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To produce and validate an Italian version of the Lymphedema Life Impact Scale version 2 (LLISv2-It), a tool measuring the impact of lymphedema on health-related quality of life, and investigate its main psychometric characteristics.After translation and cross-cultural adaptation of the LLISv2, we administered it to 156 subjects with secondary lymphedema (upper or lower limb), together with (depending on the limb involved) either the Disabilities of the Arm, Shoulder and Hand questionnaire (DASH) or the Lower Extremity Functional Scale (LEFS). We analyzed the performance of LLISv2-It using Classical Test Theory and Rasch methods.Cronbach alpha was 0.89. Item fit statistics indicated that item #12 was underfitting (Infit MnSQ = 1.56; Outfit MnSq = 1.75). Test-retest reliability of the 17-item version (without item #18, not scored, according to the original authors) and of a 16-item version (without #12 and #18-a unidimensional item set) were both excellent (ICC2.1 = 0.93; 95%). The minimum detectable change was 8.9 points. The correlation of LLISv2-It with DASH and LEFS wasThe Italian version of the LLISv2 is reliable and valid. To make the tool more psychometrically sound, we recommend to not calculate items #12 and #18 in the total score.IMPLICATIONS FOR REHABILITATIONThe Lymphedema Life Impact Scale (LLISv2) is particularly useful as a validated condition-specific health-related quality of life measure for patients with chronic edema/lymphedema. We have validated its Italian version (LLISv2-It).We also examined the psychometric properties of the LLISv2 in individuals with secondary lymphedema of either upper or lower limb, using both classical test theory and Rasch techniques, to provide insights for further refinement of the questionnaire.Based on our results, we recommend not to count item #12 in the total score (besides #18, as already suggested by the original authors). Moreover, we determined that the minimum detectable change of the LLISv2 was 9 points. This information is helpful in clinical practice to understand if the change in score is not due to chance (measurement error).Although further research is warranted, the present validation study of the LLISv2 increases the confidence in the metric quality and clinical utility of the scale to assess lymphedema-specific health-related quality of life in individuals with secondary lymphedema of either upper or lower limb.

PurposePrevious research has found mixed evidence of an attitude–behavior gap in organic food consumption. However, the complex mechanisms underlying this gap warrant further investigation. The purpose of this study is to examine the role of word-of-mouth (WOM), trust, and involvement in the relationship between consumer organic food attitudes and conative loyalty. The Theory of Planned Behavior (TPB) was used as underlying framework for modeling our conceptualized arguments.Design/methodology/approachA moderation and moderated mediation analysis was performed on a cross-sectional sample of 1,011 Australian organic food consumers.FindingsThe results support the TPB-inspired moderated-mediation model. Specifically, the authors found moderated mediation effects of WOM, trust, and involvement on conative loyalty via attitudes toward organics.Research limitations/implicationsThe cross-sectional research design and the focus solely on Australian consumers constitute limitations of this study.Practical implicationsThe authors' findings imply that an analysis of the attitude–behavior gap should go beyond the testing of contingent consistency hypotheses and instead combine moderation and mediation mechanisms to better model consumer decision-making leading to conative loyalty. Practitioners would face a resource challenge when targeting low-trust, low-involvement, and low-WOM consumers as developing conative loyalty of these segments would require a longer-term approach through building favorable attitudes toward organic foods.Originality/valueThis study is one of the first to demonstrate the potential of examining the attitude–behavior gap in the organic food context through a moderated mediation lens in explaining the dynamics of conative loyalty.

This article uses a global multilevel sample to advance our understanding of the gender gap in youth entrepreneurship by investigating the joint moderating influence of in-group support and national embeddedness values on young women’s entrepreneurial activity relative to that of young men. Based on a mixed embeddedness theoretical lens, our moderation analysis demonstrates the importance of in-group support in narrowing the gender gap in youth entrepreneurship. Moreover, in-group support enhances young women’s entrepreneurship vis-à-vis that of young men primarily in countries with strong embeddedness values. Our findings contribute to the entrepreneurial gender gap literature as well as to the comparative entrepreneurship literature, by providing evidence of the joint role of micro-level and macro-level cultural layers in reducing the entrepreneurial gender gap. Implications for theory, practice and policy are provided.

Place attachment is a key concept in understanding affective person–place relationships, and it provides an appropriate approach for the study of human behavior. This systematic literature review based on the PRISMA guidelines focuses on the relationships between place attachment and behavioral intentions. Due to the high number of studies that used place attachment as an independent or mediating variable, we categorized the studies into different research areas, which include business and management, risk and crisis, urban planning, environmental psychology, leisure, and hospitality and tourism. The results of the qualitative analysis revealed that most of the studies provided empirical evidence of a significant relationship between place attachment and willingness to pay, loyalty, risk coping behavior, land management practices, civic engagement, pro-environmental behaviors, and pro-tourism behaviors such as revisit and recommendation intentions. After we present our results and conclusion, we provide an outlook on the need for further research.

