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This study examined the acoustic and perceptual voice characteristics of patients with Parkinson's disease according to disease severity. The perceptual and acoustic voice characteristics of 30 patients with early stage PD and 30 patients with later stage PD were compared with data from 30 normal control subjects. Voice recordings consisted of prolongation of the vowel /a/, scale singing, and a 1-min monologue. In comparison with controls and previously published normative data, both early and later stage PD patients' voices were characterized perceptually by limited pitch and loudness variability, breathiness, harshness and reduced loudness. High modal pitch levels also characterized the voices of males in both early and later stages of PD. Acoustically, the voices of both groups of PD patients demonstrated lower mean intensity levels and reduced maximum phonational frequency ranges in comparison with normative data. Although less clear, the present data also suggested that the PD patients' voices were characterized by excess jitter, a high-speaking fundamental frequency for males and a reduced fundamental frequency variability for females. While several of these voice features did not appear to deteriorate with disease progression (i.e. harshness, high modal pitch and speaking fundamental frequency in males, fundamental frequency variability in females, low intensity and jitter), breathiness, monopitch and monoloudness, low loudness and reduced maximum phonational frequency range were all worse in the later stages of PD. Tremor was the sole voice feature which was associated only with later stage PD. [ABSTRACT FROM AUTHOR]

Abstract: Dawes, JJ, Lopes dos Santos, M, Kornhauser, C, Holmes, RJ, Alvar, BA, Lockie, RG, and Orr, RM. Longitudinal changes in health and fitness measures among state patrol officers by sex. J Strength Cond Res 37(4): 881-886, 2023-Research suggests that police officers lose fitness as a result of their policing vocation with occupational factors like stress, shift work, poor sleep, and poor diet all contributors to this loss The purpose of this research was to measure changes in fitness test scores of qualified police officers over a 5-year period. Archived fitness data for 523 state patrol officers ( n = 494 men; 29 women) from one agency were used for this analysis. These tests included 60-second sit-up [SU] and push-up [PU] scores (muscular endurance), vertical jump height [VJ] (lower-body power), and 20-m multistage fitness test (aerobic capacity). A series of paired-samples t-tests and effect size calculations were used to investigate mean differences in fitness tests score at the beginning and end of a 5-year period. The paired-samples t test showed significant tests score decreases among male officers over the 5-year period in VJ, PU, and V̇ o2 max , , with no differences observed in SU performance. Small effect sizes were observed in both VJ ( g = -0.20) and PU ( g = -0.27) with a trivial effect size observed in changes to V̇ o2 max ( g = -0.14). In contrast, significant improvements in performance were observed in SU performance among female officers, with a small effect size ( g = 0.38). No other significant differences were found in female measures. Whether at an organizational or individual level, annual fitness assessments for police officers can serve to educate and motivate officers regarding their personal fitness and potentially slow the negative impact of aging on health, fitness, and performance in these populations., (Copyright © 2022 Written work prepared by employees of the Federal Government as part of their official duties is, under the U.S. Copyright Act, a “work of the United States Government” for which copyright protection under Title 17 of the United States Code is not available. As such, copyright does not extend to the contributions of employees of the Federal Government.)

Polar molecules with appreciable permanent dipole moments (PDMs) are widely used as the electron transport layer (ETL) in organic light-emitting devices (OLEDs). When the PDMs spontaneously align, a macroscopic polarization field can be observed, a phenomenon known as spontaneous orientation polarization (SOP). The presence of SOP in the ETL induces considerable surface potential and charge accumulation that is capable of quenching excitons and reducing device efficiency. While prior work has shown that the degree of SOP is sensitive to film processing conditions, this work considers SOP formation by quantitatively treating the vapor-deposited film as a supercooled glass, in analogy to prior work on birefringence in organic thin films. Importantly, the impact of varying thin-film deposition rate and relative temperature is unified into a single framework, providing a useful tool to predict the SOP formation efficiency for a polar material, as well as in blends of polar materials. Finally, in situ photoluminescence characterization and efficiency measurements reveal that SOP-induced exciton-polaron quenching can be reduced through an appropriate choice of processing conditions, leading to enhanced OLED efficiency.

The purpose of this study was to determine relationships between components of physical fitness on performance in an occupation-specific physical ability test (PAT) for state patrol officers (women, n = 19; men, n = 256) using archived data. Physical fitness was assessed by 2.4 km run time (2.4 R), body fat % (BF), 1 min sit-up (SU), 1-min push-up (PU), the vertical jump (VJ), and the sit-and-reach test (SR). Principal components analysis (PCA) of the entire sample revealed that dynamic fitness (DF), related 2.4 R, SU, PU, VJ, & BF, explained 49% of variance in performance in the PAT. Lower back and hamstring flexibility explained a further 18% of variance. Law-enforcement agencies using a standard job-specific test to screen the occupational fitness of its members may use fitness tests to make fitness recommendations. Officers should prioritize developing aerobic fitness, muscular endurance, lower-body power, and flexibility to help meet the demands of occupational performance.

