Designing intrinsically photostable low band gap polymers:a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Time dependence of rotational state populations of excited hydrogen molecules in an RF excited plasma reactor

We report on time-dependent population distributions of excited rotational states of hydrogen in a capacitively coupled RF discharge. The common model to obtain the gas temperature from the rotational distribution is not applicable at all times during the discharge cycle due to the time dependence of the EEDF. The apparent temperature within a cycle assumes values between 350 K and 450 K for the discharge parameters of this experiment. We discuss the optimum time window within the discharge cycle that yields the best approximation to the actual temperature. Erroneous results can be obtained, in principle, with time-integrated measurements; we find, however, that in the present case the systematic error amounts to only approximately 20 K. This is due to the fact that the dominant contribution to the average intensity arises during that time window for which the assumptions underlying the analysis are best fulfilled. A similar analysis can be performed for N+2 rotational bands with a small amount of nitrogen added to the discharge gas. These populations do not exhibit the time variations found in the case of H2.

Asset life prediction and maintenance decision-making using a non-linear non-Gaussian state space model

Estimating and predicting degradation processes of engineering assets is crucial for reducing the cost and insuring the productivity of enterprises. Assisted by modern condition monitoring (CM) technologies, most asset degradation processes can be revealed by various degradation indicators extracted from CM data. Maintenance strategies developed using these degradation indicators (i.e. condition-based maintenance) are more cost-effective, because unnecessary maintenance activities are avoided when an asset is still in a decent health state. A practical difficulty in condition-based maintenance (CBM) is that degradation indicators extracted from CM data can only partially reveal asset health states in most situations. Underestimating this uncertainty in relationships between degradation indicators and health states can cause excessive false alarms or failures without pre-alarms. The state space model provides an efficient approach to describe a degradation process using these indicators that can only partially reveal health states. However, existing state space models that describe asset degradation processes largely depend on assumptions such as, discrete time, discrete state, linearity, and Gaussianity. The discrete time assumption requires that failures and inspections only happen at fixed intervals. The discrete state assumption entails discretising continuous degradation indicators, which requires expert knowledge and often introduces additional errors. The linear and Gaussian assumptions are not consistent with nonlinear and irreversible degradation processes in most engineering assets. This research proposes a Gamma-based state space model that does not have discrete time, discrete state, linear and Gaussian assumptions to model partially observable degradation processes. Monte Carlo-based algorithms are developed to estimate model parameters and asset remaining useful lives. In addition, this research also develops a continuous state partially observable semi-Markov decision process (POSMDP) to model a degradation process that follows the Gamma-based state space model and is under various maintenance strategies. Optimal maintenance strategies are obtained by solving the POSMDP. Simulation studies through the MATLAB are performed; case studies using the data from an accelerated life test of a gearbox and a liquefied natural gas industry are also conducted. The results show that the proposed Monte Carlo-based EM algorithm can estimate model parameters accurately. The results also show that the proposed Gamma-based state space model have better fitness result than linear and Gaussian state space models when used to process monotonically increasing degradation data in the accelerated life test of a gear box. Furthermore, both simulation studies and case studies show that the prediction algorithm based on the Gamma-based state space model can identify the mean value and confidence interval of asset remaining useful lives accurately. In addition, the simulation study shows that the proposed maintenance strategy optimisation method based on the POSMDP is more flexible than that assumes a predetermined strategy structure and uses the renewal theory. Moreover, the simulation study also shows that the proposed maintenance optimisation method can obtain more cost-effective strategies than a recently published maintenance strategy optimisation method by optimising the next maintenance activity and the waiting time till the next maintenance activity simultaneously.