Using the framework provided by the Porter hypothesis, we study the impact of environmental regulations and enforcement policies on plant-level green total factor productivity (TFP) growth and its ...

This article examines the moderating role of regional social capital in the intention–behaviour link in entrepreneurship. We investigate to what extent the regional social capital context in which aspiring entrepreneurs are embedded strengthens or weakens the translation of individual entrepreneurial intentions into new venture creation activities. Our results suggest that the intention–behaviour link is weakened by cognitive regional social capital in the form of regional hierarchy values and strengthened by structural regional capital in the form of regional cultural diversity and regional breadth of associational activity, as well as by relational regional social capital in the form of high levels of regional generalised trust. Our findings suggest that to support new venture creation activity, there is a need to grow regional social capital via the enhancement of social trust, associational activities and regional cultural diversity – and at the same time decrease hierarchical social structures within regions.

The Constellation Observing System for Meteorology, Ionosphere, and Climate 2 (COSMIC-2) mission was launched on June 25, 2019 into six evenly spaced circular orbital planes of 24° inclination with initial altitudes of 725 km. By February 2021 the COSMIC-2 satellites will be lowered to an operational altitude of about 520 km. The satellites carry an advanced Tri‐GNSS (Global Navigation Satellite System) Radio-occultation System (TGRS) instrument to provide high vertical resolution profiles of atmospheric bending angle and refractivity, as well as measurements of ionospheric total electron content, electron density, and scintillation. The TGRS payload tracks GPS and GLONASS signals on two upward looking antennas used for precise orbit determination (POD). We compute one- and two-antenna GPS and GPS+GLONASS POD solutions at both orbit altitudes and assess the orbit quality and systematic orbit errors using different metrics. In particular, we also use different POD setups to compute kinematic solutions employing single-receiver ambiguity fixing and test their contribution to selected months of gravity field recovery based on Swarm GPS data.

PurposeDrawing on the stimulus–organism–response (S-O-R) model, the purpose of this study is to investigate mediating effects of controlled and uncontrolled communications of corporate brand perceptions on consumer satisfaction and loyalty.Design/methodology/approachStructural equation modeling (SEM) was used to test the hypotheses on a sample of 271 Australian automobile consumers.FindingsThe authors find that while consumer satisfaction is indirectly influenced by corporate-level attributes via controlled and uncontrolled communication, the authors did not find an indirect effect between consumer benefits on consumer satisfaction via controlled and uncontrolled communication. By contrast, the authors find highly significant indirect effects – via controlled and uncontrolled communication as well as consumer satisfaction – for the relationship between, on the one hand, corporate-level attributes and consumer benefits and consumer brand loyalty on the other. Uncontrolled communication was significantly associated with consumer loyalty, a relevant finding that indicates an importance of tracking media coverage and maintaining favorable relationships with the media.Research limitations/implicationsThe cross-sectional method limits data collection to one point in time.Practical implicationsThis study adds to a better understanding of how to leverage corporate brand through communications in ways that it positively resonates with consumers. A fine-grained analysis of corporate brand attributes and consumer-perceived benefits can aid managers in developing specific and more effective marketing strategies.Originality/valueThe overall thrust of this empirical study, which is to investigate how corporate brand perceptions influence short term (satisfaction) and long term (loyalty) via controlled and uncontrolled communications is original. This study comprehensively conceptualizes and operationalizes the corporate brand as a multidimensional construct consisting of corporate-level attributes and brand-level attributes such as perceived consumer benefits. To examine the hypothesized relationships between and among our constructs, the authors go beyond the commonly studied single mediator model and test a multiple mediator model instead.

This paper provides novel empirical insights into the Porter hypothesis (PH) and its dynamic nature. The PH posits that well-designed environmental regulations induce eco-innovations at polluting f ...

Despite a growing demand worldwide, organic food remains a niche category, with consumers only purchasing it some of the time. This study examines the mediating effects of consumers’ perceived clar ...