Probing triplet transport in singlet fission materials can be challenging due to the presence of multiple diffusing species. We present a device-based method to measure the intrinsic triplet diffusion length ( L D ) in organic semiconductor thin films exhibiting singlet fission. Triplet states are optically injected into the singlet fission material of interest via energy transfer from an adjacent thin film characterized by strong spin-orbit coupling. Injected triplets migrate through the full thickness of the material before undergoing dissociation at a donor-acceptor interface. By modeling the ratio of injector and acceptor photocurrent as a function of layer thickness, the triplet L D is extracted separate from processes of unknown efficiency including singlet fission and diffusion. In considering three archetypical fission systems, a wide range is found for the triplet L D , ranging from 3.3 ± 0.4 nm for 5,12-bis((triisopropylsilyl)ethynyl)tetracene to 17.1 ± 1.3 nm for pentacene and 32.1 ± 2.6 nm for tetracene.

Using a pulsed-beam transmission electron microscope, we discover a reduction in damage to methylammonium lead iodide (MAPbI 3 ) as compared to conventional beams delivered at the same dose rates. For rates as low as 0.001 e·Å -2 ·s -1 , we find up to a 17% reduction in damage at a total dose of 10 e·Å -2 . We systematically study the effects of number of electrons in each pulse and the duration between pulse arrival. Damage increases for both, though the number of electrons per pulse has a larger effect. A crossover is identified, where a pulsed beam causes more damage than a conventional one. Although qualitatively similar to previous findings, the degree to which damage is reduced in MAPbI 3 is less than that observed for other materials ( e.g. , C 36 H 74 ), supporting the hypothesis that the effects are material- and damage-mechanism-dependent. Despite this, the observation here of damage reduction for relatively large electron packets (up to 200 electrons per pulse) suggests that MAPbI 3 is in fact less susceptible to irradiation than C 36 H 74 , which may be related to reported self-healing effects. This work provides insights into damage processes and durability in hybrid perovskites and also illustrates the viability of using pulsed-beam TEM to explore the associated molecular-level routes to degradation, analogous to laser-accelerated energetic pulsed electron beams and the study of damage to biomolecules, cells, and tissues in radiobiology., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Research involving law enforcement populations has suggested better fitness could enhance job task performance and reduce injuries. Academy training should lead to improvements in recruit fitness. The aim of this study was to investigate the impact of a strength and conditioning program on fitness among law enforcement recruits. Twenty-six recruits (23 males, three females) completed a 27-week academy, which incorporated 3-4 physical training sessions per week. Fitness assessment occurred during pre- (week 0), mid- (week 14), and post-testing (week 27) time points. The fitness assessments included: vertical jump, one-minute push-ups, one-minute sit-ups, posterior chain strength measured by a leg/back dynamometer, grip strength, and aerobic fitness measured by the 20-m multistage shuttle run (MSR). A repeated measures ANOVA with Bonferroni post hoc tests determined any significant changes in fitness between time points, with alpha set at p < .05. Due to the small sample size of females, statistical analysis was only conducted on male recruits. Overall, significant main effects ( p < .001) were observed in all fitness assessments except for grip strength. The results detailed general improvements in fitness. However, push-up and MSR scores decreased from mid- to post-test, while sit-ups did not change. Posterior chain strength and the vertical jump improved from mid-to post-test. The data indicated that the strength and conditioning program positively influenced the fitness of recruits. An increased focus on skill-specific work in the second-half of academy may have contributed to the plateaus in muscular endurance and aerobic fitness, and improvement of lower-body strength and power.

The purpose of this study was to examine the impact that external loads have on vertical jump height and peak anaerobic power output (PAPw) of police officers during a vertical jump (VJ) test. Retrospective data of 47 (mean age 38.79 ± 7.97 years) police officers from a US Law Enforcement Agency (LEA) were used for analysis. VJ heights and body mass were used in the Sayers Peak Power Equation to calculate PAPw. Power-to-weight (P:W) ratios were then calculated by dividing PAPw by the officer's body mass. VJ height significantly ( p < .001) decreased with load (unloaded = 49.49 ± 8.46 cm: loaded = 43.62 ± 7.68 cm). A Pearson's correlation showed a significant ( p < .01) low-moderate ( r = .387) relationship between absolute load (9.57 ± .94 kg) and change in PAPw, and a significant ( p < .01) strong ( r = .794) correlation between relative load and changes in P:W. This study supports previous research that suggests that occupational load carriage has a negative impact on VJ performance in police officers and may influence job performance, and that training programs may mitigate these negative effects.

