs, we generated two knock-in mouse lines on the C57BL/6N background harboring mutations of human AMPKγ2(NI) and AMPKγ2(RG), respectively. Similar to the reported phenotypes of mice overexpressing AMPKγ2(NI) or AMPKγ2(RG) in the heart, both lines developed WPW syndrome and cardiac hypertrophy; however, these effects were independent of cardiac glycogen accumulation. Compared with AMPKγ2(WT) mice, AMPKγ2(NI) and AMPKγ2(RG) mice exhibited reduced body weight, fat mass, and liver steatosis when fed with a high fat diet (HFD). Surprisingly, AMPKγ2(RG) but not AMPKγ2(NI) mice fed with an HFD exhibited severe kidney injury characterized by glycogen accumulation, inflammation, apoptosis, cyst formation, and impaired renal function. These results demonstrate that expression of AMPKγ2(NI) and AMPKγ2(RG) mutations at physiological levels can induce beneficial metabolic effects but that this is accompanied by WPW syndrome. Our data also reveal an unexpected effect of AMPKγ2(RG) in the kidney, linking lifelong constitutive activation of AMPK to a potential risk for kidney dysfunction in the context of an HFD. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. Long-Term Natural History of Adult Wolff-Parkinson-White Syndrome Patients Treated With and Without Catheter Ablation.

    PubMed

    Bunch, T Jared; May, Heidi T; Bair, Tami L; Anderson, Jeffrey L; Crandall, Brian G; Cutler, Michael J; Jacobs, Victoria; Mallender, Charles; Muhlestein, Joseph B; Osborn, Jeffrey S; Weiss, J Peter; Day, John D

    2015-12-01

    There are a paucity of data about the long-term natural history of adult Wolff-Parkinson-White syndrome (WPW) patients in regard to risk of mortality and atrial fibrillation. We sought to describe the long-term outcomes of WPW patients and ascertain the impact of ablation on the natural history. Three groups of patients were studied: 2 WPW populations (ablation: 872, no ablation: 1461) and a 1:5 control population (n=11 175). Long-term mortality and atrial fibrillation rates were determined. The average follow-up for the WPW group was 7.9±5.9 (median: 6.9) years and was similar between the ablation and nonablation groups. Death rates were similar between the WPW group versus the control group (hazard ratio, 0.96; 95% confidence interval, 0.83-1.11; P=0.56). Nonablated WPW patients had a higher long-term death risk compared with ablated WPW patients (hazard ratio, 2.10; 95% confidence interval: 1.50-20.93; P<0.0001). Incident atrial fibrillation risk was higher in the WPW group compared with the control population (hazard ratio, 1.55; 95% confidence interval, 1.29-1.87; P<0.0001). Nonablated WPW patients had lower risk than ablated patients (hazard ratio, 0.39; 95% confidence interval, 0.28-0.53; P<0.0001). Long-term mortality rates in WPW patients are low and similar to an age-matched and gender-matched control population. WPW patients that underwent the multifactorial process of ablation had a lower mortality compared to nonablated WPW patients. Atrial fibrillation rates are high long-term, and ablation does not reduce this risk. © 2015 American Heart Association, Inc.

  19. Dyssynchronous ventricular contraction in Wolff-Parkinson-White syndrome: a risk factor for the development of dilated cardiomyopathy.

    PubMed

    Dai, Chen-Cheng; Guo, Bao-Jing; Li, Wen-Xiu; Xiao, Yan-Yan; Jin, Mei; Han, Lin; Sun, Jing-Ping; Yu, Cheuk-Man; Dong, Jian-Zeng

    2013-11-01

    Emerging evidence suggests that significant left ventricular dysfunction may arise in right-sided septal or paraseptal accessory pathways (APs) with Wolff-Parkinson-White syndrome, even in the absence of recurrent or incessant tachycardia. During 1 year and 9 months, we identified four consecutive female children with median age of 8 years diagnosed as having dilated cardiomyopathy (DCM) combined with overt right-sided APs several years ago. Incessant or recurrent tachycardia as the cause of DCM could be excluded. Anti-heart failure chemotherapy did not produce satisfactory effects. The patients underwent radiofrequency ablations (RFCAs). This report describes the clinical and echocardiographic characteristics of the cases before and after the ablation. Dyssynchronous ventricular contraction was observed in all patients. The locations of the APs were the right-sided anteroseptum and the free wall (n = 2 each). All patients received successful RFCAs. Their physical activities and growth improved greatly, and the echocardiographic data demonstrated that their left ventricular (LV) contraction recovered to synchrony shortly after the ablation and that their LV function recovered to normal gradually during the follow-up. A causal relationship between overt ventricular preexcitation and the development of DCM is supported by the complete recovery of LV function and reversed LV remodeling after the loss of ventricular preexcitation. Preexcitation-related dyssynchrony was probably the crucial mechanism. Not only right-sided septal or paraseptal but also free wall overt APs may induce LV dysfunction and even DCM. AP-induced DCM is an indication for ablation with a good prognosis.

  20. [Wolff-Parkinson-White syndrome. Value of intravenous flecainide for detecting Kent's pathways with short refractory period].

    PubMed

    Talard, P; Cointe, R; Bru, P; Moyal, C; Lacombe, P; Bremondy, M; Levy, S; Gerard, R

    1990-04-01

    The aim of this study was to assess the value of a non-invasive test in detecting accessory pathways with short anterograde effective refractory periods (AERP) (less than or equal to 270 ms) in patients with the Wolff-Parkinson-White syndrome. An intravenous injection of Flecainide acetate was administered to 19 consecutive patients referred for electrophysiological investigation of a WPW syndrome with permanent pre-excitation of the surface electrocardiogram. The first 8 patients (Group I) received a dose of 1.5 mg/kg over 5 minutes and the following 11 patients (Group II) were given 2 mg/kg in 5 minutes. In Group I, preexcitation disappeared in 3 patients (37.5%) who all had accessory pathways with AERP greater than 270 ms. It persisted in the other 5 patients (62.5%) of whom 4 had AERP less than or equal to 270 ms and 1 an AERP greater than 270 ms (false negative). In Group II, preexcitation disappeared in 8 patients (72.2%) of whom 4 had AERP greater than 270 ms and 4 had AERP less than 270 ms (false positives). Preexcitation persisted in the 3 other patients (27.3%); the AERP was less than or equal to 270 ms in 2 patients and greater than 270 ms in the other patients. These results suggest that intravenous Flecainide acetate at the dose of 1.5 mg/kg could be useful in differentiating WPW syndromes with long refractory periods (greater than 270 ms) from those with short refractory periods (less than or equal to 270 ms) with a satisfactory sensitivity and specificity, and that further studies on larger numbers of patients are required to confirm this hypothesis.

  1. [Ablation of accessory pathways by radiofrequency current. Towards a simplified approach of Wolff-Parkinson-White syndrome?].

    PubMed

    Atallah, G; Touboul, P; Zuloaga, C; Kirkorian, G; Lavaud, P; Moncada, E; Chevalier, P; Canu, G; Claudel, J P

    1993-06-01

    From December 1990 to April 1992, 41 consecutive patients (22 men and 19 women with an average age of 35 +/- 16 years -6-72) underwent ablation of accessory atrioventricular conduction pathways (Bundles of Kent) for poorly tolerated and/or medically resistant supraventricular tachycardias. In 33 cases, the arrhythmia was a paroxysmal SVT, in 7 cases atrial fibrillation, and in 1 patient incessant junctional tachycardia causing left ventricular dysfunction. The Wolff-Parkinson-White syndrome was apparent in 30 patients and concealed in 11 cases. The location of the Kent bundle was left lateral in 22 cases (53.7%), posterior paraseptal in 9 cases (21.9%), right lateral in 5 cases (12.2%) and anterior paraseptal in 5 cases (12.2%). The Kent bundles were ablated by radiofrequency currents in 38 cases (92.7%); in 2 patients (4.9%) in whom radiofrequency could not be used (increased impedance) high energy electrical shock was successful. In one patient (2.4%), it was not possible to suppress the Kent bundle. A single session of radiofrequency ablation was sufficient in 33 cases: 7 cases (17.5%) required 2 (4) or 3 (3) sessions. The average number of sites of application per patient was 8.8 +/- 8.8. The duration and intensity were respectively 32.2 +/- 9.3 (5-60) seconds and 25 +/- 15 (20-30) watts. With an average follow-up of tachycardia or of ventricular preexcitation have been observed in the 40 patients. In addition, in 36 patients, electrophysiological control studies confirmed the initial result with absence of any disturbance of nodohisian conduction.(ABSTRACT TRUNCATED AT 250 WORDS)

  2. [Surgery of Wolff-Parkinson-White: value of the epicardial approach. Apropos of 28 surgically treated cases].

    PubMed

    Menasché, P; Leclercq, J F; Cauchemez, B; Coumel, P; Slama, R; Piwnica, A

    1987-01-01

    The authors report their experience of 28 cases of the Wolff-Parkinson-White (WPW) syndrome treated by surgery. Four patients had multiple accessory pathways; of the 32 bundles of Kent detected, 16 were in the postero-septal region. Surgery, performed under cardio-pulmonary bypass after epicardial mapping, consisted in atrioventricular disconnection using no special physical agent. With the exception of 2 cases, the left lateral accessory pathways were operated using a classical left intraatrial approach whereas in the right lateral and septal forms the main procedure of dissection of the right atrioventricular groove was carried out by an epicardial approach. There was one operative death due to haemodynamic and haemorrhagic problems in a top class athlete with two bundles of Kent, the interruption of which required two consecutive bypass procedures. In the 27 survivors, 29 of the 30 accessory pathways were successfully interrupted (96 p. 100). The only failure occurred in a patient with two bundles of Kent. On the other hand, in 2 patients, complete atrioventricular block was successfully obtained by surgical section of the His bundle during the same procedure in one case, and by postoperative catheter ablation in the other case in which surgery had failed. There were no cases of accidental permanent atrioventricular block. The results in this series confirm the value of surgery in the treatment of the WPW syndrome, especially in the septal forms which are reputed to be the most difficult but in which the approach is greatly simplified by the initial dissection of the tricuspid ring by an epicardial approach.(ABSTRACT TRUNCATED AT 250 WORDS)

  3. Exercise testing and thallium-201 myocardial perfusion scintigraphy in the clinical evaluation of patients with Wolff Parkinson White syndrome

    SciTech Connect

    Poyatos, M.E.; Suarez, L.; Lerman, J.; Guibourg, H.; Camps, J.; Perosio, A.

    1986-10-01

    In 58 patients with Wolff Parkinson White syndrome (WPW), we performed exercise stress testing in order to investigate the incidence of normalization of the auriculo-ventricular conduction and the ST-segment changes. For a more accurate evaluation of the latter, exercise and redistribution radionuclide images with Thallium-201 were obtained in 18 cases. Forty-nine had type A and nine had type B of WPW. Forty-eight had permanent, four had alternant and six had no pre-excitation (PE) when they started the test. Mean maximal functional capacity, mean maximal heart rate and mean maximal double product were not different when compared to an age-matched control group. Of the 48 patients who began the test with PE, in 23 (48%) it disappeared while PE persisted in 25 (52%). In 16 cases the disappearance of the PE was sudden and in seven it was progressive. Pre-excitation persisted in 39.5% of patients with type A and in 88.8% with type B (p less than 0.01). ST-segment depression was observed in 76.6% of patients with PE and in 28.6% of cases without PE (p less than 0.01). ST-segment depression occurred in 44.8% of patients with type A and in 100% of cases with type B (p less than 0.05). Transient abnormal Thallium-201 scans were observed in 62.5% of patients without PE and in 20% with PE. No patients showed exertional arrhythmias. This study suggests the possibility of measuring the duration of the refractory period of the accessory pathway in those patients n which the PE disappears suddenly, at a given heart rate.

  4. [Usefulness of the thoracic circle in localizing the pre-excitation zone in Wolff-Parkinson-White syndrome].

    PubMed

    Iturralde, P; de Micheli, A; Romero, L; Hernández, D; Méndez, A; Gutiérrez, A; Colin, L; González Hermosillo, J A

    1989-01-01

    In this study thoracic circle lead electrocardiogram were recorded during sinus rhythm in 50 patients with Wolff Parkinson White Syndrome. We analyzed: delta wave polarity, QRS axis in the frontal plane, ventricular preexcitation, the pattern of precordial R wave transition and QRS morphology in the unipolar leads, also concordance between electrocardiographic patterns and the site of the accessory pathway determined during electrophysiological study. Electrocardiograms from patients with left lateral sites showed negative delta waves in leads LI or a VL, V7 to V9, positive delta waves in V3R to V9R, a normal QRS axis and early precordial R wave transition (20 of 23 patients). Left posterior sites manifested negative Delta waves in L3, a VF, V7 to V9, V7R to V9R and a prominent R wave in V1 (4 of 5 patients). Left posteroparaseptal sites had the same pattern plus negative delta waves in L2, a superior QRS axis, and RS or Rs morphology in V1 (3 of 3 patients). Right posteroparaseptal sites had negative delta waves in L2, L3, a VF, V3R to V9R, positive delta waves in V7 to V9, a superior QRS axis and an R greater than S in V1 (10 of 11 patients). Right free wall locations manifested negative delta waves in L3, a VR, V3R to V9R, positive delta waves in V7 to V9, a normal QRS axis and R wave transition in V3 to V5 with QS morphology since V3R to V9R (6 of 7 patients).(ABSTRACT TRUNCATED AT 250 WORDS)

  5. Origin of the photoinduced current of strongly correlated YMnO3 ferroelectric epitaxial films

    NASA Astrophysics Data System (ADS)

    Miura, Kohei; Zhang, Lejun; Kiriya, Daisuke; Ashida, Atsushi; Yoshimura, Takeshi; Fujimura, Norifumi

    2017-10-01

    We have studied the photoinduced carrier generation and the carrier emission resulting in a photoinduced current using strongly correlated YMnO3 ferroelectric thin films. The unipolar material YMnO3 is suitable for studying the effect of the ferroelectric polarization on the photoinduced current. A clear relationship between the direction of the polarization and the photoinduced current was recognized using (0001)YMnO3 epitaxial films. The current switching corresponding to the polarization switching is also observed under white light illumination. To study the origin of the photoinduced current that originated from the photoinduced carrier generation, the light energy dependence of the photoinduced current was investigated. A small peak at 1.75 eV and a broad peak at around 2.5 eV are observed at room temperature. The peak at 1.75 eV corresponds to the optical absorption at 1.7 eV generated by the electron transition between the Mn 3d (xy,x2 - y2) (e2g state)/O 2p hybridized band and upper Mn 3d (3z 2 ‑ r 2) (a1g state) orbital. The broad peak of the photoinduced current corresponds to the broad photoluminescence excitation spectrum at around 2.5 eV, which is never observed in absorption measurement but reported as the hidden optical channel. The origin of the photoinduced current of YMnO3 is discussed in relation to the carrier generation and the emission processes.

  6. Photoinduced currents in pristine and ion irradiated kapton-H polyimide

    SciTech Connect

    Sharma, Anu Sridharbabu, Y. Quamara, J. K.

    2014-10-15

    The photoinduced currents in pristine and ion irradiated kapton-H polyimide have been investigated for different applied electric fields at 200°C. Particularly the effect of illumination intensity on the maximum current obtained as a result of photoinduced polarization has been studied. Samples were irradiated by using PELLETRON facility, IUAC, New Delhi. The photo-carrier charge generation depends directly on intensity of illumination. The samples irradiated at higher fluence show a decrease in the peak current with intensity of illumination. The secondary radiation induced crystallinity (SRIC) is responsible for the increase in maximum photoinduced currents generated with intensity of illumination.

  7. Cytoplasmic rearrangements associated with amphibian egg symmetrization

    NASA Technical Reports Server (NTRS)

    Malacinski, G. M.

    1984-01-01

    Cytoplasmic rearrangements which follow fertilization were mentioned in normal and inverted eggs. A set of yolk compartments was resolved by cytological analyses of both normally oriented and inverted eggs. Those compartments were characterized by their yolk platelet compositions and movement during egg inversion. It is found that during egg inversion the yolk compartments shift minor cytoplasmic compartments which line the egg cortex. Those yolk mass shifts occurred only after the inverted egg was activated. The direction of shift of the major yolk components, rather than the sperm entrance site, determines the dorsal/ventral polarity of the inverted egg. Among different spawnings the rate of shift varied. Eggs that displayed the fastest rate of shift exhibited the highest frequency of developmental abnormalities during organogenesis. Interpretation of novel observations on cytoplasmic organization provide criticism of some earlier models. A new density compartment model is presented as a coherent way to view the organization of the egg cytoplasm and the development of bilateral symmetry.

  8. Cytoplasmic rearrangements associated with amphibian egg symmetrization

    NASA Technical Reports Server (NTRS)

    Malacinski, G. M.

    1984-01-01

    Cytoplasmic rearrangements which follow fertilization were mentioned in normal and inverted eggs. A set of yolk compartments was resolved by cytological analyses of both normally oriented and inverted eggs. Those compartments were characterized by their yolk platelet compositions and movement during egg inversion. It is found that during egg inversion the yolk compartments shift minor cytoplasmic compartments which line the egg cortex. Those yolk mass shifts occurred only after the inverted egg was activated. The direction of shift of the major yolk components, rather than the sperm entrance site, determines the dorsal/ventral polarity of the inverted egg. Among different spawnings the rate of shift varied. Eggs that displayed the fastest rate of shift exhibited the highest frequency of developmental abnormalities during organogenesis. Interpretation of novel observations on cytoplasmic organization provide criticism of some earlier models. A new density compartment model is presented as a coherent way to view the organization of the egg cytoplasm and the development of bilateral symmetry.

  9. Androgen receptor gene mutation, rearrangement, polymorphism

    PubMed Central

    Eisermann, Kurtis; Wang, Dan; Jing, Yifeng; Pascal, Laura E.

    2013-01-01

    Genetic aberrations of the androgen receptor (AR) caused by mutations, rearrangements, and polymorphisms result in a mutant receptor that has varied functions compared to wild type AR. To date, over 1,000 mutations have been reported in the AR with most of these being associated with androgen insensitivity syndrome (AIS). While mutations of AR associated with prostate cancer occur less often in early stage localized disease, mutations in castration-resistant prostate cancer (CRPC) patients treated with anti-androgens occur more frequently with 10-30% of these patients having some form of mutation in the AR. Resistance to anti-androgen therapy usually results from gain-of-function mutations in the LBD such as is seen with bicalutamide and more recently with enzalutamide (MDV3100). Thus, it is crucial to investigate these new AR mutations arising from drug resistance to anti-androgens and other small molecule pharmacological agents. PMID:25045626

  10. Rearrangement of the bacterial chromosome: forbidden inversions.

    PubMed

    Segall, A; Mahan, M J; Roth, J R

    1988-09-09

    The order of genes in the chromosome of enteric bacteria has been evolutionarily conserved despite the existence of mechanisms for rearrangement. Homologous chromosomal sequences in the same orientation recombine to form deletions or duplications. When homologous sequences in inverse orientation recombine, one expects to form an inversion of the intervening chromosomal segment. This expectation was tested by placing pairs of homologous sequences in inverse order at various points in the chromosome. Sequences at many pairs of sites (permissive) do recombine to generate the expected inversion, while the same sequences placed at other pairs of sites (nonpermissive) do not form an inversion. For the one nonpermissive interval tested, the missing inversion type can be constructed by an alternative transductional method; strains with this inversion are viable. Thus mechanistic limitations must prevent sequences at particular sites from undergoing the recombination event required to form an inversion.

  11. Biotinylated Platinum(II) Ferrocenylterpyridine Complexes for Targeted Photoinduced Cytotoxicity.

    PubMed

    Mitra, Koushambi; Shettar, Abhijith; Kondaiah, Paturu; Chakravarty, Akhil R

    2016-06-06

    Biotinylated platinum(II) ferrocenylterpyridine (Fc-tpy) complexes [Pt(Fc-tpy)(L(1))]Cl (1) and [Pt(Fc-tpy)(L(2))]Cl (2), where HL(1) and HL(2) are biotin-containing ligands, were prepared, and their targeted photoinduced cytotoxic effect in cancer cells over normal cells was studied. A nonbiotinylated complex, [Pt(Fc-tpy)(L(3))]Cl (3), was prepared as a control to study the role of the biotin moiety in cellular uptake properties of the complexes. Three platinum(II) phenylterpyridine (Ph-tpy) complexes, viz., [Pt(Ph-tpy)(L(1))]Cl (4), [Pt(Ph-tpy)(L(2))]Cl (5), and [Pt(Ph-tpy)(L(3))]Cl (6), were synthesized and explored to understand the role of a metal-bound Fc-tpy ligand over Ph-tpy as a photoinitiator. The Fc-tpy complexes displayed an intense absorption band near 640 nm, which was absent in their Ph-tpy analogues. The Fc-tpy complexes (1 mM in 0.1 M TBAP) showed an irreversible cyclic voltammetric anodic response of the Fc/Fc(+) couple near 0.25 V. The Fc-tpy complexes displayed photodegradation in red light of 647 nm involving the formation of a ferrocenium ion (Fc(+)) and reactive oxygen species (ROS). Photoinduced release of the biotinylated ligands was observed from spectral measurements, and this possibly led to the controlled generation of an active platinum(II) species, which binds to the calf-thymus DNA used for this study. The biotinylated photoactive Fc-tpy complexes showed significant photoinduced cytotoxicity, giving a IC50 value of ∼7 μM in visible light of 400-700 nm with selective uptake in BT474 cancer cells over HBL-100 normal cells. Furthermore, ferrocenyl complexes resulted in light-induced ROS-mediated apoptosis, as indicated by DCFDA, annexin V/FITC staining, and sub-G1 DNA content determined by fluorescent activated cell sorting analysis. The phenyl analogues 4 and 5 were photostable, served as DNA intercalators, and demonstrated selective cytotoxicity in the cancer cells, giving IC50 values of ∼4 μM.

  12. [Correlation between the orientation of the data wave and the topography of pre-excitation in the Wolff-Parkinson-White syndrome].

    PubMed

    Frank, R; Fontaine, G; Guiraudon, G; Cabrol, C; Grosgogeat, Y; Facquet, J

    1977-05-01

    A comparison between the epicardial siting of the zone of pre-excitation of the ventricle in Wolff-Parkinson-White syndrome and the ECG has allowed us to distinguish 6 topographical types, according to the orientation of the delta wave in the horizontal plane, and especially in the frontal plane which is often ignored: right anterior, left lateral, right of left anterior paraseptal, and right or left posterior paraseptal. The association of a heart defect with ventricular hypertrophy, or the coexistence of several associated accessory pathways prevents such correlation and makes it imperative to carry out intracavitary investigation and epicardial mapping to localise the accessory pathway if surgery is contemplated.

  13. Contributions of the Instituto Nacional de Cardiología in the diagnosis and treatment of the Wolff-Parkinson - White syndrome.

    PubMed

    Iturralde-Torres, Pedro; Márquez, Manlio F

    2010-01-01

    Since the first description of the disease now known as Wolff-Parkinson-White syndrome, much knowledge has been gained through several experimental and clinical studies all over the world. The Instituto Nacional de Cardiología Ignacio Chávez in Mexico City has not been the exception. In this report, we describe the clinical, electrocardiographic and electrophysiologic contributions of past and present researchers at the Institute, as well as the experience in the diagnosis and treatment of the W-P-W syndrome at this Instituto Nacional de Cardiología Ignacio Chávez.

  14. Defects and Rearrangements in Disordered Solids

    NASA Astrophysics Data System (ADS)

    Wijtmans, Sven

    In this thesis, I will investigate the properties of disordered materials under strain. Disordered materials encompass a large variety of materials, including glasses, polymers, granular matter, dense colloids, and gels. There is currently no constitutive equation based on microscopic observables that describes these materials. Given the prevalence and usefulness of these materials, we derive tools to aid our understanding of them. We develop a new method to isolate localized defects from extended vibrational modes in disordered solids. This method augments particle interactions with an artificial potential that acts as a high-pass filter: it preserves small-scale structures while pushing extended vibrational modes to higher frequencies. The low-frequency modes that remain are ``bare" defects; they are exponentially localized without the quadrupolar tails associated with elastic interactions. We demonstrate that these localized excitations are excellent predictors of plastic rearrangements in the solid. We characterize several of the properties of these defects that appear in mesoscopic theories of plasticity, including their distribution of energy barriers, number density, and size, which is a first step in testing and revising continuum models for plasticity in disordered solids. We additionally study the properties of rearrangement types in 2D disordered packings of particles with a harmonic potential at a range of packing fractions above jamming. We develop a generalizable procedure that classifies events by stress drop, energy drop, and reversibility under two protocols. Somewhat surprisingly, we find a large population of contact change events that have no associated stress drop. Reversible events become more common at high pressures above a packing fraction of phi=0.865, at which point line reversible events are more common than loop reversible events. At low pressures, irreversible events are associated with spatially extended events, while at high

  15. Synthesis of Methyl Cyclopentanecarboxylate: A Laboratory Experience in Carbon Rearrangement

    ERIC Educational Resources Information Center

    Orchard, Alexandra; Maniquis, Roxanne V.; Salzameda, Nicholas T.

    2016-01-01

    We present a novel guided inquiry second semester organic chemistry laboratory rearrangement experiment. Students performed the Favorskii Rearrangement to obtain methyl cyclopentanecarboxylate in good yields. The students learned about the individual steps of the Favorskii mechanism and were required to propose a complete reaction mechanism and…

  16. Many levels of control of V gene rearrangement frequency.

    PubMed

    Feeney, Ann J; Goebel, Peter; Espinoza, Celia R

    2004-08-01

    V, D, and J gene segments rearrange at very different frequencies. As with most biological systems, there are multiple levels of control of V gene recombination frequency, and here we review some of the work from our laboratory that addresses these various control mechanisms. One of the important factors that affect non-random V gene rearrangement frequency is the natural heterogeneity in recombination signal sequences (RSSs). Not only does variation in the heptamer and nonamer affect rearrangement, but variation in the spacer can also dramatically affect recombination. However, there are clearly other factors which control V gene rearrangement, as revealed by the fact that genes with identical RSSs can rearrange at different frequencies in vivo. Some of these other influences most likely affect the earliest stages of control--the change from an inaccessible state to an accessible state. Transcription factors can play a role in inducing these changes. Rearrangement of many VkappaI genes can be induced in a non-lymphoid cell line after ectopic expression of E2A, while neighboring VkappaII and VkappaIII genes do not rearrange, demonstrating that at least one level of control of induction of accessibility occurs at the level of the individual gene. Also, changes in chromatin structure can affect accessibility and might influence individual V gene rearrangement frequency.

  17. Synthesis of Methyl Cyclopentanecarboxylate: A Laboratory Experience in Carbon Rearrangement

    ERIC Educational Resources Information Center

    Orchard, Alexandra; Maniquis, Roxanne V.; Salzameda, Nicholas T.

    2016-01-01

    We present a novel guided inquiry second semester organic chemistry laboratory rearrangement experiment. Students performed the Favorskii Rearrangement to obtain methyl cyclopentanecarboxylate in good yields. The students learned about the individual steps of the Favorskii mechanism and were required to propose a complete reaction mechanism and…

  18. Analysis of genome rearrangement by block-interchanges.

    PubMed

    Lu, Chin Lung; Lin, Ying Chih; Huang, Yen Lin; Tang, Chuan Yi

    2007-01-01

    Block-interchanges are a new kind of genome rearrangements that affect the gene order in a chromosome by swapping two nonintersecting blocks of genes of any length. More recently, the study of such rearrangements is becoming increasingly important because of its applications in molecular evolution. Usually, this kind of study requires to solve a combinatorial problem, called the block-interchange distance problem, which is to find a minimum number of block-interchanges between two given gene orders of linear/circular chromosomes to transform one gene order into another. In this chapter, we shall introduce the basics of block-interchange rearrangements and permutation groups in algebra that are useful in analyses of genome rearrangements. In addition, we shall present a simple algorithm on the basis of permutation groups to efficiently solve the block-interchange distance problem, as well as ROBIN, a web server for the online analyses of block-interchange rearrangements.

  19. Photo-induced reflectivity in the mid and far infrared

    SciTech Connect

    Haar, P.; Harrington, K.J.; Schwettman, H.A.

    1995-12-31

    Interest in switching FEL beams has motivated studies of photo-induced reflectivity in the mid and far infrared. We are particularly interested in Ge{sup 4}, GaAs, and Si{sup 5}, materials that can be pumped with a visible or near-IR conventional laser and which together cover the wavelengths from 3-100{mu}m. We have made quantitative measurements to determine the induced reflectivity, carrier lifetime, and transient absorption of these materials at several wavelengths across this range using a variety of pump laser wavelengths and pulse lengths. These measurements allow us to determine the feasibility of single pulse selection and cavity dumping with our FELs at high repetition rates.

  20. Photoinduced surface voltage mapping study for large perovskite single crystals

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojing; Liu, Yucheng; Gao, Fei; Yang, Zhou; Liu, Shengzhong Frank

    2016-05-01

    Using a series of illumination sources, including white light (tungsten-halogen lamp), 445-nm, 532-nm, 635-nm, and 730-nm lasers, the surface photovoltage (SPV) images were mapped for centimeter-sized CH3NH3PbX3 (X = Cl, Br, I) perovskite single crystals using Kelvin probe force microscopy. The significant SPV signals were observed to be wavelength-dependent. We attribute the appreciable SPV to the built-in electric field in the space charge region. This study shines light into the understanding of photoinduced charge generation and separation processes at nanoscale to help advance the development of perovskite solar cells, optoelectronics, laser, photodetector, and light-emitting diode (LED).

  1. Preparation of diarylethene copolymers and their photoinduced refractive index change

    NASA Astrophysics Data System (ADS)

    Cho, S. Y.; Yoo, M.; Shin, H.-W.; Ahn, K.-H.; Kim, Y.-R.; Kim, E.

    2003-01-01

    Diarylethene copolymers were synthesized from 1-(6 '-vinyl-2 '-methylbenzo[ b]thiophene-3 '-yl)-2-(2 ''-methylbenzo [ b]thiophene-3 ''-yl)hexafluorocyclopentene (VMBTF6) and 1-[6 '-(4 '''-vinylbenzoyl)-2 '-methylbenzo[ b]thiophene-3 '-yl]-2-(2 ''-methylbenzo[ b]thiophene-3 ''-yl)hexafluorocyclopentene (VBMBTF6) via living free radical techniques using stable TEMPO derivatives. The diarylethene content was controlled by the feed ratio of diarylethene derivatives and styrene. Transparent photochromic polymer films were prepared from the diarylethene copolymers with narrow molecular weight dispersion (PD˜1.3) by spin coating method. Photoinduced refractive index changes (Δ nTE) of the polymer films, with 25 mol% of diaryethene content, accompanied by the photochromic change were determined as 0.0009 and 0.0030 for poly(styrene- ran -VMBTF6) and poly(styrene- ran-VBMBTF6), respectively.

  2. DNA Intercalated Psoralen Undergoes Efficient Photoinduced Electron Transfer.

    PubMed

    Fröbel, Sascha; Reiffers, Anna; Torres Ziegenbein, Christian; Gilch, Peter

    2015-04-02

    The interaction of psoralens with DNA has been used for therapeutic and research purposes for decades. Still the photoinduced behavior of psoralens in DNA has never been observed directly. Femtosecond transient absorption spectroscopy is used here to gain direct insight into the photophysics of a DNA-intercalated psoralen (4'-aminomethyl-4,5',8-trimethyl-psoralen (AMT)). Intercalation reduces the excited singlet lifetime of AMT to 4 ps compared with 1400 ps for AMT in water. This singlet quenching prohibits the population of the triplet state that is accessed in free AMT. Instead, a DNA to AMT electron transfer takes place. The resulting radical pair decays primarily via charge recombination with a time constant of 30 ps. The efficient electron transfer observed here reveals a completely new aspect of the psoralen-DNA interaction.

  3. Photoinduced Acrylate Polymerization: Unexpected Reduction in Chain Branching.

    PubMed

    Wenn, Benjamin; Reekmans, Gunter; Adriaensens, Peter; Junkers, Thomas

    2015-08-01

    The branching stemming from midchain radical formation in n-butyl acrylate polymerization is investigated via melt-state (13) C NMR measurements. The dependence of the degree of branching (DB) on the monomer conversion of the system is examined for photoinduced polymerizations, revealing a steady increase in branching with conversion. For polymerization at moderate light intensities, an increase in branching from 0.03% to 0.37% is observed for polymerizations at 60 °C, which is fivefold below the level of branching observed in thermally initiated polymerizations under otherwise identical reaction conditions. The reason for this overall reduction in branching remains momentarily unclear; yet, a strong dependence of branching on light intensity is observed. While polymerization under a 1 W LED lamp results at almost full monomer conversion in branching degrees of 0.22%, polymerization under a 400 W lamp yields 1.81% of chain branches.

  4. Photoinduced Magnetization in a Thin Fe-CN-Co Film.

    NASA Astrophysics Data System (ADS)

    Huh, Y. D.; Talham, D. R.; Park, J.-H.; Meisel, M. W.

    2004-03-01

    We have studied the photoinduced magnetization of a new low dimensional system, a thin film of a Prussian blue derivative, Rb_jCo_k[Fe(CN)_6]_l. This film was synthesized by the sequential depositions of Rb^+/Co^2+ and [Fe(CN)_6]^3- ions on the surface of a templated Fe-CN-Co monolayer. In this novel 2D system, high spin states of the Fe and Co spins interact antiferromagnetically and experience long range ordering below 20 K. The spins form domains that exhibit behavior consistent with a cluster spin-glass description. Upon illumination with light, the population of the high spin states increases, resulting in a rapid increase of the magnetization of the film and a modification of the cluster spin-glass properties.

  5. Photoinduced surface voltage mapping study for large perovskite single crystals

    SciTech Connect

    Liu, Xiaojing; Liu, Yucheng; Gao, Fei; Yang, Zhou; Liu, Shengzhong

    2016-05-02

    Using a series of illumination sources, including white light (tungsten-halogen lamp), 445-nm, 532-nm, 635-nm, and 730-nm lasers, the surface photovoltage (SPV) images were mapped for centimeter-sized CH{sub 3}NH{sub 3}PbX{sub 3} (X = Cl, Br, I) perovskite single crystals using Kelvin probe force microscopy. The significant SPV signals were observed to be wavelength-dependent. We attribute the appreciable SPV to the built-in electric field in the space charge region. This study shines light into the understanding of photoinduced charge generation and separation processes at nanoscale to help advance the development of perovskite solar cells, optoelectronics, laser, photodetector, and light-emitting diode (LED).

  6. Method for characterizing bulk recombination using photoinduced absorption

    NASA Astrophysics Data System (ADS)

    Wilson, Nora M.; Sandén, Simon; Sandberg, Oskar J.; Österbacka, Ronald

    2017-03-01

    The influence of reaction order and trap-assisted recombination on continuous-wave photoinduced absorption measurements is clarified through analytical calculations and numerical simulations. The results reveal the characteristic influence of different trap distributions and enable distinguishing between shallow exponential and Gaussian distributions and systems dominated by direct recombination by analyzing the temperature dependence of the in-phase and quadrature signals. The identifying features are the intensity dependence of the in-phase at high intensity, P A I ∝ I γ HI , and the frequency dependence of the quadrature at low frequency, P A Q ∝ ω γ LF . For direct recombination, γHI and γLF are temperature independent, and for an exponential distribution, they depend on the characteristic energy Ech as γ HI = 1 / ( 1 + E ch / k T ) and γ LF = k T / E ch , while a Gaussian distribution shows γHI and γLF as functions of I and ω, respectively.

  7. Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

    NASA Astrophysics Data System (ADS)

    Zhang, Tiantian; Ma, Dongdong; Pan, Sujuan; Wu, Shijun; Jiang, Yufeng; Zeng, Di; Yang, Hongqin; Peng, Yiru

    2016-10-01

    Photo-induced electron transfer (PET) is an important and fundamental process in natural photosynthesis. To mimic such interesting PET process, a suitable donor and acceptor couple were properly chosen. Dendrimer phthalocyanines and their derivatives have emerged as promising materials for artificial photosynthesis systems. In this paper, the electron transfer between the light harvest dendrimer phthalocyanine (donor) and the 1,4-benzoquinone (acceptor) was studied by UV/Vis and fluorescence spectroscopic methods. It was found that fluorescence of phthalocyanine was quenched by benzoquinone (BQ) via excited state electron transfer, from the phthalocyanine to the BQ upon excitation at 610 nm. The Stern-Volmer constant (KSV) of electron transfer was calculated. Our study suggests that this dendritic phthalocyanine is an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.

  8. Photoinduced blinking in a solid-state quantum system

    NASA Astrophysics Data System (ADS)

    Berhane, Amanuel M.; Bradac, Carlo; Aharonovich, Igor

    2017-07-01

    Solid-state single-photon emitters (SPEs) are one of the prime components of many quantum nanophotonics devices. In this work, we report on an unusual, photoinduced blinking phenomenon of SPEs in gallium nitride. This is shown to be due to the modification in the transition kinetics of the emitter, via the introduction of additional laser-activated states. We investigate and characterize the blinking effect on the brightness of the source and the statistics of the emitted photons. Combining second-order correlation and fluorescence trajectory measurements, we determine the photodynamics of the trap states and characterize power-dependent decay rates and characteristic "off"-time blinking. Our work sheds light into understanding solid-state quantum system dynamics and, specifically, power-induced blinking phenomena in SPEs.

