Tuning energy transfer in switchable donor-acceptor systems

The synthesis and characterisation of a coumarin-dithienylcyclopentene-coumarin symmetric triad (CSC) and a perylene bisimide-dithienylcyclopentene-coumarin asymmetric triad (PSC) are reported. In both triads the switching function of the photochromic dithienylcyclopentene unit is retained. For CSC an overall 50% quenching of the coumarin fluorescence is observed upon ring-closure of the dithienylcyclopentene component, which, taken together with the low PSS (<70%), indicates that energy transfer quenching of the coumarin component by the dithienylcyclopentene in the closed state is efficient. Upon ring opening of the dithienylcyclopentene unit the coumarin emission is restored fully. The PSC triad shows efficient energy transfer from the coumarin to the perylene bisimide unit when the dithienylcyclopentene unit is in the open state. When the dithienylcyclopentene is in the closed ( PSS) state a 60% decrease in sensitized perylene bisimide emission intensity is observed due to competitive quenching of the coumarin excited state and partial quenching of the perylene excited state by the closed dithienylcyclopentene unit. This modulation of energy transfer is reversible over several cycles for both the symmetric and asymmetric tri-component systems

Indications of Universal Excess Fluctuations in Nonequilibrium Systems

The fluctuation in electric current in nonequilibrium steady states is investigated by molecular dynamics simulation of macroscopically uniform conductors. At low frequencies, appropriate decomposition of the spectral intensity of current into thermal and excess fluctuations provides a simple picture of excess fluctuations behaving as shot noise. This indicates that the fluctuation-dissipation relation may be violated in a universal manner by the appearance of shot noise for a wide range of systems with particle or momentum transport.Comment: 4 pages, 4 figures; title changed, major revision; to appear in J. Phys. Soc. Jp

Raman scattering and FT-IR spectroscopic studies on dithienylethene switches—towards non-destructive optical readout

The non-destructive readout of photochromic memory materials based on the dithienylethene unit both by IR spectroscopy and Raman scattering is explored. A representative series of C5-substituted thienyl hexahydro- and hexafluoro-cyclopentene based photochromes was investigated to explore the effect and potential usefulness of substitution for the development of multicomponent memory materials. The effect of the deposition method on the photochemistry of solid materials containing photochromic dithienylcyclopentene switches was also explored. Photoconversion in the solid state to the closed form was found to be low when starting from the open form, but, in contrast, ring opening to the open state from the closed form was found to be complete. The effect was found to be due to inner filter rather than conformational phenomena. Characteristic vibrational bands for the central dithienyl core are assigned and a comparison made of the vibrational spectroscopic properties of the perhydro- and perfluoro switches. The data enable the determination of the photoconversion achievable in the solid state as well as some assessment of the influence of the deposition method on the photoconversion. The potential of Raman spectroscopy as a method of achieving non-destructive optical readout is demonstrated through the large differences in absolute Raman scattering intensity between the open and closed states, when monitored at wavelengths which do not result in photochemical ring opening.

Грунти як об’єкт науки

Висвітлюються деякі аспекти розвитку наших уявлень про ґрунтознавство як науковий напрямок природознавства та про ґрунти як об’єкт науки.Освещаются некоторые аспекты развития наших представлений о почвоведении как научном направлении природоведения и о почвах как объекте науки.The author highlights several aspects of human knowledge about soil research as a field of natural science, and about soils as a research object

Shot noise in mesoscopic systems

This is a review of shot noise, the time-dependent fluctuations in the electrical current due to the discreteness of the electron charge, in small conductors. The shot-noise power can be smaller than that of a Poisson process as a result of correlations in the electron transmission imposed by the Pauli principle. This suppression takes on simple universal values in a symmetric double-barrier junction (suppression factor 1/2), a disordered metal (factor 1/3), and a chaotic cavity (factor 1/4). Loss of phase coherence has no effect on this shot-noise suppression, while thermalization of the electrons due to electron-electron scattering increases the shot noise slightly. Sub-Poissonian shot noise has been observed experimentally. So far unobserved phenomena involve the interplay of shot noise with the Aharonov-Bohm effect, Andreev reflection, and the fractional quantum Hall effect.Comment: 37 pages, Latex, 10 figures (eps). To be published in "Mesoscopic Electron Transport," edited by L. P. Kouwenhoven, G. Schoen, and L. L. Sohn, NATO ASI Series E (Kluwer Academic Publishing, Dordrecht

Two new rapid SNP-typing methods for classifying Mycobacterium tuberculosis complex into the main phylogenetic lineages