The efficiency of organic light-emitting devices (OLEDs) is often limited by roll-off, where efficiency decreases with increasing bias. In most OLEDs, roll-off primarily occurs due to exciton quenching, which is commonly assumed to be active only above device turn-on. Below turn-on, exciton and charge carrier densities are often presumed to be too small to cause quenching. Using lock-in detection of photoluminescence, we find that this assumption is not generally valid; luminescence can be quenched by >20% at biases below turn-on. We show that this low-bias quenching is due to hole accumulation induced by intrinsic polarization of the electron transport layer (ETL). Further, we demonstrate that selection of nonpolar ETLs or heating during deposition minimizes these losses, leading to efficiency enhancements of >15%. These results reveal design rules to optimize efficiency, clarify how ultrastable glasses improve OLED performance, and demonstrate the importance of quantifying exciton quenching at low bias., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Charge-transfer (CT) states formed at organic donor-acceptor (D-A) semiconductor heterojunctions play a critical role in optoelectronic devices. While mobile, their migration has not been extensively characterized. In addition, the factors impacting the CT state diffusion length ( L D ) have not been elucidated. Here, CT state L D is measured by using photoluminescence quenching for several D-A mixtures, with migration occurring along the bulk heterojunction. All D-A pairings considered yield a similar L D ∼ 5 nm in equal mixtures despite variations in the CT state energy and the constituent molecular structures. The CT state L D varies strongly with mixture composition and is well-correlated to the slowest charge carrier mobility, suggesting a direct method to tune CT state transport. These findings may be applied to elucidate the role of CT state migration in organic photovoltaic and light-emitting devices as well as to broadly explain the transport of interfacial excited states along inorganic and hybrid organic-inorganic heterojunctions.

Objective: To identify the risk factors identified within 1-month poststroke that predict the onset of poststroke shoulder pain (PSSP) within the first year after stroke., Methods: Five databases (AMED, CINAHL, EMBASE, Medline, and PubMed) were searched from inception to April 2019. Prospective cohort studies that measured a potential risk factor for PSSP within the first month after stroke were included. Two authors independently reviewed and selected articles for inclusion. Risk of bias was assessed using the Quality in Prognosis Studies tool. Data extracted included raw data for odds ratio (OR) calculations, definition and measurement of pain, study limitations, and baseline characteristics of participants. The review was conducted following Preferred Reporting Items for Systematic Reviews and Meta-Analyses guidelines., Results: Nine articles were retrieved that met the inclusion criteria, and 6 presented data to use in meta-analysis. Fifty-four different factors were identified as potential risk factors. Meta-analysis was possible for 4 factors; sex (OR .93, confidence interval [CI] .75-1.15), laterality (OR .78, CI .59-1.05), diabetes (OR 2.09, CI 1.16-3.78), and history of shoulder pain (OR 2.78, CI 1.29-5.97). Reduced motor function in the upper limb was also identified as a significant risk factor through qualitative synthesis., Conclusions: Reduced motor function in the upper limb, diabetes, and a history of shoulder pain were identified as significant risk factors for the development of PSSP within the first year after stroke. Recommendations to standardize future studies in this area have been made, and it is suggested that defining subtypes of PSSP may aid future interventional studies., Competing Interests: Declaration of Competing Interest This research was undertaken as part of a Clinical Improvement Scholarship by Rich Holmes. Funding gratefully received from Health Education Kent, Surrey, and Sussex was to support backfill costs only and the organization had no input into the research topic, content or design. We have no other conflicts of interest to declare., (Crown Copyright © 2020. Published by Elsevier Inc. All rights reserved.)

Self-organizing patterns with micrometre-scale features are promising for the large-area fabrication of photonic devices and scattering layers in optoelectronics. Pattern formation would ideally occur in the active semiconductor to avoid the need for further processing steps. Here, we report an approach to form periodic patterns in single layers of organic semiconductors by a simple annealing process. When heated, a crystallization front propagates across the film, producing a sinusoidal surface structure with wavelengths comparable to that of near-infrared light. These surface features initially form in the amorphous region within a micrometre of the crystal growth front, probably due to competition between crystal growth and surface mass transport. The pattern wavelength can be tuned from 800 nm to 2,400 nm by varying the film thickness and annealing temperature, and millimetre-scale domain sizes are obtained. This phenomenon could be exploited for the self-assembly of microstructured organic optoelectronic devices.

Searching for alternatives to lead-containing metal halide perovskites, we explored the properties of indium-based inorganic double perovskites Cs 2 InMX 6 with M = Cu, Ag, Au and X = Cl, Br, I, and of its organic-inorganic hybrid derivative MA 2 InCuCl 6 (MA = CH 3 NH 3 + ) using computation within Kohn-Sham density functional theory. Among these compounds, Cs 2 InCuCl 6 and MA 2 InCuCl 6 were found to be potentially promising candidates for solar cells. Calculations with different functionals provided the direct band gap of Cs 2 InCuCl 6 between 1.05 and 1.73 eV. In contrast, MA 2 InCuCl 6 exhibits an indirect band gap between 1.31 and 2.09 eV depending on the choice of exchange-correlation functional. Cs 2 InCuCl 6 exhibits a much higher absorption coefficient than that calculated for c-Si and CdTe, common semiconductors for solar cells. Even MA 2 InCuCl 6 is predicted to have a higher absorption coefficient than c-Si and CdTe across the visible spectrum despite the fact that it is an indirect band gap material. The intrinsic charge carrier mobilities for Cs 2 InCuCl 6 along the L-Γ path are predicted to be comparable to those for MAPbI 3 . Finally, we carried out calculations of the band edge positions for MA 2 InCuCl 6 and Cs 2 InCuCl 6 to offer guidance for solar cell heterojunction design and optimization. We conclude that Cs 2 InCuCl 6 and MA 2 InCuCl 6 are promising semiconductors for photovoltaic and optoelectronic applications.