  9. Luminescence and photoinduced absorption in ytterbium-doped optical fibres

    SciTech Connect

    Rybaltovsky, A A; Aleshkina, S S; Likhachev, M E; Bubnov, M M; Umnikov, A A; Yashkov, M V; Gur'yanov, Aleksei N; Dianov, Evgenii M

    2011-12-31

    Photochemical reactions induced in the glass network of an ytterbium-doped fibre core by IR laser pumping and UV irradiation have been investigated by analysing absorption and luminescence spectra. We have performed comparative studies of the photoinduced absorption and luminescence spectra of fibre preforms differing in core glass composition: Al{sub 2}O{sub 3} : SiO{sub 2}, Al{sub 2}O{sub 3} : Yb{sub 2}O{sub 3} : SiO{sub 2}, and P{sub 2}O{sub 5} : Yb{sub 2}O{sub 3} : SiO{sub 2}. The UV absorption spectra of unirradiated preform core samples show strong bands peaking at 5.1 and 6.5 eV, whose excitation plays a key role in photoinduced colour centre generation in the glass network. 'Direct' UV excitation of the 5.1- and 6.5-eV absorption bands at 244 and 193 nm leads to the reduction of some of the Yb{sup 3+} ions to Yb{sup 2+}. The photodarkening of ytterbium-doped fibres by IR pumping is shown to result from oxygen hole centre generation. A phenomenological model is proposed for the IR-pumping-induced photodarkening of ytterbium-doped fibres. The model predicts that colour centre generation in the core glass network and the associated absorption in the visible range result from a cooperative effect involving simultaneous excitation of a cluster composed of several closely spaced Yb{sup 3+} ions.

  10. Photo-induced transformations in 2,2':5',2''-terthiophene thin films on silver.

    PubMed

    Alaverdyan, Yury; Johansson, Patrik; Käll, Mikael

    2006-03-28

    We report on transient photo-induced structural changes of 2,2':5',2''-terthiophene (3T) adsorbed on silver nanoparticles. Surface-enhanced Raman scattering (SERS) data show that the film thickness predetermines the eventual course of these changes. In particular, for high molecular concentrations (thick adsorbate layers), illumination leads to a photoinduced polymerization of the 3T film. For thin layers ( approximately monolayer coverage), the photoinduced spectral evolution is qualitatively different. We interpret the latter process as a cleavage of the terthiophene molecule, resulting in isolated thiophene units. Calculations of excitation energies for 3T + 3Ag+ and 1T + Ag+ revealed visible transitions, while calculated Raman frequencies indicated 1T as a possible photoproduct. As no photoinduced transformations are observed for 3T in the solid or solution phases, it is likely that the processes reported here originate in surface-enhanced charge-transfer between the Ag-surface and the organic adsorbate.

  11. Photoinduced properties of nanocrystalline TiO2-anatase coating on Ti-based bone implants.

    PubMed

    Lorenzetti, Martina; Biglino, Daniele; Novak, Saša; Kobe, Spomenka

    2014-04-01

    The paper reports on the photoinduced properties of hydrothermally treated (HT) titanium used for bone implants. The anatase coatings composed of 30-100nm anatase crystals exhibited high photocatalytic activity and good photo-induced wettability, reaching a superhydrophilic state, despite the larger crystal dimensions than the previously reported optimal ones. These properties are due to a suitable combination of surface texture, roughness, thickness, crystal morphology and particle size, which allowed the two independent photo-induced phenomena to occur simultaneously. The results on caffeine degradation by photocatalysis and the prolonged effect (up to two weeks) of photo-induced wettability in dark suggested a possible applicability of the HT anatase coatings as bacteria-repelling surfaces for body implants, in favor of a better osseointegration in vivo.

  12. Transfection of exogenous rotavirus rearranged RNA segments in cells infected with a WT rotavirus results in subsequent gene rearrangements.

    PubMed

    Duponchel, Sarah; Troupin, Cécile; Vu, Lan Trang; Schnuriger, Aurélie; Trugnan, Germain; Garbarg-Chenon, Antoine

    2014-09-01

    Group A rotaviruses, members of the family Reoviridae, are a major cause of infantile acute gastroenteritis. The rotavirus genome consists of 11 dsRNA segments. In some cases, an RNA segment is replaced by a rearranged RNA segment, which is derived from its standard counterpart by partial sequence duplication. It has been shown that some rearranged segments are preferentially encapsidated into viral progenies after serial passages in cell culture. Based on this characteristic, a reverse genetics system was used previously to introduce exogenous segment 7 rearrangements into an infectious rotavirus. This study extends this reverse genetics system to RNA segments 5 and 11. Transfection of exogenous rotavirus rearranged RNA segment 5 or 11 into cells infected with a WT helper rotavirus (bovine strain RF) resulted in subsequent gene rearrangements in the viral progeny. Whilst recombinant viruses were rescued with an exogenous rearranged segment 11, the exogenous segment was modified by a secondary rearrangement. The occurrence of spontaneous rearrangements of WT or exogenous segments is a major hindrance to the use of this reverse genetics approach. © 2014 The Authors.

  13. Alternating photoinduced mass transport triggered by light polarization in azobenzene containing sol-gel films

    NASA Astrophysics Data System (ADS)

    Fabbri, F.; Lassailly, Y.; Lahlil, K.; Boilot, J. P.; Peretti, J.

    2010-02-01

    Combined shear-force and near-field optical microscopies are used for real-time monitoring of the formation of photoinduced surface relief gratings in photochromic thin films containing azobenzene derivatives. The correlated optical and topographical images provide evidence that the direction of the photoinduced matter migration is defined by the light polarization pattern and that, for a given light intensity pattern, modulating the polarization between two orthogonal states gives rise to alternating mass transport.

  14. Irradiance and Temperature Dependence of Photo-Induced Orientation in Two Azobenzene-Based Polymers

    DTIC Science & Technology

    1998-06-23

    and Almeria Natansohn* Department of Chemistry, Queen’s University, Kingston, Ontario, K7L 3N6 Paul Rochon Department of Physics, Royal Military...1. IRRADIANCE AND TEMPERATURE DEPENDENCE OF PHOTO-INDUCED ORIENTATION IN TWO AZOBENZENE-BASED POLYMERS Dennis Hore and Almeria Natansohn...IRRADIANCE AND TEMPERATURE DEPENDENCE OF PHOTO-INDUCED ORIENTATION IN TWO AZOBENZENE-BASED POLYMERS Dennis Hore and Almeria Natansohn Department of

  15. Identification of ALK Rearrangements in Malignant Peritoneal Mesothelioma.

    PubMed

    Hung, Yin P; Dong, Fei; Watkins, Jaclyn C; Nardi, Valentina; Bueno, Raphael; Dal Cin, Paola; Godleski, John J; Crum, Christopher P; Chirieac, Lucian R

    2017-09-14

    Malignant peritoneal mesothelioma is a rare, aggressive tumor arising from the peritoneal lining, induced by asbestos, therapeutic radiation, or germline mutations. Nevertheless, the molecular features remain largely unknown. To investigate anaplastic lymphoma kinase (ALK) rearrangements in a large series of peritoneal mesothelioma and characterize the mutational landscape of these tumors. We studied 88 consecutive patients (39 men, 49 women; median age 61, range 17-84 years) with peritoneal mesotheliomas diagnosed at a single institution between 2005 and 2015. We identified ALK-positive mesotheliomas by immunohistochemistry and confirmed ALK rearrangement by fluorescence in situ hybridization (FISH). In ALK-rearranged cases, we characterized the fusion partners using targeted next-generation sequencing of both tumor DNA and RNA. In select cases, we quantified asbestos fibers by combined scanning electron microscopy and x-ray spectroscopy. We also explored ALK rearrangement in a separate series of 205 patients with pleural mesothelioma. Identification and characterization of novel ALK rearrangements and correlations with clinicopathologic characteristics. Anaplastic lymphoma kinase was positive by immunohistochemistry in 11 (13%) peritoneal mesotheliomas (focal weak in 8, diffuse strong in 3). In focal weak ALK-positive cases, no ALK rearrangement was detected by FISH or next-generation sequencing. In strong diffuse ALK-positive cases, FISH confirmed ALK rearrangements, and next-generation sequencing identified novel fusion partners ATG16L1, STRN, and TPM1. Patients with ALK-rearranged peritoneal mesotheliomas were women and younger than patients without ALK rearrangement (median age 36 vs 62; Mann-Whitney test, P = .02), but all other clinicopathologic characteristics (size of tumor nodules, histology, treatment, and survival) were not different. No asbestos fibers were detected in ALK-rearranged cases. Furthermore, loss of chromosomal region 9p or 22q or

  16. [Wolff-Parkinson-White syndrome. Correlation between the results of electrophysiological investigation and exercise tolerance testing on the electrical aspect of preexcitation].

    PubMed

    Lévy, S; Broustet, J P; Clémenty, J; Vircoulon, B; Guern, P; Bricaud, H

    1979-06-01

    Fourteen patients with permanent electrocardiographical features of the Wolff-Parkison-White syndrome in sinus rhythm referred for electrophysiological investigation also underwent maximal exercise tolerance tests. The working hypothesis was that in patients with the Wolff-Parkinson-White syndrome with accessory pathways of longer effective refractory periods than the normal pathway (group I) the delta wave should disappear on exercise, whilst in patients with accessory pathways with shorter refractory periods than the normal pathway (group II) the delta wave should persist. Of the 9 patients in group I,the delta wave regressed in 8 and persisted in 1 patient; of the 5 patients in group II, the delta wave persisted in 4 of them. Three patients had attacks of tachycardia during or just after the exercise tolerance test. These results suggest that the exercise tolerance test may help in the identification of patients with accessory pathways with long refractory periods, less susceptible to rapid ventricular rhythms should atrial fibrillation occur, and therefore with better prognoses.

  17. Rearrangement of gas in disc galaxies

    NASA Astrophysics Data System (ADS)

    Piñol Ferrer, Núria

    Active galactic nuclei and bursts of star formation are two distinct phenomena that amply change their host environments. They are present in a significant number of galaxies at all redshifts. In this thesis, we aim toward a better understanding of the physical processes that allow for the formation and maintenance of these two phenomena. We focus on the study of the physical conditions of the interstellar gas in the central kiloparsec region of the barred active galaxy NGC 1097 (Paper I). In Paper I we present different CO transitions and the consequent analysis realized in order to derive the molecular gas content together with the molecular mass inflow toward the centre of the galactic gravitational potential well. To completely understand the physical processes that drive such gas rearrangement, a coherent picture for a dynamical system has to be considered. We have developed a code, Paper II, in order to model the dynamics of a predominantly rotating system with an arbitrary mass distribution. The formalism we have used is based on analytical solutions of the first order approximation of the equations of motion of a smooth medium that may be subject to dissipation. The most important free parameter to constrain the boundary conditions of the model is the angular frequency of the perturbing pattern, which may be assumed virtually invariant over significant ranges of galactocentric radii. We constrain the pattern velocity using the Tremaine-Weinberg method (Paper III). Hence, we have prepared all procedures needed to comprehend the physical processes that sustain the nuclear activity and bursts of star formation: the amount of gas in the region and the dynamics of the system. In Paper IV, we model the neutral and ionized gas kinematics in NGC 1097 and apply a combination of the methods described in Paper II and Paper III to comprehend the rearrangement of gas in the galaxy. In order to observationally discern the gas inflow in the nuclear region at a higher

  18. Antimatter-matter scattering including rearrangement

    NASA Astrophysics Data System (ADS)

    Kadyrov, Alisher

    2014-10-01

    Two distinct versions of the convergent close coupling (CCC) approach to ion-atom and ion-molecule collisions have been developed in the impact parameter representation. The first method starts from the exact three-body Schrödinger equation for the total scattering wave function and leads to coupled-channel Lippmann-Schwinger type integral equations for the transition amplitudes, with the relative motion of the heavy particles treated fully quantum mechanically. The second approach utilises a traditional semi-classical approximation. It is based on the time-dependent Schrödinger equation for the electronic part of the scattering wave function and leads to a system of coupled differential equations. This allows one to test the quality of approximations used in standard approaches to the problem. Both methods are applied to calculate antiproton collisions with inert gases and simple molecular targets in the energy range from 1 keV to 1 MeV. The methods are also applied to proton collisions including rearrangement channels. Interplay of direct ionisation and electron capture to continuum in target breakup is investigated. The first CCC calculations of the antiproton and proton stopping power in atomic and molecular hydrogen are presented. The work was supported by the Australian Research Council.

  19. Human Structural Variation: Mechanisms of Chromosome Rearrangements.

    PubMed

    Weckselblatt, Brooke; Rudd, M Katharine

    2015-10-01

    Chromosome structural variation (SV) is a normal part of variation in the human genome, but some classes of SV can cause neurodevelopmental disorders. Analysis of the DNA sequence at SV breakpoints can reveal mutational mechanisms and risk factors for chromosome rearrangement. Large-scale SV breakpoint studies have become possible recently owing to advances in next-generation sequencing (NGS) including whole-genome sequencing (WGS). These findings have shed light on complex forms of SV such as triplications, inverted duplications, insertional translocations, and chromothripsis. Sequence-level breakpoint data resolve SV structure and determine how genes are disrupted, fused, and/or misregulated by breakpoints. Recent improvements in breakpoint sequencing have also revealed non-allelic homologous recombination (NAHR) between paralogous long interspersed nuclear element (LINE) or human endogenous retrovirus (HERV) repeats as a cause of deletions, duplications, and translocations. This review covers the genomic organization of simple and complex constitutional SVs, as well as the molecular mechanisms of their formation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Human structural variation: mechanisms of chromosome rearrangements

    PubMed Central

    Weckselblatt, Brooke; Rudd, M. Katharine

    2015-01-01

    Chromosome structural variation (SV) is a normal part of variation in the human genome, but some classes of SV can cause neurodevelopmental disorders. Analysis of the DNA sequence at SV breakpoints can reveal mutational mechanisms and risk factors for chromosome rearrangement. Large-scale SV breakpoint studies have become possible recently owing to advances in next-generation sequencing (NGS) including whole-genome sequencing (WGS). These findings have shed light on complex forms of SV such as triplications, inverted duplications, insertional translocations, and chromothripsis. Sequence-level breakpoint data resolve SV structure and determine how genes are disrupted, fused, and/or misregulated by breakpoints. Recent improvements in breakpoint sequencing have also revealed non-allelic homologous recombination (NAHR) between paralogous long interspersed nuclear element (LINE) or human endogenous retrovirus (HERV) repeats as a cause of deletions, duplications, and translocations. This review covers the genomic organization of simple and complex constitutional SVs, as well as the molecular mechanisms of their formation. PMID:26209074

  1. TERT structural rearrangements in metastatic pheochromocytomas.

    PubMed

    Dwight, Trisha; Flynn, Aidan; Amarasinghe, Kaushalya; Benn, Diana E; Lupat, Richard; Li, Jason; Cameron, Daniel; Hogg, Annette; Balachander, Shiva; Candiloro, Ida Lm; Wong, Stephen; Robinson, Bruce G; Papenfuss, Anthony T; Gill, Anthony J; Dobrovic, Alexander; Hicks, Rodney J; Clifton-Bligh, Roderick; Tothill, Richard William

    2017-10-03

    Pheochromocytomas (PC) and paragangliomas (PGL) are endocrine tumors for which the genetic and clinico-pathological features of metastatic progression remain incompletely understood. As a result, the risk of metastasis from a primary tumor cannot be predicted. Early diagnosis of individuals at high risk of developing metastases is clinically important and the identification of new biomarkers that are predictive of metastatic potential is of high value. Activation of TERT has been associated with a number of malignant tumors, including PC/PGL. However, the mechanism of TERT activation in the majority of PC/PGL remains unclear. As TERT promoter mutations occur rarely in PC/PGL, we hypothesized that other mechanisms - such as structural variations - may underlie TERT activation in these tumors. From 35 PC and four PGL, we identified three primary PC that developed metastases with elevated TERT expression, each of which lacked TERT promoter mutations and promoter DNA methylation. Using whole genome sequencing we identified somatic structural alterations proximal to the TERT locus in two of these tumors. In both tumors, the genomic rearrangements led to positioning of super-enhancers proximal to the TERT promoter, that are likely responsible for activation of the normally tightly repressed TERT expression in chromaffin cells.

  2. Clonal immunoglobulin gene rearrangement in the infarcted lymph node syndrome.

    PubMed

    Laszewski, M J; Belding, P J; Feddersen, R M; Lutz, C T; Goeken, J A; Kemp, J D; Dick, F R

    1991-07-01

    The authors report a case of complete lymph node infarction in which a specific etiology could not be determined by morphologic or immunophenotypic studies; however, clonal rearrangement of the immunoglobulin gene was demonstrated by Southern blot hybridization of DNA extracted from the necrotic tissue. A subsequent lymph node biopsy later was diagnosed as malignant lymphoma, using morphologic, immunophenotypic and genotypic criteria. Identical clonally rearranged bands were present in DNA from both the infarcted nodal and the subsequent tissue biopsies. In the setting of lymph node necrosis, gene rearrangement studies may provide diagnostic information concerning clonality, even if morphologic and immunophenotypic studies are indeterminate for a lymphoproliferative process.

  3. Photoinduced Charge and Energy Transfer Processes in Molecular Aggregates

    SciTech Connect

    John F. Endicott

    2009-10-20

    This project involved the experimental probing of the electronic excited states generated by photoinduced (center-to-center) electron and energy transfer processes in several classes of transition metal donor/acceptor (D/A) complexes. Some of the general properties inferred from these studies should be useful in the design of new systems for energy conversion applications. Pursuit of the project goals has involved the determination of electron transfer efficiencies and the detailed study of variations in the electronic spectra of D/A complexes. This has resulted in the study of some very fundamental issues of photoinduced charge transfer and the identification of some of the constraints on its efficiency. The experimental studies of the competition between the degradative non-radiative unimolecular relaxation of transition metal excited states and their transfer of charge from these excited states to external acceptors have involved a range of techniques such as transient decay kinetics, photoacoustic calorimetry and transient or stationary state spectroscopy. The substrates synthesized for these studies were selected to provide model systems, or series of model systems to probe the validity of models of electronic excited states and their reactivity. The work during the last few years has focused largely, but not exclusively, on the use of emission spectral band shapes to probe the properties of charge transfer (CT) excited states. Bandshape variations are one of the very few approaches for systematically probing electronic excited states and good band shape resolution is necessary in order to gain information about the structural variations that correlate with excited state reactivity. Differences in molecular structure correlate with differences in chemical reactivity, and the variations in emission bandshapes are well known to relate to variations in the molecular structural differences between the excited and ground electronic states. However, it is has been

  4. Competitive reaction pathways for o-anilide aryl radicals: 1,5- or 1,6-hydrogen transfer versus nucleophilic coupling reactions. A novel rearrangement to afford an amidyl radical.

    PubMed

    Rey, Valentina; Pierini, Adriana B; Peñéñory, Alicia B

    2009-02-06

    The photoinduced reactions of o-iodoanilides (o-IC6H4N(Me)COR, 4a-d) with sulfur nucleophiles such as thiourea anion (1, -SCNH(NH2)), thioacetate anion (2, MeCOS-), and sulfide anion (3, S(2-)) follow different reaction channels, giving the sulfides by a radical nucleophilic substitution or the dehalogenated products by hydrogen atom transfer pathways. After an initial photoinduced electron transfer (PET) from 1 to iodide 4, the o-amide aryl radicals 12 are generated. These aryl radicals 12 afford alternative reaction pathways depending on the structure of the alpha-carbonyl moiety: (a) 12b (R = Me) adds to 1 to render the methylthio-substituted compounds by quenching the thiolate anion intermediate with MeI after irradiation; (b) 12c (R = -CH2Ph) follows a 1,5-hydrogen transfer to give a stabilized alpha-carbonyl radical (17); and (c) 12d (R = t-Bu) affords 1,6-hydrogen transfer, followed by a 1,4-aryl migration to render an amidyl radical (20), which is reduced to the N-benzyl-N,2-dimethylpropanamide (10). Together with this last rearranged product, the ipso substitution derivative was also observed. Similar results were obtained in the PET reactions of 4d (R = t-Bu) with anions 2 and 3 under entrainment conditions with the enolate anion from cyclohexenone (5) or the tert-butoxide anion (6). From this novel rearrangement, and only under reductive conditions by PET reaction with anion 5, iodide 4d (R = t-Bu) affords quantitatively the propanamide 10. The energetic of the intramolecular rearrangements followed by radicals 12b-d were rationalized by B3LYP/6-31+G* calculations.

  5. Developmentally Programmed, RNA-Directed Genome Rearrangement in Tetrahymena

    PubMed Central

    Mochizuki, Kazufumi

    2013-01-01

    Developmentally programmed genome rearrangement has been observed in a variety of eukaryotes from vertebrates to worms to protists, and it provides an interesting exception to the general rule of the constancy of the genome. DNA elimination in the ciliated protozoan Tetrahymena is one of the most well-characterized programmed genome rearrangement events. DNA elimination in the newly formed macronucleus of Tetrahymena is epigenetically regulated by the DNA sequence of the parental macronucleus. Dicer-produced, Piwi-associated small RNAs mediate this epigenetic regulation, probably through a whole-genome comparison of the germline micronucleus to the somatic macronucleus. However, a correlation between small RNAs and programmed genome rearrangement could not be detected in the worm Ascaris suum. Therefore, different types of eukaryotes may have developed unique solutions to perform genome rearrangement. PMID:22103557

  6. The Petasis-Ferrier rearrangement: developments and applications.

    PubMed

    Minbiole, Emily C; Minbiole, Kevin P C

    2016-04-01

    In the mid-1990s, Petasis reexamined a promising but infrequently used rearrangement strategy, the so-called Ferrier-type-II reaction, and provided it with a modern update. Previously, Ferrier had developed a strategy where carbohydrate derivatives would undergo a fragmentation/aldol-type recombination sequence, generating a carbocycle, albeit under the promotion of stoichiometric mercury salts. Petasis' new variant showed the promise to effectively and stereoselectively convert a range of cyclic vinyl acetals to useful tetrahydrofurans and tetrahydropyrans, using less toxic promoters. Since these first reports, the 'Petasis-Ferrier rearrangement' has represented a vibrant area of research and innovation for organic chemists. With numerous applications in complex natural product total synthesis, the utility of the reaction has been resoundingly established. Recent developments have extended the reaction to a broader synthetic context, allowing for in situ generation of rearrangement substrates and more liberal interpretation of what fragmentation/recombination reactions warrant the designation of a Petasis-Ferrier rearrangement.

  7. Somatic Rearrangement in B Cells: It's (Mostly) Nuclear Physics.

    PubMed

    Aiden, Erez Lieberman; Casellas, Rafael

    2015-08-13

    We discuss how principles of nuclear architecture drive typical gene rearrangements in B lymphocytes, whereas translocation hot spots and recurrent lesions reflect the extent of AID-mediated DNA damage and selection.

  8. Antiproton-hydrogen atom rearrangement-annihilation cross section

    SciTech Connect

    Morgan, D.L. Jr.

    1986-08-22

    For antiproton energies of several eV or less, annihilation in matter occurs through atomic rearrangement processes in which the antiproton becomes bound to a nucleus prior to annihilation. Existing calculations of the antiproton-hydrogen atom rearrangement cross section are semiclassical and employ the Born-Oppenheimer approximation. They also employ various arguments in regard to the behavior of the system when the Born-Oppenheimer approximation breaks down at small antiproton-proton separations. These arguments indicate that rearrangement is essentially irreversible. In the present study, a detailed investigation was made of the antiproton-hydrogen atom system when the Born-Oppenheimer approximation breaks down. The results of this study indicate that the previous arguments were approximately correct, but that there is a significant probability for rearrangement reversing prior to annihilation. This probability is estimated to be about 20%. 8 refs., 4 figs., 2 tabs.

  9. Dehydrophenylnitrenes: matrix isolation and photochemical rearrangements.

    PubMed

    Sander, Wolfram; Winkler, Michael; Cakir, Bayram; Grote, Dirk; Bettinger, Holger F

    2007-02-02

    The photochemistry of 3-iodo-2,4,5,6-tetrafluorophenyl azide 8 and 3,5-diiodo-2,4,6-trifluorophenyl azide 9 was studied by IR and EPR spectroscopy in cryogenic argon and neon matrices. Both compounds form the corresponding nitrenes as primary photoproducts in photostationary equilibria with their azirine and ketenimine isomers. In contrast to fluorinated phenylnitrenes, ring-opened products are obtained upon short-wavelength irradiation of the iodine-containing systems, indicative of C-I bond cleavage in the nitrenes or didehydroazepines under these conditions. Neither 3-dehydrophenylnitrene 6 nor 3,5-didehydrophenylnitrene 7 could be detected directly. The structures of the acyclic photoproducts were identified by extensive comparison with DFT calculated spectra. Mechanistic aspects of the rearrangements leading to the observed products and the electronic properties of the title intermediates are discussed on the basis of DFT as well as high-level ab initio calculations. The computations indicate strong through-bond coupling of the exocyclic orbital in the meta position with the singly occupied in-plane nitrene orbital in the monoradical nitrenes. In contrast to the ortho or para isomers, this interaction results in low-spin ground states for meta nitrene radicals and a weakening of the C1-C2 bond causing the kinetic instability of these species even under low-temperature conditions. 3,5-Didehydrophenylnitrenes, on the other hand, in which a strong C3-C5 interaction reduces coupling of the radical sites with the nitrene unit, might be accessible synthetic targets if the intermediate formation of labile monoradicals could be circumvented.

  10. Rearrangement and annihilation in antihydrogen-atom scattering

    SciTech Connect

    Jonsell, Svante

    2008-08-08

    I review some results for annihilation and rearrangement processes in low-energy antihydrogen-hydrogen and antihydrogen-helium scattering. For the strong nuclear force results using a {delta}-function potential are compared to a scattering length approach. It is found that the {delta}-function potential does not give correct annihilation cross sections in the case of antihydrogen-helium scattering. Problem associated with the use of the Born-Oppenheimer approximation for rearrangement calculations are reviewed.

  11. Brief report: Clinical implications of variant ALK FISH rearrangement patterns

    PubMed Central

    Gao, Xin; Sholl, Lynette M.; Nishino, Mizuki; Heng, Jennifer; Jänne, Pasi A.; Oxnard, Geoffrey R.

    2015-01-01

    Introduction Break-apart fluorescence in situ hybridization (FISH) is the FDA-approved assay for detecting anaplastic lymphoma kinase (ALK) rearrangements in non-small cell lung cancer (NSCLC), identifying patients who can gain dramatic benefit from ALK kinase inhibitors. Assay interpretation can be technically challenging, and either splitting of the 5′ and 3′ probes or loss of the 5′ probe constitute rearrangement. We hypothesized that there may be clinical differences depending upon rearrangement pattern on FISH. Methods An IRB-approved database of NSCLC patients at Dana-Farber Cancer Institute was queried for ALK rearrangement. Clinical characteristics and response to crizotinib were reviewed. Immunohistochemistry (IHC) and targeted next-generation sequencing (NGS) were obtained when available. Results Of 1,614 NSCLC patients with ALK testing, 82 (5.1%) patients had ALK rearrangement by FISH: 30 with split signals, 25 with 5′ deletion, and 27 with details unavailable. Patients with 5′ deletion were older (p=0.01) and tended to have more extensive smoking histories (p=0.08). IHC was positive for ALK rearrangement in all 27 patients with FISH split signals, while 3 of 21 patients with FISH 5′ deletion had negative IHC (p=0.05). Targeted NGS on 2 of 3 cases with discordant FISH and IHC results did not identify ALK rearrangement, instead finding driver mutations in EGFR and KRAS. Patients with 5′ deletion treated with crizotinib had a smaller magnitude of tumor response (p=0.03). Conclusions Patients with 5′ deletion on ALK FISH harbor features less typical of ALK-rearranged tumors, potentially indicating that some cases with this variant are false-positives. Corroborative testing with IHC or NGS may be beneficial. PMID:26536196

  12. In vitro irradiation is able to cause RET oncogene rearrangement.

    PubMed

    Ito, T; Seyama, T; Iwamoto, K S; Hayashi, T; Mizuno, T; Tsuyama, N; Dohi, K; Nakamura, N; Akiyama, M

    1993-07-01

    Elevated risk of thyroid cancers among the atomic bomb survivors as compared to the nonexposed population suggests that some genetic events related to thyroid cancer must be caused by ionizing radiation. Accordingly, inducibility of RET oncogene rearrangements, i.e., the generation of the RET-PTC oncogene, specific for thyroid cancer, was investigated among human undifferentiated thyroid carcinoma cells (8505C), which do not have RET oncogene rearrangement, after 0, 10, 50, and 100 Gy of in vitro X-irradiation by means of reverse transcription polymerase chain reaction. After testing 10(8) cells at each dose point, 3 independent samples obtained with 50 Gy of X-irradiation and 6 independent samples obtained with 100 Gy of X-irradiation showed a rearranged RET oncogene amplified band. No rearranged transcripts were obtained from cells irradiated with 0 or 10 Gy. All of the transcripts were sequenced and found to contain the D10S170 and RET sequence. Interestingly, two types of rearrangements were included in these transcripts: one is specific for thyroid cancer and the other, which contains a 150-base pair insert, is atypical, not usually seen in vivo. This insert was found to be the exon of D10S170. Furthermore, in fibrosarcoma cells (HT1080), X-irradiation also induced RET oncogene rearrangements, which included the same two types of rearrangements observed in the X-irradiated thyroid cells (8505C). These results are in favor of the hypothesis that some radiation-induced thyroid cancers, including those among atomic bomb survivors, might have developed when a growth advantage was obtained through a specific form of RET oncogene rearrangement induced by radiation exposure.

  13. Ultrafast infrared studies of complex ligand rearrangements in solution

    SciTech Connect

    Payne, Christine K.

    2003-01-01

    The complete description of a chemical reaction in solution depends upon an understanding of the reactive molecule as well as its interactions with the surrounding solvent molecules. Using ultrafast infrared spectroscopy it is possible to observe both the solute-solvent interactions and the rearrangement steps which determine the overall course of a chemical reaction. The topics addressed in these studies focus on reaction mechanisms which require the rearrangement of complex ligands and the spectroscopic techniques necessary for the determination of these mechanisms. Ligand rearrangement is studied by considering two different reaction mechanisms for which the rearrangement of a complex ligand constitutes the most important step of the reaction. The first system concerns the rearrangement of a cyclopentadienyl ring as the response of an organometallic complex to a loss of electron density. This mechanism, commonly referred to as ''ring slip'', is frequently cited to explain reaction mechanisms. However, the ring slipped intermediate is too short-lived to be observed using conventional methods. Using a combination of ultrafast infrared spectroscopy and electronic structure calculations it has been shown that the intermediate exists, but does not form an eighteen-electron intermediate as suggested by traditional molecular orbital models. The second example examines the initial steps of alkyne polymerization. Group 6 (Cr, Mo, W) pentacarbonyl species are generated photolytically and used to catalyze the polymerization of unsaturated hydrocarbons through a series of coordination and rearrangement steps. Observing this reaction on the femto- to millisecond timescale indicates that the initial coordination of an alkyne solvent molecule to the metal center results in a stable intermediate that does not rearrange to form the polymer precursor. This suggests that polymerization requires the dissociation of additional carbonyl ligands before rearrangement can occur. Overall

  14. Ac/Ds-induced chromosomal rearrangements in rice genomes.

    PubMed

    Xuan, Yuan Hu; Zhang, Jianbo; Peterson, Thomas; Han, Chang-Deok

    2012-03-01

    A closely-linked pair of Ac/Ds elements induces chromosomal rearrangements in Arabidopsis and maize. This report summarizes the Ac/Ds systems that generate an exceptionally high frequency of chromosomal rearrangements in rice genomes. From a line containing a single Ds element inserted at the OsRLG5 locus, plants containing a closely-linked pair of inversely-oriented Ds elements were obtained at 1% frequency among the population regenerated from tissue culture. Subsequent regeneration of the lines containing cis-paired Ds elements via tissue culture led to a high frequency (35.6%) of plants containing chromosomal rearrangements at the OsRLG5 locus. Thirty-four rearrangement events were characterized, revealing diverse chromosomal aberrations including deletions, inversions and duplications. Many rearrangements could be explained by sister chromatid transposition (SCT) and homologous recombination (HR), events previously demonstrated in Arabidopsis and maize. In addition, novel events were detected and presumably generated via a new alternative transposition mechanism. This mechanism, termed single chromatid transposition (SLCT), resulted in juxtaposed inversions and deletions on the same chromosome. This study demonstrated that the Ac/Ds system coupled with tissue culture-mediated plant regeneration could induce higher frequencies and a greater diversity of chromosomal rearrangements than previously reported. Understanding transposon-induced chromosomal rearrangements can provide new insights into the relationship between transposable elements and genome evolution, as well as a means to perform chromosomal engineering for crop improvement. Rice is a staple cereal crop worldwide. Complete genome sequencing and rich genetic resources are great advantages for the study of the genomic complexity induced by transposable elements.(1) (-) (2) The combination of tissue culture with genetic lines carrying a pair of closely located Ac/Ds elements greatly increases the

  15. N-heterocyclic carbene-catalyzed rearrangements of vinyl sulfones.

    PubMed

    Atienza, Roxanne L; Roth, Howard S; Scheidt, Karl A

    2011-01-01

    N-heterocyclic carbenes catalyze the rearrangement of 1,1-bis(arylsulfonyl)ethylene to the corresponding trans-1,2-bis(phenylsulfonyl) under mild conditions. Tandem rearrangement/cycloadditions have been developed to capitalize on this new process and generate highly substituted isoxazolines and additional heterocyclic compounds. Preliminary mechanistic studies support a new conjugate addition/Umpolung process involving the ejection and subsequent unusual re-addition of a sulfinate ion.

  16. Recurrent DNA inversion rearrangements in the human genome

    PubMed Central

    Flores, Margarita; Morales, Lucía; Gonzaga-Jauregui, Claudia; Domínguez-Vidaña, Rocío; Zepeda, Cinthya; Yañez, Omar; Gutiérrez, María; Lemus, Tzitziki; Valle, David; Avila, Ma. Carmen; Blanco, Daniel; Medina-Ruiz, Sofía; Meza, Karla; Ayala, Erandi; García, Delfino; Bustos, Patricia; González, Víctor; Girard, Lourdes; Tusie-Luna, Teresa; Dávila, Guillermo; Palacios, Rafael

    2007-01-01

    Several lines of evidence suggest that reiterated sequences in the human genome are targets for nonallelic homologous recombination (NAHR), which facilitates genomic rearrangements. We have used a PCR-based approach to identify breakpoint regions of rearranged structures in the human genome. In particular, we have identified intrachromosomal identical repeats that are located in reverse orientation, which may lead to chromosomal inversions. A bioinformatic workflow pathway to select appropriate regions for analysis was developed. Three such regions overlapping with known human genes, located on chromosomes 3, 15, and 19, were analyzed. The relative proportion of wild-type to rearranged structures was determined in DNA samples from blood obtained from different, unrelated individuals. The results obtained indicate that recurrent genomic rearrangements occur at relatively high frequency in somatic cells. Interestingly, the rearrangements studied were significantly more abundant in adults than in newborn individuals, suggesting that such DNA rearrangements might start to appear during embryogenesis or fetal life and continue to accumulate after birth. The relevance of our results in regard to human genomic variation is discussed. PMID:17389356

  17. Recurrent DNA inversion rearrangements in the human genome.

    PubMed

    Flores, Margarita; Morales, Lucía; Gonzaga-Jauregui, Claudia; Domínguez-Vidaña, Rocío; Zepeda, Cinthya; Yañez, Omar; Gutiérrez, María; Lemus, Tzitziki; Valle, David; Avila, Ma Carmen; Blanco, Daniel; Medina-Ruiz, Sofía; Meza, Karla; Ayala, Erandi; García, Delfino; Bustos, Patricia; González, Víctor; Girard, Lourdes; Tusie-Luna, Teresa; Dávila, Guillermo; Palacios, Rafael

    2007-04-10

    Several lines of evidence suggest that reiterated sequences in the human genome are targets for nonallelic homologous recombination (NAHR), which facilitates genomic rearrangements. We have used a PCR-based approach to identify breakpoint regions of rearranged structures in the human genome. In particular, we have identified intrachromosomal identical repeats that are located in reverse orientation, which may lead to chromosomal inversions. A bioinformatic workflow pathway to select appropriate regions for analysis was developed. Three such regions overlapping with known human genes, located on chromosomes 3, 15, and 19, were analyzed. The relative proportion of wild-type to rearranged structures was determined in DNA samples from blood obtained from different, unrelated individuals. The results obtained indicate that recurrent genomic rearrangements occur at relatively high frequency in somatic cells. Interestingly, the rearrangements studied were significantly more abundant in adults than in newborn individuals, suggesting that such DNA rearrangements might start to appear during embryogenesis or fetal life and continue to accumulate after birth. The relevance of our results in regard to human genomic variation is discussed.