The Ca2+-activated monovalent cation channel Trpm5 is a key element in chemotransduction of taste receptor cells of the tongue, but the extent to which Trpm5 channels are expressed in olfactory sensory neurons (OSNs) of the main olfactory epithelium (MOE) of adult mice as part of a specific pheromonal detection system is debated. Here, we used a novel Trpm5-IRES-Cre knockin strain to drive Cre recombinase expression, employed previously validated Trpm5 antibodies, performed in situ hybridization experiments to localize Trpm5 RNA, and searched extensively for Trpm5 splice variants in genetically-labeled, Trpm5-expressing MOE cells. In contrast to previous reports, we find no evidence for the existence in adult mouse OSNs of the classical Trpm5 channel known from taste cells. We show that Trpm5-expressing adult OSNs express a novel Trpm5 splice variant, Trpm5-9, that is unlikely to form a functional cation channel by itself. We also demonstrate that Trpm5 is transiently expressed in a subpopulation of mature OSNs in the embryonic olfactory epithelium, indicating that Trpm5 channels could play a specific role in utero during a narrow developmental time window. Ca2+ imaging with GCaMP3 under the control of the Trpm5-IRES-Cre allele using a newly developed MOE wholemount preparation of the adult olfactory epithelium reveals that Trpm5-GCaMP3 OSNs comprise a heterogeneous group of sensory neurons many of which can detect general odorants. Together, these studies are essential for understanding the role of transient receptor potential channels in mammalian olfaction.

Fil: Trouillet, Anne-Charlotte. University of Tours. Institut Français du Cheval et de l’Equitation. Institut National de la Recherche Agronomique. Laboratoire de Physiologie de la Reproduction et des Comportement; Francia Fil: Keller, Matthieu. University of Tours. Institut Français du Cheval et de l’Equitation. Institut National de la Recherche Agronomique. Laboratoire de Physiologie de la Reproduction et des Comportement; Francia Fil: Weiss, Jan. Saarland University. Center for Integrative Physiology and Molecular Medicine; Alemania Fil: Leinders-Zufall, Trese. Saarland University. Center for Integrative Physiology and Molecular Medicine; Alemania Fil: Birnbaumer, Lutz. Research Triangle Park. National Institute of Environmental Health Sciences. Neurobiology Laboratory; Estados Unidos Fil: Birnbaumer, Lutz. Pontificia Universidad Católica Argentina. Facultad de Ciencias Médicas. Instituto de Investigaciones Biomédicas; Argentina Fil: Zufall, Frank. Saarland University. Center for Integrative Physiology and Molecular Medicine; Alemania Fil: Chamero, Pablo. University of Tours. Institut Français du Cheval et de l’Equitation. Institut National de la Recherche Agronomique. Laboratoire de Physiologie de la Reproduction et des Comportement; Francia Abstract: Aggression is controlled by the olfactory system in many animal species. In male mice, territorial and infant-directed aggression are tightly regulated by the vomeronasal organ (VNO), but how diverse subsets of sensory neurons convey pheromonal information to limbic centers is not yet known. Here, we employ genetic strategies to show that mouse vomeronasal sensory neurons expressing the G protein subunit Gαi2 regulate male-male and infant-directed aggression through distinct circuit mechanisms. Conditional ablation of Gαi2 enhances male-male aggression and increases neural activity in the medial amygdala (MeA), bed nucleus of the stria terminalis, and lateral septum. By contrast, conditional Gαi2 ablation causes reduced infant-directed aggression and decreased activity in MeA neurons during male-infant interactions. Strikingly, these mice also display enhanced parental behavior and elevated neural activity in the medial preoptic area, whereas sexual behavior remains normal. These results identify Gαi2 as the primary G protein α-subunit mediating the detection of volatile chemosignals in the apical layer of the VNO, and they show that Gαi2+ VSNs and the brain circuits activated by these neurons play a central role in orchestrating and balancing territorial and infant-directed aggression of male mice through bidirectional activation and inhibition of different targets in the limbic system.

Summary Deletion of SCN9A encoding the voltage-gated sodium channel NaV1.7 in humans leads to profound pain insensitivity and anosmia. Conditional deletion of NaV1.7 in sensory neurons of mice also abolishes pain, suggesting that the locus of analgesia is the nociceptor. Here we demonstrate, using in vivo calcium imaging and extracellular recording, that NaV1.7 knockout mice have essentially normal nociceptor activity. However, synaptic transmission from nociceptor central terminals in the spinal cord is greatly reduced by an opioid-dependent mechanism. Analgesia is also reversed substantially by central but not peripheral application of opioid antagonists. In contrast, the lack of neurotransmitter release from olfactory sensory neurons is opioid independent. Male and female humans with NaV1.7-null mutations show naloxone-reversible analgesia. Thus, inhibition of neurotransmitter release is the principal mechanism of anosmia and analgesia in mouse and human Nav1.7-null mutants.