Organic photovoltaic cells are partiuclarly sensitive to exciton harvesting and are thus, a useful platform for the characterization of exciton diffusion. While device photocurrent spectroscopy can be used to extract the exciton diffusion length, this method is frequently limited by unknown interfacial recombination losses. We resolve this limitation and demonstrate a general, device-based photocurrent-ratio measurement to extract the intrinsic diffusion length. Since interfacial losses are not active layer specific, a ratio of the donor- and acceptor-material internal quantum efficiencies cancels this quantity. We further show that this measurement permits extraction of additional device-relevant information regarding exciton relaxation and charge separation processes. The generality of this method is demonstrated by measuring exciton transport for both luminescent and dark materials, as well as for small molecule and polymer active materials and semiconductor quantum dots. Thus, we demonstrate a broadly applicable device-based methodology to probe the intrinsic active material exciton diffusion length.

Purpose: To describe the current UK practice for the use of intramuscular Botulinum Toxin type A injections to treat hemiplegic shoulder pain., Method: A UK-based cross-sectional study using an online survey. Participants (n = 68) were medical and non-medical practitioners recruited via the membership of the British Society for Rehabilitation Medicine and the British Neurotoxin Network. Data was analysed using descriptive statistics and content analysis., Results: The majority of respondents would consider Botulinum Toxin type A for hemiplegic shoulder pain (86.8%), though most of these respondents inject for this goal infrequently (83.1%). Pectoralis major was most commonly selected to achieve this goal. Barriers to this intervention included difficulties determining the cause of pain (29.4%), difficulty isolating muscles (27.9%), and a lack of evidence (25%). The doses reported regularly deviated from guidelines and a substantial range in the volumes suggested was observed. Clinicians were mostly reliant on unstandardised measures to assess outcomes., Conclusions: Current UK practice of Botulinum Toxin type A injections for hemiplegic shoulder pain associated with spasticity is highly variable. There are large gaps between current practice and available evidence with regards to muscle selection and doses used. A number of areas for further investigation have been identified to progress current understanding of this intervention. Implications for rehabilitation There are wide variations in practice for this complex intervention and clinicians should consider that their individual decision-making could be based on their own beliefs rather than available evidence. Pectoralis major is most commonly injected to treat hemiplegic shoulder pain, but further evaluation is required to address whether it is the most effective. Clinicians most often use a limitation of shoulder abduction and external rotation, flexor patterning of the upper limb, and pain on passive movement to identify when hemiplegic shoulder pain is due to spasticity over other causes. Further research is needed to identify which patients are most likely to benefit from this intervention and at what stage post-stroke its use is most optimal.

Lockie, RG, Dawes, JJ, Kornhauser, CL, and Holmes, RJ. Cross-sectional and retrospective cohort analysis of the effects of age on flexibility, strength endurance, lower-body power, and aerobic fitness in law enforcement officers. J Strength Cond Res 33(2): 451-458, 2019-There can be a great age range in cohorts of law enforcement officers. As the tasks required of officers generally do not change with advancing age, it is important to understand how physical performance in tests that assess job-specific characteristics may be altered. Retrospective analysis of performance test data of 383 officers (362 men and 21 women) was conducted. The tests included the following: sit-and-reach to determine hamstring and lower back flexibility; maximal push-up and sit-up repetitions in 60 seconds to measure muscle endurance; vertical jump (VJ) to assess lower-body power; and 2.4-km run to ascertain aerobic capacity. Data were stratified by age into 20-29, 30-39, 40-49, and 50-59 year groups, and analyzed by sex. A 1-way analysis of variance with the Bonferroni post hoc test was used to calculate the differences between the groups. Considering the male subjects, the 40-49 and 50-59 year groups performed poorer in the VJ, sit-up test, and 2.4-km run compared with the 20-29 year group (p ≤ 0.001-0.045). For the female subjects, the 20-29 year group was superior to the 30-39 (p = 0.013) and 40-49 (p = 0.025) year groups in the push-up test. To ensure that an older officer can successfully complete occupation-specific tasks, lower-body power, abdominal strength, and aerobic training should be completed. Female officers should also attempt to maintain relative upper-body strength. Practitioners must attempt to design training programs that fit within the context of the occupational demands, and potentially using a nontraditional training design as law enforcement officers may not have the time to follow a traditional periodization model.

