Efficient Free Triplet Generation Follows Singlet Fission in Diketo-pyrrolopyrrole Polymorphs with Goldilocks Coupling.

Microcrystal electron diffraction, grazing incidence wide-angle scattering, and UV-Vis spectroscopy were used to determine the unit cell structure and the relative composition of dimethylated diketopyrrolopyrrole (MeDPP) H- and J-polymorphs within thin films subjected to vapor solvent annealing (VSA) for different times. Electronic structure and excited state deactivation pathways of the different polymorphs were examined by transient absorption spectroscopy, conductive probe atomic force microscopy, and molecular modeling. We find VSA initially converts amorphous films into mixtures of H- and J-polymorphs and promotes further conversion from H to J with longer VSA times. Though both polymorphs exhibit efficient SF to form coupled triplets, free triplet yields are higher in J-polymorph films compared to mixed films because coupling in J-aggregates is lower, and, in turn, more favorable for triplet decoupling.

Real-world evidence on time to relapse of plaque psoriasis after discontinuation of biologic treatment in Poland.

The aim of this study is analysis of time to relapse after discontinuation of biologic treatment and identification of factors associated with risk of relapse. The analysis used real-world data of 705 patients treated with biologic drugs (adalimumab [ADA], ustekinumab, infliximab, and etanercept) in Poland in 2013-2019. Time to relapse was analyzed by Kaplan-Meier estimator. Data was stratified by the number of prior relapses. Determinants of risk to relapse were analyzed with Prentice-Williams-Peterson model. Kaplan-Meier estimate of time to the first relapse was 276 days, to the second relapse was 246 days, to the third relapse was 218 days, and to the fourth relapse was 178 days. In multidimensional analysis statistically significant variables affecting risk of relapse were the following: biologic naivety (hazard ratio [HR] 0.707), ADA (HR 0.787), psoriasis area and severity index at the last follow-up visit (HR 1.049), abnormal hemoglobin level (HR 0.794), and abnormal lymphocyte counts (HR 1.278). The findings of this study suggest that periods to relapse after discontinuation of biologic drugs become shorter with the number of prior relapses experienced by the patient. Ninety-five percentage of observed relapses occurred within 613 days of the end of the first treatment cycle, within 478 of the second cycle and within 351 days of the third cycle.

Comparative Computational Study of Electronic Excitations of Neutral and Charged Small Oligothiophenes and Their Extrapolations Based on Simple Models.

This work reports electronic excitation energies of neutral and charged oligothiophenes (OT n ) with repeat unit n = 2-6 computed by routinely used semiempirical and time-dependent density functional theory (TD-DFT) methods. More specifically, for OT n , OTn +, and OTn -, we calculated vertical transition energies for electronic absorption spectroscopy employing the Zerner's version of intermediate neglect differential overlap method for structures optimized by the PM6 semiempirical method and the TD-DFT method with three different functionals, B3LYP, BVP86, and M06-2X, for structures optimized by the ground-state DFT method employing the same functionals. We also calculated vertical transition energies for the emission spectroscopy from the lowest singlet excited states by employing the TD-DFT method for the structures optimized for the lowest singlet excited states. In addition to computational results in vacuum, solution phase data calculated at the level of polarizable continuum model are reported and compared with available experimental data. Most of the data are fitted reasonably well by two simple model functions, one based on a Frenkel exciton theory and the other based on the model of independent electrons in a box with sinusoidal modulation of potential. Despite similar levels of fitting performance, the two models produce distinctively different asymptotic values of excitation energies. Comparison of these with available experimental and computational data suggests that the values based on the exciton model, while seemingly overestimating, are closer to true values than those based on the other model. This assessment is confirmed by additional calculations for a larger oligomer. The fitting parameters offer new means to understand the relationship between electronic excitations of OTs and their sizes and suggest the feasibility of constructing simple coarse-grained exciton-bath models applicable for aggregates of OTs.

The effects of payments for pharmaceuticals: a systematic literature review.

The existence of different forms of out-of-pocket payments (OOPs) for pharmaceuticals across the globe provokes the question whether they can achieve more negative or positive consequences. A systematic literature review was conducted to assess the association between drug cost sharing and health care services utilization, health care costs as well as health outcomes. Studies published in The Cochrane Library, PubMed, Embase were searched with such keywords as: drug, pharmaceutical, cost sharing, out of pocket, co-payments paired with the following: impact, health outcomes, health care costs and utilization. The final review included 18 articles. A total of 11 publications reported the association between drug cost sharing and health care utilization patterns, of which nine found a statistically significant direct relationship. In all 10 publications concerned the association between drug copayments and health care costs. Majority were limited to the impact on the drug budget. Seven studies looked into the link between drug cost sharing and health outcomes, of which five reported statistically significant inverse relationship. There is some evidence for the association between drug copayments, health outcomes and health care services consumption. The optimal system of OOPs' payments for pharmaceuticals needs to prevent drugs' overconsumption and mitigate the risks of excessive cost sharing's burden.