We examine the role of regional formal and informal institutions in the intention-behavior link in entrepreneurship. Using multilevel regression analyses on a longitudinal sample of university students embedded in 40 European regions, we find evidence that regional formal and informal institutions have distinct and unique influences on the entrepreneurial intention-action relationship. In particular, our results show that the intention-behavior link is strengthened in regions characterized by a high quality of government and weakened in regions featuring a high quality of the social security system and a strong work ethic culture. Our findings provide important insights into the interdependence between individual and contextual factors regulating the entrepreneurial process by integrating the role of regional institutions as important contingencies. Our study provides valuable theoretical and policy implications.

Background Despite the high prevalence of lymphedema in Iranian breast cancer patients, there is no valid instrument for measuring quality of life in this population. The aim of this study was to assess reliability and validity of the Persian version of Lymphedema Life Impact Scale (LLIS) in breast cancer patients. Methods Forward-backward procedure was applied to translate The LLIS from English into Persian. The LLIS is an 18-item measure of physical, psychosocial, and functional impairments caused by lymphedema. Experts and patients assessed content and face validity, respectively. Discriminant validity was evaluated by comparing breast cancer patients with and without lymphedema. Convergent validity was assessed by comparing LLIS score with SF-36 (functional component) and the EORTC-QLQ-C30 (functional component). The construct validity also was evaluated using confirmatory and exploratory factor analyses. Internal consistency was evaluated by Cronbach’s alpha coefficient. Stability was assessed by test-retest analysis over a one-week interval in 13 patients. Results In all 446 breast cancer patients were entered into the study. The content and face validity of Persian version of LLIS were acceptable and minor corrections were applied in final version. The questionnaire differentiated well in patients’ with and without lymphedema and lending support to its discriminant validity. Confirmatory factor analysis showed a good fit for the data. Cronbach’s alpha coefficient in physical, psychosocial and functional subscales were 0.873, 0.854 and 0.884 respectively. Intra-class correlation coefficient of total score of the LLIS was 0.96. Conclusions The findings of this study suggest a first indication that reliability and validity of the Persian version of LLIS in patients with breast cancer induced lymphedema was good. Application of this instrument for identifying problems of patients with upper extremity lymphedema may be helpful in designing interventions to improve quality of life.

Purpose This study aimed to examine factors associated with reported infection and symptoms among individuals with extremity lymphedema. Design A cross-sectional study was used. Methods Data were collected from a survey supported by the National Lymphedema Network from March 2006 through January 2010. A total of 1837 participants reported having extremity lymphedema. Logistic regression analyses were used. Findings Factors associated with reported infection among individuals with extremity lymphedema included male gender, decreased annual household income, decreased self-care, self-report of heaviness, and lower extremity as opposed to upper extremity. Factors associated with symptoms included infection, decreased self-care, lower knowledge level of self-care, decreased annual household income, and presence of secondary lower extremity lymphedema. Conclusions/Clinical Relevance Select factors of income, self-care status, and site of lymphedema were associated with increased occurrence of infection and symptoms among individuals with extremity lymphedema. Longitudinal studies are needed to identify risk factors contributing to infections and symptoms in individuals with lymphedema.

Using recent data on a cross-section of Swedish chemical and pulp and paper firms, this paper provides novel empirical insights into the Porter hypothesis. Well-designed environmental regulation can stimulate firms’ innovative capabilities, while at the same time generating innovation offsets that may both offset net compliance costs and yield a competitive edge over those firms that are not affected by such regulations. In doing so, we also test the alleged effectiveness of regulatory time strategies in stimulating innovation activities of regulated firms. We find evidence for the effectiveness of such well-designed regulations: announced rather than existing regulation induces innovation and some innovation offsets. Our results imply that empirical tests of the Porter hypothesis that do not account for its dynamic nature, and that do not measure well-designed regulations, might provide misleading conclusions as to its validity.

Using a unique plant-level dataset we examine total factor productivity (TFP) growth and its components, related to efficiency change and technical change. The data we use is from Sweden and for their pulp and paper industry, which is heavily regulated due to its historically large contribution to air and water pollution. Our paper contributes to the broader empirical literature on the Porter Hypothesis, which posits a positive relationship between environmental regulation and “green” TFP growth of firms. Our exercise is innovative as Sweden has a unique regulatory structure where the manufacturing plants have to comply with plant-specific regulatory standards stipulated at the national level, as well as decentralized local supervision and enforcement. Our key findings are: (1) prudential regulation limits expansion of plants with high initial pollution; (2) regulation, however, is not conducive to plants’ “green” technical change, which provides evidence against the recast version of the Porter Hypothesis; (3) decentralized command-and-control regulation is prone to regulatory bias, entailing politically motivated discriminatory treatment of plants with otherwise equal characteristics.