The purpose of this investigation was to determine the physiological and perceptual demands associated with defensive tactics (DEFTAC) training among state patrol officers of different BMI (body mass index) categories. Twenty-four male state patrol officers (n = 24, age 36.00 + 7.86 yrs) voluntarily agreed to participate in data collection during a DEFTAC gauntlet. Anthropometric information (height (HT) 182.19 + 7.43 cm and weight (WT) 96.31 + 17.45 kg), body mass index (BMI), peak and average heart rates, duty weight, BLa, and RPE, were recorded. Officers were then divided into two-groups (Healthy BMI (BMI ≤ 25), n = 12, Overweight (BMI ≥ 25), n = 12). Analyses of covariance (ANCOVAs) were conducted to determine the effect of BMI on the outcome variables. Furthermore, a Pearson's product-moment correlation coefficient was also conducted to determine if significant relationships between RPE, BLa, and HR existed between groups. Significant mean score differences between healthy and overweight officers were found in measures of age [t(22) 4.12, p< 0.01, R 2 = .44], and weight of duty gear [t(21) 3.96, p<0.01, R 2 = .33]. When used as a covariate, age also predicted average HR% [ F (1, 21) = 6.19, p < .05, partial η 2 = .24]. Significant relationships were found in the healthy group between RPE and DEFTAC time, DEFTAC time and score, as well as score and post BLa. Significant relationships for the overweight group between peak (HR) percentage and post BLa, peak (HR) percentage and RPE, DEFTAC time and duty weight, and between weight and DEFTAC time. The results of this study suggest that overweight officers may have lower DEFTAC scores when compared to their healthy counterparts. Based on the results, it seems reasonable to compare physiological variables from this population to those from combative sports as well as for officers to achieve and maintain a healthy BMI value in order to improve individual DEFTAC performance.

Degradation in organic light-emitting devices (OLEDs) is generally driven by reactions involving excitons and polarons. Accordingly, a common design strategy to improve OLED lifetime is to reduce the density of these species by engineering an emissive layer architecture to achieve a broad exciton recombination zone. Here, the effect of exciton density on device degradation is analyzed in a mixed host emissive layer (M-EML) architecture which exhibits a broad recombination zone. To gain further insight into the dominant degradation mechanism, losses in the exciton formation efficiency and photoluminescence (PL) efficiency are decoupled by tracking the emissive layer PL during device degradation. By varying the starting luminance and M-EML thickness, the rate of PL degradation is found to depend strongly on recombination zone width and hence exciton density. In contrast, losses in the exciton formation depend only weakly on the recombination zone, and thus may originate outside of the emissive layer. These results suggest that the lifetime enhancement observed in the M-EML architectures reflects a reduction in the rate of PL degradation. Moreover, the varying roles of excitons and polarons in degrading the PL and exciton formation efficiencies suggest that kinetically distinct pathways drive OLED degradation and that a single degradation mechanism cannot be assumed when attempting to model the device lifetime. This work highlights the potential to extract fundamental insight into OLED degradation by tracking the emissive layer PL during lifetime testing, while also enabling diagnostic tests on the root causes of device instability.

We report a promising set of donor-acceptor-acceptor (D-A-A) electron-donor materials based on coplanar thieno[3,2-b]/[2,3-b]indole, benzo[c][1,2,5]thiadiazole, and dicyanovinylene, which are found to show broadband absorption with high extinction coefficients. The role of the regioisomeric electron-donating thienoindole moiety on the physical and structural properties is examined. Bulk heterojunction (BHJ) organic photovoltaic cells (OPVs) based on the thieno[2,3-b]indole-based electron donor NTU-2, using C 70 as an electron acceptor, show a champion power conversion efficiency of 5.2% under AM 1.5G solar simulated illumination. This efficiency is limited by a low fill factor (FF), as has previously been the case in D-A-A systems. In order to identify the origin of the limited FF, further insight into donor layer charge-transport behavior is realized by examining planar heterojunction OPVs, with emphasis on the evolution of film morphology with thermal annealing. Compared to as-deposited OPVs that exhibit insufficient donor crystallinity, crystalline OPVs based on annealed thin films show an increase in the short-circuit current density, FF, and power conversion efficiency. These results suggest that that the crystallization of D-A-A molecules might not be realized spontaneously at room temperature and that further processing is needed to realize efficient charge transport in these materials.

The migration of weakly and non-luminescent (dark) excitons remains an understudied subset of exciton dynamics in molecular thin films. Inaccessible via photoluminescence, these states are often probed using photocurrent methods that require efficient charge collection. Here we probe exciton harvesting in both luminescent and dark materials using a photovoltage-based technique. Transient photovoltage permits a real-time measurement of the number of charges in an organic photovoltaic cell, while avoiding non-geminate recombination losses. The extracted exciton diffusion lengths are found to be similar to those determined using photocurrent. For the luminescent material boron subphthalocyanine chloride, the photovoltage determined diffusion length is less than that extracted from photoluminescence. This indicates that while photovoltage circumvents non-geminate losses, geminate recombination at the donor-acceptor interface remains the primary recombination pathway. Photovoltage thus offers a general approach for extracting a device-relevant diffusion length, while also providing insight in to the dominant carrier recombination pathways., Competing Interests: The authors declare no competing financial interests.