How can multi criteria decision analysis support value assessment of pharmaceuticals? - Findings from a systematic literature review.

INTRODUCTION: As budget constraints become more and more visible, there is growing recognition for greater transparency and greater stakeholders' engagement in the pharmaceuticals' pric-ing&reimbursement (P&R) decision making. New frameworks of drugs' value assessments are searched for. Among them, the multi-criteria decision analysis (MCDA) receives more and more attention. In 2014, ISPOR established Task Force to provide methodological recommendations for MCDA utilization in the health care decision making. Still, there is not so much knowledge about the real life experience with MCDA's adaptation to the P&R processes. AREAS COVERED: A systematic literature review was performed to understand the rationale for MCDA adaptation, methodology used as well as its impact on P&R outcomes. EXPERT COMMENTARY: In total 102 hits were found through the search of databases, out of which 18 publications were selected. Although limited in scope, the review highlighted how MCDA can im-prove the decision making processes not only regarding pricing & reimbursement but also contribute to the the risk benefit assessment as well as optimization of treatment outcomes. Still none of re-viewed studies did report how MCDA results actually impacted the real life settings.

Perylene bisbenzimidazole nonlinear dielectric material for energy storage.

A novel perylene bisbenzimidazole comprising both donor and acceptor functional groups was designed, synthesized, and characterized. This structure exhibits potentially useful physical properties, including a nonlinear dielectric response to an increasing electric field. This material can be used in energy storage devices as the dielectric part of a capacitor. Energy storage devices based on film capacitors are targeting applications in a wide range of industrial, residential and transportation systems.

Does cost sharing do more harm or more good? - a systematic literature review.

BACKGROUND: There are positive and negative consequences of the implementation of out of pocket (OOP) payments as a source of the healthcare financing. On the one hand, OOP burden increases awareness of treatment costs and limits unnecessary use of healthcare services. On the other hand, it may prevent the sick from accessing needed care. Consequently there are several aspects that ought to be taken into consideration while defining the optimal structure of OOP payments. The objective of this study was twofold. Firstly, it was to understand what actions are taken to decrease the OOP burden. Secondly, it was to address the question whether the implementation of any form of formal OOP payments may impact negatively upon fairness in financial contribution. METHODS: The literature search was conducted using the Pubmed, Embase, Cochrane Library and Center of Review and Dissemination databases. Only studies which measured the Kakwani index of progressivity in at least two time points were included. Articles written in English published between January 2004 and September 2015 were searched. No geographical restriction was imposed. An increment of more than 0.10 in the Kakwani index was considered as a significant health policy impact. RESULTS: In total 16 publications were included, of which nine studied attempts to decrease the OOP burden, four described the consequences of the introduction of formal fees, and three covered both topics. Overall, a significant health policy impact was noted in four cases. All of them related to a reduction in the OOP burden, with three and one noting a change towards the progressivity and regressivity of direct healthcare payments respectively. Among jurisdictions which introduced formal fees, none study noted a significant impact on the regressivity of OOP spendings. CONCLUSIONS: In the majority of cases, a health policy impact on the distribution of OOP health payments was insignificant. The reduction of OOP burden cannot be achieved successfully without adequate extension of healthcare coverage or engagement of other sources of healthcare financing. When formal fees are being introduced, protection against catastrophic healthcare payments is needed for the most vulnerable groups.

Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO2 Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH3)](2+) (6DHBP = 6,6'-(OH)2bpy).

Ruthenium complexes with proton-responsive ligands [Ru(tpy)(nDHBP)(NCCH3)](CF3SO3)2 (tpy = 2,2':6',2″-terpyridine; nDHBP = n,n'-dihydroxy-2,2'-bipyridine, n = 4 or 6) were examined for reductive chemistry and as catalysts for CO2 reduction. Electrochemical reduction of [Ru(tpy)(nDHBP)(NCCH3)](2+) generates deprotonated species through interligand electron transfer in which the initially formed tpy radical anion reacts with a proton source to produce singly and doubly deprotonated complexes that are identical to those obtained by base titration. A third reduction (i.e., reduction of [Ru(tpy)(nDHBP-2H(+))](0)) triggers catalysis of CO2 reduction; however, the catalytic efficiency is strikingly lower than that of unsubstituted [Ru(tpy)(bpy)(NCCH3)](2+) (bpy = 2,2'-bipyridine). Cyclic voltammetry, bulk electrolysis, and spectroelectrochemical infrared experiments suggest the reactivity of CO2 at both the Ru center and the deprotonated quinone-type ligand. The Ru carbonyl formed by the intermediacy of a metallocarboxylic acid is stable against reduction, and mass spectrometry analysis of this product indicates the presence of two carbonates formed by the reaction of DHBP-2H(+) with CO2.