Producción Científica, Signal transduction in sensory neurons of the mammalian vomeronasal organ (VNO) involves the opening of the canonical transient receptor potential channel Trpc2, a Ca2+-permeable cation channel that is activated by diacylglycerol and inhibited by Ca2+-calmodulin. There has been a long-standing debate about the extent to which the second messenger inositol 1,4,5-trisphosphate (InsP3) and type 3 InsP3 receptor (InsP3R3) are involved in the opening of Trpc2 channels and in sensory activation of the VNO. To address this question, we investigated VNO function of mice carrying a knockout mutation in the Itpr3 locus causing a loss of InsP3R3. We established a new method to monitor Ca2+ in the endoplasmic reticulum of vomeronasal sensory neurons (VSNs) by employing the GFP-aequorin protein sensor erGAP2. We also performed simultaneous InsP3 photorelease and Ca2+ monitoring experiments, and analysed Ca2+ dynamics, sensory currents, and action potential or field potential responses in InsP3R3-deficient VSNs. Disruption of Itpr3 abolished or minimized the Ca2+ transients evoked by photoactivated InsP3, but there was virtually no effect on sensory activation of VSNs. Therefore, InsP3R3 is dispensable for primary chemoelectrical transduction in mouse VNO. We conclude that InsP3R3 is not required for gating of Trpc2 in VSNs., Deutsche Forschungsgemeinschaf (grant CH920/2-1), Sonderforschungsbereich 894 (project A17), Transregio - SFB (projects P09 and P10), Ministerio de Economía, Industria y Competitividad (grant BFU2014-53469P)

Exporting firms in a region may reduce export entry costs for other local firms either through market or non-market interactions. This paper tests this proposition by analyzing whether the probability of exporting among Swedish firms is positively associated with the local presence of exporters in their region and industry. Our results support this conjecture, while also providing some support for such export spillovers being more important in contract-intensive industries and small firms. The results for different industries and size-classes of firms are also sensitive to whether we focus on firms' export status or restrict the sample to export starters.

The copolymerization of an excess of a functionalized styrene monomer, 4-vinylbenzyl methoxytetrakis(oxyethylene) ether, with various N-substituted maleimides yields tapered diblock copolymers in a one-step procedure, when applying reversible deactivation radical polymerization (RDRP) methods, such as ATRP and RAFT. The particular chemical structure of the diblock copolymers prepared results in reversible temperature-responsive two-step aggregation behavior in dilute aqueous solution. In this way, a double hydrophilic block copolymer is transformed step by step into an amphiphilic macrosurfactant, and finally into a double hydrophobic copolymer, as followed by turbidimetry and dynamic light scattering. Copolymers in which the maleimide repeat units bear short hydrophobic side chains are freely water-soluble at low temperature and form micellar aggregates above their cloud point. Further heating above the phase transition temperature of the second block results in secondary aggregation. Copolymers with maleimides that bear strongly hydrophobic substituents undergo two thermally induced aggregation steps upon heating, too, but show in addition intramolecular hydrophobic association in water already at low temperatures, similar to the behavior of polysoaps.

Random copolymers of 4-vinylbenzyl tri(oxyethylene) and tetra(oxyethylene) ethers, as well as alternating copolymers of 4-vinylbenzyl methoxytetra(oxyethylene) ether and a series of N-substituted maleimides, were synthesised by conventional free radical polymerisation, reversible addition fragmentation chain transfer (RAFT) and atom transfer radical polymerisation (ATRP). Their thermosensitive behaviour in aqueous solution was studied by turbidimetry and dynamic light scattering. Depending on the copolymer composition, a LCST type phase transition was observed in water. The transition temperature of the obtained random as well as alternating copolymers could be varied within a broad temperature window. In the case of the random copolymers, transition temperatures could be easily fine-tuned, as they showed a linear dependence on the copolymer composition, and were additionally modified by the nature of the polymer end-groups. Alternating copolymers were extremely versatile for implementing a broad range of variations of the phase transition temperatures. Further, while alternating copolymers derived from 4-vinylbenzyl methoxytetra(oxyethylene) ether and maleimides with small hydrophobic side chains underwent macroscopic phase separation when dissolved in water and heated above their cloud point, the incorporation of maleimides bearing larger hydrophobic substituents resulted in the formation of mesoglobules above the phase transition temperature, with hydrodynamic diameters of less than 100 nm.