  18. Evolution of atomic rearrangements in deformation in metallic glasses.

    PubMed

    Shang, B S; Li, M Z; Yao, Y G; Lu, Y J; Wang, W H

    2014-10-01

    Atomic rearrangements induced by shear stress are fundamental for understanding deformation mechanisms in metallic glasses (MGs). Using molecular dynamic simulation, the atomic rearrangements characterized by nonaffine displacements (NADs) and their spatial distribution and evolution with tensile stress in Cu50Zr50 MG were investigated. It was found that in the elastic regime the atomic rearrangements with the largest NADs are relatively homogeneous in space, but exhibit strong spatial correlation, become localized and inhomogeneous, and form large clusters as strain increases, which may facilitate the so-called shear transformation zones. Furthermore, initially they prefer to take place around Cu atoms which have more nonicosahedral configurations. As strain increases, the preference decays and disappears in the plastic regime. The atomic rearrangements with the smallest NADs are preferentially located around Cu atoms, too, but with more icosahedral or icosahedral-like atomic configurations. The preference is maintained in the whole deformation process. In contrast, the atomic rearrangements with moderate NADs distribute homogeneously, and do not show explicit preference or spatial correlation, acting as matrix during deformation. Among the atomic rearrangements with different NADs, those with largest and smallest NADs are nearest neighbors initially, but separating with increasing strain, while those with largest and moderate NADs always avoid to each other. The correlations in the fluctuations of the NADs confirm the long-range strain correlation and the scale-free characteristic of NADs in both elastic and plastic deformation, which suggests a universality of the scaling in the plastic flow in MGs.

  19. Photoinduced isomerization of lycopene and application to tomato cultivation.

    PubMed

    Heymann, Thomas; Raeke, Julia; Glomb, Marcus A

    2013-11-20

    The present study aimed to investigate if growth conditions have an impact on the isomeric composition of lycopene in tomatoes. First a model system for photoinduced isomerization was established. Tomato extracts were irradiated with a halogen lamp, whose wavelength spectrum is close to the spectrum of daylight and thus mimics field-grown cultivation. Different optical filters were interposed between lamp and samples to simulate greenhouse conditions. 5-cis-Lycopene was formed preferentially while the concentration of 7-cis-lycopene decreased in field-grown model systems. The change of isomerization in greenhouse model systems led to a significantly different ratio. Consequently 5-cis- and 7-cis-lycopene were identified as potent markers for the differentiation of various lighting conditions during cultivation. This result was verified in biological samples. Authentic field-grown tomatoes (var. Lycopersicon esculentum Mill. var. commune L. H. Bailey "Harzfeuer") showed a significantly higher content of 5-cis-lycopene 5.90 ± 0.45% compared to tomatoes of the same variety grown under electric lighting 4.11 ± 0.10%. Additionally, the ratio of 7-cis-lycopene was significantly lower under field-grown conditions.

  20. Fourth-order perturbative model for photoinduced internal conversion processes.

    PubMed

    Molesky, Brian P; Moran, Andrew M

    2013-12-27

    Essential to the functionality of numerous biological and synthetic molecular systems is the ability to rapidly convert electronic excitation energy into heat. Such internal conversion (IC) transitions often cannot be described by traditional second-order kinetic theories because of time-coincident electronic and nuclear relaxation processes. Here, we present a perturbative fourth-order phenomenological model for photoinduced IC that incorporates effects associated with finite laser bandwidths and nonequilibrium nuclear motions. Specialized knowledge of first-principles computational methods is not required, and many parameters can be obtained with standard spectroscopic measurements. The model is applied to the IC processes that precede electrocyclic ring-opening in α-terpinene. It is shown that the primary factor governing the shape of the population decay profile (Gaussian versus exponential) is the rate at which the wavepacket approaches the geometry corresponding to degeneracy between the excited states. Other parameters such as the displacement in the promoting mode and the thermal fluctuation amplitudes affect the sensitivity of the IC dynamics to motion of the wavepacket but do not alter the basic physical picture. Finally, we suggest a wavepacket representation of the IC process to visualize correlations between population-transfer dynamics and the amount of energy transferred from the system to the bath.

  1. Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells.

    PubMed

    Juarez-Perez, Emilio J; Sanchez, Rafael S; Badia, Laura; Garcia-Belmonte, Germá; Kang, Yong Soo; Mora-Sero, Ivan; Bisquert, Juan

    2014-07-03

    Organic-inorganic lead trihalide perovskites have emerged as an outstanding photovoltaic material that demonstrated a high 17.9% conversion efficiency of sunlight to electricity in a short time. We have found a giant dielectric constant (GDC) phenomenon in these materials consisting on a low frequency dielectric constant in the dark of the order of ε0 = 1000. We also found an unprecedented behavior in which ε0 further increases under illumination or by charge injection at applied bias. We observe that ε0 increases nearly linearly with the illumination intensity up to an additional factor 1000 under 1 sun. Measurement of a variety of samples of different morphologies, compositions, and different types of contacts shows that the GDC is an intrinsic property of MAPbX3 (MA = CH3NH3(+)). We hypothesize that the large dielectric response is induced by structural fluctuations. Photoinduced carriers modify the local unit cell equilibrium and change the polarizability, assisted by the freedom of rotation of MA. The study opens a way for the understanding of a key aspect of the photovoltaic operation of high efficiency perovskite solar cells.

  2. Electric Field Dependence of Photo-Induced Field Emission Current.

    NASA Astrophysics Data System (ADS)

    Egert, Charles Michael

    We have measured the photo-induced field emission current from a tungsten field emitter as a function of electric field. These experiments were performed with a retardation energy analyzer to measure total current and a 127(DEGREES) cylindrical differential energy analyzer to measure the energy resolved PFE current. The results of these experiments are compared with a simple theory of PFE, developed by Schwartz and Schaich, which is an extension of field emission theory including the surface photoeffect, but assuming constant photoexcitation matrix elements. Our experimental results disagree with this theory in two ways: First, for high fields and photon energy (electrons emitted above the field emission barrier maximum) theory predicts a larger increase in PFE current than is observed experimentally. Second, we have also confirmed the existence of a field dependent oscillatory component of the PFE current emitted from the W(110) surface with photon energies of 2.7 eV and 3.5 eV. The simple theory described here, as well as more sophisticated calculations, have been unable to explain this oscillatory feature. We have also reported, for the first time, the field dependence of the energy resolved PFE current measured with a 127(DEGREES) cylindrical energy analyzer. These preliminary results show evidence of the oscillatory component previously only observed in the total PFE current.

  3. Theoretical approach to photoinduced inhomogeneous anisotropy in bacteriorhodopsin films.

    PubMed

    Acebal, P; Carretero, L; Blaya, S; Murciano, A; Fimia, A

    2007-07-01

    The aim of this work was to perform a complete study of the dynamic and steady-state photoinduced processes of thick bacteriorhodopsin (bR) films, taking into account all the physical parameters and the coupling of rate equations with the energy transfer equation. The theoretical approach was compared with experimental data, and good concordance was found between both sets of data. The theoretical approach shows that the values of the rate constants for solid bR films are about two or three orders of magnitude lower than those observed in solution. It can also be noted that the temperature change during the experiment had a great influence on the final values of transmittance and, consequently, on the inhomogeneous distribution along the coordinate of light propagation. The study shows that, depending on the intensity and wavelength of the pump beam, we can obtain a very inhomogeneous profile of the population densities, which implies an inhomogeneous profile of the birefringence and dichroism. Therefore, this must be taken into account in the applications described for this system.

  4. Origin of photo-induced transmitting oscillations in chalcogenide glasses.

    PubMed

    Tao, HaiZheng; Yang, ZhiYong; Lucas, Pierre

    2009-09-28

    Light-induced oscillatory behaviors of transmission in chalcogenide glasses are investigated using a continuous wave tunable Ti-sapphire laser. It is shown that phase change, thermal fluctuation, nonlinear index change and periodic self focusing are not at the origin of light-induced oscillatory transmittance in chalcogenide glasses. Instead, results indicate that the interference of transmitting and reflecting light is at the origin of the oscillatory behaviors of transmitted light. Just like the principle of Fabry-Pérot interferometer, these interferences result in a periodic change in transmission as the related interferential beams get in and out of phase. However, this transmitting oscillatory behavior can be registered by the detector only when the change of optical path length difference initiated by photo-induced effects is slower enough compared with the corresponding response time of the detector. Several photo-structural effects contribute to that phenomenon including photo-expansion, photo-darkening, and permanent self focusing. It appears that fluctuations of the light source intensity induce a wide distribution of the oscillatory periods.

  5. Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

    NASA Astrophysics Data System (ADS)

    Zhang, Song; Sun, Simei; Zhou, Miaomiao; Wang, Lian; Zhang, Bing

    2017-02-01

    We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products.

  6. Ultrafast photoinduced electron transfer in viologen-linked BODIPY dyes.

    PubMed

    Frath, Denis; Yarnell, James E; Ulrich, Gilles; Castellano, Felix N; Ziessel, Raymond

    2013-10-07

    New boron-dipyrromethene (BODIPY) dyes linked to viologen are prepared and their photophysical and electrochemical properties are investigated. Both synthesized molecules have similar electronic absorption spectra with the absorption maximum localized at 517 and 501 nm for dye 1 and dye 2, respectively. They exhibit well-defined redox behavior, highlighting the presence of BODIPY and viologen subunits, with little perturbation of the redox potential of both subunits with respect to the parent compounds. Both dyes are heavily quenched by photoinduced electron transfer from the BODIPY to the viologen subunit. The transient absorption technique demonstrates that dye 2 forms the viologen radical within a timeframe of 7.1 ps, and that the charge-separated species has a lifetime of 59 ps. Sustained irradiation of dye 2 in the presence of a tertiary amine allows for the accumulation of BODIPY-methyl-4,4'-bipyridinium (BODIPY-MV(+)), as observed by its characteristic absorption at 396 and 603 nm. However, dye 2 does not generate catalytic amounts of hydrogen under standard conditions. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Photoinduced Magnetism in Nanoparticles of Prussian Blue Derivatives

    NASA Astrophysics Data System (ADS)

    Anderson, N. E.; Park, J.-H.; Meisel, M. W.; Frye, F.; Talham, D. R.

    2006-03-01

    Nanoparticles of the Prussian blue family are of great interest due to the possibility for applications in magnetic memory, biosensing, and magnetic filtering. Nanoparticles also serve to better investigate fascinating phenomena, such as the anisotropic photomagnetic properties seen in thin films of Prussian blue derivatives. Here, we present results on RbjCok[Fe(CN)6]l.nH2O Prussian blue analog nanoparticles, which exhibit photoinduced magnetism. The nanoparticles are synthesized in a controlled manner, which allows for particle growth in the range of 5-50 nm. Early experiments show that upon irradiation with light at 5 K for a period of 2 hours, the final magnetization increases on the order of 10-100% compared to the initial dark state value. This increase is comparable in magnitude with the results reported for bulk materials. The change in magnetization is also accompanied by an increase in Tc. Furthermore, the effect of the dispersing agent on the photomagnetism, the size effect on characteristic magnetic properties, and ac susceptibility data will be presented. J.-H. Park, E. Cizm'ar, M. W. Meisel, Y. D. Huh, F. Frye, S. Lane, and D. R. Talham, Appl. Phys. Lett. 85, 3797 (2004).

  8. Photoinduced force microscopy: A technique for hyperspectral nanochemical mapping

    NASA Astrophysics Data System (ADS)

    Murdick, Ryan A.; Morrison, William; Nowak, Derek; Albrecht, Thomas R.; Jahng, Junghoon; Park, Sung

    2017-08-01

    Advances in nanotechnology have intensified the need for tools that can characterize newly synthesized nanomaterials. A variety of techniques has recently been shown which combines atomic force microscopy (AFM) with optical illumination including tip-enhanced Raman spectroscopy (TERS), scattering-type scanning near-field optical microscopy (sSNOM), and photothermal induced resonance microscopy (PTIR). To varying degrees, these existing techniques enable optical spectroscopy with the nanoscale spatial resolution inherent to AFM, thereby providing nanochemical interrogation of a specimen. Here we discuss photoinduced force microscopy (PiFM), a recently developed technique for nanoscale optical spectroscopy that exploits image forces acting between an AFM tip and sample to detect wavelength-dependent polarization within the sample to generate absorption spectra. This approach enables ∼10 nm spatial resolution with spectra that show correlation with macroscopic optical absorption spectra. Unlike other techniques, PiFM achieves this high resolution with virtually no constraints on sample or substrate properties. The applicability of PiFM to a variety of archetypal systems is reported here, highlighting the potential of PiFM as a useful tool for a wide variety of industrial and academic investigations, including semiconducting nanoparticles, nanocellulose, block copolymers, and low dimensional systems, as well as chemical and morphological mixing at interfaces.

  9. Photoinduced absorption in disubstituted polyacetylenes: Comparison of theory with experiments

    NASA Astrophysics Data System (ADS)

    Sony, Priya; Shukla, Alok

    2005-04-01

    In a recently performed experiment, [Korovyanko Phys. Rev. B 67, 035114 (2003)] have measured the photoinduced absorption (PA) spectrum of phenyl-disubstituted polyacetylenes (PDPA’s) from the 1Bu and 2Ag excited states. In the 1Bu PA spectrum they identified two main features, namely, PA1 and PA2, while in the 2Ag spectrum they identified only one feature called PAg . In this paper we present a theoretical study of the 1Bu and 2Ag PA spectra of oligo-PDPA’s using the correlated-electron Pariser-Parr-Pople model and various configuration interaction methodologies. We compare the calculated spectra with the experiments, as well as with the calculated spectra of polyenes of the same conjugation lengths. The calculated spectra are in good agreement with the experiments. Based upon our calculations, we identify PA1 as the mAg state and PAg as the nBu state of the polymer. Regarding the PA2 feature, we present our speculations. Additionally, it is argued that the nature of the excited states contributing to the 2Ag -PA spectra of oligo-PDPA’s is qualitatively different from those contributing to the spectra of polyenes.

  10. Diel variations in photoinduced oxidation of Hg0 in freshwater.

    PubMed

    Garcia, Edenise; Poulain, Alexandre J; Amyot, Marc; Ariya, Parisa A

    2005-05-01

    Experiments have been conducted to determine diel variations in photoinduced Hg0 oxidation in lake water under natural Hg0(aq) concentrations. Pseudo-first-order rates of photooxidation (k') were calculated for water freshly collected in a Canadian Shield lake, Lake Croche (45 degrees 56' N, 74 degrees 00' W), at different periods of the day and subsequently incubated in the dark. Hg0 oxidation rates ranged from 0.02 to 0.07 h(-1), increasing from sunrise to noon and then decreasing throughout the remainder of the day. These changes paralleled those in sunlight intensity integrated over 1 h preceding water collection, and suggested that the water freshly collected in daylight was rich in photochemically produced Hg0 oxidants. It was also estimated that under intense solar radiation, even if oxidation rates reached a peak, reduction of Hg(II) was the prevalent redox process. Inversely, Hg0 oxidation overcame DGM production during the night or at periods of weaker light intensity. Overall, these findings explain the decreases in the DGM pool generally observed overnight. They also support previous reports that, during summer days, volatilization of Hg0 from water represent an important step in the Hg cycle in freshwater systems.

  11. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids.

    PubMed

    Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W

    2015-11-19

    Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

  12. Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

    PubMed Central

    Zhang, Song; Sun, Simei; Zhou, Miaomiao; Wang, Lian; Zhang, Bing

    2017-01-01

    We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products. PMID:28233835

  13. Photo-induced chemical reaction of trans-resveratrol.

    PubMed

    Zhao, Yue; Shi, Meng; Ye, Jian-Hui; Zheng, Xin-Qiang; Lu, Jian-Liang; Liang, Yue-Rong

    2015-03-15

    Photo-induced chemical reaction of trans-resveratrol has been studied. UV B, liquid state and sufficient exposure time are essential conditions to the photochemical change of trans-resveratrol. Three principal compounds, cis-resveratrol, 2,4,6-phenanthrenetriol and 2-(4-hydroxyphenyl)-5,6-benzofurandione, were successively generated in the reaction solution of trans-resveratrol (0.25 mM, 100% ethanol) under 100 μW cm(-2) UV B radiation for 4h. cis-Resveratrol, originated from isomerization of trans-resveratrol, resulted in 2,4,6-phenanthrenetriol through photocyclisation reaction meanwhile loss of 2 H. 2,4,6-Phenanthrenetriol played a role of photosensitizer producing singlet oxygen in the reaction pathway. The singlet oxygen triggered [4+2] cycloaddition reaction of trans-resveratrol, and then resulted in the generation of 2-(4-hydroxyphenyl)-5,6-benzofurandione through photorearrangement and oxidation reaction. The singlet oxygen reaction was closely related to the substrate concentration of trans-resveratrol in solution. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Highly Twisted Triarylamines for Photoinduced Intramoleculer ChargeTransfer

    SciTech Connect

    Chudomel, J. M.; Yang, B. Q.; Barnes, M. D.; Achermann, M.; Mague, J. T.; Lahti, P. M.

    2011-08-04

    9-(N,N-Dianisylamino)anthracene (9DAAA), 9-(N,N-dianisylamino)dinaphth([1,2-a:2'-1'-j]-anthracene (9DAAH), and 9,10-bis(N,N-dianisylamino)anthracene (910BAA) were synthesized as highly twisted triarylamines with potential for photoexcited internal charge transfer. Crystallography of 9DAAA shows its dianisylamino group to be twisted nearly perpendicular to its anthracene unit, similar to a report for 910BAA. The solution fluorescence spectra show strong bathochromic shifts for each of the three molecular systems with strongly decreased quantum efficiency in higher polarity solvents. Solution-phase (ensemble) time-resolved photoluminescence measurements show up to 4-fold decreases in fluorescence lifetime in acetonitrile compared to hexane. The combined results are consistent with photoinduced, transient intramolecular charge-transfer from the bis-anisylamine unit to the polycyclic aromatic unit. Computational modeling is in accord with intramolecular transfer of electron density from the bis-anisylamino unit to the anthracene, based on in comparisons of HOMO and LUMO.

  15. Photoinduced superhydrophilicity: a kinetic study of time dependent photoinduced contact angle changes on TiO2 surfaces.

    PubMed

    Foran, Philip S; Boxall, Colin; Denison, Kieth R

    2012-12-21

    Transparent TiO(2) thin films were prepared on quartz substrates via a reverse micelle, sol-gel, spin-coating technique. The time dependence of the TiO(2) film photoinduced superhydrophilicity (PISH) was measured by goniometric observation of the contact angle, θ, of sessile water drops at the film surfaces. In these measurements, the TiO(2) substrate was illuminated by 315 nm light and drops were sequentially applied at a range of illumination times. Using a model for the wetting of heterogeneous surfaces derived by Israelachvili and Gee, these measurements were used to calculate the time dependence of f(2), the fractional surface coverage of the TiO(2) surface by adventitious contaminating organics (Israelachvili, J. N.; Gee, M. L. Contact angles on chemically heterogeneous surfaces. Langmuir 1989, 5, 288). Extending this model to include a Langmuir-Hinshelwood based kinetic analysis of f(2) as a function of time allowed for calculation of an expected value for θ immediately prior to illumination, that is, at illumination time t = 0. Such expected values of θ at t = 0 were calculated using two possible values of θ(1), the contact angle on a pristine unilluminated homogeneous TiO(2) surface: (i) θ(1) = 4° as suggested by, inter alia, Zubkov et al. (Zubkov, T.; Stahl, D.; Thompson, T. L.; Panayotov, D.; Diwald, O.; Yates, J. T. Ultraviolet Light-Induced Hydrophilicity Effect on TiO(2)(110)(1 × 1). Dominant Role of the Photooxidation of Adsorbed Hydrocarbons Causing Wetting by Water Droplets. J. Phys. Chem. B2005, 109, 15454); and (ii) where θ(1) = 25°, as suggested by Fujishima et al., representative of a more hydrophobic homogeneous TiO(2) surface that reconstructs upon exposure to ultraband gap illumination into a hydrophilic surface where θ(1) → 0° (Fujishima, A.; Zhang, X.; Tryk, D. A. TiO(2) photocatalysis and related surface phenomena Surf. Sci. Rep.2008, 63, 515). Analysis of data from our experiments and from selected literature sources

  16. Retardation of the orientation relaxation of azo-dye doped amorphous polymers upon photoinduced isomerization

    NASA Astrophysics Data System (ADS)

    Chan, S. W.; Quatela, A.; Casalboni, M.; Nunzi, J.-M.

    2006-08-01

    The orientation relaxation upon photo-induced isomerization of azo-dyes was studied. All-optical poling (AOP) and photo-induced birefringence, which are based on the mechanism of angular selective photo-isomerization, were employed to manipulate the angular distribution of azo-dyes (Disperse-red 1) doped in three different amorphous polymers: (poly(methyl methacrylate) PMMA, poly(carbonate) PC and poly(sulfone) PSU), with different glass transition temperature (T g). In the case of AOP, quasi-permanent macroscopic second-order nonlinear optical susceptibility χ (2) was inscribed in the dye-doped centro-symmetric polymer systems, while in the case of photo-induced birefringence, quasi-permanent birefringence Δn was inscribed in the dye-doped isotropic polymer systems. Relaxation of χ (2) and Δn were monitored upon different duration of AOP and photo-induced birefringence preparation. Experimental results show that azo-dye orientation relaxation follows the duration of the photo-nduced isomerization process: the longer the photo-induced isomerization process, the slower the relaxation of the inscribed χ (2) and Δn. In addition, retardation of the orientation relaxation does not follow a simple relation with hardness (T g) of the polymer host. Causes of the orientation relaxation retardation are discussed.

  17. QSARs for photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs)

    SciTech Connect

    Mekenyan, O.; Call, D.; Ankley, G.; Veith, G.

    1994-12-31

    Photo-induced toxicity of polycyclic aromatic hydrocarbons (PAHs) was found to be a result of competing internal and external factors which interact to produce a complex, multilinear relationship between toxicity and chemical structure. The relationship between molecular electronic structure and photo-dynamic effects was studied in both ground and excited states. A measure of the energy required for an electron to be elevated from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), or HOMO-LUMO gap, provided a useful ground state index to explain the persistence, light absorption, and eventual photo-induced toxicity of PAHs to Daphnia magna. The derived QSARs clearly distinguished photo-induced toxicity differences between pairs of structurally similar PAHs, such as phenanthrene and anthracene, benzo[a]anthracene and tetracene, etc. Those PAHs exhibiting photo-induced toxicity were consistently within a specific HOMO-LUMO gap range. The relationship between the excited state electronic parameters and toxicity was also studied. Significant correlations were found with the measured energies of singlet and triplet states from spectroscopic data. An investigation of the effect of substituent additions on photo-induced acute toxicity of parent PAHs revealed that alkyl and hydroxy moieties did not significantly reduce the HOMO-LUMO gap of the parent PAHs. Nitro, alkene and chloro substituents cause gap reductions, whereby certain derivatives of parent chemicals that were close to the ``toxic region`` of the electronic gap could become phototoxic with such additions.

  18. [Surgical treatment of supraventricular tachycardias (Wolff Parkinson White and Occult Kent). Experience at the "Ignacio Chávez" National Institute of cardiology].

    PubMed

    Barragán, R; Iturralde, P; Colín, L; Ramírez, S; Romero, L; Molina, J; García, J; de Micheli, A; González Hermosillo, J A

    1991-01-01

    We report our initial experience in the surgical section of the accessory pathway in thirteen patients: eight patients with Wolff Parkinson White syndrome and five with accessory pathway functioning only in direction ventricle to atrium (Kent concealed), with recurrent episodes of paroxysmal supraventricular tachycardia with no response to medical treatment. Three of these patients had episodes of auricular fibrillation with interval RR lower than 250 msec and one patient presented syncope. A total of fifteen accessory pathways were sectioned: 7 left lateral, 5 left posterior, one left posterolateral, one right lateral, and another one right anteroseptal. In the same procedure two patients had correction of another heart malformation: one with patent ductus arteriosus and another with and another with atrial septal defect. All patients had successful outcome, one of them needed a second surgery for persistent accessory pathway. We had two post-operatory complications: one mediastinitis and one patient with ectopic auricular tachycardia.

  19. Atrial fibrillation with wide QRS tachycardia and undiagnosed Wolff-Parkinson-White syndrome: diagnostic and therapeutic dilemmas in a pediatric patient.

    PubMed

    Panduranga, Prashanth; Al-Farqani, Abdullah; Al-Rawahi, Najib

    2012-11-01

    A 10-year-old girl presented to the emergency department of a regional hospital with 1 episode of generalized tonic-clonic seizures. Postictal monitoring followed by a 12-lead electrocardiogram showed fast atrial fibrillation with intermittent wide QRS regular tachycardia. Immediately following this, her rhythm changed to wide QRS irregular tachycardia without hemodynamic compromise. She was suspected to have ventricular tachycardia and was treated with intravenous amiodarone with cardioversion to sinus rhythm. Subsequent electrocardiogram in sinus rhythm showed typical features of manifest Wolff-Parkinson-White (WPW) accessory pathway. This case illustrates the diagnostic and therapeutic dilemmas in patients with atrial fibrillation, wide QRS tachycardia, and undiagnosed WPW syndrome with antidromic conduction of atrial arrhythmias through the accessory pathway. Furthermore, this case demonstrates that undiagnosed wide QRS tachycardias need to be treated with drugs acting on the accessory pathway, thus keeping in mind underlying WPW syndrome as a possibility to avoid potentially catastrophic events.

  20. Form--a matter of generation: the relation of generation, form, and function in the epigenetic theory of Caspar F. Wolff.

    PubMed

    Witt, Elke

    2008-12-01

    The question, how organisms obtain their specific complex and functional forms, was widely discussed during the eighteenth century. The theory of preformation, which was the dominant theory of generation, was challenged by different alternative epigenetic theories. By the end of the century it was the vitalist approach most famously advocated by Johann Friedrich Blumenbach that prevailed. Yet the alternative theory of generation brought forward by Caspar Friedrich Wolff was an important contribution to the treatment of this question. He turned his attention from the properties of matter and the forces acting on it towards the level of the processes of generation in order to explain the constitution of organismic forms. By regarding organic structures and forms to be the result of the lawfulness of ongoing processes, he opened up the possibility of a functional but non-teleological explanation of generation, and thereby provided an important complement to materialist and vitalist approaches.

  1. Identification of mtDNA mutation in a pedigree with gestational diabetes, deafness, Wolff-Parkinson-White syndrome and placenta accreta.

    PubMed

    Aggarwal, P; Gill-Randall, R; Wheatley, T; Buchalter, M B; Metcalfe, J; Alcolado, J C

    2001-01-01

    Mitochondrial DNA (mtDNA) defects are associated with a number of human disorders. Although many occur sporadically, maternal transmission is the hallmark of diseases due to mtDNA point mutations. The same mutation may manifest strikingly different phenotypes; for example, the A to G substitution at np 3243 was first reported in patients with mitochondrial encephalomyopathy, lactic acidosis and stroke-like episodes (the MELAS syndrome), but is also found in patients with diabetes and deafness. Here we present a case of gestational diabetes, deafness, premature greying, placenta accreta and Wolff-Parkinson-White (WPW) syndrome associated with a mtDNA mutation. Although this is the first report of such an association, study of 27 other patients with WPW syndrome failed to confirm that this mtDNA mutation is a common cause of such pre-excitation disorders.

  2. [1:1 atrial flutter in an elderly patient: one of the methods of discovering Wolff-Parkinson-White syndrome. Apropos of a case in an adult].

    PubMed

    Parmeggiani, L; Adamec, R; Perrenoud, J J

    1984-01-01

    Atrial flutter with 1:1 atrioventricular conduction giving rise to a ventricular rhythm of 240/min in an 80 year old man was the first sign of the Wolff-Parkinson-White syndrome; all previous electrocardiogrammes had shown no evidence of pre-excitation. It was only on the fifth day of hospitalisation that the ECG showed a short PR interval with a delta wave. This case illustrates that: --all supraventricular arrhythmias with abnormally high ventricular rates (over 220/min in adults) should alert to the possibility of an accessory atrioventricular pathway; --rapid atrioventricular conduction may be the first sign of an accessory pathway; --the differential diagnosis lies between an accessory atrioventricular pathway and an atriohisian tract; --digitalis, which may shorten the refractory period of the accessory pathway, is contraindicated in patients with a Kent bundle.

  3. [Wolff-Parkinson-White syndrome caused by association of atrio-hisian fibers and Mahaim's fibers. Comparison between the electrophysiology and histology].

    PubMed

    Brechenmacher, C; Courtadon, M; Jourde, M; Yermia, J C; Cheynel, J; Voegtlin, R

    1976-12-01

    A child of six who had had several losses of consciousness died suddenly during a spell of tachycardia. The EKG showed at times a type B Wolff-Parkinson-White syndrome, at times a Lown-Ganong-Levine syndrome. Intracavitary electrophysiological explorations had been carried out. The interest of this case lies in the comparison between these electrophysiological explorations and the histological examination of the normal and accessory conduction pathways. The short PR interval, which did not lengthen under the effect of premature atrial stimulation, was accounted for by the presence of atrio-His bundle tracts. The intermittent delta wave was due to Hissio-ventricular Mahaim fibres. These two accessory conduction pathways are considered as abnormal.

  4. Supernormal conduction in the anomalous bundles of the Wolff-Parkinson-White syndrome: an overlooked electrophysiologic property with potential clinical implications.

    PubMed

    Chiale, Pablo A; Albino, Ernesto; Garro, Hugo A; Selva, Horacio; Levi, Raúl J; Sánchez, Rubén A; Elizari, Marcelo V; Alvarez, Carlos B

    2007-09-01

    The anterograde refractory period (RP) of the accessory pathway (AP) is the main determinant factor of ventricular rate during atrial fibrillation in the Wolff-Parkinson-White (WPW) syndrome. We describe 3 examples of anterograde supernormal conduction (SNC) and 1 of retrograde SNC in APs. The paradoxical early recovery of propagation due to SNC, well inside a prolonged anterograde RP in the AP, may play a relevant role to determine the rate of ventricular response during atrial fibrillation, eventually leading to extremely fast ventricular rates, syncope, and even ventricular fibrillation in patients with WPW syndrome supposed a priori to be exposed to a low risk of sudden cardiac death. This may require very precise conditions, including an enhanced adrenergic influence on the heart. Retrograde SNC in APs may also participate in the mechanism of paroxysmal supraventricular tachycardias that are not easily induced by programmed cardiac stimulation.

  5. Regional genomic instability predisposes to complex dystrophin gene rearrangements.

    PubMed

    Oshima, Junko; Magner, Daniel B; Lee, Jennifer A; Breman, Amy M; Schmitt, Eric S; White, Lisa D; Crowe, Carol A; Merrill, Michelle; Jayakar, Parul; Rajadhyaksha, Aparna; Eng, Christine M; del Gaudio, Daniela

    2009-09-01

    Mutations in the dystrophin gene (DMD) cause Duchenne and Becker muscular dystrophies and the majority of cases are due to DMD gene rearrangements. Despite the high incidence of these aberrations, little is known about their causative molecular mechanism(s). We examined 792 DMD/BMD clinical samples by oligonucleotide array-CGH and report on the junction sequence analysis of 15 unique deletion cases and three complex intragenic rearrangements to elucidate potential underlying mechanism(s). Furthermore, we present three cases with intergenic rearrangements involving DMD and neighboring loci. The cases with intragenic rearrangements include an inversion with flanking deleted sequences; a duplicated segment inserted in direct orientation into a deleted region; and a splicing mutation adjacent to a deletion. Bioinformatic analysis demonstrated that 7 of 12 breakpoints combined among 3 complex cases aligned with repetitive sequences, as compared to 4 of 30 breakpoints for the 15 deletion cases. Moreover, the inversion/deletion case may involve a stem-loop structure that has contributed to the initiation of this rearrangement. For the duplication/deletion and splicing mutation/deletion cases, the presence of the first mutation, either a duplication or point mutation, may have elicited the deletion events in an attempt to correct preexisting mutations. While NHEJ is one potential mechanism for these complex rearrangements, the highly complex junction sequence of the inversion/deletion case suggests the involvement of a replication-based mechanism. Our results support the notion that regional genomic instability, aided by the presence of repetitive elements, a stem-loop structure, and possibly preexisting mutations, may elicit complex rearrangements of the DMD gene.

  6. Detecting rearrangements in children using subtelomeric FISH and SKY.

    PubMed

    Clarkson, Blaise; Pavenski, Katerina; Dupuis, Lucie; Kennedy, Shelley; Meyn, Stephen; Nezarati, Marjan M; Nie, Gloria; Weksberg, Rosanna; Withers, Stephen; Quercia, Nada; Teebi, Ahmad S; Teshima, Ikuko

    2002-02-01

    The etiology of mental retardation (MR), often presenting as developmental delay in childhood, is unknown in approximately one-half of cases. G-banding is the standard method for investigating those suspected of having a chromosomal etiology; however, detection of structural abnormalities is limited by the size and pattern of the G-bands involved. Rearrangements involving subtelomeric regions have been shown to cause MR and this has generated interest in investigating the prevalence of these rearrangements using telomere-specific probes. In addition, because cryptic interchromosomal rearrangements may not be small or confined to chromosomal ends, spectral karyotyping (SKY) using chromosome-specific painting probes may be of value. We report here a study using these two FISH-based techniques in 50 children with idiopathic MR or developmental delay and normal GTG-banded karyotypes. Our objective was to assess the prevalence of cryptic rearrangements in this population using subtelomeric FISH and SKY. Three rearrangements were detected by subtelomeric FISH: a derivative 5 from a maternal t(5;21); a recombinant 11 from a paternal pericentric inversion; and a 2q deletion that was also present in the mother. Only the derivative 5 was detected by SKY. SKY did not detect any interstitial interchromosomal rearrangement. The prevalence of clinically significant cryptic rearrangements by subtelomeric FISH and SKY was thus 4% (95% confidence interval 0.5-13.7) and 2% (95% CI 0.05-10.7), respectively. This study supports the view that G-banding does not detect all clinically significant chromosomal abnormalities and that subtelomeric FISH and SKY can detect some of these abnormalities. Copyright 2001 Wiley-Liss, Inc.

  7. Photo-induced and electrooptic properties of (Pb,La)(Zr,Ti)O{sub 3} films

    SciTech Connect

    Dimos, D.; Warren, W.L.; Tuttle, B.A.

    1993-07-01

    Photo-induced changes in the hysteresis behavior of sol-gel derived Pb(Zr,Ti)O{sub 3} (PZT) and (Pb,La)(Zr,Ti)O{sub 3} (PLZT) films have been characterized. Film photosensitivity has been evaluated with respect to magnitude of effects, time response and spectral dependence. Photo-induced hysteresis changes exhibit a stretched-exponential time dependence, which implies a dispersive mechanism. The spectral dependence is strongly peaked at the band edge ({approximately} 3.4 eV), which indicates that generation of electron-hole pairs in the material is critical. The photo-induced hysteresis changes are reproducible and stable, which indicates that the controlling charge traps are stable. However, improvements in film photosensitivity will be required to develop these materials for optical memory applications.

  8. Photoinduced Charge Transport in a BHJ Solar Cell Controlled by an External Electric Field

    PubMed Central

    Li, Yongqing; Feng, Yanting; Sun, Mengtao

    2015-01-01

    This study investigated theoretical photoinduced charge transport in a bulk heterojunction (BHJ) solar cell controlled by an external electric field. Our method for visualizing charge difference density identified the excited state properties of photoinduced charge transfer, and the charge transfer excited states were distinguished from local excited states during electronic transitions. Furthermore, the calculated rates for the charge transfer revealed that the charge transfer was strongly influenced by the external electric field. The external electric field accelerated the rate of charge transfer by up to one order when charge recombination was significantly restrained. Our research demonstrated that photoinduced charge transport controlled by an external electric field in a BHJ solar cell is efficient, and the exciton dissociation is not the limiting factor in organic solar cells.Our research should aid in the rational design of a novel conjugated system of organic solar cells. PMID:26353997

  9. Photo-induced Doping in GaN Epilayers with Graphene Quantum Dots

    PubMed Central

    Lin, T. N.; Inciong, M. R.; Santiago, S. R. M. S.; Yeh, T. W.; Yang, W. Y.; Yuan, C. T.; Shen, J. L.; Kuo, H. C.; Chiu, C. H.

    2016-01-01

    We demonstrate a new doping scheme where photo-induced carriers from graphene quantum dots (GQDs) can be injected into GaN and greatly enhance photoluminescence (PL) in GaN epilayers. An 8.3-fold enhancement of PL in GaN is observed after the doping. On the basis of time-resolved PL studies, the PL enhancement is attributed to the carrier transfer from GQDs to GaN. Such a carrier transfer process is caused by the work function difference between GQDs and GaN, which is verified by Kelvin probe measurements. We have also observed that photocurrent in GaN can be enhanced by 23-fold due to photo-induced doping with GQDs. The improved optical and transport properties from photo-induced doping are promising for applications in GaN-based optoelectronic devices. PMID:26987403

  10. Static and dynamic photoinduced magnetic effects in yttrium-iron garnet lightly doped with barium ions

    SciTech Connect

    Vorob'eva, N. V. Khalilov, R. Z.