Institutional framework for integrated Pharmaceutical Benefits Management: results from a systematic review.

OBJECTIVES: In this paper, we emphasised that effective management of health plans beneficiaries access to reimbursed medicines requires proper institutional set-up. The main objective was to identify and recommend an institutional framework of integrated pharmaceutical care providing effective, safe and equitable access to medicines. METHOD: The institutional framework of drug policy was derived on the basis of publications obtained by systematic reviews. A comparative analysis concerning adaptation of coordinated pharmaceutical care services in the USA, the UK, Poland, Italy, Denmark and Germany was performed. RESULTS: While most European Union Member States promote the implementation of selected e-Health tools, like e-Prescribing, these efforts do not necessarily implement an integrated package. There is no single agent who would manage an insured patients' access to medicines and health care in a coordinated manner, thereby increasing the efficiency and safety of drug policy. More attention should be paid by European Union Member States as to how to integrate various e-Health tools to enhance benefits to both individuals and societies. One solution could be to implement an integrated "pharmacy benefit management" model, which is well established in the USA and Canada and provides an integrated package of cost-containment methods, implemented within a transparent institutional framework and powered by strong motivation of the agent.

New water oxidation chemistry of a seven-coordinate ruthenium complex with a tetradentate polypyridyl ligand.

The mononuclear ruthenium(II) complex [Ru](2+) (Ru = Ru(dpp)(pic)2, where dpp is the tetradentate 2,9-dipyrid-2'-yl-1,10-phenanthroline ligand and pic is 4-picoline) reported by Thummel's group (Inorg. Chem. 2008, 47, 1835-1848) that contains no water molecule in its primary coordination shell is evaluated as a catalyst for water oxidation in artificial photosynthesis. A detailed theoretical characterization of the energetics, thermochemistry, and spectroscopic properties of intermediates allowed us to interpret new electrochemical and spectroscopic experimental data, and propose a mechanism for the water oxidation process that involves an unprecedented sequence of seven-coordinate ruthenium complexes as intermediates. This analysis provides insights into a mechanism that generates four electrons and four protons in the solution and a gas-phase oxygen molecule at different pH values. On the basis of the calculations and corroborated substantially by experiments, the catalytic cycle goes through [(2)Ru(III)](3+) and [(2)Ru(V)(O)](3+) to [(1)Ru(IV)(OOH)](3+) then [(2)Ru(III)(···(3)O2)](3+) at pH 0, and through [(3)Ru(IV)(O)](2+), [(2)Ru(V)(O)](3+), and [(1)Ru(IV)(OO)](2+) at pH 9 before reaching the same [(2)Ru(III)(···(3)O2)](3+) species, from which the liberation of the weakly bound O2 might require an additional oxidation to form [(3)Ru(IV)(O)](2+) to initiate further cycles involving all seven-coordinate species.

Strategies for coping with pain presented by adolescents with hematopoietic malignancies.

INTRODUCTION: Leukaemias and lymphomas are the most common malignant diseases diagnosed among adolescents and they are associated with pain and anxiety. As a result they may affect the way patients accept their disease and determine subjective assessment of quality of life. The objective of this study was to recognise strategies for coping with pain, evaluate the process of accepting the disease and assess quality of life among adolescents diagnosed with hematopoietic malignancies. MATERIAL AND METHODS: The study group comprised 66 patients aged between 14 and 21 and diagnosed with leukaemia or lymphoma. The following measuring tools were used: the Pain Coping Strategies Questionnaire (CSQ), Zung Self-Rating Anxiety Scale (SAS), Acceptance of Illness Scale (AIS), and WHOQOL-BREF for quality of life evaluation. RESULTS: Coping self-statements and praying or hoping were the two most common strategies used by our respondents when coping with pain. In the study group the level of anxiety had no influence on pain control and the ability to reduce it. A statistically significant relation was found between the level of catastrophizing as a method of coping with pain and quality of life in the physical domain. An additional correlation was observed between quality of life in the psychological domain and the level of pain control. CONCLUSIONS: The ability of coping with pain promotes the acceptance of illness and improves patient's quality of life. The age and duration of the disease were factors affecting strategies for coping with pain. A small percentage of respondents who experienced anxiety suggests that further and deeper research is needed in this field.