We report on the controlled free radical homopolymerization of 1-ferrocenylethyl acrylate as well as of three new ferrocene bearing monomers, namely 4-ferrocenylbutyl acrylate, 2-ferrocenylamido-2-methylpropyl acrylate, and 4-ferrocenylbutyl methacrylate, by the RAFT technique. For comparison, the latter monomer was polymerized using ATRP, too. The ferrocene containing monomers were found to be less reactive than their analogues free of ferrocene. The reasons for the low polymerizability are not entirely clear. As the addition of free ferrocene to the reaction mixture did not notably affect the polymerizations, sterical hindrance by the bulky ferrocene moiety fixed on the monomers seems to be the most probable explanation. Molar masses found for 1-ferrocenylethyl acrylate did not exceed 10,000 g mol-1, while for 4-ferrocenylbutyl (meth)acrylate molar masses of 15,000 g mol-1 could be obtained. With PDIs as low as 1.3 in RAFT polymerization of the monomers, good control over the polymerization was achieved. © 2011 Wiley Periodicals, Inc.

A series of triple-thermoresponsive triblock copolymers from poly(N-n-propylacrylamide) (PNPAM, A), poly(methoxydiethylene glycol acrylate) (PMDEGA, B), and poly(N-ethylacrylamide) (PNEAM, C) was synthesized by sequential reversible addition-fragmentation chain transfer polymerizations. Polymers of differing block sequences, ABC, BAC, and ACB, with increasing phase transition temperatures in the order ABC were prepared. Their aggregation behavior in dilute aqueous solution was investigated using dynamic light scattering, turbidimetry, and NMR spectroscopy. The self-organization of such polymers was found to dependent strongly on the block sequence. While polymers with a terminal low-LCST (lower critical solution temperature) block undergo aggregation above the first phase transition temperature at 20-25 °C, triblock copolymers with the low-LCST block in the middle show aggregation only above the second phase transition. The collapse of the middle block is not sufficient to induce aggregation but produces instead stable, unimolecular micelles with a collapsed middle block, as supported by NMR and fluorescence probe data. Continued heating of all copolymers led to two additional thermal transitions at 40-55 and 70-80 °C, which could be correlated to the phase transitions of the B and C blocks, respectively. All polymers show a high tendency for cluster formation, once aggregation is induced. The carrier abilities of the triple responsive triblock copolymers for hydrophobic agents were probed with the solvatochromic fluorescence dye Nile Red. With passing through the first thermal transition, the block copolymers are capable of solubilizing Nile Red. In the case of block copolymers with sequences ABC or ACB, which bear the low-LCST block at one terminus, notable amounts of dye are solubilized already at this stage. In contrast, the hydrophobic probe is much less efficiently incorporated by the BAC triblock copolymer, which forms unimolecular micelles. Only after the collapse of the B block, when reaching the second phase transition at about 45 °C, does aggregation occur and solubilization becomes efficient. In the case of ABC and ACB polymers, the hydrophobic probe seems to partition between the originally collapsed A chains and the additional hydrophobic chains formed after the collapse of the less hydrophobic B block.

A set of double thermoresponsive diblock copolymers poly(N-n-propylacrylamide)-block-poly(N-ethylacrylamide) (PNPAM-b-PNEAM) was synthesised by sequential reversible addition–fragmentation chain transfer (RAFT) polymerisations. Using a twofold trimethylsilyl (TMS)-labeled RAFT-agent, the relative size of the two blocks was varied. While soluble as unimers below 15 °C, all copolymers exhibited thermally induced two-step self-assembly in water, due to distinct lower critical solution temperature (LCST) phase transitions of PNPAM (around 20 °C) and PNEAM (around 70 °C). Their temperature-dependent self-organisation in dilute aqueous solution was studied by turbidimetry, dynamic light scattering, transmission electron microscopy, and 1H NMR spectroscopy. The copolymers show distinct, two-step self-organisation behaviour with respect to transition temperatures, aggregate type and size, which can be correlated to the relative lengths of the low and high LCST blocks. For polymers having short blocks with low LCST, the first thermal transition induces the formation of individual micelles. Further heating above the second thermal transition results reversibly either in a shrink of the micelle size or in aggregation of the micelles, with hydrodynamic diameters below 250 nm. In contrast in the case of polymers having a long block with low LCST, the first thermal transition already leads to clusters of micelles, while the second thermal transition makes the clusters shrink. Noteworthy, the twofold TMS-labeled end groups report not only on the molar masses of the polymers, but can simultaneously serve as NMR-probes for the self-assembly process. The signal of the TMS-aryl end group displays a reversible temperature dependent, two-step splitting that is indicative of the self-organisation of the block copolymers.