    2012-04-15

    In yttrium-iron garnet lightly doped with barium, direct measurements of the photoinduced changes in magnetostrictive strains disagree with those in magnetostriction constants at 78-100 K. This is attributed to a considerable photoinduced modification of the initial state in this sample due to a redistribution of the charge (during illumination) between cations of the ferromagnetic octahedral sublattice. In the same sample, the temperature dependence of the photoinduced disaccomodation of magnetic permeability characterizing the initial demagnetized state is measured and calculated. A change in the electron mechanism of the phenomenon during the transition to room temperature is shown. The conclusion about the promising prospects for using such samples for remagnetization by light is advanced.

  11. Improved Photo-Induced Stability in Amorphous Metal-Oxide Based TFTs for Transparent Displays.

    PubMed

    Koo, Sang-Mo; Ha, Tae-Jun

    2015-10-01

    In this paper, we investigate the origin of photo-induced instability in amorphous metal-oxide based thin-film transistors (oxide-TFTs) by exploring threshold voltage (Vth) shift in transfer characteristics. The combination of photo irradiation and prolonged gate bias stress enhanced the shift in Vth in amorphous hafnium-indium-zinc-oxide (a-HfIZO) TFTs. Such results stem from the extended trapped charges at the localized defect states related to oxygen vacancy which play a role in a screening effect on the electric field induced by gate voltage. We also demonstrate the chemically clean interface in oxide-TFTs by employing oxygen annealing which reduces the density of trap states, thereby resulting in improved photo-induced stability. We believe that this work stimulates the research society of transparent electronics by providing a promising approach to suppress photo-induced instability in metal-oxide TFTs.

  12. Synthetic control over photoinduced electron transfer in phosphorescence zinc sensors.

    PubMed

    Woo, Hana; Cho, Somin; Han, Yejee; Chae, Weon-Sik; Ahn, Dae-Ro; You, Youngmin; Nam, Wonwoo

    2013-03-27

    Despite the promising photofunctionalities, phosphorescent probes have been examined only to a limited extent, and the molecular features that provide convenient handles for controlling the phosphorescence response have yet to be identified. We synthesized a series of phosphorescence zinc sensors based on a cyclometalated heteroleptic Ir(III) complex. The sensor construct includes two anionic cyclometalating ligands and a neutral diimine ligand that tethers a di(2-picolyl)amine (DPA) zinc receptor. A series of cyclometalating ligands with a range of electron densities and band gap energies were used to create phosphorescence sensors. The sensor series was characterized by variable-temperature steady-state and transient photoluminescence spectroscopy studies, electrochemical measurements, and quantum chemical calculations based on time-dependent density functional theory. The studies demonstrated that the suppression of nonradiative photoinduced electron transfer (PeT) from DPA to the photoexcited Ir(IV) species provided the underlying mechanism that governed the phosphorescent response to zinc ions. Importantly, the Coulombic barrier, which was located on either the cyclometalating ligand or the diimine ligand, negligibly influenced the PeT process. Phosphorescence modulation by PeT strictly obeyed the Rehm-Weller principle, and the process occurred in the Marcus-normal region. These findings provide important guidelines for improving sensing performance; an efficient phosphorescence sensor should include a cyclometalating ligand with a wide band gap energy and a deep oxidation potential. Finally, the actions of the sensor were demonstrated by visualizing the intracellular zinc ion distribution in HeLa cells using a confocal laser scanning microscope and a photoluminescence lifetime imaging microscope.

  13. Ultrafast dynamics during the photoinduced phase transition in VO2

    NASA Astrophysics Data System (ADS)

    Wegkamp, Daniel; Stähler, Julia

    2015-12-01

    The phase transition of VO2 from a monoclinic insulator to a rutile metal, which occurs thermally at TC = 340 K, can also be driven by strong photoexcitation. The ultrafast dynamics during this photoinduced phase transition (PIPT) have attracted great scientific attention for decades, as this approach promises to answer the question of whether the insulator-to-metal (IMT) transition is caused by electronic or crystallographic processes through disentanglement of the different contributions in the time domain. We review our recent results achieved by femtosecond time-resolved photoelectron, optical, and coherent phonon spectroscopy and discuss them within the framework of a selection of latest, complementary studies of the ultrafast PIPT in VO2. We show that the population change of electrons and holes caused by photoexcitation launches a highly non-equilibrium plasma phase characterized by enhanced screening due to quasi-free carriers and followed by two branches of non-equilibrium dynamics: (i) an instantaneous (within the time resolution) collapse of the insulating gap that precedes charge carrier relaxation and significant ionic motion and (ii) an instantaneous lattice potential symmetry change that represents the onset of the crystallographic phase transition through ionic motion on longer timescales. We discuss the interconnection between these two non-thermal pathways with particular focus on the meaning of the critical fluence of the PIPT in different types of experiments. Based on this, we conclude that the PIPT threshold identified in optical experiments is most probably determined by the excitation density required to drive the lattice potential change rather than the IMT. These considerations suggest that the IMT can be driven by weaker excitation, predicting a transiently metallic, monoclinic state of VO2 that is not stabilized by the non-thermal structural transition and, thus, decays on ultrafast timescales.

  14. Recent advances in photoinduced donor/acceptor copolymerization

    NASA Astrophysics Data System (ADS)

    Jönsson, S.; Viswanathan, K.; Hoyle, C. E.; Clark, S. C.; Miller, C.; Morel, F.; Decker, C.

    1999-05-01

    Photoinitiated free radical polymerization of donor (D)/acceptor (A) type monomers has gained considerable interest due to the possibility to efficiently photopolymerize non-acrylate based systems. Furthermore, this photoinduced alternating copolymerization can be accomplished without the presence of a conventional free radical generating photoinitiator. In the past, we have shown that the structural influences in the direct photolysis of N-Alkyl and N-Arylmaleimides as well as their corresponding ground state charge transfer complexes (CTC) with suitable donors have carefully been investigated. For certain combinations of A and D type monomers, a direct photolysis of the ground state complex or the excitation of the acceptor, followed by the formation of an exciplex, has been shown to initiate the copolymerization. Herein, we show that the main route of initiation is based on inter or intra molecular H-abstraction from an excited state maleimide, whereby no exciplex formation takes place. H-abstraction will predominantly take place in systems where easily abstractable hydrogens are present. Our laser flash photolysis investigation, ESR [1] (A. Hiroshi, I. Takasi, T. Nosi, Macromol. Chem. 190 (1989) 2821) and phosphorescence emissions [2,3] (K.S. Chen, T. Foster, J.K.S. Wan, J. Phys. Chem. 84 (1980) 2473; C.J. Seliskar, S.P. McGlynn, J. Chem. Phys. 55 (1971) 4337) studies show that triplet excited states of N-alkyl substituted maleimides (RMI), which are well known strong precursors for direct H-abstractions from aliphatic ethers and secondary alcohols, are formed upon excitation. Rates of copolymerization and degrees of conversion for copolymerization of maleimide/vinyl ether pairs in air and nitrogen have been measured as a function of hydrogen abstractability of the excited triplet state MI as well as the influence of concentration and hydrogen donating effect of the hydrogen donor.

  15. Oxygen radicals photo-induced by ferric nitrilotriacetate complex.

    PubMed

    Tsuchiya, Koichiro; Akai, Kaori; Tokumura, Akira; Abe, Shinji; Tamaki, Toshiaki; Takiguchi, Yoshiharu; Fukuzawa, Kenji

    2005-08-30

    This study examined the photo-induced generation of reactive oxygen species (ROS) by the carcinogenic iron(III)-NTA complex. Iron(III)-NTA complex (1:1) has three conformations (type (a) in acidic conditions of pH 1-6, type (n) in neutral conditions of pH 3-9, and type (b) in basic conditions of pH 7-10) with two pK(a) values (pK(a1) approximately 4, pK(a2) approximately 8). The iron(III)-NTA complex was reduced to iron(II) under cool-white fluorescent light without the presence of any reducing agent, and the reduction rates of the three conformations of iron(III)-NTA were in the order type (a)>type (n)>type (b) as reported previously (Akai K. et al., Free Radic. Res. 38, 951-962, 2004). ROS generation was investigated by electron paramagnetic resonance (EPR) spectroscopy with a spin-trapping technique. Apparent EPR signals attributed to PBN/*(13)CH(3) and PBN/*OCH(3) spin adducts were observed after incubation of the iron(III)-NTA complex was mixed with alpha-phenyl-tert-butylnitrone (PBN) and (13)C-DMSO in an aerobic condition. The addition of catalase effectively attenuated the PBN adducts, but superoxide dismutase enhanced them. Taken together, these results indicate that the iron(III)-NTA complex is spontaneously reduced to the iron(II)-NTA complex by light under acidic to neutral pH, and in turn transfers an electron to molecular oxygen to form ROS.

  16. Convergent synthesis and photoinduced processes in multi-chromophoric rotaxanes.

    PubMed

    Megiatto, Jackson D; Li, Ke; Schuster, David I; Palkar, Amit; Herranz, M Ángeles; Echegoyen, Luis; Abwandner, Silke; de Miguel, Gustavo; Guldi, Dirk M

    2010-11-18

    A series of [2]rotaxane materials, in which [60]fullerene is linked to a macrocycle and ferrocene (Fc) moieties are placed at the termini of a thread, both of which possess a central Cu(I)-1,10-phenanthroline [Cu(phen)(2)](+) complex, were synthesized by self-assembly using Sauvage metal template methodology. Two types of threads were constructed, one with terminal ester linkages, and a second with terminal 1,2,3-triazole linkages derived from Cu(I)-catalyzed "click" 1,3-cycloaddition reactions. Model compounds lacking the fullerene moiety were prepared in an analogous manner. The ability of the interlocked Fc-[Cu(phen)(2)](+)-C(60) hybrids to undergo electron transfer upon photoexcitation in benzonitrile, dichloromethane, and ortho-dichlorobenzene was investigated by means of time-resolved fluorescence and transient absorption spectroscopy, using excitation wavelengths directed at the fullerene and [Cu(phen)(2)](+) subunits. The energies of the electronic excited states and charge separated (CS) states that might be formed upon photoexcitation were determined from spectroscopic and electrochemical data. These studies showed that MLCT excited states of the copper complex in the fullerenerotaxanes were quenched by electron transfer to the fullerene in benzonitrile, resulting in charge separated states with oxidized copper and reduced fullerene moieties, (Fc)(2)-[Cu(phen)(2)](2+)-C(60)(•-). Even though electron transfer from Fc to the oxidized copper complex is predicted to be exergonic by 0.16 to 0.20 eV, no unequivocal evidence in support of such a process was obtained. The conclusion that Fc plays no role in the photoinduced processes in our systems rests on the lack of enhancement of the lifetime of the charge separated state, as measured by decay of C(60)(•-) at ∼1000 nm, since one-electron oxidized Fc is very difficult to detect spectroscopically in the 500-800 nm spectral region.

  17. Gold-Catalyzed Rearrangements and Beyond

    PubMed Central

    2013-01-01

    Cycloisomerizations of enynes are probably the most representative carbon–carbon bond forming reactions catalyzed by electrophilic metal complexes. These transformations are synthetically useful because chemists can use them to build complex architectures under mild conditions from readily assembled starting materials. However, these transformations can have complex mechanisms. In general, gold(I) activates alkynes in the presence of any other unsaturated functional group by forming an (η2-alkyne)–gold complex. This species reacts readily with nucleophiles, including electron-rich alkenes. In this case, the reaction forms cyclopropyl gold(I) carbene-like intermediates. These can come from different pathways depending on the substitution pattern of the alkyne and the alkene. In the absence of external nucleophiles, 1,n-enynes can form products of skeletal rearrangement in fully intramolecular reactions, which are mechanistically very different from metathesis reactions initiated by the [2 + 2] cycloaddition of a Grubbs-type carbene or other related metal carbenes. In this Account, we discuss how cycloisomerization and addition reactions of substituted enynes, as well as intermolecular reactions between alkynes and alkenes, are best interpreted as proceeding through discrete cationic intermediates in which gold(I) plays a significant role in the stabilization of the positive charge. The most important intermediates are highly delocalized cationic species that some chemists describe as cyclopropyl gold(I) carbenes or gold(I)-stabilized cyclopropylmethyl/cyclobutyl/homoallyl carbocations. However, we prefer the cyclopropyl gold(I) carbene formulation for its simplicity and mnemonic value, highlighting the tendency of these intermediates to undergo cyclopropanation reactions with alkenes. We can add a variety of hetero- and carbonucleophiles to the enynes in the presence of gold(I) in intra- or intermolecular reactions, leading to the corresponding adducts with

  18. A comprehensive molecular cytogenetic analysis of chromosome rearrangements in gibbons.

    PubMed

    Capozzi, Oronzo; Carbone, Lucia; Stanyon, Roscoe R; Marra, Annamaria; Yang, Fengtang; Whelan, Christopher W; de Jong, Pieter J; Rocchi, Mariano; Archidiacono, Nicoletta

    2012-12-01

    Chromosome rearrangements in small apes are up to 20 times more frequent than in most mammals. Because of their complexity, the full extent of chromosome evolution in these hominoids is not yet fully documented. However, previous work with array painting, BAC-FISH, and selective sequencing in two of the four karyomorphs has shown that high-resolution methods can precisely define chromosome breakpoints and map the complex flow of evolutionary chromosome rearrangements. Here we use these tools to precisely define the rearrangements that have occurred in the remaining two karyomorphs, genera Symphalangus (2n = 50) and Hoolock (2n = 38). This research provides the most comprehensive insight into the evolutionary origins of chromosome rearrangements involved in transforming small apes genome. Bioinformatics analyses of the human-gibbon synteny breakpoints revealed association with transposable elements and segmental duplications, providing some insight into the mechanisms that might have promoted rearrangements in small apes. In the near future, the comparison of gibbon genome sequences will provide novel insights to test hypotheses concerning the mechanisms of chromosome evolution. The precise definition of synteny block boundaries and orientation, chromosomal fusions, and centromere repositioning events presented here will facilitate genome sequence assembly for these close relatives of humans.

  19. A comprehensive molecular cytogenetic analysis of chromosome rearrangements in gibbons

    PubMed Central

    Capozzi, Oronzo; Carbone, Lucia; Stanyon, Roscoe R.; Marra, Annamaria; Yang, Fengtang; Whelan, Christopher W.; de Jong, Pieter J.; Rocchi, Mariano; Archidiacono, Nicoletta

    2012-01-01

    Chromosome rearrangements in small apes are up to 20 times more frequent than in most mammals. Because of their complexity, the full extent of chromosome evolution in these hominoids is not yet fully documented. However, previous work with array painting, BAC-FISH, and selective sequencing in two of the four karyomorphs has shown that high-resolution methods can precisely define chromosome breakpoints and map the complex flow of evolutionary chromosome rearrangements. Here we use these tools to precisely define the rearrangements that have occurred in the remaining two karyomorphs, genera Symphalangus (2n = 50) and Hoolock (2n = 38). This research provides the most comprehensive insight into the evolutionary origins of chromosome rearrangements involved in transforming small apes genome. Bioinformatics analyses of the human–gibbon synteny breakpoints revealed association with transposable elements and segmental duplications, providing some insight into the mechanisms that might have promoted rearrangements in small apes. In the near future, the comparison of gibbon genome sequences will provide novel insights to test hypotheses concerning the mechanisms of chromosome evolution. The precise definition of synteny block boundaries and orientation, chromosomal fusions, and centromere repositioning events presented here will facilitate genome sequence assembly for these close relatives of humans. PMID:22892276

  20. Modeling of the primary rearrangement stage of liquid phase sintering

    NASA Astrophysics Data System (ADS)

    Malik Tahir, Abdul; Malik, Amer; Amberg, Gustav

    2016-10-01

    The dimensional variations during the rearrangement stage of liquid phase sintering could have a detrimental effect on the dimensional tolerances of the sintered product. A numerical approach to model the liquid phase penetration into interparticle boundaries and the accompanied dimensional variations during the primary rearrangement stage of liquid phase sintering is presented. The coupled system of the Cahn-Hilliard and the Navier-Stokes equations is used to model the penetration of the liquid phase, whereas the rearrangement of the solid particles due to capillary forces is modeled using the equilibrium equation for a linear elastic material. The simulations are performed using realistic physical properties of the phases involved and the effect of green density, wettability and amount of liquid phase is also incorporated in the model. In the first step, the kinetics of the liquid phase penetration and the rearrangement of solid particles connected by a liquid bridge is modeled. The predicted and the calculated (analytical) results are compared in order to validate the numerical model. The numerical model is then extended to simulate the dimensional changes during primary rearrangement stage and a qualitative match with the published experimental data is achieved.

  1. Rearrangements in a two-dimensional packing of disks.

    PubMed

    Aguirre, M A; Calvo, A; Ippolito, I; Medus, A; Mancuso, M

    2006-04-01

    Several aspects of the dynamics of a granular two-dimensional (2D) packing of disks slowly tilted until the system loses stability and an avalanche takes place are discussed. The evolution of the system, constructed with monodisperse disks placed on a thin cell, is studied by image analysis. As in the 3D case (packing of spheres), the system undergoes several rearrangements of different magnitude before the avalanche takes place. For thick systems, not only are small rearrangements detected but also displacements of large clusters of disks are observed in the bulk and on the free surface of the packing. In particular, characteristic angles and the avalanche mass were determined for samples of different heights. On thick systems, velocity fields of large rearrangements are presented and changes in the internal structure of the packing produced by these rearrangements are analyzed. It is found that the main effects of rearrangements is to increase the disorder of the system. Also, as the disorder of the system increases its stability threshold decreases.

  2. Chromosome Rearrangements That Involve the Nucleolus Organizer Region in Neurospora

    PubMed Central

    Perkins, D. D.; Raju, N. B.; Barry, E. G.; Butler, D. K.

    1995-01-01

    In ~3% of Neurospora crassa rearrangements, part of a chromosome arm becomes attached to the nucleolus organizer region (NOR) at one end of chromosome 2 (linkage group V). Investigations with one inversion and nine translocations of this type are reported here. They appear genetically to be nonreciprocal and terminal. When a rearrangement is heterozygous, about one-third of viable progeny are segmental aneuploids with the translocated segment present in two copies, one in normal position and one associated with the NOR. Duplications from many of the rearrangements are highly unstable, breaking down by loss of the NOR-attached segment to restore normal chromosome sequence. When most of the rearrangements are homozygous, attenuated strands can be seen extending through the unstained nucleolus at pachytene, joining the translocated distal segment to the remainder of chromosome 2. Although the rearrangements appear genetically to be nonreciprocal, molecular evidence shows that at least several of them are physically reciprocal, with a block of rDNA repeats translocated away from the NOR. Evidence that NOR-associated breakpoints are nonterminal is also provided by intercrosses between pairs of translocations that transfer different-length segments of the same donor-chromosome arm to the NOR. PMID:8582636

  3. Chromosomal rearrangement interferes with meiotic X chromosome inactivation.

    PubMed

    Homolka, David; Ivanek, Robert; Capkova, Jana; Jansa, Petr; Forejt, Jiri

    2007-10-01

    Heterozygosity for certain mouse and human chromosomal rearrangements is characterized by the incomplete meiotic synapsis of rearranged chromosomes, by their colocalization with the XY body in primary spermatocytes, and by male-limited sterility. Previously, we argued that such X-autosomal associations could interfere with meiotic sex chromosome inactivation. Recently, supporting evidence has reported modifications of histones in rearranged chromosomes by a process called the meiotic silencing of unsynapsed chromatin (MSUC). Here, we report on the transcriptional down-regulation of genes within the unsynapsed region of the rearranged mouse chromosome 17, and on the subsequent disturbance of X chromosome inactivation. The partial transcriptional suppression of genes in the unsynapsed chromatin was most prominent prior to the mid-pachytene stage of primary spermatocytes. Later, during the mid-late pachytene, the rearranged autosomes colocalized with the XY body, and the X chromosome failed to undergo proper transcriptional silencing. Our findings provide direct evidence on the MSUC acting at the mRNA level, and implicate that autosomal asynapsis in meiosis may cause male sterility by interfering with meiotic sex chromosome inactivation.

  4. Induced dicentric chromosome formation promotes genomic rearrangements and tumorigenesis.

    PubMed

    Gascoigne, Karen E; Cheeseman, Iain M

    2013-07-01

    Chromosomal rearrangements can radically alter gene products and their function, driving tumor formation or progression. However, the molecular origins and evolution of such rearrangements are varied and poorly understood, with cancer cells often containing multiple, complex rearrangements. One mechanism that can lead to genomic rearrangements is the formation of a "dicentric" chromosome containing two functional centromeres. Indeed, such dicentric chromosomes have been observed in cancer cells. Here, we tested the ability of a single dicentric chromosome to contribute to genomic instability and neoplastic conversion in vertebrate cells. We developed a system to transiently and reversibly induce dicentric chromosome formation on a single chromosome with high temporal control. We find that induced dicentric chromosomes are frequently damaged and mis-segregated during mitosis, and that this leads to extensive chromosomal rearrangements including translocations with other chromosomes. Populations of pre-neoplastic cells in which a single dicentric chromosome is induced acquire extensive genomic instability and display hallmarks of cellular transformation including anchorage-independent growth in soft agar. Our results suggest that a single dicentric chromosome could contribute to tumor initiation.

  5. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations.

    PubMed

    Cao, Jun

    2015-06-28

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π(*) transition induces a cleavage of the C-N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π(*) excitation of the imine chromophore results in a cleavage of the C-C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N-O bond cleavages on both S1((1)ππ(*)) and S2((1)nNπ(*)) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  6. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    NASA Astrophysics Data System (ADS)

    Cao, Jun

    2015-06-01

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π* transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π* excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S1(1ππ*) and S2(1nNπ*) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  7. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    SciTech Connect

    Cao, Jun

    2015-06-28

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  8. The nature of photoinduced changes in the magnetostriction of yttrium-iron garnet single crystals

    SciTech Connect

    Vorob'eva, N. V.

    2011-05-15

    A model of the occurrence of photoinduced changes in linear magnetostriction is proposed based on a complex experimental study of magnetostrictive strains in yttrium-iron garnets Y{sub 3}Fe{sub 5}O{sub 12} with low contents of different impurities. Analytical expressions for calculating the magnetostriction in yttrium-iron garnet single crystals with different types of doping are presented. The correlation of the photoinduced change in the magnetostriction with the crystallographic features of the samples is demonstrated. The changes in the magnetostriction constants are analyzed quantitatively for samples prepared in different ways.

  9. Determination of photoinduced and intrinsic birefringences in PMMA/DR13 guest-host film

    NASA Astrophysics Data System (ADS)

    Dall'Agnol, Fernando Fuzinatto; Shimizu, Flávio Makoto; Giacometti, José A.

    2014-07-01

    We report measurements and analysis of photoinduced birefringence (PIB) in polymeric stretched films, hence, with an intrinsic birefringence (IB) associated to the polymeric chain orientation. It was found that transmittance signal is dependent on the angle between the film stretching direction and the probe light polarization, increasing or decreasing relatively to IB signal. Theoretical analysis considered that light propagates through the film having a photoinduced and intrinsic birefringences with independent optical axes. The transmittance signal dependence on the film angle is correctly accounted and our approach could give a phenomenological elucidation to the effect known as the inverse relaxation effect.

  10. Stretched exponential kinetics for photoinduced birefringence in azo dye doped PVA films

    NASA Astrophysics Data System (ADS)

    Yang, Hye Ri; Kim, Eun Ju; Lee, Sang Jo; Kim, Gun Yeup; Kwak, Chong Hoon

    2009-05-01

    We fabricated azo dye (methylorange) doped poly vinyl alcohol (MO/PVA) thin films and measured the photoinduced birefringence (PIB) kinetics for several pump beam intensities and for various MO concentrations by using the pump-probe technique. A novel approach to explain the transient behaviors of the photoinduced anisotropy is presented by employing an empirical stretched exponential time response in the course of the trans-cis-trans photoisomerization of azo molecules and is compared with the experimental data, showing excellent agreement. The stretched exponent is estimated to be β = 0.34 ± 0.04, revealing amorphous nature of the MO/PVA system.

  11. Photoinduced dimerization of macrocyclic complexes mediated by a metal-assisted oxidation of the macrocycle

    SciTech Connect

    Ferraudi, G.; Muralidharan, S.

    1981-12-01

    The triplet state of benzophenone oxidizes Ni((14)aneN/sub 4//sup 2 +/ to a Ni(III) intermediate which subsequently produces the dimer of the complex as a product. The nature of the product was confirmed by structural studies. (Ni(13-At))/sup +/ reacts with the triplet of fluorenone and /sup 2/Estate of Cr(bpy)/sub 3//sup 3 +/ forming also a dimer in a reaction that involves different intermediates. Intermediates in the photoinduced oxidations of the macrocycles have been investigated by flash photolysis. The mechanism of the photoinduced oxidation is discussed in terms of the reported properties of the macrocycles.

  12. Photoinduced color centers creation in superionic crystals RbAg 4 I 5

    NASA Astrophysics Data System (ADS)

    Kovaleva, N.; Boris, A.; Bredikhin, S.; Awano, T.

    1995-12-01

    A new phenomenon of a reversible photoinduced coloration caused by light irradiation is discovered and investigated in superionic RbAg 4 I 5 crystals. The reversible photoinduced absorption is found to be a result of irradiation by light with wavelengths in the region from 420 nm to 450 nm. The proposed mechanism of the discovered effect is associated with ambipolar diffusion of screened by mobile ions optically excited electronic carriers. The processes of color centers creation in superionic crystals RbAg 4 I 5 due to additive coloring in iodine vapours, ionic implantation and ?-ray irradiation are considered.

  13. Band Structure Simulations of the Photoinduced Changes in the MgB2:Cr Films

    PubMed Central

    Kityk, Iwan V.; Fedorchuk, Anatolii O.; Ozga, Katarzyna; AlZayed, Nasser S.

    2015-01-01

    An approach for description of the photoinduced nonlinear optical effects in the superconducting MgB2:Cr2O3 nanocrystalline film is proposed. It includes the molecular dynamics step-by-step optimization of the two separate crystalline phases. The principal role for the photoinduced nonlinear optical properties plays nanointerface between the two phases. The first modified layers possess a form of slightly modified perfect crystalline structure. The next layer is added to the perfect crystalline structure and the iteration procedure is repeated for the next layer. The total energy here is considered as a varied parameter. To avoid potential jumps on the borders we have carried out additional derivative procedure.

  14. Photoinduced phase transition in tetrathiafulvalene- p -chloranil observed in femtosecond reflection spectroscopy

    NASA Astrophysics Data System (ADS)

    Okamoto, H.; Ishige, Y.; Tanaka, S.; Kishida, H.; Iwai, S.; Tokura, Y.

    2004-10-01

    Photoinduced transitions from ionic (I) to neutral (N) and neutral (N) to ionic (I) phases in an organic charge transfer (CT) complex, tetrathiafulvalene- p -chloranil (TTF-CA), were investigated by femtosecond pump-probe reflection spectroscopy. Transient reflectivity changes of the intramolecular transition band of TTF sensitive to the degree of CT between a donor molecule of TTF and an acceptor molecule of CA are measured as a function of excitation energy, excitation density, and temperature. By adopting the multilayer model for the analysis of the obtained transient reflectivity spectra, we have derived the time characteristics of amounts and spatial distributions of photoinduced N(I) states in the I(N) phase. The results reveal that the I to N(IN) transition induced by the resonant excitation of the CT band at 4K is composed of three processes; (1) formation of a confined one-dimensional (1D) N domain, that is, a sequence of D0A0 pairs, just after the photoexcitation, (2) multiplication of the 1D N domains to the semimacroscopic N states up to 20ps within the absorption depth of the excitation light, and (3) proceeding of the IN transition along the direction normal to the sample surface. At 77K near the NI transition temperature (Tc=81K) , the size of the 1D N domain initially produced is enlarged and its multiplication process is strongly enhanced. When the excitation energy is increased, the initial photoproduct is changed from the confined 1D N domain to the positively and negatively charged N states. The spatial size of the latter is considerably larger than that of the former, indicating that the introduction of charge carriers makes the neighboring I state strongly unstable. The dynamics of the photoinduced N to I(NI) transition has also been investigated. The 1D I domains are initially produced by lights, however, they decay within 20ps even if the density of the I domains is increased. The results demonstrate that there is a clear difference of the

  15. Novel mechanism of photoinduced reversible phase transitions in molecule-based magnets.

    PubMed

    Kawamoto, T; Asai, Y; Abe, S

    2001-01-08

    A novel microscopic mechanism of bidirectional structural changes is proposed for the photoinduced magnetic phase transition in Co-Fe Prussian blue analogs on the basis of ab initio quantum chemical cluster calculations. It is shown that the local potential energies of various spin states of Co are sensitive to the number of nearest neighbor Fe vacancies. As a result, the forward and backward structural changes are most readily initiated by excitation of different local regions by different photons. This mechanism suggests an effective strategy to realize photoinduced reversible phase transitions in a general system consisting of two local components.

  16. Qsars for photoinduced toxicity: 1. acute lethality of polycyclic aromatic hydrocarbons to daphnia magna'

    SciTech Connect

    Mekenyan, O.G.; Ankley, G.T.; Veith, G.D.; Call, D.J.

    1994-01-01

    Research with a variety of aquatic species has shown that while polycyclic aromatic hydrocarbons (PAHs) are generally not acutely toxic in conventional laboratory tests, many are extremely toxic in the presence of sunlight. In an effort to develop a model for predicting which PAHs may exhibit photo-induced toxicity, Newsted and Giesy (1987) reported a parabolic relationship between the toxicity and the energy of the triplet state of a variety of PAHs. The authors have reexamined these data and propose a more mechanistic explanation for the prediction of photo-induced PAH toxicity. They sought a molecular descriptor which could be computed from structure rather than measured empirically.

  17. Photoinduced adsorption of hydrogen and methane on gamma-alumina. the photoinduced chesorluminescence (PhICL) effect.

    PubMed

    Andreev, N S; Emeline, A V; Polikhova, S V; Ryabchuk, V K; Serpone, N

    2004-01-06

    Adsorption of hydrogen and methane on a preirradiated surface of gamma-Al2O3 produces an afterglow, which has been described as a photoinduced chesorluminescence (PhICL), whose spectral features identify with the intrinsic photoluminescence of alumina. The emission spectrum consists of at least four overlapping single emission bands. For methane adsorption, the PhICL phenomenon is seen only if the solid is preirradiated in the presence of oxygen. Emission decay kinetics of the PhICL effect for gamma-Al2O3 reveal two wavelength regimes: a short wavelength regime at lambda = 300-370 nm (decay time tau = 1.1 +/- 0.2 s; signal width = 2.8 s), and a longer wavelength regime at lambda = 380-700 nm (decay time tau = 2.1 +/- 0.1 s; signal width = 4.3 s). A model is proposed in which there exist two different emission centers and, thus, two different pathways for emission decay. In the first, emission originates with electron trapping by such deep energy traps as anion vacancies {e- + Va --> F+ + hv1} to yield electron F-type color centers, whereas in the second, emission originates from electron/trapped hole recombination {e- + Os*- --> Os2- + hv2}. The first common step of the pathways is homolytic dissociative chemisorption of hydrogen and methane upon interaction with surface-active hole centers Os*-, produced upon preirradiation of alumina, to give atomic hydrogen H* and methyl radicals CH3*. Thermoprogrammed desorption spectra of photoadsorbed or postsorbed oxygen show that adsorbed oxygen interacts with atomic hydrogen and methyl radicals. The products of thermodesorption were H2O for hydrogen and H2O, CO2, and CH3CH3 for methane. The Solonitsyn memory effect coefficient was also evaluated for oxygen photoadsorption.

  18. Chromosome catastrophes involve replication mechanisms generating complex genomic rearrangements.

    PubMed

    Liu, Pengfei; Erez, Ayelet; Nagamani, Sandesh C Sreenath; Dhar, Shweta U; Kołodziejska, Katarzyna E; Dharmadhikari, Avinash V; Cooper, M Lance; Wiszniewska, Joanna; Zhang, Feng; Withers, Marjorie A; Bacino, Carlos A; Campos-Acevedo, Luis Daniel; Delgado, Mauricio R; Freedenberg, Debra; Garnica, Adolfo; Grebe, Theresa A; Hernández-Almaguer, Dolores; Immken, LaDonna; Lalani, Seema R; McLean, Scott D; Northrup, Hope; Scaglia, Fernando; Strathearn, Lane; Trapane, Pamela; Kang, Sung-Hae L; Patel, Ankita; Cheung, Sau Wai; Hastings, P J; Stankiewicz, Paweł; Lupski, James R; Bi, Weimin

    2011-09-16

    Complex genomic rearrangements (CGRs) consisting of two or more breakpoint junctions have been observed in genomic disorders. Recently, a chromosome catastrophe phenomenon termed chromothripsis, in which numerous genomic rearrangements are apparently acquired in one single catastrophic event, was described in multiple cancers. Here, we show that constitutionally acquired CGRs share similarities with cancer chromothripsis. In the 17 CGR cases investigated, we observed localization and multiple copy number changes including deletions, duplications, and/or triplications, as well as extensive translocations and inversions. Genomic rearrangements involved varied in size and complexities; in one case, array comparative genomic hybridization revealed 18 copy number changes. Breakpoint sequencing identified characteristic features, including small templated insertions at breakpoints and microhomology at breakpoint junctions, which have been attributed to replicative processes. The resemblance between CGR and chromothripsis suggests similar mechanistic underpinnings. Such chromosome catastrophic events appear to reflect basic DNA metabolism operative throughout an organism's life cycle.

  19. Cell Division Drives Epithelial Cell Rearrangements during Gastrulation in Chick.

    PubMed

    Firmino, Joao; Rocancourt, Didier; Saadaoui, Mehdi; Moreau, Chloe; Gros, Jerome

    2016-02-08

    During early embryonic development, cells are organized as cohesive epithelial sheets that are continuously growing and remodeled without losing their integrity, giving rise to a wide array of tissue shapes. Here, using live imaging in chick embryo, we investigate how epithelial cells rearrange during gastrulation. We find that cell division is a major rearrangement driver that powers dramatic epithelial cell intercalation events. We show that these cell division-mediated intercalations, which represent the majority of epithelial rearrangements within the early embryo, are absolutely necessary for the spatial patterning of gastrulation movements. Furthermore, we demonstrate that these intercalation events result from overall low cortical actomyosin accumulation within the epithelial cells of the embryo, which enables dividing cells to remodel junctions in their vicinity. These findings uncover a role for cell division as coordinator of epithelial growth and remodeling that might underlie various developmental, homeostatic, or pathological processes in amniotes.

  20. DNA Oligonucleotide Fragment Ion Rearrangements Upon Collision-Induced Dissociation

    NASA Astrophysics Data System (ADS)

    Harper, Brett; Neumann, Elizabeth K.; Solouki, Touradj

    2015-08-01

    Collision-induced dissociation (CID) of m/z-isolated w type fragment ions and an intact 5' phosphorylated DNA oligonucleotide generated rearranged product ions. Of the 21 studied w ions of various nucleotide sequences, fragment ion sizes, and charge states, 18 (~86%) generated rearranged product ions upon CID in a Synapt G2-S HDMS (Waters Corporation, Manchester, England, UK) ion mobility-mass spectrometer. Mass spectrometry (MS), ion mobility spectrometry (IMS), and theoretical modeling data suggest that purine bases can attack the free 5' phosphate group in w type ions and 5' phosphorylated DNA to generate sequence permuted [phosphopurine]- fragment ions. We propose and discuss a potential mechanism for generation of rearranged [phosphopurine]- and complementary y-B type product ions.

  1. Rearrangement Reactions Catalyzed by Cytochrome P450s

    PubMed Central

    Ortiz de Montellano, Paul R.; Nelson, Sidney D.

    2010-01-01

    Cytochrome P450s promote a variety of rearrangement reactions both as a consequence of the nature of the radical and other intermediates generated during catalysis, and of the neighboring structures in the substrate that can interact either with the initial radical intermediates or with further downstream products of the reactions. This article will review several kinds of previously published cytochrome P450-catalyzed rearrangement reactions, including changes in stereochemistry, radical clock reactions, allylic rearrangements, “NIH” and related shifts, ring contractions and expansions, and cyclizations that result from neighboring group interactions. Although most of these reactions can be carried out by many members of the cytochrome P450 superfamily, some have only been observed with select P450s, including some reactions that are catalyzed by specific endoperoxidases and cytochrome P450s found in plants. PMID:20971058

  2. Conditions for predicting quasistationary states by rearrangement formula.

    PubMed

    Yamaguchi, Yoshiyuki Y; Ogawa, Shun

    2015-10-01

    Predicting the long-lasting quasistationary state for a given initial state is one of central issues in Hamiltonian systems having long-range interaction. A recently proposed method is based on the Vlasov description and uniformly redistributes the initial distribution along contours of the asymptotic effective Hamiltonian, which is defined by the obtained quasistationary state and is determined self-consistently. The method, to which we refer as the rearrangement formula, was suggested to give precise prediction under limited situations. Restricting initial states consisting of a spatially homogeneous part and small perturbation, we numerically reveal two conditions that the rearrangement formula prefers: One is a no Landau damping condition for the unperturbed homogeneous part, and the other comes from the Casimir invariants. Mechanisms of these conditions are discussed. Clarifying these conditions, we validate to use the rearrangement formula as the response theory for an external field, and we shed light on improving the theory as a nonequilibrium statistical mechanics.