There is increasing evidence that strain variation in Mycobacterium tuberculosis complex (MTBC) might influence the outcome of tuberculosis infection and disease. To assess genotype-phenotype associations, phylogenetically robust molecular markers and appropriate genotyping tools are required. Most current genotyping methods for MTBC are based on mobile or repetitive DNA elements. Because these elements are prone to convergent evolution, the corresponding genotyping techniques are suboptimal for phylogenetic studies and strain classification. By contrast, single nucleotide polymorphisms (SNP) are ideal markers for classifying MTBC into phylogenetic lineages, as they exhibit very low degrees of homoplasy. In this study, we developed two complementary SNP-based genotyping methods to classify strains into the six main human-associated lineages of MTBC, the 'Beijing' sublineage, and the clade comprising Mycobacterium bovis and Mycobacterium caprae. Phylogenetically informative SNPs were obtained from 22 MTBC whole-genome sequences. The first assay, referred to as MOL-PCR, is a ligation-dependent PCR with signal detection by fluorescent microspheres and a Luminex flow cytometer, which simultaneously interrogates eight SNPs. The second assay is based on six individual TaqMan real-time PCR assays for singleplex SNP-typing. We compared MOL-PCR and TaqMan results in two panels of clinical MTBC isolates. Both methods agreed fully when assigning 36 well-characterized strains into the main phylogenetic lineages. The sensitivity in allele-calling was 98.6% and 98.8% for MOL-PCR and TaqMan, respectively. Typing of an additional panel of 78 unknown clinical isolates revealed 99.2% and 100% sensitivity in allele-calling, respectively, and 100% agreement in lineage assignment between both methods. While MOL-PCR and TaqMan are both highly sensitive and specific, MOL-PCR is ideal for classification of isolates with no previous information, whereas TaqMan is faster for confirmation. Furthermore, both methods are rapid, flexible and comparably inexpensive

Новые языковые реальности употребления претерита в немецком гипотаксисе

Целью статьи являются обобщение и теоретическое обоснование нового употребления претерита в относительном значении в конкретных видах придаточных предложений с презенсом в главном предложении. В статье анализируются коннотативные нюансы относительного значения претерита, регулярность замены префекта-пассива и перфекта именного составного сказуемого с глаголом "sein" на претеритальные формы в гипотаксисе, а также особое место претерита в системе немецких временных форм.Метою статті є узагальнення та теоретичне обґрунтування нового вживання претериту у релятивному значенні у конкретних видах сурядно-підрядних речень з презентом у сурядному реченні. У статті подано аналіз конототивні нюанси претериту і регулярність зміни перфекту пасиву та іменного присудка з дієсловом "sein" на претеритальні форми у гіпотаксису, а також особливе місце претериту у системі німецьких часових форм.The article aims at generalization and theoretical Explanation of modern preterit usage in relative meaning in certain types of clauses, with the Present tense in the main clause. The article deals with the analysis of connotative component meanings of the relative preterit and the regularity of substitution of preterit forms in hypotaxes for the passive perfect tense and the perfect form of the nominal compound predicate with the verb 'sein' as well as the specificity of preterit in the system of German tenses

ALIFE2 study : low-molecular-weight heparin for women with recurrent miscarriage and inherited thrombophilia : study protocol for a randomized controlled trial

Background A large number of studies have shown an association between inherited thrombophilia and recurrent miscarriage. It has been hypothesized that anticoagulant therapy might reduce the number of miscarriages and stillbirth in these women. In the absence of randomized controlled trials evaluating the efficacy of anticoagulant therapy in women with inherited thrombophilia and recurrent miscarriage, a randomized trial with adequate power that addresses this question is needed. The objective of the ALIFE2 study is therefore to evaluate the efficacy of low-molecular-weight heparin (LMWH) in women with inherited thrombophilia and recurrent miscarriage, with live birth as the primary outcome. Methods/Design Randomized study of LMWH plus standard pregnancy surveillance versus standard pregnancy surveillance alone. Study population: pregnant women of less than 7 weeks’ gestation, and confirmed inherited thrombophilia with a history of 2 or more miscarriages or intra-uterine fetal deaths, or both. Setting: multi-center study in centers from the Dutch Consortium of Fertility studies; centers outside the Netherlands are currently preparing to participate. Intervention: LMWH enoxaparin 40 mg subcutaneously once daily started prior to 7 weeks gestational age plus standard pregnancy surveillance or standard pregnancy surveillance alone. Main study parameters/endpoints: the primary efficacy outcome is live birth. Secondary efficacy outcomes include adverse pregnancy outcomes, such as miscarriage, pre-eclampsia, syndrome of hemolysis, elevated liver enzymes and low platelets (HELLP syndrome), fetal growth restriction, placental abruption, premature delivery and congenital malformations. Safety outcomes include bleeding episodes, thrombocytopenia and skin reactions. Discussion After an initial period of slow recruitment, the recruitment rate for the study has increased. Improved awareness of the study and acknowledgement of the need for evidence are thought to be contributing to the improved recruitment rates. We aim to increase the number of recruiting centers in order to increase enrollment into the ALIFE2 study. The study website can be accessed via www.ALIFE2study.org. Trial registration The ALIFE2 study was registered on 19 March 2012 under registration number NTR336