Three diacetylene macromonomers based on oligopeptide-polymer conjugates were designed to self-organize into uniform supramolecular polymers which exhibited multiple-helical superstructures constituted from a defined, finite number of laminated single β-sheet tapes. These supramolecular polymers were then converted into poly(diacetylene)s with multiple-helical quaternary structures. The nature of the latter in solution was investigated by UV, CD, and Raman spectroscopy. The polymerization proceeded under preservation of the previously assembled multiple-helical superstructures, and the deaggregation of the oligopeptide β-sheets before and after polymerization proved the mutual stabilization of the helical poly(diacetylene) backbone conformation and hydrogen bonded β-sheet arrays.

In the field of solar fuel cells, the development of efficient photo-converting semiconductors remains a major challenge. A rational analysis of experimental photocatalytic results obtained with material in colloidal suspensions is needed to access fundamental knowledge required to improve the design and properties of new materials. In this study, a simple system electron donor/nano-TiO2 is considered and examined via spin scavenging electron paramagnetic resonance as well as a panel of analytical techniques (composition, optical spectroscopy and dynamic light scattering) for selected type of nano-TiO2. Independent variables (pH, electron donor concentration and TiO2 amount) have been varied and interdependent variables (aggregate size, aggregate surface vs. volume and acid/base groups distribution) are discussed. This work shows that reliable understanding involves thoughtful combination of interdependent parameters, whereas the specific surface area seems not a pertinent parameter. The conclusion emphasizes the difficulty to identify the key features of the mechanisms governing photocatalytic properties in nano-TiO2.

The purposes of this study were (a) to evaluate self-care, symptom burden, and reported infections among individuals with lower-extremity primary lymphedema; (b) to examine the differences in self-care, symptom burden, and reported infections between individuals with unilateral and those with bilateral lower-extremity primary lymphedema; and (c) to examine the associations among self-care status, symptom burden, and reported infections in individuals with lower-extremity primary lymphedema.A secondary data analysis was used. Data were collected from a cross-sectional survey study supported by the National Lymphedema Network from March 2006 through January 2010. The surveys were available both online and in hard copy in order to increase accessibility.Descriptive statistics were conducted and associations between variables were assessed using Mann-Whitney tests and chi-square tests of independence. Multiple logistic regression was used to test for associations while controlling for potentially confounding variables.A total of 803 participants reported having lower-extremity primary lymphedema. The majority of the participants were female (82.9%), White (74.2%), and from the United States (90.7%). Approximately two thirds of the respondents conducted some home daily lymphedema self-care. Over half of the respondents reported experiencing symptom burden and 44.8% reported at least one episode of infection. Compared to individuals with unilateral lower-extremity primary lymphedema, individuals with bilateral lower-extremity lymphedema were more likely to conduct skin care (p = .004), use alternative medications (p = .005), more frequently reported symptoms (p.05), and more likely to report at least one episode of infection (p = .002). Respondents who reported use of compression garments also were less likely to have self-reported pain (p = .002), poor range of motion (p = .026), and numbness (p = .001). Participants who reported exercising also were less likely to have self-reported pain (p = .003). Participants who reported at least one episode of infection also reported experiencing more symptoms (p.001).Individuals with lower-extremity primary lymphedema experienced substantial symptom burden and infection episodes. Significant associations were identified among self-care, symptom burden, and reported infections.The findings support the need for clinicians to educate patients with lower-extremity primary lymphedema regarding the importance of self-care, symptom management, and infection control. It is critically important for clinicians to evaluate symptom burden and reduce infections in individuals with lower-extremity primary lymphedema.

We investigated the role of voltage-activated calcium (Cav) channels for synaptic transmission at mouse olfactory and vomeronasal nerve terminals at the first synapse of the main and accessory olfactory pathways, respectively. We provided evidence for a central role of the N-type Cav channel subunit Cav2.2 in presynaptic transmitter release at these synapses. Striking Cav2.2 immunoreactivity was localised to the glomerular neuropil of the main olfactory bulb (MOB) and accessory olfactory bulb (AOB), and co-localised with presynaptic molecules such as bassoon. Voltage-clamp recordings of sensory nerve-evoked, excitatory postsynaptic currents (EPSCs) in mitral/tufted (M/T) and superficial tufted cells of the MOB and mitral cells of the AOB, in combination with established subtype-specific Cav channel toxins, indicated a predominant role of N-type channels in transmitter release at these synapses, whereas L-type, P/Q-type, and R-type channels had either no or only relatively minor contributions. In Cacna1b mutant mice lacking the Cav2.2 (α1B) subunit of N-type channels, olfactory nerve-evoked M/T cell EPSCs were not reduced but became blocker-resistant, thus indicating a major reorganisation and compensation of Cav channel subunits as a result of the Cav2.2 deletion at this synapse. Cav2.2-deficient mice also revealed that Cav2.2 was critically required for paired-pulse depression of olfactory nerve-evoked EPSCs in M/T cells of the MOB, and they demonstrated an essential requirement for Cav2.2 in vomeronasal nerve-evoked EPSCs of AOB mitral cells. Thus, Cacna1b loss-of-function mutations are unlikely to cause general anosmia but Cacna1b emerges as a strong candidate in the search for mutations causing altered olfactory perception, such as changes in general olfactory sensitivity and altered social responses to chemostimuli.