Role of the triplet state in the green emission peak of polyfluorene films: A time evolution study

The blue emission of ethyl-hexyl substituted polyfluorene (PF2/6) films is accompanied by a low energy green emission peak around 500 nm in inert atmosphere. The intensity of this 500 nm peak is large in electroluminescence (EL) compared to photoluminescence (PL)measurements. Furthermore, the green emission intensity reduces dramatically in the presence of molecular oxygen. To understand this, we have modeled various nonradiative processes by time dependent quantum many body methods. These are (i) intersystem crossing to study conversion of excited singlets to triplets leading to a phosphorescence emission, (ii) electron-hole recombination (e-hR) process in the presence of a paramagnetic impurity to follow the yield of triplets in a polyene system doped with paramagnetic metal atom, and (iii) quenching of excited triplet states in the presence of oxygen molecules to understand the low intensity of EL emission in ambient atmosphere, when compared with that in nitrogen atmosphere. We have employed the Pariser-Parr-Pople Hamiltonian to model the molecules and have invoked electron-electron repulsions beyond zero differential approximation while treating interactions between the organic molecule and the rest of the system. Our time evolution methods show that there is a large cross section for triplet formation in the e-hR process in the presence of paramagnetic impurity with degenerate orbitals. The triplet yield through e-hR process far exceeds that in the intersystem crossing pathway, clearly pointing to the large intensity of the 500 nm peak in EL compared to PL measurements. We have also modeled the triplet quenching process by a paramagnetic oxygen molecule which shows a sizable quenching cross section especially for systems with large sizes. These studies show that the most probable origin of the experimentally observed low energy EL emission is the triplets.

Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study

The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR3) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (mu s). Interestingly, TR3 spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ assigned to n pi* and pi pi* of which the pi pi* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (similar to 2 ns) between the T-2(1(3)n pi*) and T-1(1(3)pi pi*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents J. Chem. Phys. 2015, 142, 24305] suggest that the lowest n pi* and pi pi* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

Space and time resolved rotational state populations and gas temperatures in an inductively coupled hydrogen RF discharge

Gas temperature is of major importance in plasma based surface treatment, since the surface processes are strongly temperature sensitive. The spatial distribution of reactive species responsible for surface modification is also influenced by the gas temperature. Industrial applications of RF plasma reactors require a high degree of homogeneity of the plasma in contact with the substrate. Reliable measurements of spatially resolved gas temperatures are, therefore, of great importance. The gas temperature can be obtained, e.g. by optical emission spectroscopy (OES). Common methods of OES to obtain gas temperatures from analysis of rotational distributions in excited states do not include the population dynamics influenced by cascading processes from higher electronic states. A model was developed to evaluate this effect on the apparent rotational temperature that is observed. Phase resolved OES confirmed the validity of this model. It was found that cascading leads to higher apparent temperatures, but the deviation (similar or equal to 25 K) is relatively small and can be ignored in most cases. This analysis is applied to investigate axially and radially resolved temperature profiles in an inductively coupled hydrogen RF discharge.

TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY OF TRIPLET-STATE METALATED AND FREE-BASE TETRAARYLPORPHYRINS

Resonance Raman spectra of the T-1 excited states of Zn and free-base tetra-4-sulfonatophenylporphyrin (TPPS) have been recorded at room temperature in aqueous solution using two-colour time-resolved methods. The spectra of both sulfonated molecules are very similar to their tetraphenylporphyrin (TPP) analogues, which have been recorded in THF solution using the same pump-probe conditions, but they have higher signal-to-noise ratios because interference from strong solvent bands is reduced. Although two different T-1 spectra of Zn(TPP) have been reported these spectra differ slightly from each other and from the spectrum reported here, which has band positions very close (+/-6 cm(-1)) to those of Zn(TPPS). The high S/N ratios obtainable for the water-soluble porphyrins have allowed reliable polarization data to be recorded for their S-0 and T-1 states. This data set allows a realistic comparison of the changes in bonding associated with excitation of both free-base and Zn tetraarylporphyrins to the T-1 state.

TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY OF EXCITED SINGLET AND TRIPLET-STATES OF FREE-BASE MESO-TETRAPHENYLPORPHYRIN

Two-color time-resolved resonance Raman spectroscopy has been used to probe the lowest excited singlet (S1) and triplet (T1) states of free-base meso-tetraphenylporphyrin and meso-tetrakis(4-sulphonatophenyl)porphyrin in solution at room temperature. The spectra were recorded using 532-nm excitation pulses and time-delayed probe pulses (DELTAT = 0-30 ns, 447 and 460 nm) near lambda(max) of the S1 and T1 states. Significant shifts in frequency of the porphyrin core vibrations were observed upon excitation to either the S1 or T1 state. Several of the strongest polarized bands in the spectra of both excited states, including nu1, nu2, nu4, nu6, and phi4, are assigned, and the information they give on the differences in electron distribution in the ground, S1, and T1 states is discussed.

Quality of life profile and correlated factors in chronic leg ulcer patients in the mid-west of São Paulo State, Brazil

BACKGROUND: Chronic leg ulcer may have an impact on patients' quality of life.OBJECTIVES:This study aimed to identify the impact of leg ulcers on patient's quality of life using the Dermatology Life Quality Index and to define the main factors correlated with this perception.METHOD:Cross-sectional, non-probabilistic sampling study. We included patients with chronic leg ulcers being treated for at least 3 months. A sociodemographic and clinical survey was conducted to assess the profile of the ulcers. We administered a screening for depressive symptoms and the Dermatology Life Quality Index. We performed a descriptive statistical analysis, chi-square test and Mann-Whitney test for categorical data, Pearson for numeric variables, and multiple regression for categorical data.RESULTS:Forty-one patients were assessed. Their mean age was 61.78 years. Venous ulcers (48.8%) were the most prevalent. Seventy-three percent of the sample perceived no impact/low impact on quality of life in the past week, and 26.8% perceived moderate/high impact. A multiple regression analysis identified the causes of lesion, pain related to the ulcers, time of onset, and severity of the depressive symptoms as the variables that had an influence on quality of life.CONCLUSIONS:The majority of the sample perceived low or no impact of the condition on the quality of the life. The variables etiology of the lesion (p<0.001), pain related to the ulcers (p=0.001), time of onset (p=0.006), and severity of the depressive symptoms (p<0.001) had an influence on the quality of life, suggesting the need for further studies with more robust designs to confirm the causal relationship between these characteristics and quality of life.

Effects of fixed night shift work on 24 hour blood pressure regulation, state anxiety levels and total sleep time

Nearly 22 million Americans operate as shift workers, and shift work has been linked to the development of cardiovascular disease (CVD). This study is aimed at identifying pivotal risk factors of CVD by assessing 24 hour ambulatory blood pressure, state anxiety levels and sleep patterns in 12 hour fixed shift workers. We hypothesized that night shift work would negatively affect blood pressure regulation, anxiety levels and sleep patterns. A total of 28 subjects (ages 22-60) were divided into two groups: 12 hour fixed night shift workers (n=15) and 12 hour fixed day shift workers (n=13). 24 hour ambulatory blood pressure measurements (Space Labs 90207) were taken twice: once during a regular work day and once on a non-work day. State anxiety levels were assessed on both test days using the Speilberger’s State Trait Anxiety Inventory. Total sleep time (TST) was determined using self recorded sleep diary. Night shift workers demonstrated increases in 24 hour systolic (122 ± 2 to 126 ± 2 mmHg, P=0.012); diastolic (75 ± 1 to 79 ± 2 mmHg, P=0.001); and mean arterial pressures (90 ± 2 to 94 ± 2mmHg, P<0.001) during work days compared to off days. In contrast, 24 hour blood pressures were similar during work and off days in day shift workers. Night shift workers reported less TST on work days versus off days (345 ± 16 vs. 552 ± 30 min; P<0.001), whereas day shift workers reported similar TST during work and off days (475 ± 16 minutes to 437 ± 20 minutes; P=0.231). State anxiety scores did not differ between the groups or testing days (time*group interaction P=0.248), suggesting increased 24 hour blood pressure during night shift work is related to decreased TST, not short term anxiety. Our findings suggest that fixed night shift work causes disruption of the normal sleep-wake cycle negatively affecting acute blood pressure regulation, which may increase the long-term risk for CVD.