  3. Conditions for predicting quasistationary states by rearrangement formula

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Yoshiyuki Y.; Ogawa, Shun

    2015-10-01

    Predicting the long-lasting quasistationary state for a given initial state is one of central issues in Hamiltonian systems having long-range interaction. A recently proposed method is based on the Vlasov description and uniformly redistributes the initial distribution along contours of the asymptotic effective Hamiltonian, which is defined by the obtained quasistationary state and is determined self-consistently. The method, to which we refer as the rearrangement formula, was suggested to give precise prediction under limited situations. Restricting initial states consisting of a spatially homogeneous part and small perturbation, we numerically reveal two conditions that the rearrangement formula prefers: One is a no Landau damping condition for the unperturbed homogeneous part, and the other comes from the Casimir invariants. Mechanisms of these conditions are discussed. Clarifying these conditions, we validate to use the rearrangement formula as the response theory for an external field, and we shed light on improving the theory as a nonequilibrium statistical mechanics.

  4. Rearrangement and Grouping of Data Bits for Efficient Lossless Encoding

    NASA Astrophysics Data System (ADS)

    B, Ajitha Shenoy K.; Ajith, Meghana; Mantoor, Vinayak M.

    2017-01-01

    This paper describes the efficacy of rearranging and grouping of data bits. Lossless encoding techniques like Huffman Coding, Arithmetic Coding etc., works well on data which contains redundant information. The idea behind these techniques is to encode more frequently occurring symbols with less number of bits and more seldom occurring symbols with more number of bits. Most of the methods fail if there is a non-redundant data. We propose a method to re arrange and group data bits there by making the data redundant and then different lossless encoding techniques can be applied. In this paper we propose three different methods to rearrange the data bits, and efficient way of grouping them. This is first such attempt. We also justify the need of rearranging and grouping data bits for efficient lossless encoding.

  5. Low-Temperature Cationic Rearrangement in a Bulk Metal Oxide.

    PubMed

    Li, Man-Rong; Retuerto, Maria; Stephens, Peter W; Croft, Mark; Sheptyakov, Denis; Pomjakushin, Vladimir; Deng, Zheng; Akamatsu, Hirofumi; Gopalan, Venkatraman; Sánchez-Benítez, Javier; Saouma, Felix O; Jang, Joon I; Walker, David; Greenblatt, Martha

    2016-08-16

    Cationic rearrangement is a compelling strategy for producing desirable physical properties by atomic-scale manipulation. However, activating ionic diffusion typically requires high temperature, and in some cases also high pressure in bulk oxide materials. Herein, we present the cationic rearrangement in bulk Mn2 FeMoO6 at unparalleled low temperatures of 150-300 (o) C. The irreversible ionic motion at ambient pressure, as evidenced by real-time powder synchrotron X-ray and neutron diffraction, and second harmonic generation, leads to a transition from a Ni3 TeO6 -type to an ordered-ilmenite structure, and dramatic changes of the electrical and magnetic properties. This work demonstrates a remarkable cationic rearrangement, with corresponding large changes in the physical properties in a bulk oxide at unprecedented low temperatures.

  6. The carbon-skeleton rearrangement in tropane alkaloid biosynthesis.

    PubMed

    Sandala, Gregory M; Smith, David M; Radom, Leo

    2008-08-13

    High-level quantum chemistry calculations have been performed to examine the carbon-skeleton rearrangement of the tropane alkaloid littorine to hyoscyamine. Two pathways involving radical and carbocation intermediates have been investigated in this regard, namely, stepwise (or fragmentation-recombination) and concerted. The fragmentation products are calculated to be of high energy for both the radical- and carbocation-based mechanisms (136.3 and 170.9 kJ mol(-1), respectively). Similarly, the rearrangement barrier for the radical-based concerted pathway is calculated to be quite high (135.6 kJ mol(-1)). In contrast, the carbocation-based concerted pathway is found to be associated with a relatively low barrier (47.4 kJ mol(-1)). The ionization energy of the substrate-derived radical 3a is calculated to be 7.01 eV, suggesting that its oxidation to generate the substrate-derived carbocation 3b ought to be facile. In an attempt to investigate how an enzyme might modulate the rearrangement barriers, the separate and combined influences of partially protonating the migrating group and partially deprotonating the spectator OH group of the substrate were investigated. Such interactions can lead to significant reductions in the rearrangement barrier for both the radical- and carbocation-based concerted pathways, although the carbocation pathway continues to have significantly lower energy requirements. Also, the relatively high (gas-phase) acidity of the OH group of the product-related carbocation 4b indicates that the direct formation of hyoscyamine aldehyde (6) is a highly exothermic process. Although we would not wish to rule out alternative possibilities, our calculations suggest that a concerted rearrangement mechanism involving carbocations constitutes a viable low-energy pathway for the carbon-skeleton rearrangement in tropane alkaloid biosynthesis.

  7. Telomerase activation by genomic rearrangements in high-risk neuroblastoma

    PubMed Central

    Peifer, Martin; Hertwig, Falk; Roels, Frederik; Dreidax, Daniel; Gartlgruber, Moritz; Menon, Roopika; Krämer, Andrea; Roncaioli, Justin L.; Sand, Frederik; Heuckmann, Johannes M.; Ikram, Fakhera; Schmidt, Rene; Ackermann, Sandra; Engesser, Anne; Kahlert, Yvonne; Vogel, Wenzel; Altmüller, Janine; Nürnberg, Peter; Thierry-Mieg, Jean; Thierry-Mieg, Danielle; Mariappan, Aruljothi; Heynck, Stefanie; Mariotti, Erika; Henrich, Kai-Oliver; Glöckner, Christian; Bosco, Graziella; Leuschner, Ivo; Schweiger, Michal R.; Savelyeva, Larissa; Watkins, Simon C.; Shao, Chunxuan; Bell, Emma; Höfer, Thomas; Achter, Viktor; Lang, Ulrich; Theissen, Jessica; Volland, Ruth; Saadati, Maral; Eggert, Angelika; de Wilde, Bram; Berthold, Frank; Peng, Zhiyu; Zhao, Chen; Shi, Leming; Ortmann, Monika; Büttner, Reinhard; Perner, Sven; Hero, Barbara; Schramm, Alexander; Schulte, Johannes H.; Herrmann, Carl; O’Sullivan, Roderick J.; Westermann, Frank; Thomas, Roman K.; Fischer, Matthias

    2016-01-01

    Neuroblastoma is a malignant paediatric tumour of the sympathetic nervous system1. Roughly half of these tumours regress spontaneously or are cured by limited therapy. By contrast, high-risk neuroblastomas have an unfavourable clinical course despite intensive multimodal treatment, and their molecular basis has remained largely elusive2–4. Here we have performed whole-genome sequencing of 56 neuroblastomas (high-risk, n = 39; low-risk, n = 17) and discovered recurrent genomic rearrangements affecting a chromosomal region at 5p15.33 proximal of the telomerase reverse transcriptase gene (TERT). These rearrangements occurred only in high-risk neuroblastomas (12/39, 31%) in a mutually exclusive fashion with MYCN amplifications and ATRX mutations, which are known genetic events in this tumour type1,2,5. In an extended case series (n = 217), TERT rearrangements defined a subgroup of high-risk tumours with particularly poor outcome. Despite a large structural diversity of these rearrangements, they all induced massive transcriptional upregulation of TERT. In the remaining high-risk tumours, TERT expression was also elevated in MYCN-amplified tumours, whereas alternative lengthening of telomeres was present in neuroblastomas without TERT or MYCN alterations, suggesting that telomere lengthening represents a central mechanism defining this subtype. The 5p15.33 rearrangements juxtapose the TERT coding sequence to strong enhancer elements, resulting in massive chromatin remodelling and DNA methylation of the affected region. Supporting a functional role of TERT, neuroblastoma cell lines bearing rearrangements or amplified MYCN exhibited both upregulated TERT expression and enzymatic telomerase activity. In summary, our findings show that remodelling of the genomic context abrogates transcriptional silencing of TERT in high-risk neuroblastoma and places telomerase activation in the centre of transformation in a large fraction of these tumours. PMID:26466568

  8. Telomerase activation by genomic rearrangements in high-risk neuroblastoma.

    PubMed

    Peifer, Martin; Hertwig, Falk; Roels, Frederik; Dreidax, Daniel; Gartlgruber, Moritz; Menon, Roopika; Krämer, Andrea; Roncaioli, Justin L; Sand, Frederik; Heuckmann, Johannes M; Ikram, Fakhera; Schmidt, Rene; Ackermann, Sandra; Engesser, Anne; Kahlert, Yvonne; Vogel, Wenzel; Altmüller, Janine; Nürnberg, Peter; Thierry-Mieg, Jean; Thierry-Mieg, Danielle; Mariappan, Aruljothi; Heynck, Stefanie; Mariotti, Erika; Henrich, Kai-Oliver; Gloeckner, Christian; Bosco, Graziella; Leuschner, Ivo; Schweiger, Michal R; Savelyeva, Larissa; Watkins, Simon C; Shao, Chunxuan; Bell, Emma; Höfer, Thomas; Achter, Viktor; Lang, Ulrich; Theissen, Jessica; Volland, Ruth; Saadati, Maral; Eggert, Angelika; de Wilde, Bram; Berthold, Frank; Peng, Zhiyu; Zhao, Chen; Shi, Leming; Ortmann, Monika; Büttner, Reinhard; Perner, Sven; Hero, Barbara; Schramm, Alexander; Schulte, Johannes H; Herrmann, Carl; O'Sullivan, Roderick J; Westermann, Frank; Thomas, Roman K; Fischer, Matthias

    2015-10-29

    Neuroblastoma is a malignant paediatric tumour of the sympathetic nervous system. Roughly half of these tumours regress spontaneously or are cured by limited therapy. By contrast, high-risk neuroblastomas have an unfavourable clinical course despite intensive multimodal treatment, and their molecular basis has remained largely elusive. Here we have performed whole-genome sequencing of 56 neuroblastomas (high-risk, n = 39; low-risk, n = 17) and discovered recurrent genomic rearrangements affecting a chromosomal region at 5p15.33 proximal of the telomerase reverse transcriptase gene (TERT). These rearrangements occurred only in high-risk neuroblastomas (12/39, 31%) in a mutually exclusive fashion with MYCN amplifications and ATRX mutations, which are known genetic events in this tumour type. In an extended case series (n = 217), TERT rearrangements defined a subgroup of high-risk tumours with particularly poor outcome. Despite a large structural diversity of these rearrangements, they all induced massive transcriptional upregulation of TERT. In the remaining high-risk tumours, TERT expression was also elevated in MYCN-amplified tumours, whereas alternative lengthening of telomeres was present in neuroblastomas without TERT or MYCN alterations, suggesting that telomere lengthening represents a central mechanism defining this subtype. The 5p15.33 rearrangements juxtapose the TERT coding sequence to strong enhancer elements, resulting in massive chromatin remodelling and DNA methylation of the affected region. Supporting a functional role of TERT, neuroblastoma cell lines bearing rearrangements or amplified MYCN exhibited both upregulated TERT expression and enzymatic telomerase activity. In summary, our findings show that remodelling of the genomic context abrogates transcriptional silencing of TERT in high-risk neuroblastoma and places telomerase activation in the centre of transformation in a large fraction of these tumours.

  9. Submillisecond organic synthesis: Outpacing Fries rearrangement through microfluidic rapid mixing.

    PubMed

    Kim, Heejin; Min, Kyoung-Ik; Inoue, Keita; Im, Do Jin; Kim, Dong-Pyo; Yoshida, Jun-ichi

    2016-05-06

    In chemical synthesis, rapid intramolecular rearrangements often foil attempts at site-selective bimolecular functionalization. We developed a microfluidic technique that outpaces the very rapid anionic Fries rearrangement to chemoselectively functionalize iodophenyl carbamates at the ortho position. Central to the technique is a chip microreactor of our design, which can deliver a reaction time in the submillisecond range even at cryogenic temperatures. The microreactor was applied to the synthesis of afesal, a bioactive molecule exhibiting anthelmintic activity, to demonstrate its potential for practical synthesis and production.

  10. Rearrangement and evolution of mitochondrial genomes in parrots.

    PubMed

    Eberhard, Jessica R; Wright, Timothy F

    2016-01-01

    Mitochondrial genome rearrangements that result in control region duplication have been described for a variety of birds, but the mechanisms leading to their appearance and maintenance remain unclear, and their effect on sequence evolution has not been explored. A recent survey of mitochondrial genomes in the Psittaciformes (parrots) found that control region duplications have arisen independently at least six times across the order. We analyzed complete mitochondrial genome sequences from 20 parrot species, including representatives of each lineage with control region duplications, to document the gene order changes and to examine effects of genome rearrangements on patterns of sequence evolution. The gene order previously reported for Amazona parrots was found for four of the six independently derived genome rearrangements, and a previously undescribed gene order was found in Prioniturus luconensis, representing a fifth clade with rearranged genomes; the gene order resulting from the remaining rearrangement event could not be confirmed. In all rearranged genomes, two copies of the control region are present and are very similar at the sequence level, while duplicates of the other genes involved in the rearrangement show signs of degeneration or have been lost altogether. We compared rates of sequence evolution in genomes with and without control region duplications and did not find a consistent acceleration or deceleration associated with the duplications. This could be due to the fact that most of the genome rearrangement events in parrots are ancient, and additionally, to an effect of body size on evolutionary rate that we found for mitochondrial but not nuclear sequences. Base composition analyses found that relative to other birds, parrots have unusually strong compositional asymmetry (AT- and GC-skew) in their coding sequences, especially at fourfold degenerate sites. Furthermore, we found higher AT skew in species with control region duplications. One

  11. The Amadori Rearrangement for Carbohydrate Conjugation: Scope and Limitations

    PubMed Central

    Hojnik, Cornelia; Müller, Anne; Gloe, Tobias‐Elias

    2016-01-01

    The Amadori rearrangement was investigated for the synthesis of C‐glycosyl‐type neoglycoconjugates. Various amines including diamines, amino‐functionalized glycosides, lysine derivatives, and peptides were conjugated with two different heptoses to generate non‐natural C‐glycosyl‐type glycoconjugates of the d‐gluco and d‐manno series. With these studies, the scope and limitations of the Amadori rearrangement as a conjugation method have been exemplified with respect to the carbohydrate substrate, as well as the amino components. PMID:27840588

  12. Revising Intramolecular Photoinduced Electron Transfer (PET) from First-Principles.

    PubMed

    Escudero, Daniel

    2016-09-20

    Photoinduced electron transfer (PET) plays relevant roles in many areas of chemistry, including charge separation processes in photovoltaics, natural and artificial photosynthesis, and photoluminescence sensors and switches. As in many other photochemical scenarios, the structural and energetic factors play relevant roles in determining the rates and efficiencies of PET and its competitive photodeactivation processes. Particularly, in the field of fluorescent sensors and switches, intramolecular PET is believed (in many cases without compelling experimental proof) to be responsible of the quench of fluorescence. There is an increasing experimental interest in fluorophore's molecular design and on achieving optimal excitation/emission spectra, excitation coefficients, and fluorescence quantum yields (importantly for bioimaging purposes), but less efforts are devoted to fundamental mechanistic studies. In this Account, I revise the origins of the fluorescence quenching in some of these systems with state-of-the-art quantum chemical tools. These studies go beyond the common strategy of analyzing frontier orbital energy diagrams and performing PET thermodynamics calculations. Instead, the potential energy surfaces (PESs) of the lowest-lying excited states are explored with time-dependent density functional theory (TD-DFT) and complete active space self-consistent field (CASSCF) calculations and the radiative and nonradiative decay rates from the involved excited states are computed from first-principles using a thermal vibration correlation function formalism. With such a strategy, this work reveals the real origins of the fluorescence quenching, herein entitled as dark-state quenching. Dark states (those that do not absorb or emit light) are often elusive to experiments and thus, computational investigations can provide novel insights into the actual photodeactivation mechanisms. The success of the dark-state quenching mechanism is demonstrated for a wide variety of

  13. Photoinduced bimolecular electron transfer kinetics in small unilamellar vesicles

    SciTech Connect

    Choudhury, Sharmistha Dutta; Kumbhakar, Manoj; Nath, Sukhendu; Pal, Haridas

    2007-11-21

    Photoinduced electron transfer (ET) from N,N-dimethylaniline to some coumarin derivatives has been studied in small unilamellar vesicles (SUVs) of the phospholipid, DL-{alpha}-dimyristoyl-phosphatidylcholine, using steady-state and time-resolved fluorescence quenching, both below and above the phase transition temperature of the vesicles. The primary interest was to examine whether Marcus inversion [H. Sumi and R. A. Marcus, J. Chem. Phys. 84, 4894 (1986)] could be observed for the present ET systems in these organized assemblies. The influence of the topology of SUVs on the photophysical properties of the reactants and consequently on their ET kinetics has also been investigated. Absorption and fluorescence spectral data of the coumarins in SUVs and the variation of their fluorescence decays with temperature indicate that the dyes are localized in the bilayer of the SUVs. Time-resolved area normalized emission spectra analysis, however, reveals that the dyes are distributed in two different microenvironments in the SUVs, which we attribute to the two leaflets of the bilayer, one toward bulk water and the other toward the inner water pool. The microenvironments in the two leaflets are, however, not indicated to be that significantly different. Time-resolved anisotropy decays were biexponential for all the dyes in SUVs, and this has been interpreted in terms of the compound motion model according to which the dye molecules can experience a fast wobbling-in-cone type of motion as well as a slow overall rotating motion of the cone containing the molecule. The expected bimolecular diffusion-controlled rates in SUVs, as estimated by comparing the microviscosities in SUVs (determined from rotational correlation times) and that in acetonitrile solution, are much slower than the observed fluorescence quenching rates, suggesting that reactant diffusion (translational) does not play any role in the quenching kinetics in the present systems. Accordingly, clear inversions are

  14. Photoinduced axial ligation and deligation dynamics of nonplanar nickel dodecaarylporphyrins.

    PubMed

    Retsek, Jennifer L; Drain, Charles Michael; Kirmaier, Christine; Nurco, Daniel J; Medforth, Craig J; Smith, Kevin M; Sazanovich, Igor V; Chirvony, Vladimir S; Fajer, Jack; Holten, Dewey

    2003-08-13

    and open new avenues for exploring photoinduced ligand association and dissociation behavior.

  15. Hetero-cycloreversions mediated by photoinduced electron transfer.

    PubMed

    Pérez-Ruiz, Raúl; Jiménez, M Consuelo; Miranda, Miguel A

    2014-04-15

    Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest. In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies. In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited. In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the

  16. Design of Polymer Networks Involving a Photoinduced Electronic Transmission Circuit toward Artificial Photosynthesis.

    PubMed

    Okeyoshi, Kosuke; Kawamura, Ryuzo; Yoshida, Ryo; Osada, Yoshihito

    2016-01-19

    Many strategies have been explored to achieve artificial photosynthesis utilizing mediums such as liposomes and supramolecules. Because the photochemical reaction is composed of multiple functional molecules, the surrounding microenvironment is expected to be rationally integrated as observed during photosynthesis in chloroplasts. In this study, photoinduced electronic transmission surrounding the microenvironment of Ru(bpy)3(2+) in a polymer network was investigated using poly(N-isopropylacrylamide-co-Ru(bpy)3), poly(acrylamide-co-Ru(bpy)3), and Ru(bpy)3-conjugated microtubules. Photoinduced energy conversion was evaluated by investigating the effects of (i) Ru(bpy)3(2+) immobilization, (ii) polymer type, (iii) thermal energy, and (iv) cross-linking. The microenvironment surrounding copolymerized Ru(bpy)3(2+) in poly(N-isopropylacrylamide) suppressed quenching and had a higher radiative process energy than others. This finding is related to the nonradiative process, i.e., photoinduced H2 generation with significantly higher overall quantum efficiency (13%) than for the bulk solution. We envision that useful molecules will be generated by photoinduced electronic transmission in polymer networks, resulting in the development of a wide range of biomimetic functions with applications for a sustainable society.

  17. EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOINDUCED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light received. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

  18. Distance dependence in photoinduced intramolecular electron transfer. Additional remarks and calculations

    NASA Astrophysics Data System (ADS)

    Larsson, Sven; Volosov, Andrey

    1987-12-01

    Rate constants for photoinduced intramolecular electron transfer are calculated for four of the molecules studied by Hush et al. The electronic factor is obtained in quantum chemical calculations using the CNDO/S method. The results agree reasonably well with experiments for the forward reaction. Possible reasons for the disagreement for the charge recombination process are offered.

  19. Exothermic rate restrictions in long-range photoinduced charge separations in rigid media.

    PubMed

    Gomes, Paulo J S; Serpa, Carlos; Nunes, Rui M D; Arnaut, Luis G; Formosinho, Sebastião J

    2010-03-04

    Glycerol/methanol (9:1) mixtures at 255 K behave as rigid media for photoinduced electron transfers that take place within a few hundred nanoseconds. This media also provides enough polarity and plasticity to accommodate charge separations with reaction free energies ranging from +3 to -34 kcal/mol. The distance dependence of the electron transfer rates from electronically excited aromatic hydrocarbons to nitriles in this medium is accurately described by an exponential decay constant of 1.65 per angstrom. These photoinduced electron transfers display, for the first time in charge separations between independent electron donors and acceptors, a free-energy relationship with a maximum rate followed by a decrease in the rate for more exothermic reactions. According to this free-energy relationship, Franck-Condon factors are maximized at DeltaG(0) approximately -15 kcal/mol. It is suggested that the inverted region observed for these first-order photoinduced charge separations originates from a slower increase of their reorganization energies with DeltaG(0) than that of the analogous second-order photoinduced charge separations, for which inverted regions have never been clearly observed.

  20. Water-soluble fullerene materials for bioapplications: photoinduced reactive oxygen species generation

    USDA-ARS?s Scientific Manuscript database

    The photoinduced reactive oxygen species (ROS) generation from several water-soluble fullerenes was examined. Macromolecular or small molecular water-soluble fullerene complexes/derivatives were prepared and their 1O2 and O2•- generation abilities were evaluated by EPR spin-trapping methods. As a r...

  1. Photoinduced electron transfer from rail to rung within a self-assembled oligomeric porphyrin ladder

    SciTech Connect

    She, Chunxing; Lee, Suk Joong; McGarrah, James E.; Vura-Weis, Josh; Wasielewski, Michael; Chen, Hanning; Schatz, George C.; Ratner, Mark A.; Hupp, Joseph T.

    2010-01-01

    Photoinduced electron transfer in a self-assembled supramolecular ladder structure comprising oligomeric porphyrin rails and ligated dipyridyltetrazine rungs was characterized by transient absorption spectroscopy and transient direct current photoconductivity to be mainly from an oligomer (rail) to the center of a terminal tetrazine (rung), with the remaining hole being delocalized on the oligomer and subsequent charge recombination in 0.19 ns.

  2. Photoinduced formation of stable Ag-nanoparticles from a ternary ligand-DNA-Ag(+) complex.

    PubMed

    Berdnikova, Daria V; Ihmels, Heiko; Schönherr, Holger; Steuber, Marc; Wesner, Daniel

    2015-03-28

    The combination of (i) the light-harvesting nature and excited-state redox reactivity of a cationic DNA intercalator, (ii) a conjugated Ag(+)-binding crown ether, and (iii) the stabilizing effect of DNA on AgNPs in one integral ternary complex enables the mild photoinduced formation of Ag nanoparticles.

  3. EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOINDUCED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light received. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

  4. Photoinduced refractive index change and absorption bleaching in poly(methylphenylsilane) under varied atmospheres.

    SciTech Connect

    Potter, Barrett George, Jr.; Simmons-Potter, Kelly; Chandra, Haripin; Thomes, William Joseph, Jr.; Jamison, Gregory Marks

    2005-06-01

    Polysilane materials exhibit large photo-induced refractive index changes under low incident optical fluences, making them attractive candidates for applications in which rapid patterning of photonic device structures is desired immediately prior to their use. This agile fabrication strategy for integrated photonics inherently requires that optical exposure, and associated material response, occurs in nonlaboratory environments, motivating the study of environmental conditions on the photoinduced response of the material. The present work examines the impact of atmosphere on the photosensitive response of poly(methylphenylsilane) (PMPS) thin films in terms of both photoinduced absorption change and refractive index modification. Material was subjected to UV light exposure resonant with the lowest energy optical transition associated with the conjugated Si-Si backbone. Exposures were performed in both aerobic and anaerobic atmospheres (oxygen, air, nitrogen, and 5% H{sub 2}/95% N{sub 2}). The results clearly demonstrate that the photosensitive response of this model polysilane material was dramatically affected by local environment, exhibiting a photoinduced refractive index change, when exposed under an oxygen containing atmosphere, that was twice that observed under anaerobic conditions. This effect is discussed in terms of photo-oxidation processes within the polysilane structure and in the context of the need for predictable photosensitive refractive index change in varied photoimprinting environments.

  5. Wolff-Parkinson-White syndrome type B with tachycardia-dependent (phase 3) block in the accessory pathway and in left bundle-branch coexisting with rate-unrelated right bundle-branch block.

    PubMed Central

    Mendoza, I J; Castellanos, A; Sung, R J

    1980-01-01

    A patient with Wolff-Parkinson-White syndrome type B developed 2:1 atrioventricular block resulting from the association of persistent right bundle-branch block with tachycardia-dependent (phase 3) left bundle-branch block. Electrophysiological studies disclosed the coexistence of a tachycardia-dependent (phase 3) block in the accessory pathway. This conduction disturbance was exposed, not by carotid sinus massage as in previous studies, but by pacing-induced prolongation of the interval between two consecutively conducted atrial impulses. Furthermore, the surface electrocardiogram showed, at different times, ventricular complexes resulting from: (1) exclusive atrioventricular conduction through the normal pathway without bundle-branch block; (2) predominant, or exclusive, atrioventricular conduction through a right-sided accessory pathway; (3) exclusive atrioventricular conduction through the normal pathway with right bundle-branch block; (4) exclusive conduction through the normal pathway, with left bundle-branch block; (5) fusion between (1) and (2); and finally, (6) fusion between (2) and (3) However, QRS complexes resulting from simultaneously occurring Wolff-Parkinson-White syndrome type B and left bundle-branch block could not be identified. Future electrophysiological investigations should re-evaluate the criteria used to diffrentiate between true and false patterns of Wolff-Parkinson-White syndrome type B coexisting with left bundle-branch block. PMID:7397051

  6. Si-free enolate Claisen rearrangements of enamido substrates.

    PubMed

    Harker, Wesley R R; Carswell, Emma L; Carbery, David R

    2012-02-21

    α-Alkyl β-amino esters are available in high diastereoselectivity through a silicon-free Claisen enolate [3,3]-sigmatropic rearrangement of enamide esters. Optimisation studies have probed the crucial role of the initial enolisation and the nature of the enamide N-centre. The demonstration of chirality transfer and the formation of β-proline systems, is also presented.

  7. Gold-catalysed cascade rearrangements of ynamide propargyl esters.

    PubMed

    Heffernan, Stephen J; Beddoes, James M; Mahon, Mary F; Hennessy, Alan J; Carbery, David R

    2013-03-21

    The Au(I)-catalysed rearrangement of propargylic esters formed from an ynamide has been studied. The reaction is facile, and when conducted in the presence of a reactive indole nucleophile, leads to a cascade process whereby γ-indolyl α-acyloxyenamides are formed in good yield and excellent E-stereoselectivity.

  8. Radical [1,3]-Rearrangements of Breslow Intermediates

    PubMed Central

    Alwarsh, Sefat; Xu, Yi; Qian, Steven

    2015-01-01

    Breslow intermediates that bear radical stabilizing N-substituents including benzyl, cinnamyl, and diarylmethyl undergo facile homolytic C-N bond scission under mild conditions to give products of formal [1,3]-rearrangement rather than benzoin condensation. EPR experiments and computational analysis support a radical mechanism. Implications for thiamine based enzymes are discussed. PMID:26553753

  9. Computational Analysis of Stereospecificity in the Cope Rearrangement

    ERIC Educational Resources Information Center

    Glish, Laura; Hanks, Timothy W.

    2007-01-01

    The Cope rearrangement is a highly stereospecific, concerted reaction of considerable synthetic utility. Experimental product distributions from the reaction of disubstituted 1,5-hexadienes can be readily understood by computer modeling of the various possible transitions states. Semi-empirical methods give relative energies of transition states…

  10. The Basel Problem as a Rearrangement of Series

    ERIC Educational Resources Information Center

    Benko, David; Molokach, John

    2013-01-01

    We give an elementary solution to the famous Basel Problem, originally solved by Euler in 1735. We square the well-known series for arctan(1) due to Leibniz, and use a surprising relation among the re-arranged terms of this squared series.

  11. Computational Analysis of Stereospecificity in the Cope Rearrangement

    ERIC Educational Resources Information Center

    Glish, Laura; Hanks, Timothy W.

    2007-01-01

    The Cope rearrangement is a highly stereospecific, concerted reaction of considerable synthetic utility. Experimental product distributions from the reaction of disubstituted 1,5-hexadienes can be readily understood by computer modeling of the various possible transitions states. Semi-empirical methods give relative energies of transition states…

  12. Chromosome rearrangements via template switching between diverged repeated sequences

    PubMed Central

    Anand, Ranjith P.; Tsaponina, Olga; Greenwell, Patricia W.; Lee, Cheng-Sheng; Du, Wei; Petes, Thomas D.

    2014-01-01

    Recent high-resolution genome analyses of cancer and other diseases have revealed the occurrence of microhomology-mediated chromosome rearrangements and copy number changes. Although some of these rearrangements appear to involve nonhomologous end-joining, many must have involved mechanisms requiring new DNA synthesis. Models such as microhomology-mediated break-induced replication (MM-BIR) have been invoked to explain these rearrangements. We examined BIR and template switching between highly diverged sequences in Saccharomyces cerevisiae, induced during repair of a site-specific double-strand break (DSB). Our data show that such template switches are robust mechanisms that give rise to complex rearrangements. Template switches between highly divergent sequences appear to be mechanistically distinct from the initial strand invasions that establish BIR. In particular, such jumps are less constrained by sequence divergence and exhibit a different pattern of microhomology junctions. BIR traversing repeated DNA sequences frequently results in complex translocations analogous to those seen in mammalian cells. These results suggest that template switching among repeated genes is a potent driver of genome instability and evolution. PMID:25367035

  13. Stochastic rearrangement of immunoglobulin variable-region genes in chicken B-cell development.

    PubMed

    Benatar, T; Tkalec, L; Ratcliffe, M J

    1992-08-15

    The molecular mechanism by which immunoglobulin (Ig) gene rearrangement occurs is highly conserved between mammalian and avian species. However, in avian species, an equivalent to the mammalian pre-B cell, which has undergone Ig heavy-chain gene rearrangement and expresses mu heavy chains in the absence of Ig light-chain rearrangement, has not been convincingly demonstrated. It is consequently unclear whether an ordered progression of gene rearrangement events leading to functional Ig expression occurs in avian species. To examine the sequence of Ig gene rearrangement events in chicken B-cell development, we transformed day 12 embryo bursal cells with the REV-T(CSV) retrovirus. More than 100 clones were analyzed by Southern blotting and polymerase chain reaction for the presence of Ig gene rearrangements. The majority of these clones contained only germline Ig sequences. Several clones contained complete heavy- and light-chain rearrangements and 13 clones contained only heavy-chain rearrangements analogous to stages of mammalian B-cell development. However, 5 clones contained rearrangements of light-chain genes in the absence of complete heavy-chain rearrangement. Consequently, we conclude that rearrangement of chicken Ig light-chain genes does not require heavy-chain variable-region rearrangement. This observation suggests that chicken Ig gene rearrangement events required for Ig expression occur stochastically rather than sequentially.

  14. Chemical Detection Based on Adsorption-Induced and Photo-Induced Stresses in MEMS Devices

    SciTech Connect

    Datskos, P.G.

    1999-04-05

    Recently there has been an increasing demand to perform real-time in-situ chemical detection of hazardous materials, contraband chemicals, and explosive chemicals. Currently, real-time chemical detection requires rather large analytical instrumentation that are expensive and complicated to use. The advent of inexpensive mass produced MEMS (micro-electromechanical systems) devices opened-up new possibilities for chemical detection. For example, microcantilevers were found to respond to chemical stimuli by undergoing changes in their bending and resonance frequency even when a small number of molecules adsorb on their surface. In our present studies, we extended this concept by studying changes in both the adsorption-induced stress and photo-induced stress as target chemicals adsorb on the surface of microcantilevers. For example, microcantilevers that have adsorbed molecules will undergo photo-induced bending that depends on the number of absorbed molecules on the surface. However, microcantilevers that have undergone photo-induced bending will adsorb molecules on their surfaces in a distinctly different way. Depending on the photon wavelength and microcantilever material, the microcantilever can be made to bend by expanding or contracting the irradiated surface. This is important in cases where the photo-induced stresses can be used to counter any adsorption-induced stresses and increase the dynamic range. Coating the surface of the microstructure with a different material can provide chemical specificity for the target chemicals. However, by selecting appropriate photon wavelengths we can change the chemical selectivity due to the introduction of new surface states in the MEMS device. We will present and discuss our results on the use of adsorption-induced and photo-induced bending of microcantilevers for chemical detection.

  15. Tissue cohesion and the mechanics of cell rearrangement.

    PubMed

    David, Robert; Luu, Olivia; Damm, Erich W; Wen, Jason W H; Nagel, Martina; Winklbauer, Rudolf

    2014-10-01

    Morphogenetic processes often involve the rapid rearrangement of cells held together by mutual adhesion. The dynamic nature of this adhesion endows tissues with liquid-like properties, such that large-scale shape changes appear as tissue flows. Generally, the resistance to flow (tissue viscosity) is expected to depend on the cohesion of a tissue (how strongly its cells adhere to each other), but the exact relationship between these parameters is not known. Here, we analyse the link between cohesion and viscosity to uncover basic mechanical principles of cell rearrangement. We show that for vertebrate and invertebrate tissues, viscosity varies in proportion to cohesion over a 200-fold range of values. We demonstrate that this proportionality is predicted by a cell-based model of tissue viscosity. To do so, we analyse cell adhesion in Xenopus embryonic tissues and determine a number of parameters, including tissue surface tension (as a measure of cohesion), cell contact fluctuation and cortical tension. In the tissues studied, the ratio of surface tension to viscosity, which has the dimension of a velocity, is 1.8 µm/min. This characteristic velocity reflects the rate of cell-cell boundary contraction during rearrangement, and sets a limit to rearrangement rates. Moreover, we propose that, in these tissues, cell movement is maximally efficient. Our approach to cell rearrangement mechanics links adhesion to the resistance of a tissue to plastic deformation, identifies the characteristic velocity of the process, and provides a basis for the comparison of tissues with mechanical properties that may vary by orders of magnitude.

  16. [Lung adenocarcinoma with concomitant EGFR mutation and ALK rearrangement].

    PubMed

    Caliez, J; Monnet, I; Pujals, A; Rousseau-Bussac, G; Jabot, L; Boudjemaa, A; Leroy, K; Chouaid, C

    2017-05-01

    Among patients with non-small-cell lung cancer, coexistence of EGFR mutation and ALK rearrangement is rare. We describe the clinical features of two patients with this double anomaly. A 62-year-old Caucasian non-smoking woman was diagnosed with cT4N0M0 lung adenocarcinoma. Initial biopsy showed EGFR mutation and ALK rearrangement. She received cisplatin-gemcitabine, followed by 17 months of gemcitabine. Owing to progression, she received erlotinib for 14 months, then paclitaxel for 6 months and finally crizotinib. A partial response was achieved and maintained for 24 months. A 45-year-old Caucasian woman, light smoker, was diagnosed with cT2N3M0 lung adenocarcinoma. Only EGFR mutation was found on initial analysis. She underwent treatment with cisplatin-gemcitabine and thoracic radiotherapy. Progression occurred after 8 months and afatinbib was started. Eight months later, progression was observed with a neoplasic pleural effusion in which tumor cells expressing ALK rearrangement were found. A new FISH analysis was performed on the initial tumor but did not find this rearrangement. Despite a third line of crizotinib, the patient died one month later. The literature shows 45 other cases of these two abnormalities, observed either from the start or during follow-up. EGFR's TKI were almost always given before ALK's TKI. Therapeutic strategy needs to be clarified in cases of double alteration. With regard to the second patient, appearance of ALK rearrangement may constitute a resistance mechanism to EGFR's TKI. Copyright © 2016 SPLF. Published by Elsevier Masson SAS. All rights reserved.