We describe here three alkynyl substituted naphthalenes that display promising luminescence characteristics. Each compound is easily and efficiently synthesized in three steps by capitalizing on the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction in which an intermediate benzyne is captured by tetraphenylcyclopentadienone, a classical trap for benzyne itself. These compounds luminesce in the deep blue when stimulated either optically (i.e., photoluminescence in both solution and solid films) or electrically [in a light-emitting diode (LED)]. The photophysical properties are relatively insensitive to the electronic nature of the substituents (H, OMe, CO 2 Me) that define these otherwise identical compounds. Overall, our observations suggest that the twisted nature of the five adjacent aryl groups serves to minimize the intermolecular interaction between core naphthalene units in different sample morphologies. These compounds represent promising leads for the identification of others of value as the emissive component of organic LEDs (OLEDs).

Vapor deposited thin films of copper phthalocyanine (CuPc) were investigated using transient absorption spectroscopy. Exciton-exciton annihilation dominated the kinetics at high exciton densities. When annihilation was minimized, the observed lifetime was measured to be 8.6 ± 0.6 ns, which is over an order of magnitude longer than previous reports. In comparison with metal free phthalocyanine (H2Pc), the data show evidence that the presence of copper induces an ultrafast relaxation process taking place on the ca. 500 fs timescale. By comparison to recent time-resolved photoemission studies, this is assigned as ultrafast intersystem crossing. As the intersystem crossing occurs ca. 10(4) times faster than lifetime decay, it is likely that triplets are the dominant excitons in vapor deposited CuPc films. The exciton lifetime of CuPc thin films is ca. 35 times longer than H2Pc thin films, while the diffusion lengths reported in the literature are typically quite similar for the two materials. These findings suggest that despite appearing to be similar materials at first glance, CuPc and H2Pc may transport energy in dramatically different ways. This has important implications on the design and mechanistic understanding of devices where phthalocyanines are used as an excitonic material.

In order to further improve the performance of organic photovoltaic cells (OPVs), it is essential to better understand the factors that limit the open-circuit voltage (VOC). Previous work has sought to correlate the value of VOC in donor-acceptor (D-A) OPVs to the interface energy level offset (EDA). In this work, measurements of electroluminescence are used to extract the charge transfer (CT) state energy for multiple small molecule D-A pairings. The CT state as measured from electroluminescence is found to show better correlation to the maximum VOC than EDA. The difference between EDA and the CT state energy is attributed to the Coulombic binding energy of the CT state. This correlation is demonstrated explicitly by inserting an insulating spacer layer between the donor and acceptor materials, reducing the binding energy of the CT state and increasing the measured VOC. These results demonstrate a direct correlation between maximum VOC and CT state energy.

Exciton transport in organic semiconductors is a critical, mediating process in many optoelectronic devices. Often, the diffusive and subdiffusive nature of excitons in these systems can limit device performance, motivating the development of strategies to direct exciton transport. In this work, directed exciton transport is achieved with the incorporation of exciton permeable interfaces. These interfaces introduce a symmetry-breaking imbalance in exciton energy transfer, leading to directed motion. Despite their obvious utility for enhanced exciton harvesting in organic photovoltaic cells (OPVs), the emergent properties of these interfaces are as yet uncharacterized. Here, directed exciton transport is conclusively demonstrated in both dilute donor and energy-cascade OPVs where judicious optimization of the interface allows exciton transport to the donor-acceptor heterojunction to occur considerably faster than when relying on simple diffusion. Generalized systems incorporating multiple exciton permeable interfaces are also explored, demonstrating the ability to further harness this phenomenon and expeditiously direct exciton motion, overcoming the diffusive limit.

In planar heterojunction organic photovoltaic devices (OPVs), broad spectral coverage can be realized by incorporating multiple molecular absorbers in an energy-cascade architecture. Here, this approach is combined with a host-guest donor layer architecture previously shown to optimize exciton transport for the fluorescent organic semiconductor boron subphthalocyanine chloride (SubPc) when diluted in an optically transparent host. In order to maximize the absorption efficiency, energy-cascade OPVs that utilize both photoactive host and guest donor materials are examined using the pairing of SubPc and boron subnaphthalocyanine chloride (SubNc), respectively. In a planar heterojunction architecture, excitons generated on the SubPc host rapidly energy transfer to the SubNc guest, where they may migrate toward the dissociating, donor-acceptor interface. Overall, the incorporation of a photoactive host leads to a 13% enhancement in the short-circuit current density and a 20% enhancement in the power conversion efficiency relative to an optimized host-guest OPV combining SubNc with a nonabsorbing host. This work underscores the potential for further design refinements in planar heterojunction OPVs and demonstrates progress toward the effective separation of functionality between constituent OPV materials.

