Variation of Donor and Acceptor Strength in Analogues of Brooker's Merocyanine and Generalization to Various Classes of Charge Transfer Compounds.

Derivatives of Brooker's merocyanine (BM) have been investigated, which possess different donors and acceptors and therefore vary their donor-acceptor strength SDA. The 00 energies have been extracted from the spectra and compared. Under basic conditions, where the neutral (merocyanine) form is present, the absorption energies for all compounds are similar, whereas there is a large difference for acidic conditions where the cationic (cyanine) form is present. This behavior could be explained by a simple theoretical model involving the dependence of the excitation energy Δ E01 on SDA. This model can be generalized to describe in a consistent way two different well-known classes of neutral chromophores with a certain degree of charge separation, namely merocyanine I (TICT) and merocyanine II (often betainic) compounds. Merocyanines I are characterized by a medium polar aromatic ground state and a zwitterionic quinoid excited state and hence positive solvatochromism, whereas merocyanines II are formally characterized by a zwitterionic aromatic ground state and a less polar quinoid excited state and, accordingly, by negative solvatochromism. On increasing the donor-acceptor strength SDA sufficiently, merocyanines II can, however, move to the so-called overcritical region with the excited state dominated by the zwitterionic valence bond structure. For many of the merocyanine II molecules investigated here, a weakly positive solvatochromic behavior is observed indicating that the ground state contains less of the zwitterionic valence bond wave function than the excited state and that these compounds belong to the overcritical region. The fluorescence spectra have been analyzed in terms of the Franck-Condon model and confirm these conclusions.

Computerized Cognitive Testing for Use in Clinical Trials: A Comparison of the NIH Toolbox and Cogstate C3 Batteries.

BACKGROUND: As prevention trials for Alzheimer's disease move into asymptomatic populations, identifying older individuals who manifest the earliest cognitive signs of Alzheimer's disease is critical. Computerized cognitive testing has the potential to replace current gold standard paper and pencil measures and may be a more efficient means of assessing cognition. However, more empirical evidence about the comparability of novel computerized batteries to paper and pencil measures is required. OBJECTIVES: To determine whether two computerized IPad batteries, the NIH Toolbox Cognition Battery and Cogstate-C3, similarly predict subtle cognitive impairment identified using the Preclinical Alzheimer Cognitive Composite (PACC). DESIGN, SETTING, PARTICIPANTS: A pilot sample of 50 clinically normal older adults (Mage=68.5 years±7.6, 45% non-Caucasian) completed the PACC assessment, and the NIH Toolbox and Cogstate-C3 at research centers of Massachusetts General and Brigham and Women's Hospitals. Participants made 3-4 in-clinic visits, receiving the PACC first, then the NIH Toolbox, and finally the Cogstate-C3.>= 0.5SD), versus subtle cognitive impairment (<0.5SD). Composites for each computerized battery were created using principle components analysis, and compared with the PACC using non-parametric Spearman correlations. Logistic regression analyses were used to determine which composite was best able to classify subtle cognitive impairment from typical performance. RESULTS: The NIH Toolbox formed one composite and exhibited the strongest within-battery alignment, while the Cogstate-C3 formed two distinct composites (Learning-Memory and Processing Speed-Attention). The NIH Toolbox and C3 Learning-Memory composites exhibited positive correlations with the PACC (ρ=0.49, p<0.001; ρ=0.58, p<0.001, respectively), but not the C3 Processing Speed-Attention composite, ρ=-0.18, p=0.22. The C3 Learning-Memory was the only composite that classified subtle cognitive impairment, and demonstrated the greatest sensitivity (62%) and specificity (81%) for that subtle cognitive impairment. CONCLUSIONS: Preliminary findings suggest that the NIH Toolbox has the advantage of showing the strongest overall clustering and alignment with standardized paper-and-pencil tasks. By contrast, Learning-Memory tasks within the Cogstate-C3 battery have the greatest potential to identify cross-sectional, subtle cognitive impairment as defined by the PACC.

[The results of endoscopic gastroduodenal, enteral and colorectal stenting for blastomatous stenosis: 8-year experience].

INTRODUCTION: Gastroduodenal, enteral and colorectal stenting of blastomatous stenosis is a reasonable alternative to operative treatment of unresectable tumors. Moreover in some cases it allows to gain time and to prepare the patient for radical surgery. MATERIAL AND METHODS: For the period from 2007 to 2015 in endoscopic department of acad. B.V. Petrovskiy Russian Research Center for Surgery 76 patients with piloroduodenal, enteral and colic stenoses successfully underwent self-expanding metal stents installation. There were 21 patients with malignant stenosis of the stomach and pilorobulbar area, 17 with secondary duodenal stenosis, 17 after gastrectomy and distal gastric resection; 2 with stenosing colorectal cancer, 4 patients with rectal cancer involving rectosigmoid junction, 7 with rectosigmoid junction cancer and 8 with sigmoid cancer. RESULTS: Ambulatory and hospital interventions were performed in 35.5% and 64.5% of cases respectively. Hospital-stay did not exceed 2 days. The total complication rate was 11.8% (9/76), 3 of 9 patients required surgical intervention. The attention is given to important technical aspects of intervention as well as to those clinical situations when stenting is inappropriate because of absence of favourable functional outcome. CONCLUSION: Stenting should be more actively implemented in clinical practice, especially in emergency surgical hospitals. However it requires adequate technical support of hospitals with different endoprostheses, because it provides simultaneous diagnostic survey and remedial procedure.

Brownian motor with competing spatial and temporal asymmetry of potential energy.

A Brownian motor is considered which operates due to asymmetric dichotomic fluctuations of the spatially periodic asymmetric potential energy. As shown, the motion direction and stopping points of this motor are dictated by the competition between the spatial and temporal asymmetry of the potential energy (or solely by temporal asymmetry in the case that the potential energy sign fluctuates). For an asymmetric sawtooth potential, the Brownian-particle average velocity is calculated numerically as a function of certain parameters of the model, whereas the low-frequency and low-energy approximations allow the corresponding analytical relationships to be derived for an arbitrarily shaped potential profile. It is shown that temporal asymmetry is not necessary for stopping point occurrence provided that the potential profile fluctuates not only in amplitude but in shape as well. This inference is illustrated by photoinduced fluctuations of the potential energy for a number of substituted arylpyrene molecules on a substrate with symmetrically distributed charge density.

Charge-transfer transitions in twisted stilbenoids: interchangeable features and generic distinctions of single- and double-bond twists.

The charge-transfer transitions relevant to single- and double-bond photochemical twisting have been studied in the framework of the biradicaloid state theory using the AM1 method for a family of donor-acceptor-substituted stilbenoids and a series of sparkle-simulated model stilbenes. Features in common and mutually interchangeable properties for the two transition types as well as their peculiarities are revealed; they are considered in relation to the varied donor-acceptor strength of the substituents, with particular attention given to the occurrence of S0-S1 state conical intersections. The difference in critical points at which the conical intersections occur for double-bond and single-bond twisted stilbenoids is shown to be related to the splitting of the cyanine limit of their planar counterparts.