  17. Development of the Ireland-Claisen rearrangement of alkoxy- and aryloxy-substituted allyl glycinates.

    PubMed

    Tellam, James P; Carbery, David R

    2010-11-19

    The Ireland-Claisen rearrangement of 3-alkoxy- and 3-aryloxy-substituted allyl glycinates is presented. This [3,3]-sigmatropic rearrangement route offers direct access to syn β-alkoxy and β-aryloxy α-amino acid systems. In particular, N,N-diboc glycine esters rearrange with excellent diastereoselectivities (dr > 25:1). The synthesis of substrates, rearrangement optimization, and a discussion of stereoselection are presented.

  18. [Outcome of Wolff-Parkinson-White syndrome in children. Transesophageal study of anterograde permeability of the accessory pathway and of atrial vulnerability].

    PubMed

    Villain, E; Attali, T; Iserin, L; Aggoun, Y; Kachaner, J

    1994-05-01

    Twenty-nine children with the Wolff-Parkinson-White syndrome (WPW) were evaluated by transoesophageal electrophysiological studies to determine the quality of anterograde-conduction in the accessory pathway and the atrial vulnerability. The study group included 15 neonates, 1 to 30 days old, and 14 children from 5 to 15 years of age; Anterograde conduction through the bundle of Kent was tested by incremental transoesophageal atrial pacing and by the determination of the shortest conducted cycle with preexcited RR waves; bursts of atrial pacing were then used to try to trigger an atrial arrhythmia. In the group of the 15 neonates, 11 had accessory pathways capable of conduction to the ventricules at frequencies > 300/min (stimulation cycle < or = 2.00 ms) but no atrial arrhythmias could be induced. The older children had slower conduction in the accessory pathways with the shortest conducted cycle length > 200 ms in 11/14 cases; on the other hand, atrial fibrillation was easily induced in 4 children, all over 12 years of age. The risk of syncope by rapid conduction of an atrial arrhythmia through the accessory pathway is negligeable in young children, including those on digoxin. This study suggests that this low risk is explained more by the absence of atrial vulnerability than by the electrophysiological properties of the accessory pathways.

  19. Reply to comment by E. W. Wolff et al. on "Low time resolution analysis of polar ice cores cannot detect impulsive nitrate events"

    NASA Astrophysics Data System (ADS)

    Smart, D. F.; Shea, M. A.; Melott, A. L.; Laird, C. M.

    2016-03-01

    Wolff et al. (2016) comment on Smart et al. (2014) and in doing so concentrate on issues other than the main point. They do not dispute our central assertion, the inadequate resolution of nearly all extant ice cores for detection of impulsive nitrate events (spikes) from any source, including past solar proton events (SPEs). We explain why comparing two short-length cores from other researchers and analyzed by different methods is insufficient for disputing subannual reproducibility, and call for a multiple, fine-resolution, replicate core study to resolve this issue. While acknowledging the creation of nitrate by SPEs and the existence of ice core nitrate spikes detected by others, they present several weak arguments, such as alleged scavenging of nitrate by some unnamed and unmeasured aerosol, and why no enhanced nitrate signal for documenting SPE statistics should be distinguishable in the ice. These are not derived from the main points in our Smart et al. (2014) paper. We address these briefly and show that ionization from the February 1956 SPE was sufficient to produce a winter, likely acidic, nitrate spike at Summit, Greenland. While noting some convergence of interpretation, we show why their claim that nitrate spikes cannot be used for deriving SPE statistics is unproven and why rejection of fine resolution core studies as unreliable is premature.

  20. Nucleotide resolution analysis of TMPRSS2 and ERG rearrangements in prostate cancer

    PubMed Central

    Weier, Christopher; Haffner, Michael C.; Mosbruger, Timothy; Esopi, David M.; Hicks, Jessica; Zheng, Qizhi; Fedor, Helen; Isaacs, William B.; De Marzo, Angelo M.; Nelson, William G.; Yegnasubramanian, Srinivasan

    2013-01-01

    TMPRSS2-ERG rearrangements occur in approximately 50% of prostate cancers and therefore represent one of the most frequently observed structural rearrangements in all cancers. However, little is known about the genomic architecture of such rearrangements. We therefore designed and optimized a pipeline involving target-capture of TMPRSS2 and ERG genomic sequences coupled with paired-end next generation sequencing to resolve genomic rearrangement breakpoints in TMPRSS2 and ERG at nucleotide resolution in a large series of primary prostate cancer specimens (n = 83). This strategy showed >90% sensitivity and specificity in identifying TMPRSS2-ERG rearrangements, and allowed identification of intra- and inter-chromosomal rearrangements involving TMPRSS2 and ERG with known and novel fusion partners. Our results indicate that rearrangement breakpoints show strong clustering in specific intronic regions of TMPRSS2 and ERG. The observed TMPRSS2-ERG rearrangements often exhibited complex chromosomal architecture associated with several intra- and inter-chromosomal rearrangements. Nucleotide resolution analysis of breakpoint junctions revealed that the majority of TMPRSS2 and ERG rearrangements (~88%) occurred at or near regions of microhomology or involved insertions of one or more base pairs. This architecture implicates nonhomologous end joining (NHEJ) and microhomology mediated end joining (MMEJ) pathways in the generation of such rearrangements. These analyses have provided important insights into the molecular mechanisms involved in generating prostate cancer-specific recurrent rearrangements. PMID:23447416

  1. Long-lived photoinduced charge separation for solar cell applications in supramolecular complexes of multi-metalloporphyrins and fullerenes.

    PubMed

    Fukuzumi, Shunichi; Ohkubo, Kei

    2013-12-07

    Monomers, dimers, trimers, dendrimers and oligomers of metalloporphyrins form supramolecular complexes with fullerene derivatives via electrostatic interactions, π-π interactions and coordination bonds. Photoexcitation of the supramolecular complexes resulted in photoinduced electron transfer from the porphyrin moiety to the fullerene moiety to produce the charge-separated states as revealed by laser flash photolysis measurements. The rate constants of photoinduced charge separation and charge recombination in supramolecular complexes of multi-metalloporphyrins and fullerenes were also determined by laser flash photolysis measurements and the results depending on the number of porphyrins in the supramolecular complexes are discussed in terms of efficiency of photoinduced energy transfer and charge separation as well as the lifetimes of charge-separated states. The photoelectrochemical performances of solar cells composed of supramolecular complexes of monomers, dimers, dendrimers and oligomers of metalloporphyrins with fullerenes are compared in relation to the rate constants of photoinduced charge separation and charge recombination.

  2. Photoinduced modulation and relaxation characteristics in LaAlO3/SrTiO3 heterointerface

    PubMed Central

    Jin, K. X.; Lin, W.; Luo, B. C.; Wu, T.

    2015-01-01

    We report the modulation and relaxation characteristics in the two-dimensional electron gas system at LaAlO3/SrTiO3 heterointerface induced by the ultraviolet light illumination (365 nm). The suppression of Kondo effect at the interface illuminated by the light originates from the light irradiation-induced decoherence effect of localized states. It is interesting to note that the persistent and transient photoinduced effects are simultaneously observed and the photoinduced maximum change values in resistance are 80.8% and 51.4% at T = 20 K, respectively. Moreover, the photoinduced relaxation processes after the irradiation are systematically analyzed using the double exponential model. These results provide the deeper understanding of the photoinduced effect and the experimental evidence of tunable Kondo effect in oxides-based two-dimensional electron gas systems. PMID:25739889

  3. Photo-induced and electrooptic properties of (Pb,La)(Zr,Ti)O3 films for optical memories

    NASA Astrophysics Data System (ADS)

    Dimos, D.; Potter, B. G.; Sinclair, M. B.; Tuttle, B. A.; Warren, W. L.

    Photo-induced hysteresis changes and electro-optic effects in sol-gel Pb(Zr,Ti)03 (PZT) and PLZT films have been studied in an effort to evaluate these materials for optical memory applications. The films exhibit two types of photo-induced changes in their hysteresis behavior which are suitable for optical storage. Both types of photo-induced hysteresis changes are due to trapping of photo-generated charge carriers at sites which minimize internal depolarizing fields. The photo-induced changes are reproducible and stable, which indicates that the charge traps are stable. However, improvements in photosensitivity will be required to develop a competitive technology for optical memories. In addition, polarization-dependent changes in the refractive indices can be the basis of a nondestructive optical readout technique. The index changes of films have been determined using a waveguide refractometry technique, which allows the extraordinary and ordinary index changes to be obtained independently.

  4. Photo-induced current amplification in L-histidine modified nanochannels based on a highly charged photoacid in solution.

    PubMed

    Zhang, Minghui; Meng, Zheyi; Zhai, Jin; Jiang, Lei

    2013-03-21

    By UV light irradiation, we can adjust the charge of bistable photoacid molecules reversibly, so that photo-induced current amplification can be obtained, which offers a way to control nanochannels by turning the UV light on and off, alternately.

  5. Photo-induced and electrooptic properties of (Pb,La)(Zr,Ti) O{sub 3} films for optical memories

    SciTech Connect

    Dimos, D.; Potter, B.G.; Sinclair, M.B.; Tuttle, B.A.; Warren, W.L.

    1993-09-01

    Photo-induced hysteresis changes and electrooptic effects in sol-gel Pb(Zr,Ti)0{sub 3} (PZT) and PLZT films have been studied in an effort to evaluate these materials for optical memory applications. The films exhibit two types of photo-induced changes in their hysteresis behavior which are suitable for optical storage. Both types of photo-induced hysteresis changes are due to trapping of photo-generated charge carriers at sites which minimize internal depolarizing fields. The photo-induced changes are reproducible and stable, which indicates that the charge traps are stable. However, improvements in photosensitivity will be required to develop a competitive technology for optical memories. In addition, polarization-dependent changes in the refractive indices can be the basis of a nondestructive optical readout technique. The index changes of films have been determined using a waveguide refractometry technique, which allows the extraordinary and ordinary index changes to be obtained independently.

  6. Release of Pro-Aggregation Substances from Rabbit Leukocytes Exposed to UV Light: Role of Photo-Induced Apoptosis.

    PubMed

    Anosov, A K; Gorbach, M M

    2015-12-01

    Accumulation of pro-aggregation substances in the incubation medium of isolated UV-irradiated rabbit leukocytes showed stronger correlation with photo-induced apoptotic death of leukocytes (r=0.92) than with their photo-induced necrotic death (r=0.70). It can be suggested that pro-aggregation substances release form leukocytes exposed to irradiation during preparation of these cells to apoptosis after UV irradiation.

  7. Photoinduced electron transfer reaction in polymer-surfactant aggregates: Photoinduced electron transfer between N,N-dimethylaniline and 7-amino coumarin dyes

    SciTech Connect

    Chakraborty, Anjan; Seth, Debabrata; Setua, Palash; Sarkar, Nilmoni

    2008-05-28

    Photoinduced electron transfer between coumarin dyes and N,N-dimethylaniline has been investigated by using steady state and picosecond time resolved fluorescence spectroscopy in sodium dodecyl sulphate (SDS) micelles and PVP-polyvinyl pyrrolidone (SDS) polymer-surfactant aggregates. A slower rate of electron transfer is observed in PVP-SDS aggregates than in polymer-free SDS micelles. A Marcus type inversion is observed in the correlation of free energy change in comparison with the electron transfer rate. The careful investigation reveals that C-151 deviates from the normal Marcus inverted region compared to its analogs C-152 and C-481 due to slower rotational relaxation and smaller translational diffusion coefficient.

  8. Acute photo-induced toxicity and toxicokinetics of single compounds and mixtures of polycyclic aromatic hydrocarbons in zebrafish.

    PubMed

    Willis, Alison M; Oris, James T

    2014-09-01

    The present study examined photo-induced toxicity and toxicokinetics for acute exposure to selected polycyclic aromatic hydrocarbons (PAHs) in zebrafish. Photo-enhanced toxicity from co-exposure to ultraviolet (UV) radiation and PAHs enhanced the toxicity and exhibited toxic effects at PAH concentrations orders of magnitude below effects observed in the absence of UV. Because environmental exposure to PAHs is usually in the form of complex mixtures, the present study examined the photo-induced toxicity of both single compounds and mixtures of PAHs. In a sensitive larval life stage of zebrafish, acute photo-induced median lethal concentrations (LC50s) were derived for 4 PAHs (anthracene, pyrene, carbazole, and phenanthrene) to examine the hypothesis that phototoxic (anthracene and pyrene) and nonphototoxic (carbazole and phenanthrene) pathways of mixtures could be predicted from single exposures. Anthracene and pyrene were phototoxic as predicted; however, carbazole exhibited moderate photo-induced toxicity and phenanthrene exhibited weak photo-induced toxicity. The toxicity of each chemical alone was used to compare the toxicity of mixtures in binary, tertiary, and quaternary combinations of these PAHs, and a predictive model for environmental mixtures was generated. The results indicated that the acute toxicity of PAH mixtures was additive in phototoxic scenarios, regardless of the magnitude of photo-enhancement. Based on PAH concentrations found in water and circumstances of high UV dose to aquatic systems, there exists potential risk of photo-induced toxicity to aquatic organisms.

  9. Chromosome-specific staining to detect genetic rearrangements

    SciTech Connect

    Gray, Joe W.; Pinkel, Daniel; Tkachuk, Douglas; Westbrook, Carol

    2013-04-09

    Methods and compositions for staining based upon nucleic acid sequence that employ nucleic acid probes are provided. Said methods produce staining patterns that can be tailored for specific cytogenetic analyzes. Said probes are appropriate for in situ hybridization and stain both interphase and metaphase chromosomal material with reliable signals. The nucleic acid probes are typically of a complexity greater than 50 kb, the complexity depending upon the cytogenetic application. Methods and reagents are provided for the detection of genetic rearrangements. Probes and test kits are provided for use in detecting genetic rearrangements, particularly for use in tumor cytogenetics, in the detection of disease related loci, specifically cancer, such as chronic myelogenous leukemia (CML) and for biological dosimetry. Methods and reagents are described for cytogenetic research, for the differentiation of cytogenetically similar but genetically different diseases, and for many prognostic and diagnostic applications.

  10. Incremental exposure facilitates adaptation to sensory rearrangement. [vestibular stimulation patterns

    NASA Technical Reports Server (NTRS)

    Lackner, J. R.; Lobovits, D. N.

    1978-01-01

    Visual-target pointing experiments were performed on 24 adult volunteers in order to compare the relative effectiveness of incremental (stepwise) and single-step exposure conditions on adaptation to visual rearrangement. The differences between the preexposure and postexposure scores served as an index of the adaptation elicited during the exposure period. It is found that both single-step and stepwise exposure to visual rearrangement elicit compensatory changes in sensorimotor coordination. However, stepwise exposure, when compared to single-step exposur in terms of the average magnitude of visual displacement over the exposure period, clearly enhances the rate of adaptation. It seems possible that the enhancement of adaptation to unusual patterns of sensory stimulation produced by incremental exposure reflects a general principle of sensorimotor function.

  11. RNA-Mediated Epigenetic Programming of Genome Rearrangements

    PubMed Central

    Nowacki, Mariusz; Shetty, Keerthi; Landweber, Laura F.

    2012-01-01

    RNA, normally thought of as a conduit in gene expression, has a novel mode of action in ciliated protozoa. Maternal RNA templates provide both an organizing guide for DNA rearrangements and a template that can transport somatic mutations to the next generation. This opportunity for RNA-mediated genome rearrangement and DNA repair is profound in the ciliate Oxytricha, which deletes 95% of its germline genome during development in a process that severely fragments its chromosomes and then sorts and reorders the hundreds of thousands of pieces remaining. Oxytricha’s somatic nuclear genome is therefore an epigenome formed through RNA templates and signals arising from the previous generation. Furthermore, this mechanism of RNA-mediated epigenetic inheritance can function across multiple generations, and the discovery of maternal template RNA molecules has revealed new biological roles for RNA and has hinted at the power of RNA molecules to sculpt genomic information in cells. PMID:21801022

  12. Interspecific chromosomal rearrangements in monosomic addition lines of Allium.

    PubMed

    Barthes, L; Ricroch, A

    2001-10-01

    Monosomic alien addition lines (MAALs) are useful for assigning linkage groups to chromosomes. We examined whether the chromosomal rearrangements following the introduction of a single onion (Allium cepa) chromosome into the Allium fistulosum genome were produced by homeologous crossing over or by a nonreciprocal conversion event. Among the monosomic lines available, 17 were studied by fluorescent genomic in situ hybridisation, using total A. cepa genomic DNA as the probe and total A. fistulosum genomic DNA as the competitor. In this way, rearrangements such as chromosomal translocations between A. cepa and A. fistulosum were identified as terminal regions consisting of tandem DNA repeats. Homeologous crossing over between the two closely related genomes occurred in 4 of the 17 lines, suggesting that such events are not rare. On the basis of a detailed molecular cytogenetic characterisation, we identified true monosomic alien addition lines for A. cepa chromosomes 3, 4, 5, 7, and 8 that can reliably be used in genetic studies.

  13. Incremental exposure facilitates adaptation to sensory rearrangement. [vestibular stimulation patterns

    NASA Technical Reports Server (NTRS)

    Lackner, J. R.; Lobovits, D. N.

    1978-01-01

    Visual-target pointing experiments were performed on 24 adult volunteers in order to compare the relative effectiveness of incremental (stepwise) and single-step exposure conditions on adaptation to visual rearrangement. The differences between the preexposure and postexposure scores served as an index of the adaptation elicited during the exposure period. It is found that both single-step and stepwise exposure to visual rearrangement elicit compensatory changes in sensorimotor coordination. However, stepwise exposure, when compared to single-step exposur in terms of the average magnitude of visual displacement over the exposure period, clearly enhances the rate of adaptation. It seems possible that the enhancement of adaptation to unusual patterns of sensory stimulation produced by incremental exposure reflects a general principle of sensorimotor function.

  14. The stress driven 'rearrangement' instability in crystalline films

    NASA Astrophysics Data System (ADS)

    Grinfeld, Michael A.

    1993-01-01

    It has been demonstrated that, in the absence of surface tension, a flat boundary of non-hydrostatically stressed elastic solids is always unstable with respect to 'mass rearrangement'. Specific mechanisms of the rearrangement can be different, for instance: (1) melting-freezing or vaporization-sublimation processes at liquid-solid or vapor-solid phase boundaries, (2) surface diffusion of particles along free or interface boundaries, and (3) adsorption-desorption of atoms in epitaxial crystal growth. In this paper, the role of this instability in the problems of epitaxy is discussed; in particular, the new opportunities delivered by this instability are considered for realistic explanation of the recently discovered phenomena of dislocation-free Stranski-Krastanow pattern of epitaxial growth. These phenomena cannot be interpreted in the framework of traditional viewpoints, since, according to the classical theory, the Stranski-Krastanow pattern develops as the result of proliferation of misfit dislocations appearing at the interface 'crystalline film-substrate'.

  15. Recent applications of ring-rearrangement metathesis in organic synthesis

    PubMed Central

    Meshram, Milind; Khedkar, Priti; Banerjee, Shaibal; Deodhar, Deepak

    2015-01-01

    Summary Ring-rearrangement metathesis (RRM) involves multiple metathesis processes such as ring-opening metathesis (ROM)/ring-closing metathesis (RCM) in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we have covered literature that appeared during the last seven years (2008–2014). PMID:26664603

  16. Recent applications of ring-rearrangement metathesis in organic synthesis.

    PubMed

    Kotha, Sambasivarao; Meshram, Milind; Khedkar, Priti; Banerjee, Shaibal; Deodhar, Deepak

    2015-01-01

    Ring-rearrangement metathesis (RRM) involves multiple metathesis processes such as ring-opening metathesis (ROM)/ring-closing metathesis (RCM) in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we have covered literature that appeared during the last seven years (2008-2014).

  17. Pyridine to aniline: an exceptional biologically driven rearrangement.

    PubMed

    Arnauld, Thomas; Beaumal, Jean-Yves; Lefoulon, François; Petit, Alain; Renaud, Tristan

    2013-04-01

    During the course of our study on the innovative ligand for nicotinic acetylcholinergic receptors, LNAChR, and in order to assess activity and toxicity profiles of the drug's metabolites, synthesis of the main metabolites was undertaken. This synthesis work was done in parallel by organic chemistry and by biotransformation of LNAChR. Filamentous fungus Aspergillus alliaceus (NRRL 315) neatly afforded three of the main metabolites, one of which arose from a very unexpected and very uncommon rearrangement.

  18. Chromosomal rearrangements maintain a polymorphic supergene controlling butterfly mimicry

    PubMed Central

    Joron, Mathieu; Frezal, Lise; Jones, Robert T.; Chamberlain, Nicola L.; Lee, Siu F.; Haag, Christoph R.; Whibley, Annabel; Becuwe, Michel; Baxter, Simon W.; Ferguson, Laura; Wilkinson, Paul A.; Salazar, Camilo; Davidson, Claire; Clark, Richard; Quail, Michael A.; Beasley, Helen; Glithero, Rebecca; Lloyd, Christine; Sims, Sarah; Jones, Matthew C.; Rogers, Jane; Jiggins, Chris D.; ffrench-Constant, Richard H.

    2013-01-01

    Supergenes are tight clusters of loci that facilitate the co-segregation of adaptive variation, providing integrated control of complex adaptive phenotypes1. Polymorphic supergenes, in which specific combinations of traits are maintained within a single population, were first described for ‘pin’ and ‘thrum’ floral types in Primula1 and Fagopyrum2, but classic examples are also found in insect mimicry3–5 and snail morphology6. Understanding the evolutionary mechanisms that generate these co-adapted gene sets, as well as the mode of limiting the production of unfit recombinant forms, remains a substantial challenge7–10. Here we show that individual wing-pattern morphs in the polymorphic mimetic butterfly Heliconius numata are associated with different genomic rearrangements at the supergene locus P. These rearrangements tighten the genetic linkage between at least two colour-pattern loci that are known to recombine in closely related species9–11, with complete suppression of recombination being observed in experimental crosses across a 400-kilobase interval containing at least 18 genes. In natural populations, notable patterns of linkage disequilibrium (LD) are observed across the entire P region. The resulting divergent haplotype clades and inversion breakpoints are found in complete association with wing-pattern morphs. Our results indicate that allelic combinations at known wing-patterning loci have become locked together in a polymorphic rearrangement at the Plocus, forming a supergene that acts as a simple switch between complex adaptive phenotypes found in sympatry. These findings highlight how genomic rearrangements can have a central role in the coexistence of adaptive phenotypes involving several genes acting in concert, by locally limiting recombination and gene flow. PMID:21841803

  19. Skeletal rearrangements of cage compounds with medium rings

    NASA Astrophysics Data System (ADS)

    Lerman, Berta M.

    1991-04-01

    Data on skeletal rearrangements in the chemistry of cage compounds are reviewed. The main principles of thermodynamically controlled isomerisation of cage hydrocarbons and syntheses of mono- and polycage structures are considered. Data on skeletal reconstruction accompanying functionally substituted carbo- and thia-containing cage-type polycyclanes are systematised. The rules for skeletal interconversions of isomeric tricyclic structures are considered. The bibliography contains 99 references.

  20. A system for the detection of chromosomal rearrangements using Sordaria macrospora.

    PubMed

    Arnaise, S; Leblon, G; Lares, L

    1984-01-01

    A system is described for the detection and diagnosis of induced chromosomal rearrangement using Sordaria macrospora. The system uses the property of the rearrangement to produce defective white ascospores as meiotic progeny from heterozygous crosses. Two reconstruction experiments have shown that this system is able to give reliable quantitative measures of rearrangement frequencies. Evidence for a photoreactivation process was obtained, suggesting that pyrimidine dimers may well be an important lesion in UV-induced chromosomal rearrangement. No evidence of induction of chromosomal rearrangement was obtained in experiments with the powerful chemical mutagen N-methyl-N'-nitro-N-nitrosoguanidine.

  1. Rapid identification of chromosomal rearrangements by PRINS technique

    SciTech Connect

    Pellestor, F.; Giradet, A.; Andreo, B.

    1994-09-01

    Chromosomal rearrangements contribute significantly to human reproductive failure, malformation/mental retardation syndromes and carcinogenesis. The variety of structural rearrangements is almost infinite and an identification by conventional cytogenetics is often labor intensive and may remain doubtful. Recent advances in molecular cytogenetics have provided new tools for detecting chromosomal abnormalities. The fluorescence in situ hybridization (FISH) procedure is actually the most employed technique and has led to numerous clinical applications. However, techniques required to produce suitable probes are time consuming and not accessible to all cytogenetics laboratories. The PRimed In Situ labeling (PRINS) method provides an alternate way for in situ chromosome screening. In this procedure, the chromosomal detection is performed by in situ annealing of a specific primer and subsequent primer extension by a Taq DNA polymerase in the presence of labeled nucleotides. Application of PRINS in clinical diagnosis is still limited. We have developed a semi-automatic PRINS protocol and used it to identify the origin of several chromosomal abnormalities. We report here the results of studies of three structural rearrangements: a translocation t(21;21), a supernumerary ring marker chromosome 18 and a complex chromosome 13 mosaicism involving a 13;13 Robertsonian translocation and a ring chromosome 13.

  2. Elevated Rate of Genome Rearrangements in Radiation-Resistant Bacteria

    PubMed Central

    Repar, Jelena; Supek, Fran; Klanjscek, Tin; Warnecke, Tobias; Zahradka, Ksenija; Zahradka, Davor

    2017-01-01

    A number of bacterial, archaeal, and eukaryotic species are known for their resistance to ionizing radiation. One of the challenges these species face is a potent environmental source of DNA double-strand breaks, potential drivers of genome structure evolution. Efficient and accurate DNA double-strand break repair systems have been demonstrated in several unrelated radiation-resistant species and are putative adaptations to the DNA damaging environment. Such adaptations are expected to compensate for the genome-destabilizing effect of environmental DNA damage and may be expected to result in a more conserved gene order in radiation-resistant species. However, here we show that rates of genome rearrangements, measured as loss of gene order conservation with time, are higher in radiation-resistant species in multiple, phylogenetically independent groups of bacteria. Comparison of indicators of selection for genome organization between radiation-resistant and phylogenetically matched, nonresistant species argues against tolerance to disruption of genome structure as a strategy for radiation resistance. Interestingly, an important mechanism affecting genome rearrangements in prokaryotes, the symmetrical inversions around the origin of DNA replication, shapes genome structure of both radiation-resistant and nonresistant species. In conclusion, the opposing effects of environmental DNA damage and DNA repair result in elevated rates of genome rearrangements in radiation-resistant bacteria. PMID:28188144

  3. Metalla-cope rearrangements: bridging organic and inorganic chemistry.

    PubMed

    Greer, Edyta M; Hoffmann, Roald

    2010-08-26

    Density functional theory calculations are performed to explore both concerted chairlike and boatlike as well as stepwise mechanisms of the Cope rearrangement of two hypothetical metalladienes. An osma-1,5-hexadiene is designed by substituting CH(2) in 1,5-hexadiene by its isolobal analogue, 16-electron Os(PH(3))(4). The energy of activation corresponding to the rearrangement of osma-1,5-hexadiene involving the chairlike saddle point is computed as 37.4 kcal/mol, 3.9 kcal/mol above the energy barrier of the parent 1,5-hexadiene calculated with the same method and basis set, and is 4.5 kcal/mol below that of the boatlike pathway. In another isolobal replacement, the CH in 1,5-hexadiene is substituted by a 15-electron Re(PH(3))(3) fragment. Now the chairlike rearrangement of the rhenia-1,5-hexadiene has an E(a) value of 23.0 kcal/mol, 10.8 kcal/mol less than the energy barrier of the parent 1,5-hexadiene calculated at the same level of theory. The ring inversion of the chair and osma-chair diradical intermediates of the stepwise reaction pathway is also examined and is found in both cases to proceed through a very flat potential energy surface involving twist intermediates.

  4. Extended Rearrangement Inequalities and Applications to Some Quantitative Stability Results

    NASA Astrophysics Data System (ADS)

    Lemou, Mohammed

    2016-12-01

    In this paper, we prove a new functional inequality of Hardy-Littlewood type for generalized rearrangements of functions. We then show how this inequality provides quantitative stability results of steady states to evolution systems that essentially preserve the rearrangements and some suitable energy functional, under minimal regularity assumptions on the perturbations. In particular, this inequality yields a quantitative stability result of a large class of steady state solutions to the Vlasov-Poisson systems, and more precisely we derive a quantitative control of the L 1 norm of the perturbation by the relative Hamiltonian (the energy functional) and rearrangements. A general non linear stability result has been obtained by Lemou et al. (Invent Math 187:145-194, 2012) in the gravitational context, however the proof relied in a crucial way on compactness arguments which by construction provides no quantitative control of the perturbation. Our functional inequality is also applied to the context of 2D-Euler systems and also provides quantitative stability results of a large class of steady-states to this system in a natural energy space.

  5. Engineering the Drosophila Genome: Chromosome Rearrangements by Design

    PubMed Central

    Golic, K. G.; Golic, M. M.

    1996-01-01

    We show that site-specific recombination can be used to engineer chromosome rearrangements in Drosophila melanogaster. The FLP site-specific recombinase acts on chromosomal target sites located within specially constructed P elements to provide an easy screen for the recovery of rearrangements with breakpoints that can be chosen in advance. Paracentric and pericentric inversions are easily recovered when two elements lie in the same chromosome in opposite orientation. These inversions are readily reversible. Duplications and deficiencies can be recovered by recombination between two elements that lie in the same orientation on the same chromosome or on homologues. We observe that the frequency of recombination between FRTs at ectopic locations decreases as the distance that separates those FRTs increases. We also describe methods to determine the absolute orientation of these P elements within the chromosome. The ability to produce chromosome rearrangements precisely between preselected sites provides a powerful new tool for investigations into the relationships between chromosome arrangement, structure, and function. PMID:8978056

  6. Eigenmodes of a quartz tuning fork and their application to photoinduced force microscopy

    NASA Astrophysics Data System (ADS)

    Kim, Bongsu; Jahng, Junghoon; Khan, Ryan Muhammad; Park, Sung; Potma, Eric O.

    2017-02-01

    We examine the mechanical eigenmodes of a quartz tuning fork (QTF) for the purpose of facilitating its use as a probe for multifrequency atomic force microscopy (AFM). We perform simulations based on the three-dimensional finite element method and compare the observed motions of the beams with experimentally measured resonance frequencies of two QTF systems. The comparison enabled us to assign the first seven asymmetric eigenmodes of the QTF. We also find that a modified version of single beam theory can be used to guide the assignment of mechanical eigenmodes of QTFs. The usefulness of the QTF for multifrequency AFM measurements is demonstrated through photoinduced force microscopy measurements. By using the QTF in different configurations, we show that the vectorial components of the photoinduced force can be independently assessed and that lateral forces can be probed in true noncontact mode.

  7. Photo-induced changes in a hybrid amorphous chalcogenide/silica photonic crystal fiber

    SciTech Connect

    Markos, Christos

    2014-01-06

    Photostructural changes in a hybrid photonic crystal fiber with chalcogenide nanofilms inside the inner surface of the cladding holes are experimentally demonstrated. The deposition of the amorphous chalcogenide glass films inside the silica capillaries of the fiber was made by infiltrating the nanocolloidal solution-based As{sub 25}S{sub 75}, while the photoinduced changes were performed by side illuminating the fiber near the bandgap edge of the formed glass nanofilms. The photoinduced effect of the chalcogenide glass directly red-shifts the transmission bandgap position of the fiber as high as ∼20.6 nm at around 1600 nm wavelength, while the maximum bandgap intensity change at ∼1270 nm was −3 dB.

  8. Enhanced diffraction properties of photoinduced gratings in nematic liquid crystals doped with Disperse Red 1.

    PubMed

    Li, Hongjing; Wang, Jianhao; Wang, Changshun; Zeng, Pengfei; Pan, Yujia; Yang, Yifei

    2016-01-01

    Diffraction properties of photoinduced gratings recorded by overlapping two coherent beams at 532 nm in nematic liquid crystals doped with Disperse Red 1 were investigated with a probe beam at 632.8 nm. The grating was formed due to the alignment of dye molecules that leaded to the reorientation of the liquid crystal phase. The diffraction efficiency of the photoinduced grating was found to increase rapidly when the sample temperature was close to the clearing point in the nematic phase and a nearly 30-fold enhancement of the first-order diffraction efficiency was obtained. The pretransitional enhancement of the diffraction efficiency was discussed in terms of the reorientation of liquid crystals, optical nonlinearity effects and the onset of critical opalescence near the nematic-isotropic phase transition. Moreover, a peak shift of diffraction efficiency towards the lower temperature was observed with the increase of recording light intensity, which was attributed to laser induced photochemical disordering.

  9. Broadband optical limiter based on nonlinear photoinduced anisotropy in bacteriorhodopsin film

    SciTech Connect

    Huang Yuhua; Siganakis, Georgios; Moharam, M.G.; Wu, S.-T.

    2004-11-29

    Nonlinear photoinduced anisotropy in a bacteriorhodopsin film was theoretically and experimentally investigated and a broadband active optical limiter was demonstrated in the visible spectral range. A diode-pumped second harmonic yttrium aluminum garnet laser was used as a pumping beam and three different wavelengths at {lambda}=442, 532, and 655 nm from different lasers were used as probing beams. The pump and probe beams overlap at the sample. When the pumping beam is absent, the probing beam cannot transmit the crossed polarizers. With the presence of the pumping beam, a portion of the probing light is detected owing to the photoinduced anisotropy. Due to the optical nonlinearity, the transmitted probing beam intensity is clamped at a certain value, which depends on the wavelength, when the pumping beam intensity exceeds 5 mW/mm{sup 2}. Good agreement between theory and experiment is found.

  10. Photo-Induced Bending Behavior of Post-Crosslinked Liquid Crystalline Polymer/Polyurethane Blend Films.

    PubMed

    Pang, Xinlei; Xu, Bo; Qing, Xin; Wei, Jia; Yu, Yanlei

    2017-06-30

    Photoresponsive blend films with post-crosslinked liquid crystalline polymer (CLCP) as a photosensitive component and flexible polyurethane (PU) as the matrix are successfully fabricated. After being uniaxially stretched, even at low concentration, the azobenzene-containing CLCP effectively transfers its photoresponsiveness to the photoinert PU matrix, resulting in the fast photo-induced bending behavior of whole blend film thanks to the effective dispersion of CLCP. Specifically, the blend film shows photo-induced deformations upon exposure to unpolarized UV light at ambient temperature. The film unbends after thermal treatment, and the randomly orientated mesogens in the film can be realigned by the mechanical stretching, which endows the film with a reversible deformation behavior. The photosensitive blend film possesses favorable mechanical property and good processability at low cost, and it is a promising candidate for a new generation of actuators. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Effect of pyrrolidine dithiocarbamate on photo-induced proton transport through chloroplast membranes.

    PubMed

    Po, E S; Ho, J W

    1997-12-01

    pH changes produced by photo-induced proton transport through chloroplast membranes in spinach were measured by a glass microelectrode. Effect of pyrrolidine dithiocarbamate on proton translocation through chloroplast membranes has been studied. Kinetic analysis of proton translocation shows that the rate is reduced as the carbamate concentration increases. The rate of proton uptake follows first-order kinetics and diminishes with increasing carbamate concentrations. The outward leakage of accumulated protons through thylakoid membranes in the dark also decreases likewise. However, the leakage of protons takes a much longer time. Pyrrolidine dithiocarbamate is an effective inhibitor of proton transport through chloroplast membranes. The results suggest that the photo-induced proton translocation is regulated by conformation change in the membrane. Higher concentration of carbamate disrupts the tertiary conformation of the membrane. The inhibition of proton transport would affect ATPase function; thus, an excess use or accumulation of pyrrolidine thiocarbamate may compromise ATP production.

  12. Photo-induced Modulation Doping in Graphene/Boron nitride Heterostructures

    NASA Astrophysics Data System (ADS)

    Velasco, Jairo, Jr.; Ju, Long; Hwang, Edwin; Kahn, Salman; Nosiglia, Casey; Tsai, Hsin-Zon; Yang, Wei; Zhang, Guangyu; Taniguchi, Takashi; Watanabe, Kenji; Zhang, Yuanbo; Crommie, Michael; Zettl, Alex; Wang, Feng

    2014-03-01

    Van der Waals heterostructures (VDH) provide an exciting new platform for materials engineering, where a variety of layered materials with different electrical, optical and mechanical responses can be stacked together to enable new physics and novel functionalities. We report an emerging optoelectronic phenomenon (i.e. photo-induced modulation doping) in the graphene-boron nitride VDH (G/BN heterostructure). We find it enables flexible and repeatable writing and erasing of charge doping in graphene with optical light. We show that the photo-induced modulation doping maintains the remarkable carrier mobility of the G/BN heterostructure, and it can be used to generate spatially varying doping profiles like pn junctions. Our work contributes towards understanding light matter interactions in VDHs, and introduces a simple technique for creating inhomogeneous doping in high mobility graphene devices. J. Velasco Jr. acknowledges support from UC President's Postdoctoral Fellowship.

  13. A chemical-bond approach to doping, compensation and photo-induced degradation in amorphous silicon

    NASA Astrophysics Data System (ADS)

    Mueller, Gerhard; Kalbitzer, S.; Mannsperger, H.