Background: Health-care-acquired infections (HAIs) are a leading cause of morbidity and mortality after cardiac surgery. Prior work has identified several patient-related risk factors associated with HAIs. We hypothesized that rates of HAIs would differ across institutions, in part attributed to differences in case mix., Methods and Results: We analyzed 20 896 patients undergoing isolated coronary artery bypass grafting surgery at 33 medical centers in Michigan between January 1, 2009, and June 30, 2012. Overall HAIs included pneumonia, sepsis/septicemia, and surgical site infections, including deep sternal wound, thoracotomy, and harvest/cannulation site infections. We excluded patients presenting with endocarditis. Predicted rates of HAIs were estimated using multivariable logistic regression. Overall rate of HAI was 5.1% (1071 of 20 896; isolated pneumonia, 3.1% [n=644]; isolated sepsis/septicemia, 0.5% [n=99]; isolated deep sternal wound infection, 0.5% [n=96]; isolated harvest/cannulation site, 0.5% [n=97]; isolated thoracotomy, 0.02% [n=5]; multiple infections, 0.6% [n=130]). HAI subtypes differed across strata of center-level HAI rates. Although predicted risk of HAI differed in absolute terms by 2.8% across centers (3.9-6.7%; min:max), observed rates varied by 18.2% (0.9-19.1%)., Conclusions: There was a 18.2% difference in observed HAI rates across medical centers among patients undergoing isolated coronary artery bypass grafting surgery. This variability could not be explained by patient case mix. Future work should focus on the impact of other factors (eg, organizational and systems of clinical care) on risk of HAIs., (© 2014 American Heart Association, Inc.)

Direct observation of an unexpected product from excited state fusion of two excited triplet states in platinum octaethylporphyrin is reported. Transient spectroscopy was used to identify the product as a metal centered (d, d) state that decays slowly compared with the rate of fusion. The reaction was demonstrated to be second order with a rate coefficient of k(TTF) = (5.4 ± 0.4) × 10(-10) cm(3) · s(-1). The results contrast with the common assumption that fusion proceeds directly to annihilation via rapid non-radiative deactivation of the products. Following visible photo-excitation, the fusion process results in energetic upconversion of the incident photons stored in the higher energy (d, d) state at irradiances below the threshold for multi-photon absorption.

Connecting molecular structure and exciton diffusion length in rubrene derivatives demonstrates how the diffusion length of rubrene can be enhanced through targeted functionalization aiming to enhance self-Förster energy transfer. Functionalization adds steric bulk, forcing the molecules farther apart on average, and leading to increased photoluminescence efficiency. A diffusion length enhancement greater than 50% is realized over unsubstituted rubrene., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photoconversion in planar-heterojunction organic photovoltaic cells (OPVs) is limited by a short exciton diffusion length (L(D)) that restricts migration to the dissociating electron donor/acceptor interface. Consequently, bulk heterojunctions are often used to realize high efficiency as these structures reduce the distance an exciton must travel to be dissociated. Here, we present an alternative approach that seeks to directly engineer L(D) by optimizing the intermolecular separation and consequently, the photophysical parameters responsible for excitonic energy transfer. By diluting the electron donor boron subphthalocyanine chloride into a wide-energy-gap host material, we optimize the degree of interaction between donor molecules and observe a ~50% increase in L(D). Using this approach, we construct planar-heterojunction OPVs with a power conversion efficiency of (4.4 ± 0.3)%, > 30% larger than the case of optimized devices containing an undiluted donor layer. The underlying correlation between L(D) and the degree of molecular interaction has wide implications for the design of both OPV active materials and device architectures.

The RAD9-RAD1-HUS1 (9-1-1) complex is a heterotrimeric PCNA-like clamp that responds to DNA damage in somatic cells by promoting DNA repair as well as ATR-dependent DNA damage checkpoint signaling. In yeast, worms, and flies, the 9-1-1 complex is also required for meiotic checkpoint function and efficient completion of meiotic recombination; however, since Rad9, Rad1, and Hus1 are essential genes in mammals, little is known about their functions in mammalian germ cells. In this study, we assessed the meiotic functions of 9-1-1 by analyzing mice with germ cell-specific deletion of Hus1 as well as by examining the localization of RAD9 and RAD1 on meiotic chromosomes during prophase I. Hus1 loss in testicular germ cells resulted in meiotic defects, germ cell depletion, and severely compromised fertility. Hus1-deficient primary spermatocytes exhibited persistent autosomal γH2AX and RAD51 staining indicative of unrepaired meiotic DSBs, synapsis defects, an extended XY body domain often encompassing partial or whole autosomes, and an increase in structural chromosome abnormalities such as end-to-end X chromosome-autosome fusions and ruptures in the synaptonemal complex. Most of these aberrations persisted in diplotene-stage spermatocytes. Consistent with a role for the 9-1-1 complex in meiotic DSB repair, RAD9 localized to punctate, RAD51-containing foci on meiotic chromosomes in a Hus1-dependent manner. Interestingly, RAD1 had a broader distribution that only partially overlapped with RAD9, and localization of both RAD1 and the ATR activator TOPBP1 to the XY body and to unsynapsed autosomes was intact in Hus1 conditional knockouts. We conclude that mammalian HUS1 acts as a component of the canonical 9-1-1 complex during meiotic prophase I to promote DSB repair and further propose that RAD1 and TOPBP1 respond to unsynapsed chromatin through an alternative mechanism that does not require RAD9 or HUS1., Competing Interests: The authors have declared that no competing interests exist.