The unimolecular dissociation of the (v1,0,0) pure OH stretching states of hypochlorous acid (HOCl) in the ground electronic state is investigated for v1=6–9. The dynamics calculations are performed on an accurate potential energy surface and employ filter diagonalization in connection with an imaginary absorbing potential. The dependence of the linewidth (or dissociation rate) on the total angular momentum is emphasized. Resonance enhancements due to mixings with other vibrational states, which have substantially larger rates, are clearly observed—in qualitative agreement with recent measurements. The average width increases, in quantitative agreement with experiments, by four orders of magnitude, from 10−4 cm−1 for v1=6 to about 1 cm−1 for v1=9.

The unimolecular dissociation of HCO in its ground electronic state is considered. By performing calculations (filter diagonalization, absorbing potential) for nonzero angular momentum quantum numbers, it is demonstrated how mixings with near-by “background” states affect the linewidths of the narrower resonance states. This explains qualitatively the theoretically as well as experimentally observed behavior of the linewidth as a function of the vibrational quantum numbers.

The predissociation dynamics in the A 1A″ electronic state of HNO is investigated. The quantum mechanical dynamics calculations take into account the Renner–Teller (or electronic Coriolis) coupling with the electronic ground state X 1A′, which appears to be the dominant decay mechanism for the quasi-bound vibrational states in the A 1A″ upper state. All three internal vibrational degrees of freedom are incorporated and two ab initio potential energy surfaces are used. The linewidths, Γ, are directly calculated by the filter diagonalization method and an absorbing optical potential in the exit channel. They are generally small (∼1 cm−1) and increase with excitation of the bending mode (bent-to-bent transition). On average, Γ increases with K, the a-axis rotational quantum number. However, for some vibrational states the linewidth shows a non-monotonic behavior with K, which is the result of mixing with highly excited vibrational levels in the continuum of the ground electronic state. This effect is even m...

We present new calculations on the Renner–Teller induced decay of the vibrational states of HCO(A 2A″) using accurate ab initio potential energy surfaces. The dynamics calculations are performed by employing filter diagonalization and an absorbing optical potential in the exit channel. The objective of this investigation is twofold: the completion of earlier time-dependent wave packet calculations by determining resonance widths for all vibrational states for projection quantum number K=1—up to 2.75 eV above the H+CO(re) dissociation threshold—and the determination of the widths for the long-lived K=0 states. In the latter case, a clear-cut J2(J+1)2 dependence, where J is the total angular momentum, is observed indicating that the rate determining step is K-resonance interaction between K=0 and 2 states. The experimentally observed J-independent contribution (0.22–0.5 cm−1), which dominates the linewidth for small values of J, is not accounted for by our calculations. Arguments are put forward, that it is...

A detailed analysis of the bound-state spectrum of HOCl (hypoclorous acid) in the ground electronic state is presented. Exact quantum mechanical calculations (filter diagonalization) are performed employing an ab initio potential energy surface, which has been constructed using the multireference configuration-interaction method and a quintuple-zeta one-particle basis set. The wave functions of all bound states up to the HO+Cl dissociation threshold are visually inspected in order to assign the spectrum in a rigorous way and to elucidate how the spectrum develops with energy. The dominant features are (1) a 2:1 anharmonic resonance between the bending mode and the OCl stretching mode, which is gradually tuned in as the energy increases, and (2) a saddle-node bifurcation, i.e., the sudden birth of a new family of states. The bifurcation is further investigated in terms of the structure of the classical phase space (periodic orbits, continuation/bifurcation diagram). It is also discussed how the spectrum of...

The dissociation of HOCl in its electronic ground state is investigated by means of quantum dynamics calculations (filter diagonalization and harmonic inversion of the autocorrelation function) and an ab initio potential energy surface. At threshold, the state-resolved rate constants are scattered over seven orders of magnitude, which is significantly broader than the distribution predicted by random matrix theory. This remarkable state specificity is the fingerprint of the regular dynamics of HOCl even at high energies.