    A model for the generalization of the doping theories of Street and Robertson is proposed. The basic idea is that during deposition of an Si:H film, a chemical equilibrium is established, relating the density of dangling-bond defects near mid-gap to the densities of electrons and holes in the conduction and valence band states. The appropriate chemical reaction formalism was developed. It is shown that the model allows doping, compensation, and photo-induced degradation to be treated within a single and unifying approach. The model can easily explain the existence of a low defect density in fully compensated material. By reducing the model to the intrinsic reactions (I-III), the bias-induced effects in p-i-n junctions and the photo-induced degradation in Si:H films are explained.

  14. Photoinduced current of CuO/ZnO thin-film heterojunction in humid atmosphere

    NASA Astrophysics Data System (ADS)

    Ushio, Yoshijiro; Miyayama, Masaru; Yanagida, Hiroaki

    1994-02-01

    The effects of the light illumination on the humidity sensing properties of a CuO/ZnO thin-film heterojunction where the interface is partly exposed to atmosphere were investigated. When ultraviolet light (approximately 400 nm) was applied to the heterojunction, a very large photoinduced current, about two orders of magnitude larger than that in dry air, was observed under humid conditions at the forward bias of the p-n junction above about 1 V. The increase of photoinduced current is assumed to be due to desorption of adsorbed oxygen species on ZnO promoted by the adsorption of water molecules and the application of the forward bias, which caused the changes of interface states.

  15. Photoinduced Current of a CuO/ZnO Thin-Film Heterojunction in Humid Atmosphere

    NASA Astrophysics Data System (ADS)

    Ushio, Yoshijiro; Miyayama, Masaru; Yanagida, Hiroaki

    1994-02-01

    The effects of the light illumination on the humidity sensing properties of a CuO/ZnO thin-film heterojunction where the interface is partly exposed to atmosphere were investigated. When ultraviolet light ( ˜400 nm) was applied to the heterojunction, a very large photoinduced current, about two orders of magnitude larger than that in dry air, was observed under humid conditions at the forward bias of the p-n junction above about 1 V. The increase of photoinduced current is assumed to be due to desorption of adsorbed oxygen species on ZnO promoted by the adsorption of water molecules and the application of the forward bias, which caused the changes of interface states.

  16. Photoinduced small polarons bound to hydrogen defects in rutile TiO2

    NASA Astrophysics Data System (ADS)

    Hupfer, A.; Vines, L.; Monakhov, E. V.; Svensson, B. G.; Herklotz, F.

    2017-08-01

    Photoinduced absorption in rutile TiO2 has been studied by means of Fourier transform infrared spectroscopy. It is shown that near-band-gap illumination results in a charge-state transition of a hydrogen defect with an O-H stretch mode at 3500 cm-1, as evidenced by the appearance of an anticorrelated vibrational mode with a blueshift of ˜1.3 cm-1 . The charge-state transition is accompanied by a broad near-infrared absorption band with maximum intensity at ˜7000 cm-1 . Our data on both the photoinduced vibrational mode and the near-infrared absorption can be conclusively explained in the framework of a model of small electron polarons bound to a Ti atom adjacent to the O-H group of the hydrogen defect.

  17. Genetically engineered photoinducible homodimerization system with improved dimer-forming efficiency.

    PubMed

    Nihongaki, Yuta; Suzuki, Hideyuki; Kawano, Fuun; Sato, Moritoshi

    2014-03-21

    Vivid (VVD) is a photoreceptor derived from Neurospora Crassa that rapidly forms a homodimer in response to blue light. Although VVD has several advantages over other photoreceptors as photoinducible homodimerization system, VVD has a critical limitation in its low dimer-forming efficiency. To overcome this limitation of wild-type VVD, here we conduct site-directed saturation mutagenesis in the homodimer interface of VVD. We have found that the Ile52Cys mutation of VVD (VVD-52C) substantially improves its homodimer-forming efficiency up to 180%. We have demonstrated the utility of VVD-52C for making a light-inducible gene expression system more robust. In addition, using VVD-52C, we have developed photoactivatable caspase-9, which enables optical control of apoptosis of mammalian cells. The present genetically engineered photoinducible homodimerization system can provide a powerful tool to optically control a broad range of molecular processes in the cell.

  18. Enhanced diffraction properties of photoinduced gratings in nematic liquid crystals doped with Disperse Red 1

    PubMed Central

    LI, Hongjing; WANG, Jianhao; WANG, Changshun; ZENG, Pengfei; PAN, Yujia; YANG, Yifei

    2016-01-01

    Diffraction properties of photoinduced gratings recorded by overlapping two coherent beams at 532 nm in nematic liquid crystals doped with Disperse Red 1 were investigated with a probe beam at 632.8 nm. The grating was formed due to the alignment of dye molecules that leaded to the reorientation of the liquid crystal phase. The diffraction efficiency of the photoinduced grating was found to increase rapidly when the sample temperature was close to the clearing point in the nematic phase and a nearly 30-fold enhancement of the first-order diffraction efficiency was obtained. The pretransitional enhancement of the diffraction efficiency was discussed in terms of the reorientation of liquid crystals, optical nonlinearity effects and the onset of critical opalescence near the nematic-isotropic phase transition. Moreover, a peak shift of diffraction efficiency towards the lower temperature was observed with the increase of recording light intensity, which was attributed to laser induced photochemical disordering. PMID:27725471

  19. Photoinduced electron transfer reactions of ruthenium(II)-complexes containing amino acid with quinones.

    PubMed

    Eswaran, Rajkumar; Kalayar, Swarnalatha; Paulpandian, Muthu Mareeswaran; Seenivasan, Rajagopal

    2014-05-01

    With the aim of mimicking, at basic level the photoinduced electron transfer process in the reaction center of photosystem II, ruthenium(II)-polypyridyl complexes, carrying amino acids were synthesized and studied their photoinduced electron transfer reactions with quinones by steady state and time resolved measurements. The reaction of quinones with excited state of ruthenium(II)-complexes, I-V in acetonitrile has been studied by luminescence quenching technique and the rate constant, k(q), values are close to the diffusion controlled rate. The detection of the semiquinone anion radical in this system using time-resolved transient absorption spectroscopy confirms the electron transfer nature of the reaction. The semiclassical theory of electron transfer has been successfully applied to the photoluminescence quenching of Ru(II)-complexes with quinones.

  20. Polarization holograms in a bifunctional amorphous polymer exhibiting equal values of photoinduced linear and circular birefringences.

    PubMed

    Provenzano, Clementina; Pagliusi, Pasquale; Cipparrone, Gabriella; Royes, Jorge; Piñol, Milagros; Oriol, Luis

    2014-10-09

    Light-controlled molecular alignment is a flexible and useful strategy introducing novelty in the fields of mechanics, self-organized structuring, mass transport, optics, and photonics and addressing the development of smart optical devices. Azobenzene-containing polymers are well-known photocontrollable materials with large and reversible photoinduced optical anisotropies. The vectorial holography applied to these materials enables peculiar optical devices whose properties strongly depend on the relative values of the photoinduced birefringences. Here is reported a polarization holographic recording based on the interference of two waves with orthogonal linear polarization on a bifunctional amorphous polymer that, exceptionally, exhibits equal values of linear and circular birefringence. The peculiar photoresponse of the material coupled with the holographic technique demonstrates an optical device capable of decomposing the light into a set of orthogonally polarized linear components. The holographic structures are theoretically described by the Jones matrices method and experimentally investigated.

  1. Monte-Carlo simulations of photoinduced fluorescence enhancement in semiconductor quantum dot arrays

    NASA Astrophysics Data System (ADS)

    Maenosono, Shinya

    2005-03-01

    Photoinduced fluorescence enhancement (PFE) in semiconductor quantum dot (QD) arrays is simulated by a Monte-Carlo method based on the distributed tunneling model. PFE, a property of a QD ensemble, is directly related to the blinking behavior of single QDs. The origin of PFE is attributed not to an increase in the emission intensity during the 'on' period, but to the prolongation of average 'on' time.

  2. Quantum Dot–Bridge–Fullerene Heterodimers with Controlled Photoinduced Electron Transfer

    SciTech Connect

    Cotlet, M.; Xu, Z.

    2011-06-27

    A series of donor-bridge-acceptor systems in the form of core/shell CdSe/ZnS quantum dot-bridge-fullerene heterodimers (see picture) with varying bridge length and varying quantum dot size were self-assembled by a surface-based stepwise method to demonstrate control of the rate and of the magnitude of fluctuations of photoinduced electron transfer at the single-molecule level.

  3. Photoinduced changes in refractive index of nanostructured shungite-containing polyimide systems

    NASA Astrophysics Data System (ADS)

    Kamanina, N. V.; Serov, S. V.; Shurpo, N. A.; Rozhkova, N. N.

    2011-10-01

    Photoinduced changes in the refractive index of a conjugate polyimide (PI) matrix sensitized by shungite carbon nanoparticles have been studied for the first time. The results are compared to the data of previous investigations of the photorefractive properties of PI matrices doped with fullerenes, carbon nanotubes, and quantum dots. The nonlinear refractive index of the proposed material has been determined using the dynamic holography techniques. The position of conjugate polymer materials of this type among the other nonlinear optical systems is considered.

  4. Electron Donor-Acceptor Quenching and Photoinduced Electron Transfer for Coumarin Dyes.

    DTIC Science & Technology

    1983-10-31

    Mechanism of cousarin photodegradation . Ithe behavior of eoiuma dyes is water ad In aqueous detergent media,. and the effsects of medism aud, additives on...D-i36 345 ELECTRON DONOR-ACCEPTOR UENCHING AND PHOTOINDUCED i/i Ai ELECTRON TRANSFER FOR COUMARIN DYES (U) BOSTON UNIY MR DEPT OF CHEMISTRY G JONES...TYPE OF REPORT & PEIOD COVERED Electron Donor-acceptor Quenching and Photo- Technical, 1/1/82-10/31/82 induced Electron Transfer for Coumarin Dyes S

  5. Procedure for quantitative determination of effectiveness of photoinduced destruction of malignant tumors

    NASA Astrophysics Data System (ADS)

    Bizyuk, S. A.; Istomin, Yu. P.; Dzhagarov, B. M.

    2006-07-01

    We have developed a procedure for analysis of the functional status of blood vessels in tumor tissues using computer-assisted color scanning of tumor slices and also for a quantitative assessment of the effectiveness of photoinduced destruction of tumor tissues in animal experiments. Its major advantage is direct determination of the size of the tumor necrosis zone. The procedure has been tested in an experiment on three strains of malignant tumors with different morphologies.

  6. A dinuclear Ru(II) complex capable of photoinduced ligand exchange at both metal centers.

    PubMed

    Albani, B A; Peña, B; Saha, S; White, J K; Schaeffer, A M; Dunbar, K R; Turro, C

    2015-11-28

    {[Ru(CH3CN)3]2(tppz)}(4+) (tppz = tetra-2-pyridylpyrazine) undergoes photoinduced CH3CN exchange with λirr ≥ 610 nm in H2O. In contrast, cis-{[Ru(tpy)(L)]2(bpm)}(4+) (tpy = 2,2':6',2''-terpyridine, bpm = 2,2'-bipyrimidine, L = CH3CN) is not reactive, but the complex with L = DMSO is photoactive. These complexes are potentially useful for the release of multiply caged drugs.

  7. Stochastic model for photoinduced surface relief grating formation through molecular transport in polymer films.

    SciTech Connect

    Juan, M.; Plain, J.; Bachelot, R.; Royer, P.; Gray, S. K.; Wiederrecht, G. P.; Univ. de Technologie de Troyes

    2008-09-01

    We use a stochastic model to study photoinduced surface relief grating (SRG) formation due to molecular transport in azobenzene polymer films. The model is shown to reproduce the essential experimental features of SRG formation. In particular, it predicts SRG formation under both p and s polarizations, and the double peaked topographies that can occur at early times of the process. The evolving molecular positions and orientations during exposure are also followed, providing a useful mechanistic picture of SRG dynamics.

  8. Stochastic model for photoinduced surface relief grating formation through molecular transport in polymer films

    SciTech Connect

    Juan, M. L.; Plain, J.; Bachelot, R.; Royer, P.; Gray, S. K.; Wiederrecht, G. P.

    2008-10-13

    We use a stochastic model to study photoinduced surface relief grating (SRG) formation due to molecular transport in azobenzene polymer films. The model is shown to reproduce the essential experimental features of SRG formation. In particular, it predicts SRG formation under both p and s polarizations, and the double peaked topographies that can occur at early times of the process. The evolving molecular positions and orientations during exposure are also followed, providing a useful mechanistic picture of SRG dynamics.

  9. 8-Methoxypsoralen photoinduced plasmid-chromosome recombination in Saccharomyces cerevisiae using a centromeric vector.

    PubMed Central

    Meira, L B; Henriques, J A; Magaña-Schwencke, N

    1995-01-01

    The characterization of a new system to study the induction of plasmid-chromosome recombination is described. Single-stranded and double-stranded centromeric vectors bearing 8-methoxypsoralen photoinduced lesions were used to transform a wild-type yeast strain bearing the leu2-3,112 marker. Using the SSCP methodology and DNA sequencing, it was demonstrated that repair of the lesions in plasmid DNA was mainly due to conversion of the chromosomal allele to the plasmid DNA. Images PMID:7784218

  10. Time-Resolved Studies of Photoinduced Birefringence in Azobenzene Dye-Doped Polymer Films

    DTIC Science & Technology

    2008-09-23

    Here we report on transient photoinduced birefrin- gence ( PIB ) measurements on several azo dye films using a nanosecond laser source with a 20ns time re...Our results show the response time of PIB to be sys- tematically related to the size of the lowest optical transition energy. Furthermore, our results...suggest that PIB effects can be used to discriminate between0003-6935/08/285074-04$15.00/0 © 2008 Optical Society of America 5074 APPLIED OPTICS / Vol

  11. Complex X chromosome rearrangement associated with multiorgan autoimmunity.

    PubMed

    Haltrich, Irén; Pikó, Henriett; Pamjav, Horolma; Somogyi, Anikó; Völgyi, Antónia; David, Dezső; Beke, Artúr; Garamvölgyi, Zoltán; Kiss, Eszter; Karcagi, Veronika; Fekete, György

    2015-01-01

    Turner syndrome, a congenital condition that affects 1/2,500 births, results from absence or structural alteration of the second sex chromosome. Turner syndrome is usually associated with short stature, gonadal dysgenesis and variable dysmorphic features. The classical 45,X karyotype accounts approximately for half of all patients, the remainder exhibit mosaicism or structural abnormalities of the X chromosome. However, complex intra-X chromosomal rearrangements involving more than three breakpoints are extremely rare. We present a unique case of a novel complex X chromosome rearrangement in a young female patient presenting successively a wide range of autoimmune diseases including insulin dependent diabetes mellitus, Hashimoto's thyroiditis, celiac disease, anaemia perniciosa, possible inner ear disease and severe hair loss. For the genetic evaluation, conventional cytogenetic analysis and FISH with different X specific probes were initially performed. The complexity of these results and the variety of autoimmune problems of the patient prompted us to identify the exact composition and breakpoints of the rearranged X as well as methylation status of the X chromosomes. The high resolution array-CGH (assembly GRCh37/hg19) detected single copy for the whole chromosome X short arm. Two different sized segments of Xq arm were present in three copies: one large size of 80,3 Mb from Xq11.1 to Xq27.3 region and another smaller (11,1 Mb) from Xq27.3 to Xq28 region. An 1,6 Mb Xq27.3 region of the long arm was present in two copies. Southern blot analysis identified a skewed X inactivation with ≈ 70:30 % ratios of methylated/unmethylated fragments. The G-band and FISH patterns of the rearranged X suggested the aspect of a restructured i(Xq) chromosome which was shattered and fortuitously repaired. The X-STR genotype analysis of the family detected that the patient inherited intact maternal X chromosome and a rearranged paternal X chromosome. The multiple Xq

  12. The nature of photoinduced phase transition and metastable states in vanadium dioxide

    NASA Astrophysics Data System (ADS)

    Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; Torres, David; Wang, Tongyu; Sepulveda, Nelson; Chang, Kiseok; Young, Margaret; Lunt, Richard R.; Ruan, Chong-Yu

    2016-12-01

    Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium.

  13. Photo-induced toxicity of Deepwater Horizon slick oil to blue crab (Callinectes sapidus) larvae.

    PubMed

    Alloy, Matthew M; Boube, Idrissa; Griffitt, Robert J; Oris, James T; Roberts, Aaron P

    2015-09-01

    The 2010 Deepwater Horizon oil spill resulted in the accidental release of approximately 700 million L of crude oil into the Gulf of Mexico. Photo-induced toxicity after co-exposure to ultraviolet (UV) radiation is 1 mechanism by which polycyclic aromatic hydrocarbons (PAHs) from oil spills may exert toxicity. Blue crab are an important commercial and ecological resource in the Gulf of Mexico, and their largely transparent larvae may make them sensitive to PAH photo-induced toxicity. The goal of the present study was to examine the sensitivity of early lifestage blue crab (Callinectes sapidus) zoea to slick oil collected during the Deepwater Horizon spill. Blue crab zoea were exposed to 1 of several dilutions of water accommodated fractions from 1 of 2 sources of oil and gradations of natural sunlight in a factorial design. Two 7-h solar exposures were carried out with a recovery period (dark) in between. Survival was found to be UV- and PAH-dependent. Toxicity was observed within the range of surface PAH concentrations reported in the Gulf of Mexico during the Deepwater Horizon spill. These findings indicate that early lifestage blue crab are sensitive to photo-induced toxicity from Deepwater Horizon slick oil.

  14. Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

    NASA Astrophysics Data System (ADS)

    Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

    2012-04-01

    We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

  15. The photoinduced dynamics of X[M(dmit)2]2 salts

    NASA Astrophysics Data System (ADS)

    Ishikawa, Tadahiko; Hayes, Stuart A.; Miller, R. J. Dwayne; Hada, Masaki; Koshihara, Shinya

    2017-03-01

    We review our work on the photoinduced dynamics of X[M(dmit)2]2 salts in the charge-separated (CS) phase from the viewpoints of both electronic structural change and lattice or molecular structural change. The driving force for the CS phase formation is a strong correlation among the charge distribution, orbital energies, and the molecular structure; this is in contrast to frequently studied charge-ordered systems such as EDOTTF2PF6, whose formation is mainly driven by the intersite Coulomb repulsion. Despite the localized nature of the structural component, the cooperativity inherent to the crystal is likely to play an important role in photoinduced phenomena. In this review, we summarize the results obtained by a series of optical pump-probe experiments on this class of materials. We have also recently extended these studies using ultrafast electron diffraction to follow the nuclear motion in one of these systems. Such information is crucial for a full understanding of the photoinduced phenomena and it is anticipated that combining the results of the optical and diffraction studies will lead to more fruitful insight than either technique can offer in isolation.

  16. Highly active ppm level organic copper catalyzed photo-induced ICAR ATRP of methyl methacrylate.

    PubMed

    Jiang, Xiaowu; Wu, Jian; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2014-11-01

    A novel photo-induced homogeneous atom transfer radical polymerization (ATRP) system is constructed using an organic copper salt (Cu(SC(S)N(C2 H5 )2 )2 ) as a photo-induced catalyst at 30 °C. Herein, N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) is used as a ligand, ethyl 2-bromophenylacetate (EBPA) as an ATRP initiator, and (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) as a photo-induced radical initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP using methyl methacrylate (MMA) as a modal monomer. The effect of the concentration of the organic copper on the polymerization is investigated in detail. It is found that well-controlled polymerization can be obtained even with the amount of (Cu(SC(S)N(C2 H5 )2 )2 decreasing to a 1.56 ppm level, with the molecular weight of the resultant polymers increasing linearly with monomer conversion while maintaining a narrow molecular weight distribution (M¯w/M¯n < 1.3).

  17. Photocatalysis and photoinduced hydrophilicity of WO3 thin films with underlying Pt nanoparticles.

    PubMed

    Miyauchi, Masahiro

    2008-11-07

    The photocatalytic oxidation and photoinduced hydrophilicity of thin tungsten trioxide (WO(3)) films coupled with platinum (Pt) nanoparticles were investigated. WO(3) films with underlying Pt nanoparticles (WO(3)/Pt/substrate) and those with overlying Pt nanoparticles (Pt/WO(3)/substrate) were synthesized by sputtering and sol-gel methods. Between these films, underlying Pt nanoparticles greatly enhanced the photocatalytic oxidation activity of WO(3) without decreasing the photoinduced hydrophilic conversion. However, overlying Pt nanoparticles deteriorated the hydrophilicity of WO(3) because the Pt nanoparticle surface was hydrophobic. The enhanced photocatalytic reaction by the Pt nanoparticles was attributed to the multi-electron reduction in Pt, which is caused by the injected electrons from the conduction band of WO(3). The relationship between photocatalytic activity and thin film structure, including the size of Pt nanoparticles, the thickness and porosity of the WO(3) layer, were investigated. Consequently, the optimum structure for high performance in both photocatalysis and photoinduced hydrophilicity was WO(3) (50 nm)/Pt(1.5 nm)/substrate, and this film exhibited a significant self-cleaning property even under visible light irradiation.

  18. The nature of photoinduced phase transition and metastable states in vanadium dioxide

    PubMed Central

    Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; Torres, David; Wang, Tongyu; Sepulveda, Nelson; Chang, Kiseok; Young, Margaret; Lunt, Richard R.; Ruan, Chong-Yu

    2016-01-01

    Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium. PMID:27982066

  19. Photoinduced Oxidative DNA Damage Revealed by an Agarose Gel Nicking Assay: A Biophysical Chemistry Laboratory Experiment

    NASA Astrophysics Data System (ADS)

    Shafirovich, Vladimir; Singh, Carolyn; Geacintov, Nicholas E.

    2003-11-01

    Oxidative damage of DNA molecules associated with electron-transfer reactions is an important phenomenon in living cells, which can lead to mutations and contribute to carcinogenesis and the aging processes. This article describes the design of several simple experiments to explore DNA damage initiated by photoinduced electron-transfer reactions sensitized by the acridine derivative, proflavine (PF). A supercoiled DNA agarose gel nicking assay is employed as a sensitive probe of DNA strand cleavage. A low-cost experimental and computer-interfaced imaging apparatus is described allowing for the digital recording and analysis of the gel electrophoresis results. The first experiment describes the formation of direct strand breaks in double-stranded DNA induced by photoexcitation of the intercalated PF molecules. The second experiment demonstrates that the addition of the well-known electron acceptor, methylviologen, gives rise to a significant enhancement of the photochemical DNA strand cleavage effect. This occurs by an electron transfer step to methylviologen that renders the inital photoinduced charge separation between photoexcited PF and DNA irreversible. The third experiment demonstrates that the action spectrum of the DNA photocleavage matches the absorption spectrum of DNA-bound, intercalated PF molecules, which differs from that of free PF molecules. This result demonstrates that the photoinduced DNA strand cleavage is initiated by intercalated rather than free PF molecules.

  20. Investigating plausible mechanisms for the photo-induced partial unfolding of a globular protein

    NASA Astrophysics Data System (ADS)

    Parker, James E.

    Two hypotheses are proposed to explain the photo-induced unfolding of β-lactoglobulin (BLG) that occurs when non-covalently bound to a dye molecule, meso-tetrakis (p-sulfonatophenyl) porphyrin (TSPP), and illuminated by a laser in the post-Tanford transition configuration. The first involves a photo-induced electron transfer from the porphyrin to the protein. The second involves the production of kynurenine by singlet oxygen that is generated during photo-excitation of the porphyrin. To evaluate these hypotheses, a series of computational and experimental results have been combined to establish the physical state of the BLG-TSPP complex and to estimate the likelihood of a post-irradiation event to initiate the partial unfolding. Determining the binding site location is crucial to establish the position of the photo-induced events and the likely end-product. A study of the vibronic state of the BLG-TSPP complex using resonant Raman and absorption spectroscopy coupled with density functional theory (DFT) and docking simulations is used to estimate the location of the binding site. Once the binding site is found, molecular dynamics simulations of the post-irradiation event relaxations in the protein are used to estimate the resulting secondary structure. This structure is compared to experimental estimates of the secondary structure of the unfolded protein to determine which hypothesis is the most likely mechanism to explain the unfolding.

  1. Neuronal regulation of photo-induced pineal photoreceptor proteins in carp Catla catla.

    PubMed

    Seth, Mohua; Maitra, Saumen Kumar

    2010-08-01

    In the present in vitro study on the pineal in carp Catla catla, specific agonist and antagonists of receptors for different neuronal signals and regulators of intra-cellular Ca(++) and cAMP were used to gather basic information on the neuronal signal transduction cascade mechanisms in the photo-induced expression of rod-like opsin and alpha-transducin-like proteins in any fish pineal. Western-blot analysis followed by quantitative analysis of respective immunoblot data for both the proteins revealed that photo-induced expression of each protein was stimulated by cholinergic (both nicotinic and muscarinic) agonists and a dopaminergic antagonist, inhibited by both cholinergic antagonists and a dopaminergic agonist, but not affected by any agonists or antagonists of adrenergic (alpha(1), alpha(2) and beta(1)) receptors. Moreover, expression of each protein was stimulated by voltage gated L type calcium channel blocker, adenylate cyclase inhibitor and phosphodiesterase activator; but suppressed by the activators of both calcium channel and adenylate cyclase, and by phosphodiesterase inhibitor. Collectively, we report for the first time that both cholinergic and dopaminergic signals play an important, though antagonistic, role in the photo-induced expression of photoreceptor proteins in the fish pineal through activation of a signal transduction pathway in which both calcium and cAMP may act as the intracellular messengers.

  2. Enantiomer-Selective Photo-Induced Reaction of Protonated Tryptophan with Disaccharides in the Gas Phase.

    PubMed

    Doan, Thuc N; Fujihara, Akimasa

    2017-07-08

    In order to investigate chemical evolution in interstellar molecular clouds, enantiomer-selective photo-induced chemical reactions between an amino acid and disaccharides in the gas phase were examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of protonated tryptophan (Trp) enantiomers with disaccharides consisting of two D-glucose units, such as D-maltose or D-cellobiose, were obtained by photoexcitation of the indole ring of Trp. NH2CHCOOH loss via cleavage of the Cα-Cβ bond in Trp induced by hydrogen atom transfer from the NH3(+) group of a protonated Trp was observed in a noncovalent heterochiral H(+)(L-Trp)(D-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H(+)(D-Trp)(D-maltose). For D-cellobiose, both NH2CHCOOH elimination and the m/z 282 product ion were observed, and no enantiomer-selective phenomena occurred. The m/z 282 product ion indicates that the photo-induced C-glycosylation, which links D-glucose residues to the indole moiety of Trp via a C-C bond, can occur in cold gas-phase noncovalent complexes, and its enantiomer-selectivity depends on the structure of the disaccharide.

  3. Supramolecular photomagnetic materials: photoinduced dimerization of ferrocene-based polychlorotriphenylmethyl radicals.

    PubMed

    Ratera, Imma; Ruiz-Molina, Daniel; Vidal-Gancedo, José; Novoa, Juan J; Wurst, Klaus; Letard, Jean-François; Rovira, Concepció; Veciana, Jaume

    2004-02-06

    New ferrocenyl Schiff-base polychlorotriphenylmethyl radicals have been synthesized and characterized. The imino group of one such radical undergoes an irreversible trans to cis structural isomerization induced by light. Such photoinduced isomerization has been monitored by UV/Vis and ESR spectroscopy and also monitored by HPLC. ESR frozen solution experiments at low temperature revealed that the cis isomer dimerizes, showing a strong antiferromagnetic interaction. Although numerous photochromic supramolecular systems have been described, such a photoinduced self-assembly process represents the first example of a one-way photoswitchable magnetic system in which a conversion between a doublet and a singlet ground state species is promoted by a photoinduced dimerization process driven by the formation of hydrogen bonds. DFT calculations on the minimized structure and on the rotational barriers have been performed to establish the origin of such behavior. The effect of the substituents and the media polarity on the photoisomerization of this imine chromophore have also been studied. It has been observed that the efficiency of the process is markedly dependent on the presence and characteristics of electron-donor and electron-acceptor substituents of the ferrocenyl Schiff-base polychlorotriphenylmethyl radicals as well as on the polarity of the solvent.

  4. The nature of photoinduced phase transition and metastable states in vanadium dioxide

    DOE PAGES

    Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; ...

    2016-12-16

    Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at themore » above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium.« less

  5. The nature of photoinduced phase transition and metastable states in vanadium dioxide

    SciTech Connect

    Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; Torres, David; Wang, Tongyu; Sepulveda, Nelson; Chang, Kiseok; Young, Margaret; Lunt, Richard R.; Ruan, Chong-Yu

    2016-12-16

    Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium.

  6. Enantiomer-Selective Photo-Induced Reaction of Protonated Tryptophan with Disaccharides in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Doan, Thuc N.; Fujihara, Akimasa

    2017-07-01

    In order to investigate chemical evolution in interstellar molecular clouds, enantiomer-selective photo-induced chemical reactions between an amino acid and disaccharides in the gas phase were examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of protonated tryptophan (Trp) enantiomers with disaccharides consisting of two uc(d)-glucose units, such as uc(d)-maltose or uc(d)-cellobiose, were obtained by photoexcitation of the indole ring of Trp. NH2CHCOOH loss via cleavage of the Cα-Cβ bond in Trp induced by hydrogen atom transfer from the NH3 + group of a protonated Trp was observed in a noncovalent heterochiral H+(uc(l)-Trp)(uc(d)-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H+(uc(d)-Trp)(uc(d)-maltose). For uc(d)-cellobiose, both NH2CHCOOH elimination and the m/z 282 product ion were observed, and no enantiomer-selective phenomena occurred. The m/z 282 product ion indicates that the photo-induced C-glycosylation, which links uc(d)-glucose residues to the indole moiety of Trp via a C-C bond, can occur in cold gas-phase noncovalent complexes, and its enantiomer-selectivity depends on the structure of the disaccharide.

  7. [The surgical section of the bundle of Kent as an operative treatment of the Wolff-Parkinson-White syndrome: apropos a series of 82 operated cases].

    PubMed

    Bodegas, A; Leenhardt, A; Cauchemez, B; Meslindrey, P; Menasche, P; Leclercq, J F; Coumel, P; Piwnica, A; Slama, R

    1991-01-01

    Eighty two patients diagnosed of the Wolff-Parkinson-White syndrome (WPW) underwent operation for the surgical section of the Kent-His bundle. In these cases, posteroseptal localization (PS) occurred in 32, left lateral (LL) in 25, right lateral (RL) in six, anteroseptal (AS) in one, posteroseptal and left lateral in 14, right and left posteroseptal in two, anteroseptal and left lateral in one, and left lateral and right and left posteroseptal in one. All of the patients presented an invalidating clinical of palpitations and/or loss of consciousness, and episodes of atrial fibrillation and/or reciprocal rhythm were registered in all cases. The mean anterograde refractory period in the accessory pathways was 244 +/- 60 msec, and the shortest RR in atrial fibrillation was 190 +/- 36 msec. A mitral commissurotomy was carried out in 3 patients during surgery, mitral prostheses were implanted in two, a double aorto-coronary bypass was made in three and an interventricular communication was closed in one. After a follow-up of 36 +/- 18 months, the surgical section of the Kent bundle was found to be effective in 77 out 82 patients (94%). (In 70 out of 77 cases, both anterograde and retrograde conduction were totally abolished and in seven out of 77 obtunded. All patients were asymptomatic during the follow-up period). In 5 out of 82 patients, surgical treatment was ineffective all five showed a PS Kent-His and two presented a second Kent-His fascicle (LL).(ABSTRACT TRUNCATED AT 250 WORDS)

  8. [Wolff-Parkinson-White syndrome. Value of transesophageal atrial stimulation coupled with exercise test for the study of anterograde conduction in the accessory pathway].

    PubMed

    Cebron, J P; Le Marec, H; Victor, J; Chevallier, J C; Borgat, C; Godin, J F

    1989-02-01

    In patients with Wolff-Parkinson-White syndrome the anterograde conduction properties of the accessory pathway determine the ventricular rate in case of atrial fibrillation (AF). Anterograde conduction in the accessory pathway was evaluated in 20 patients (mean age 31 years) by means of transoesophageal atrial pacing with increasing frequency (up to 460 per minute), first at rest, then during exercise on an ergometric bicycle and upon immediate recovery. The exploration was completed by a search for the disappearance of pre-excitation during exercise and after an intravenous injection of ajmaline 1 mg/kg. The shortest cycle (SC) of atrial pacing with 1:1 conduction by the accessory pathway regularly decreased by 80 +/- 26 ms (n = 18), i.e. 27 p. 100 of its value at rest. At immediate recovery SC increased by 40 +/- 53 ms (n = 9). Atrial fibrillation was induced at rest and/or during exercise in 12 patients. The shortest interval (SI) between two pre-excited ventricular complexes was 290 +/- 80 ms (n = 8) at rest and 244 +/- 53 ms (n = 8) during exercise. With a substantial group of values (n = 12) there was good correlation between SC and SI both at rest and during exercise. With a smaller group of values (n = 3) SI was clearly greater than SC, suggesting a concealed conduction in the accessory pathway during atrial fibrillation. Disappearance of pre-excitation during exercise was observed in 4 patients, 3 of whom had a short (less than 250 ms) SC and/or SI.(ABSTRACT TRUNCATED AT 250 WORDS)

  9. Results of a comparative study of low energy direct current with radiofrequency ablation in patients with the Wolff-Parkinson-White syndrome.

    PubMed Central

    Lemery, R; Talajic, M; Roy, D; Lavoie, L; Coutu, B; Hii, J T; Radzik, D; Lavallee, E; Cartier, R

    1993-01-01

    OBJECTIVE--To compare two new power sources for catheter ablation in patients with the Wolff-Parkinson-White syndrome. DESIGN--120 consecutive patients with accessory pathways had catheter ablation. Low energy direct current (DC) was used in the first 60 patients and radio-frequency current in the next 60 patients. SETTING--Electrophysiological laboratory of a large heart institute. PATIENTS--72 men and 48 women (mean (SD) age 35 (14) years (range 9-75)). The accessory pathways were in the left free wall in 73 patients. They were posteroseptal in 35 patients, in the right free wall in five, and anteroseptal in seven. There was no significant difference in the clinical or electrophysiological variables between the two ablation groups. RESULTS--Catheter ablation with low energy direct current was successful in 55/60 patients (92%) and radiofrequency energy was successful in 52/60 patients (87%). Low energy direct current was also successful in four of the eight patients in whom radiofrequency ablation had failed. Radiofrequency ablation was successful in two of the five patients in whom low energy direct current ablation had failed. The mean (SD) procedure and fluoroscopy times for successful ablation were 3.2 (1.5) h and 61 (40) min respectively. These times were similar for both power sources. Accessory pathway conduction recurred in 17 patients (28%) who had low energy direct current and four patients (7%) who received radiofrequency energy (p < 0.004). All patients with recurrence of an accessory pathway had successful re-ablation. CONCLUSIONS--Both new power sources successfully ablated accessory pathways, (overall success rate 94% (113/120 patients)). Radiofrequency ablation, however, did not require general anaesthesia and was associated with a significantly lower rate of recurrence of accessory pathway conduction. Therefore radiofrequency should be used initially for ablation. Low energy direct current may be most useful as a back-up in patients in whom

  10. Detection of Gene Rearrangements in Targeted Clinical Next-Generation Sequencing

    PubMed Central

    Abel, Haley J.; Al-Kateb, Hussam; Cottrell, Catherine E.; Bredemeyer, Andrew J.; Pritchard, Colin C.; Grossmann, Allie H.; Wallander, Michelle L.; Pfeifer, John D.; Lockwood, Christina M.; Duncavage, Eric J.