We demonstrate an all-organic, one-dimensional photonic crystal tuned to the regime of strong exciton-photon coupling. The structure consists of a high index of refraction light-absorbing active layer periodically distributed in a low index of refraction nonabsorbing background medium. The strongly coupled state in this structure is shared between multiple active layers separated by distances longer than the wavelength of light in the structure. In order to investigate the potential for long-range energy transfer, photon-mediated exciton hybridization is demonstrated between multiple absorbing species spatially separated in the photonic crystal.

The four mammalian Argonaute family members are thought to share redundant functions in the microRNA pathway, yet only AGO2 possesses the catalytic "slicer" function required for RNAi. Whether AGO1, AGO3, or AGO4 possesses specialized functions remains unclear. Here we show that AGO4 localizes to spermatocyte nuclei during meiotic prophase I, specifically at sites of asynapsis and the transcriptionally silenced XY subdomain, the sex body. We generated Ago4 knockout mice and show that Ago4(-/-) spermatogonia initiate meiosis early, resulting from premature induction of retinoic acid-response genes. During prophase I, the sex body assembles incorrectly in Ago4(-/-) mice, leading to disrupted meiotic sex chromosome inactivation (MSCI). This is associated with a dramatic loss of microRNAs, >20% of which arises from the X chromosome. Thus, AGO4 regulates meiotic entry and MSCI in mammalian germ cells, implicating small RNA pathways in these processes., (Copyright © 2012 Elsevier Inc. All rights reserved.)

We present an all-gas-phase approach for the fabrication of nanocrystal-based light-emitting devices. In a single reactor, silicon nanocrystals are synthesized, surface-functionalized, and deposited onto substrates precoated with a transparent electrode. Devices are completed by evaporation of a top metal electrode. The devices exhibit electroluminescence centered at a wavelength of λ = 836 nm with a peak external quantum efficiency exceeding 0.02%. This all-gas-phase approach permits controlled deposition of dense, functional nanocrystal films suitable for application in electronic devices.

A direct synthesis of new donor materials for organic photovoltaic cells is reported. Diaryindenotetracenes were synthesized utilizing a Kumada-Tamao-Corriu cross-coupling of peri-substituted tetrachlorotetracene with spontaneous indene annulation via C-H activation. Vacuum deposited planar heterojunction organic photovoltaic cells incorporating these molecules as electron donors exhibit power conversion efficiencies exceeding 1.5% with open-circuit voltages ranging from 0.7 to 1.1 V when coupled with C(60) as an electron acceptor.

Polymeric bicontinuous microemulsions (BμE), found in well-designed ternary blends of two homopolymers and a diblock copolymer, have been extensively studied in the bulk, for example, as versatile templates for the synthesis of nanoporous materials. However, there have been few reports regarding BμE-forming blends as films and the potential impact of confinement on the morphology of such blends. We have investigated the morphology of ternary blends of polyethylene (PE), poly(ethylene-alt-propylene) (PEP), and poly(ethylene-b-ethylene-alt-propylene) (PE-PEP) on a variety of substrates. The films were rendered nanoporous by selective extraction of the PEP component, which also created contrast for scanning electron microscopy (SEM). Blends that form BμEs in the bulk were found to undergo an evolution of morphology from a BμE to a macro-phase separated state, induced by the segregation of blend components to the film interfaces. The dynamics of the transformation are accelerated by decreasing film thickness. The results presented indicate that BμEs can be kinetically trapped on arbitrary substrates, which has important implications for the production of bicontinuous, nanoporous films., (© 2011 American Chemical Society)

Polymethylmethacrylate (PMMA) microfluidic devices have been fabricated using a hot embossing technique to incorporate micro-pillar features on the bottom wall of the device which when combined with either a plasma treatment or the coating of a diamond-like carbon (DLC) film presents a range of surface modification profiles. Experimental results presented in detail the surface modifications in the form of distinct changes in the static water contact angle across a range from 44.3 to 81.2 when compared to pristine PMMA surfaces. Additionally, capillary flow of water (dyed to aid visualization) through the microfluidic devices was recorded and analyzed to provide comparison data between filling time of a microfluidic chamber and surface modification characteristics, including the effects of surface energy and surface roughness on the microfluidic flow. We have experimentally demonstrated that fluid flow and thus filling time for the microfluidic device was significantly faster for the device with surface modifications that resulted in a lower static contact angle, and also that the incorporation of micro-pillars into a fluidic device increases the filling time when compared to comparative devices.

We demonstrate highly efficient electroluminescence from silicon nanocrystals (SiNCs). In an optimized nanocrystal-organic light-emitting device, peak external quantum efficiencies of up to 8.6% can be realized with emission originating solely from the SiNCs. The high efficiencies reported here demonstrate for the first time that with an appropriate choice of device architecture it is possible to achieve highly efficient electroluminescence from nanocrystals of an indirect band gap semiconductor.