    2015-01-01

    The identification of recurrent gene rearrangements in the clinical laboratory is the cornerstone for risk stratification and treatment decisions in many malignant tumors. Studies have reported that targeted next-generation sequencing assays have the potential to identify such rearrangements; however, their utility in the clinical laboratory is unknown. We examine the sensitivity and specificity of ALK and KMT2A (MLL) rearrangement detection by next-generation sequencing in the clinical laboratory. We analyzed a series of seven ALK rearranged cancers, six KMT2A rearranged leukemias, and 77 ALK/KMT2A rearrangement–negative cancers, previously tested by fluorescence in situ hybridization (FISH). Rearrangement detection was tested using publicly available software tools, including Breakdancer, ClusterFAST, CREST, and Hydra. Using Breakdancer and ClusterFAST, we detected ALK rearrangements in seven of seven FISH-positive cases and KMT2A rearrangements in six of six FISH-positive cases. Among the 77 ALK/KMT2A FISH-negative cases, no false-positive identifications were made by Breakdancer or ClusterFAST. Further, we identified one ALK rearranged case with a noncanonical intron 16 breakpoint, which is likely to affect its response to targeted inhibitors. We report that clinically relevant chromosomal rearrangements can be detected from targeted gene panel–based next-generation sequencing with sensitivity and specificity equivalent to that of FISH while providing finer-scale information and increased efficiency for molecular oncology testing. PMID:24813172

  11. Mitochondrial DNA Rearrangement Spectrum in Brain Tissue of Alzheimer’s Disease: Analysis of 13 Cases

    PubMed Central

    Chen, Yucai; Liu, Changsheng; Parker, William Davis; Chen, Hongyi; Beach, Thomas G.; Liu, Xinhua; Serrano, Geidy E.; Lu, Yanfen; Huang, Jianjun; Yang, Kunfang; Wang, Chunmei

    2016-01-01

    Background Mitochondrial dysfunction may play a central role in the pathologic process of Alzheimer’s disease (AD), but there is still a scarcity of data that directly links the pathology of AD with the alteration of mitochondrial DNA. This study aimed to provide a comprehensive assessment of mtDNA rearrangement events in AD brain tissue. Patients and Methods Postmortem frozen human brain cerebral cortex samples were obtained from the Banner Sun Health Research Institute Brain and Body Donation Program, Sun City, AZ. Mitochondria were isolated and direct sequence by using MiSeq®, and analyzed by relative software. Results Three types of mitochondrial DNA (mtDNA) rearrangements have been seen in post mortem human brain tissue from patients with AD and age matched control. These observed rearrangements include a deletion, F-type rearrangement, and R-type rearrangement. We detected a high level of mtDNA rearrangement in brain tissue from cognitively normal subjects, as well as the patients with Alzheimer's disease (AD). The rate of rearrangements was calculated by dividing the number of positive rearrangements by the coverage depth. The rearrangement rate was significantly higher in AD brain tissue than in control brain tissue (17.9%versus 6.7%; p = 0.0052). Of specific types of rearrangement, deletions were markedly increased in AD (9.2% versus 2.3%; p = 0.0005). Conclusions Our data showed that failure of mitochondrial DNA in AD brain might be important etiology of AD pathology. PMID:27299301

  12. ROS1 rearrangements define a unique molecular class of lung cancers.

    PubMed

    Bergethon, Kristin; Shaw, Alice T; Ou, Sai-Hong Ignatius; Katayama, Ryohei; Lovly, Christine M; McDonald, Nerina T; Massion, Pierre P; Siwak-Tapp, Christina; Gonzalez, Adriana; Fang, Rong; Mark, Eugene J; Batten, Julie M; Chen, Haiquan; Wilner, Keith D; Kwak, Eunice L; Clark, Jeffrey W; Carbone, David P; Ji, Hongbin; Engelman, Jeffrey A; Mino-Kenudson, Mari; Pao, William; Iafrate, A John

    2012-03-10

    Chromosomal rearrangements involving the ROS1 receptor tyrosine kinase gene have recently been described in a subset of non-small-cell lung cancers (NSCLCs). Because little is known about these tumors, we examined the clinical characteristics and treatment outcomes of patients with NSCLC with ROS1 rearrangement. Using a ROS1 fluorescent in situ hybridization (FISH) assay, we screened 1,073 patients with NSCLC and correlated ROS1 rearrangement status with clinical characteristics, overall survival, and when available, ALK rearrangement status. In vitro studies assessed the responsiveness of cells with ROS1 rearrangement to the tyrosine kinase inhibitor crizotinib. The clinical response of one patient with ROS1-rearranged NSCLC to crizotinib was investigated as part of an expanded phase I cohort. Of 1,073 tumors screened, 18 (1.7%) were ROS1 rearranged by FISH, and 31 (2.9%) were ALK rearranged. Compared with the ROS1-negative group, patients with ROS1 rearrangements were significantly younger and more likely to be never-smokers (each P < .001). All of the ROS1-positive tumors were adenocarcinomas, with a tendency toward higher grade. ROS1-positive and -negative groups showed no difference in overall survival. The HCC78 ROS1-rearranged NSCLC cell line and 293 cells transfected with CD74-ROS1 showed evidence of sensitivity to crizotinib. The patient treated with crizotinib showed tumor shrinkage, with a near complete response. ROS1 rearrangement defines a molecular subset of NSCLC with distinct clinical characteristics that are similar to those observed in patients with ALK-rearranged NSCLC. Crizotinib shows in vitro activity and early evidence of clinical activity in ROS1-rearranged NSCLC.

  13. Deep cytoplasmic rearrangements in axis-respecified Xenopus embryos

    NASA Technical Reports Server (NTRS)

    Denegre, J. M.; Danilchik, M. V.

    1993-01-01

    In fertilized eggs of the frog Xenopus, the vegetal yolk mass rotates away from the future dorsal side (J. P. Vincent and J. Gerhart, 1987, Dev. Biol. 123, 526-539), and a major rearrangement of the deep animal hemisphere cytoplasm produces a characteristic swirl in the prospective dorsal side (M. V. Danilchik and J. M. Denegre, 1991, Development 111, 845-856). The relationship between this swirl and determination of the dorsal-ventral axis was further investigated by attempting to experimentally separate the positions of the swirl and the dorsal-ventral axis. Eggs were obliquely oriented in the gravity field to respecify the direction of yolk mass rotation and the position of the dorsal-ventral axis. When yolk mass rotation occurred in the absence of a sperm, as in activated eggs, a swirl pattern formed on the side away from which the yolk mass had rotated. In fertilized eggs tipped with the sperm entry point (SEP) down or to the side, swirl patterns were always found to form on the side away from which the yolk mass was displaced. However, in eggs tipped SEP up, in which the yolk mass was forced to rotate away from the SEP, more complicated rearrangements were observed in addition to the rotation-oriented swirl. Because the direction of yolk mass rotation was found to be influenced by both gravity and the actual position of the SEP in obliquely oriented eggs (SEP to the side), such complicated rearrangement patterns may result from opposing forces generated by both yolk mass rotation and the expanding sperm aster. Thus, except in cases in which the influences of SEP position and unit gravity opposed each other, it was not possible to experimentally separate the position of the deep cytoplasmic swirl from the direction of yolk mass rotation, and therefore the position of the prospective dorsal side.

  14. Deep cytoplasmic rearrangements in axis-respecified Xenopus embryos

    NASA Technical Reports Server (NTRS)

    Denegre, J. M.; Danilchik, M. V.

    1993-01-01

    In fertilized eggs of the frog Xenopus, the vegetal yolk mass rotates away from the future dorsal side (J. P. Vincent and J. Gerhart, 1987, Dev. Biol. 123, 526-539), and a major rearrangement of the deep animal hemisphere cytoplasm produces a characteristic swirl in the prospective dorsal side (M. V. Danilchik and J. M. Denegre, 1991, Development 111, 845-856). The relationship between this swirl and determination of the dorsal-ventral axis was further investigated by attempting to experimentally separate the positions of the swirl and the dorsal-ventral axis. Eggs were obliquely oriented in the gravity field to respecify the direction of yolk mass rotation and the position of the dorsal-ventral axis. When yolk mass rotation occurred in the absence of a sperm, as in activated eggs, a swirl pattern formed on the side away from which the yolk mass had rotated. In fertilized eggs tipped with the sperm entry point (SEP) down or to the side, swirl patterns were always found to form on the side away from which the yolk mass was displaced. However, in eggs tipped SEP up, in which the yolk mass was forced to rotate away from the SEP, more complicated rearrangements were observed in addition to the rotation-oriented swirl. Because the direction of yolk mass rotation was found to be influenced by both gravity and the actual position of the SEP in obliquely oriented eggs (SEP to the side), such complicated rearrangement patterns may result from opposing forces generated by both yolk mass rotation and the expanding sperm aster. Thus, except in cases in which the influences of SEP position and unit gravity opposed each other, it was not possible to experimentally separate the position of the deep cytoplasmic swirl from the direction of yolk mass rotation, and therefore the position of the prospective dorsal side.

  15. Synthesis of Neoglycoconjugates by the Desulfurative Rearrangement of Allylic Disulfides

    PubMed Central

    Crich, David; Yang, Fan

    2009-01-01

    Two series of neoglucosyl donors are prepared based on connection of the allylic disulfide motif to the anomeric center via either a simple O-glycosyl linkage or N-glycosyl amide unit. Conjugation of both sets of donors to cysteine in peptides is demonstrated through classical disulfide exchange followed by the phosphine-mediated desulfurative allylic rearrangement resulting in neoglycopeptides characterized by a simple thioether spacer. The conjugation reaction functions in the absence of protecting groups on both the neoglycosyl donor and peptide in aqueous media at room temperature. PMID:18729514

  16. Thermal rearrangement of novolak resins used in microlithography

    NASA Astrophysics Data System (ADS)

    Hardy, Ricky; Zampini, Anthony; Monaghan, Michael J.; O'Leary, Michael J.; Cardin, William J.; Eugster, Timothy J.

    1995-06-01

    Changes in phenolic-formaldehyde resin properties are described in terms of thermal exposure. At high temperature, resin molecular weight, dissolution properties and chemical composition change depending on the presence or absence of monomers. Without monomer in the resin melt at 220 degree(s)C, resin molecular weight increases with a corresponding decrease in dissolution rate. In the presence of monomer, molecular weight generally decreases. Dissolution rate may fluctuate depending on the monomer mixture. Three,five- Xylenol and 2,3,5-trimethylphenol co-monomers induced the most extreme changes in resin properties with thermal treatment. Resin degradation-recombination processes suggest a classical Friedel-Craft rearrangement mechanism.

  17. Investigation of a stereoselective co-mediated rearrangement reaction.

    PubMed

    Carbery, David R; Reignier, Serge; Miller, Neil D; Adams, Harry; Harrity, Joseph P A

    2003-05-30

    A stereocontrolled approach to alpha-alkyl beta-alkynyl cyclohexanones is reported through a Lewis acid mediated rearrangement reaction of enol ethers bearing an Co-alkyne moiety. The reaction proceeds with high levels of stereoselectivity in the presence of Ti- and B-Lewis acids to provide a range of alpha,beta-disubstituted cyclohexanones in high yield although the products are prone to epimerization at the alpha-position in the presence of the B-promoter system. The potential for an enantioselective variant of this process is outlined, and a rationale for the observed stereochemical trends and detailed structural analyses of the ketone products are described.

  18. Absence of Heterozygosity Due to Template Switching during Replicative Rearrangements

    PubMed Central

    Carvalho, Claudia M.B.; Pfundt, Rolph; King, Daniel A.; Lindsay, Sarah J.; Zuccherato, Luciana W.; Macville, Merryn V.E.; Liu, Pengfei; Johnson, Diana; Stankiewicz, Pawel; Brown, Chester W.; Shaw, Chad A.; Hurles, Matthew E.; Ira, Grzegorz; Hastings, P.J.; Brunner, Han G.; Lupski, James R.

    2015-01-01

    We investigated complex genomic rearrangements (CGRs) consisting of triplication copy-number variants (CNVs) that were accompanied by extended regions of copy-number-neutral absence of heterozygosity (AOH) in subjects with multiple congenital abnormalities. Molecular analyses provided observational evidence that in humans, post-zygotically generated CGRs can lead to regional uniparental disomy (UPD) due to template switches between homologs versus sister chromatids by using microhomology to prime DNA replication—a prediction of the replicative repair model, MMBIR. Our findings suggest that replication-based mechanisms might underlie the formation of diverse types of genomic alterations (CGRs and AOH) implicated in constitutional disorders. PMID:25799105

  19. Controlled order rearrangement encryption for quantum key distribution

    SciTech Connect

    Deng Fuguo; Long, G.L.

    2003-10-01

    A technique is devised to perform orthogonal state quantum key distribution. In this scheme, entangled parts of a quantum information carrier are sent from Alice to Bob through two quantum channels. However, before the transmission, the order of the quantum information carrier in one channel is reordered so that Eve cannot steal useful information. At the receiver's end, the order of the quantum information carrier is restored. The order rearrangement operation in both parties is controlled by a prior shared control key which is used repeatedly in a quantum key distribution session.

  20. [Clonality lymphoid study through rearrangement analysis of antigen receptor].

    PubMed

    Villamizar-Rivera, Nicolás; Olaya, Natalia

    2015-01-01

    As a rule, malignant lymphoid proliferations are clonal. While most of the time the biological potential can be established through routine pathologic examination and auxiliary techniques, some cases are difficult to classify. Moreover, there are situations in which there are dominant clones whose analysis are important, such as occur in autoimmune diseases and immunodeficiency. This paper presents in an understandable way the main techniques for the study of clonality in lymphoid lesions, i.e. the analysis of rearrangements of antigen receptor genes by multiplex polymerase chain reaction (PCR) based tests.

  1. Chromosomal rearrangements detected by FISH and G-banding.

    PubMed

    Hou, J W; Wang, T R

    1996-09-01

    Fluorescence in situ hybridization (FISH) using chromosome-specific DNA libraries as painting probes, locus-specific unique sequence (cosmid) probes, and Y-specific repetitive sequences was applied in the analysis of eighteen cases of chromosomal rearrangements of undetermined nature. FISH clarified the origin of the extra or translocated chromosome segments in seventeen patients, one with 2q+, two with 4q+, one each with 6p+, 7p+, 9q+, 10p+, 11q+ and 12p+, two with 13q+, and one each with 15q+, 17p+, 18p+, 20p+, 21p+ and Yq+, as well as the nature of a de novo supernumerary chromosome marker in a previously reported case. By G-banding and molecular cytogenetic studies of the family members, six cases were determined to have unbalanced translocations inherited from the carrier parent. The extra translocated genetic material may cause specific trisomic syndromes, including partial 6p21.3-p23, 9q32-q34.3, 13q32-q34, 15q24-q26, and 17p11.2-p13 trisomies in those patients. A translocated 21q segment on 12p was shown by a painting probe in a patient with Down features. A patient with cat cry syndrome resulting from a loss of the terminal segment of the short arm of chromosome 5 was confirmed by a cosmid probe showing de novo reciprocal translocation between chromosomes 5 and 18:t(5;18) (p13.3;p11.31). With FISH, the extra material on the rearranged chromosome could also be identified as duplicated or translocated. The FISH technique thus provides a method for the analysis of extra structurally abnormal chromosomes (especially in de novo cases), recognizable syndromes (contiguous gene syndromes) caused by translocated deletion from parental balanced chromosome rearrangements, and supernumerary marker chromosomes. FISH subsequent to G-banding is also of great help in the confirmation of preliminary abnormal G-banded karyotypes after a modified destaining procedure. In conclusion, the combination of G-banding and FISH is very useful in the accurate diagnosis of chromosomal

  2. Collective epithelial migration and cell rearrangements drive mammary branching morphogenesis.

    PubMed

    Ewald, Andrew J; Brenot, Audrey; Duong, Myhanh; Chan, Bianca S; Werb, Zena

    2008-04-01

    Epithelial organs are built through the movement of groups of interconnected cells. We observed cells in elongating mammary ducts reorganize into a multilayered epithelium, migrate collectively, and rearrange dynamically, all without forming leading cellular extensions. Duct initiation required proliferation, Rac, and myosin light-chain kinase, whereas repolarization to a bilayer depended on Rho kinase. We observed that branching morphogenesis results from the active motility of both luminal and myoepithelial cells. Luminal epithelial cells advanced collectively, whereas myoepithelial cells appeared to restrain elongating ducts. Significantly, we observed that normal epithelium and neoplastic hyperplasias are organized similarly, suggesting common mechanisms of epithelial growth.

  3. [Synthetic biology and rearrangements of microbial genetic material].

    PubMed

    Liang, Quan-Feng; Wang, Qian; Qi, Qing-Sheng

    2011-10-01

    As an emerging discipline, synthetic biology has shown great scientific values and application prospects. Although there have been many reviews of various aspects on synthetic biology over the last years, this article, for the first time, attempted to discuss the relationship and difference between microbial genetics and synthetic biology. We summarized the recent development of synthetic biology in rearranging microbial genetic materials, including synthesis, design and reduction of genetic materials, standardization of genetic parts and modularization of genetic circuits. The relationship between synthetic biology and microbial genetic engineering was also discussed in the paper.

  4. Somatic engineering of oncogenic chromosomal rearrangements: a perspective

    PubMed Central

    Maddalo, Danilo; Ventura, Andrea

    2016-01-01

    The ability to engineer specific mutations in mice has proven essential to advancing our understanding of the molecular basis of cancer. Chromosomal rearrangements, a common and clinically relevant class of cancer-causing mutations, have however remained difficult to faithfully recapitulate in vivo. The development of genetic tools for in vivo somatic genome editing has recently overcome this limitation and led to the generation of more sophisticated and accurate preclinical models of human cancers. Here we review the potential applications of these new technologies to the study of tumor biology and discuss their advantages over more conventional strategies, their limitations, and the remaining challenges. PMID:27520450

  5. Precise detection of rearrangement breakpoints in mammalian chromosomes

    PubMed Central

    Lemaitre, Claire; Tannier, Eric; Gautier, Christian; Sagot, Marie-France

    2008-01-01

    Background Genomes undergo large structural changes that alter their organisation. The chromosomal regions affected by these rearrangements are called breakpoints, while those which have not been rearranged are called synteny blocks. We developed a method to precisely delimit rearrangement breakpoints on a genome by comparison with the genome of a related species. Contrary to current methods which search for synteny blocks and simply return what remains in the genome as breakpoints, we propose to go further and to investigate the breakpoints themselves in order to refine them. Results Given some reliable and non overlapping synteny blocks, the core of the method consists in refining the regions that are not contained in them. By aligning each breakpoint sequence against its specific orthologous sequences in the other species, we can look for weak similarities inside the breakpoint, thus extending the synteny blocks and narrowing the breakpoints. The identification of the narrowed breakpoints relies on a segmentation algorithm and is statistically assessed. Since this method requires as input synteny blocks with some properties which, though they appear natural, are not verified by current methods for detecting such blocks, we further give a formal definition and provide an algorithm to compute them. The whole method is applied to delimit breakpoints on the human genome when compared to the mouse and dog genomes. Among the 355 human-mouse and 240 human-dog breakpoints, 168 and 146 respectively span less than 50 Kb. We compared the resulting breakpoints with some publicly available ones and show that we achieve a better resolution. Furthermore, we suggest that breakpoints are rarely reduced to a point, and instead consist in often large regions that can be distinguished from the sequences around in terms of segmental duplications, similarity with related species, and transposable elements. Conclusion Our method leads to smaller breakpoints than already published ones

  6. Rearrangement patterns of the canine TCRγ locus in a distinct group of T cell lymphomas.

    PubMed

    Keller, Stefan M; Moore, Peter F

    2012-01-15

    The T cell antigen receptor chains are assembled through a rearrangement process that combines variable (V), diversity (D) and joining (J) region genes. Recently, the entire canine T cell receptor γ (TRG) locus was described. It is arranged in 8 cassettes with up to 3 V genes, 2 J genes and 1 C gene each. However, no data is available beyond the level of sequence analysis. The objective of this study was to identify rearranged genes of the canine TRG locus through experimental analysis and to assess gene usage and patterns of rearrangement in a series of canine T cell lymphomas. Rearranged genes were identified through computational analysis of recombination signal sequences (RSSs), a gene's potential to generate a polyclonal smear, and through sequencing of clonal rearrangements in a series of T cell lymphomas. Out of a total of 32 Vγ and Jγ genes, 21 genes were found to rearrange, 8 genes were considered not rearranged and 3 genes were suspected to rearrange but their status could not be determined definitely. Rearrangements of the canine TRG locus were assessed in a group of canine T cell lymphomas as well as 3 neoplastic T cell lines. An average of 4.6 rearrangements per lymphoma was found suggesting that canine T cells routinely rearrange multiple cassettes per allele. The most commonly rearranged Vγ genes belonged to subgroups Vγ2, Vγ3, and Vγ7. Genes in cassettes 2 and 3 preferentially rearranged within their respective cassettes, while Vγ genes in cassette 7 rearranged to a Jγ gene in cassette 8. There was a strong preference for Vγ2 genes to rearrange to a 3' Jγ gene and for Vγ3 and Vγ7 genes to rearrange to a 5' Jγ gene. This rearrangement pattern coincided with the conservation of the spacer sequence between V and J gene subgroups rather than the topologic location of genes. These data show that highly divergent spacer sequences allow for equally efficient recombination and suggest that spacer sequences can mediate compatibility between V

  7. Developmental arrest at early stages of Chinese hamster embryos homozygous for chromosomal rearrangements

    SciTech Connect

    Sonta, S.; Yamada, M.; Iida, T.; Ohashi, H. )

    1991-03-01

    Forty-three Chinese hamster stocks with autosomal rearrangements produced by X-irradiation were used. These rearrangements, 38 reciprocal translocations and 5 inversions, were chromosomally balanced. Heterozygotes for these rearrangements were all fertile and morphologically normal in both sexes except for one line with growth retardation. By crossing male and female heterozygotes for the same rearrangements, homozygotes were obtained in 37 lines. In the remaining 6 lines (5 with reciprocal translocations and 1 with an inversion), no homozygotes were viable. These 6 lines revealed arrested development of homozygous embryos at the two-cell stage, around the eight-cell stage, and after implantation, respectively. The bands of the breakpoints of rearrangements associated with lethality of homozygous embryos were different for each rearrangement. These results suggest that abnormal expression including embryonic lethality in homozygotes may be due to an influence of genes at the breakpoints.

  8. Compositions and methods for detecting gene rearrangements and translocations

    DOEpatents

    Rowley, Janet D.; Diaz, Manuel O.

    2000-01-01

    Disclosed is a series of nucleic acid probes for use in diagnosing and monitoring certain types of leukemia using, e.g., Southern and Northern blot analyses and fluorescence in situ hybridization (FISH). These probes detect rearrangements, such as translocations involving chromosome band 11q23 with other chromosomes bands, including 4q21, 6q27, 9p22, 19p13.3, in both dividing leukemic cells and interphase nuclei. The breakpoints in all such translocations are clustered within an 8.3 kb BamHI genomic region of the MLL gene. A novel 0.7 kb BamH1 cDNA fragment derived from this gene detects rearrangements on Southern blot analysis with a single BamHI restriction digest in all patients with the common 11q23 translocations and in patients with other 11q23 anomalies. Northern blot analyses are presented demonstrating that the MLL gene has multiple transcripts and that transcript size differentiates leukemic cells from normal cells. Also disclosed are MLL fusion proteins, MLL protein domains and anti-MLL antibodies.

  9. Insights into structural variations and genome rearrangements in prokaryotic genomes.

    PubMed

    Periwal, Vinita; Scaria, Vinod

    2015-01-01

    Structural variations (SVs) are genomic rearrangements that affect fairly large fragments of DNA. Most of the SVs such as inversions, deletions and translocations have been largely studied in context of genetic diseases in eukaryotes. However, recent studies demonstrate that genome rearrangements can also have profound impact on prokaryotic genomes, leading to altered cell phenotype. In contrast to single-nucleotide variations, SVs provide a much deeper insight into organization of bacterial genomes at a much better resolution. SVs can confer change in gene copy number, creation of new genes, altered gene expression and many other functional consequences. High-throughput technologies have now made it possible to explore SVs at a much refined resolution in bacterial genomes. Through this review, we aim to highlight the importance of the less explored field of SVs in prokaryotic genomes and their impact. We also discuss its potential applicability in the emerging fields of synthetic biology and genome engineering where targeted SVs could serve to create sophisticated and accurate genome editing. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  10. FASEB Summer Research Conference. Genetic Recombination and Chromosome Rearrangements

    SciTech Connect

    Jinks-Robertson, Sue

    2002-02-01

    The 2001 meeting entitled ''Genetic Recombination and Genome Rearrangements'' was held July 21-26 in Snowmass, Colorado. The goal of the meeting was to bring together scientists using diverse approaches to study all aspects of genetic recombination. This goal was achieved by integrating talks covering the genetics, biochemistry and structural biology of homologous recombination, site-specific recombination, and nonhomologous recombination. The format of the meeting consisted of a keynote address on the opening evening, two formal plenary sessions on each of the four full meeting days, a single afternoon workshop consisting of short talks chosen from among submitted abstracts, and afternoon poster sessions on each of the four full meeting days. The eight plenary session were entitled: (1) Recombination Mechanisms, (2) Prokaryotic Recombination, (3) Repair and Recombination, (4) Site-specific Recombination and Transposition, (5) Eukaryotic Recombination I, (6) Genome Rearrangements, (7) Meiosis, and (8) Eukaryotic Recombination II. Each session included a mix of genetic, biochemical and structural talks; talks were limited to 20 minutes, followed by 10 minutes of very lively, general discussion. Much of the data presented in the plenary sessions was unpublished, thus providing attendees with the most up-to-date knowledge of this rapidly-moving field.

  11. Exploring the Conformational States and Rearrangements of Yarrowia lipolytica Lipase

    PubMed Central

    Bordes, Florence; Barbe, Sophie; Escalier, Pierre; Mourey, Lionel; André, Isabelle; Marty, Alain; Tranier, Samuel

    2010-01-01

    We report the 1.7 Å resolution crystal structure of the Lip2 lipase from Yarrowia lipolytica in its closed conformation. The Lip2 structure is highly homologous to known structures of the fungal lipase family (Thermomyces lanuginosa, Rhizopus niveus, and Rhizomucor miehei lipases). However, it also presents some unique features that are described and discussed here in detail. Structural differences, in particular in the conformation adopted by the so-called lid subdomain, suggest that the opening mechanism of Lip2 may differ from that of other fungal lipases. Because the catalytic activity of lipases is strongly dependent on structural rearrangement of this mobile subdomain, we focused on elucidating the molecular mechanism of lid motion. Using the x-ray structure of Lip2, we carried out extensive molecular-dynamics simulations in explicit solvent environments (water and water/octane interface) to characterize the major structural rearrangements that the lid undergoes under the influence of solvent or upon substrate binding. Overall, our results suggest a two-step opening mechanism that gives rise first to a semi-open conformation upon adsorption of the protein at the water/organic solvent interface, followed by a further opening of the lid upon substrate binding. PMID:20923657

  12. Transposon Domestication versus Mutualism in Ciliate Genome Rearrangements

    PubMed Central

    Vogt, Alexander; Goldman, Aaron David; Mochizuki, Kazufumi; Landweber, Laura F.

    2013-01-01

    Ciliated protists rearrange their genomes dramatically during nuclear development via chromosome fragmentation and DNA deletion to produce a trimmer and highly reorganized somatic genome. The deleted portion of the genome includes potentially active transposons or transposon-like sequences that reside in the germline. Three independent studies recently showed that transposase proteins of the DDE/DDD superfamily are indispensible for DNA processing in three distantly related ciliates. In the spirotrich Oxytricha trifallax, high copy-number germline-limited transposons mediate their own excision from the somatic genome but also contribute to programmed genome rearrangement through a remarkable transposon mutualism with the host. By contrast, the genomes of two oligohymenophorean ciliates, Tetrahymena thermophila and Paramecium tetraurelia, encode homologous PiggyBac-like transposases as single-copy genes in both their germline and somatic genomes. These domesticated transposases are essential for deletion of thousands of different internal sequences in these species. This review contrasts the events underlying somatic genome reduction in three different ciliates and considers their evolutionary origins and the relationships among their distinct mechanisms for genome remodeling. PMID:23935529

  13. Regioselective 1-N-Alkylation and Rearrangement of Adenosine Derivatives.

    PubMed

    Oslovsky, Vladimir E; Drenichev, Mikhail S; Mikhailov, Sergey N

    2015-01-01

    Several methods for the preparation of some N(6)-substituted adenosines based on selective 1-N-alkylation with subsequent Dimroth rearrangement were developed. The proposed methods seem to be effective for the preparation of natural N(6)-isopentenyl- and N(6)-benzyladenosines, which are known to possess pronounced biological activities. Direct 1-N-alkylation of 2',3',5'-tri-O-acetyladenosine and 3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides in N,N-dimethylformamide (DMF) in the presence of BaCO3 and KI gave 1-N-substituted derivatives with quantitative yields, whereas 1-N-alkylation of adenosine was accompanied by significant O-alkylation. Moreover, the reaction of trimethylsilyl derivatives of N(6)-acetyl-2',3',5'-tri-O-acetyladenosine and N(6)-acetyl-3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides leads to the formation of the stable 1-N-substituted adenosines. Dimroth rearrangement of 1-N-substituted adenosines in aqueous ammonia yields pure N(6)-substituted adenosines.

  14. Dynamic rearrangement of surface proteins is essential for cytokinesis.

    PubMed

    Bauer, Tobias; Motosugi, Nami; Miura, Koichi; Sabe, Hisataka; Hiiragi, Takashi

    2008-03-01

    Cytokinesis is a complex process that involves dynamic cortical rearrangement. Our recent time-lapse recordings of the mouse egg unexpectedly revealed a high motility of the second polar body (2pb). Experiments to address its underlying mechanism show that neither mechanical compression by the zona pellucida nor the connection via the mid-body is required for the 2pb movement. Time-lapse recordings establish that the 2pb moves together with the cell membrane. These recordings, in which cell surface proteins are labeled with fluorescent latex-microbeads or monovalent antibodies against whole mouse proteins, indicate that the majority of the surface proteins dynamically accumulate in the cleavage furrow at every cell division. Comparable dynamics of the cell surface proteins, and specifically of E-cadherin, are also observed in cultured epithelial cells. The surface protein dynamics are closely correlated with, and dependent on, those of the underlying cortical actin. The cortical actin network may form a scaffold for membrane proteins and thereby transfer them during contractile ring formation toward the cleavage furrow. Immobilization of surface proteins by tetravalent lectin-mediated crosslinking results in the failure of cleavage, demonstrating that the observed protein dynamics are essential for cytokinesis. We propose that dynamic rearrangement of the cell surface proteins is a common feature of cytokinesis, playing a key role in modifying the mechanical properties of the cell membrane during cortical ingression. (c) 2008 Wiley-Liss, Inc.

  15. FOXL2 mutations and genomic rearrangements in BPES.

    PubMed

    Beysen, Diane; De Paepe, Anne; De Baere, Elfride

    2009-02-01

    The FOXL2 gene is one of 10 forkhead genes, the mutations of which lead to human developmental disorders, often with ocular manifestations. Mutations in FOXL2 are known to cause blepharophimosis syndrome (BPES), an autosomal dominant eyelid malformation associated (type I) or not (type II) with ovarian dysfunction, leading to premature ovarian failure (POF). In addition, a few mutations have been described in patients with isolated POF. Here, we review all currently described FOXL2 sequence variations and genomic rearrangements in BPES and POF. Using a combined mutation detection approach, it is possible to identify the underlying genetic defect in a major proportion (88%) of typical BPES patients. Of all genetic defects found in our BPES cohort, intragenic mutations represent 81%. They include missense changes, frameshift and nonsense mutations, in-frame deletions, and duplications, that are distributed along the single-exon gene. Genomic rearrangements comprising both deletions encompassing FOXL2 and deletions located outside its transcription unit, represent 12% and 5% of all genetic defects in our BPES cohort, respectively. One of the challenges of genetic testing in BPES is the establishment of genotype-phenotype correlations, mainly with respect to the ovarian phenotype. Genetic testing should be performed in the context of genetic counseling, however, and should be systematically complemented by a multidisciplinary clinical follow-up. Another challenge for health care professionals involved in BPES is the treatment of the eyelid phenotype and the prevention or treatment of POF.

  16. Chromosome rearrangements and survival of androgenetic rainbow trout (Oncorhynchus mykiss).

    PubMed

    Ocalewicz, K; Dobosz, S; Kuzminski, H; Nowosad, J; Goryczko, K

    2010-01-01

    The purpose of this work was to quantify the impact of spontaneous and X-radiation-induced chromosome rearrangements on survival rate of androgenetic rainbow trout (Oncorhynchus mykiss). Various doses of X irradiation (50, 150, 250, 350 Gy) were used for inactivation of nuclear DNA in oocytes. After the irradiation, eggs were inseminated with normal sperm from 4 males derived from a strain characterized by Robertsonian rearrangements and length polymorphism of the Y chromosome. The haploid zygotes were exposed to a high hydrostatic pressure (7000 psi) to duplicate the paternal DNA. Neither Robertsonian chromosome polymorphism nor the Y chromosome morphology impaired the viability of the androgenetic embryos and alevins. Moreover, survival of eyed embryos of the androgenetic rainbow trout increased significantly with increasing doses of oocyte X irradiation. After 6 months of rearing, only specimens from the 250 and 350 Gy variants survived. The number of fingerlings with remnants of the maternal genome in the forms of chromosome fragments was higher in the 250 Gy group. Intraindividual variation of chromosome fragment number was observed, and some individuals exhibited haploid/diploid mosaicism and body malformations. Individuals irradiated with less than 250 Gy died, presumably because of the conflict between intact paternally derived chromosomes and the residues of maternal genome in the form of chromosome fragments.

  17. Frequent chromatin rearrangements in myelodysplastic syndromes--what stands behind?

    PubMed

    Pagáčová, E; Falk, M; Falková, I; Lukášová, E; Michalová, K; Oltová, A; Raška, I; Kozubek, S

    2014-01-01

    Myelodysplastic syndromes (MDS) represent a clinically and genetically heterogeneous group of clonal haematopoietic diseases characterized by a short survival and high rate of transformation to acute myeloid leukaemia (AML). In spite of this variability, MDS is associated with typical recurrent non-random cytogenetic defects. Chromosomal abnormalities are detected in the malignant bone-marrow cells of approximately 40-80 % of patients with primary or secondary MDS. The most frequent chromosomal rearrangements involve chromosomes 5, 7 and 8. MDS often shows presence of unbalanced chromosomal changes, especially large deletions [del(5), del(7q), del(12p), del(18q), del(20q)] or losses of whole chromosomes (7 and Y). The most typical cytogenetic abnormality is a partial or complete deletion of 5q- that occurs in roughly 30 % of all MDS cases either as the sole abnormality or in combination with other aberrations as a part of frequently complex karyotypes. The mechanisms responsible for the formation of MDS-associated recurrent translocations and complex karyotypes are unknown. Since some of the mentioned aberrations are characteristic for several haematological malignancies, more general cellular conditions could be expected to play a role. In this article, we introduce the most common rearrangements linked to MDS and discuss the potential role of the non-random higher-order chromatin structure in their formation. A contribution of the chromothripsis - a catastrophic event discovered only recently - is considered to explain how complex karyotypes may occur (during a single event).

  18. Transcriptome-guided characterization of genomic rearrangements in a breast cancer cell line.

    PubMed

    Zhao, Qi; Caballero, Otavia L; Levy, Samuel; Stevenson, Brian J; Iseli, Christian; de Souza, Sandro J; Galante, Pedro A; Busam, Dana; Leversha, Margaret A; Chadalavada, Kalyani; Rogers, Yu-Hui; Venter, J Craig; Simpson, Andrew J G; Strausberg, Robert L

    2009-02-10

    We have identified new genomic alterations in the breast cancer cell line HCC1954, using high-throughput transcriptome sequencing. With 120 Mb of cDNA sequences, we were able to identify genomic rearrangement events leading to fusions or truncations of genes including MRE11 and NSD1, genes already implicated in oncogenesis, and 7 rearrangements involving other additional genes. This approach demonstrates that high-throughput transcriptome sequencing is an effective strategy for the characterization of genomic rearrangements in cancers.

  19. Intrachromosomal Rearrangements in Rodents from the Perspective of Comparative Region-Specific Painting

    PubMed Central

    Serdyukova, Natalya A.; Perelman, Polina L.; Pavlova, Svetlana V.; Bulatova, Nina S.; Golenishchev, Feodor N.; Stanyon, Roscoe

    2017-01-01

    It has long been hypothesized that chromosomal rearrangements play a central role in different evolutionary processes, particularly in speciation and adaptation. Interchromosomal rearrangements have been extensively mapped using chromosome painting. However, intrachromosomal rearrangements have only been described using molecular cytogenetics in a limited number of mammals, including a few rodent species. This situation is unfortunate because intrachromosomal rearrangements are more abundant than interchromosomal rearrangements and probably contain essential phylogenomic information. Significant progress in the detection of intrachromosomal rearrangement is now possible, due to recent advances in molecular biology and bioinformatics. We investigated the level of intrachromosomal rearrangement in the Arvicolinae subfamily, a species-rich taxon characterized by very high rate of karyotype evolution. We made a set of region specific probes by microdissection for a single syntenic region represented by the p-arm of chromosome 1 of Alexandromys oeconomus, and hybridized the probes onto the chromosomes of four arvicolines (Microtus agrestis, Microtus arvalis, Myodes rutilus, and Dicrostonyx torquatus). These experiments allowed us to show the intrachromosomal rearrangements in the subfamily at a significantly higher level of resolution than previously described. We found a number of paracentric inversions in the karyotypes of M. agrestis and M. rutilus, as well as multiple inversions and a centromere shift in the karyotype of M. arvalis. We propose that during karyotype evolution, arvicolines underwent a significant number of complex intrachromosomal rearrangements that were not previously detected. PMID:28867774

  20. A New Genomic Evolutionary Model for Rearrangements, Duplications, and Losses That Applies across Eukaryotes and Prokaryotes

    NASA Astrophysics Data System (ADS)

    Lin, Yu; Moret, Bernard M. E.

    Background: Genomic rearrangements have been studied since the beginnings of modern genetics and models for such rearrangements have been the subject of many papers over the last 10 years. However, none of the extant models can predict the evolution of genomic organization into circular unichromosomal genomes (as in most prokaryotes) and linear multichromosomal genomes (as in most eukaryotes). Very few of these models support gene duplications and losses - yet these events may be more common in evolutionary history than rearrangements and themselves cause apparent rearrangements.