50 Years Ago We Marched: What began on the grounds of Lincoln University, ended on the steps of the Alabama State Capitol

LINCOLN UNIVERSITY - On March 25, 1965, a bus loaded with Lincoln University students and staff arrived in Montgomery, Ala. to join the Selma march for racial and voting equality. Although the Civil Rights Act of 1964 was in force, African-Americans continued to feel the effects of segregation. The 1960s was a decade of social unrest and change. In the Deep South, specifically Alabama, racial segregation was a cultural norm resistant to change. Governor George Wallace never concealed his personal viewpoints and political stance of the white majority, declaring “Segregation now, segregation tomorrow, segregation forever.” The march was aimed at obtaining African-Americans their constitutionally protected right to vote. However, Alabama’s deep-rooted culture of racial bias began to be challenged by a shift in American attitudes towards equality. Both black and whites wanted to end discrimination by using passive resistance, a movement utilized by Dr. Martin Luther King Jr. That passive resistance was often met with violence, sometimes at the hands of law enforcement and local citizens. The Selma to Montgomery march was a result of a protest for voting equality. The Student Nonviolent Coordinating Committee (SNCC) and the Southern Christian Leadership Counsel (SCLC) among other students marched along the streets to bring awareness to the voter registration campaign, which was organized to end discrimination in voting based on race. Violent acts of police officers and others were some of the everyday challenges protesters were facing. Forty-one participants from Lincoln University arrived in Montgomery to take part in the 1965 march for equality. Students from Lincoln University’s Journalism 383 class spent part of their 2015 spring semester researching the historical event. Here are their stories: Peter Kellogg “We’ve been watching the television, reading about it in the newspapers,” said Peter Kellogg during a February 2015 telephone interview. “Everyone knew the civil rights movement was going on, and it was important that we give him (Robert Newton) some assistance … and Newton said we needed to get involve and do something,” Kellogg, a lecturer in the 1960s at Lincoln University, discussed how the bus trip originated. “That’s why the bus happened,” Kellogg said. “Because of what he (Newton) did - that’s why Lincoln students went and participated.” “People were excited and the people along the sidewalk were supportive,” Kellogg said. However, the mood flipped from excited to scared and feeling intimidated. “It seems though every office building there was a guy in a blue uniform with binoculars standing in the crowd with troops and police. And if looks could kill me, we could have all been dead.” He says the hatred and intimidation was intense. Kellogg, being white, was an immediate target among many white people. He didn’t realize how dangerous the event in Alabama was until he and the others in the bus heard about the death of Viola Liuzzo. The married mother of five from Detroit was shot and killed by members of the Ku Klux Klan while shuttling activists to the Montgomery airport. “We found out about her death on the ride back,” Kellogg recalled. “Because it was a loss of life, and it shows the violence … we could have been exposed to that danger!” After returning to LU, Kellogg’s outlook on life took a dramatic turn. Kellogg noted King’s belief that a person should be willing to die for important causes. “The idea is that life is about something larger and more important than your own immediate gratification, and career success or personal achievements,” Kellogg said. “The civil rights movement … it made me, it made my life more significant because it was about something important.” The civil rights movement influenced Kellogg to change his career path and to become a black history lecturer. Until this day, he has no regrets and believes that his choices made him as a better individual. The bus ride to Alabama, he says, began with the actions of just one student. Robert Newton Robert Newton was the initiator, recruiter and leader of the Lincoln University movement to join Dr. Martin Luther King’s march in Selma. “In the 60s much of the civil rights activists came out of college,” said Newton during a recent phone interview. Many of the events that involved segregation compelled college students to fight for equality. “We had selected boycotts of merchants, when blacks were not allowed to try on clothes,” Newton said. “You could buy clothes at department stores, but no blacks could work at the department stores as sales people. If you bought clothes there you couldn’t try them on, you had to buy them first and take them home and try them on.” Newton said the students risked their lives to be a part of history and influence change. He not only recognized the historic event of his fellow Lincolnites, but also recognized other college students and historical black colleges and universities who played a vital role in history. “You had the S.N.C.C organization, in terms of voting rights and other things, including a lot of participation and working off the bureau,” Newton said. Other schools and places such as UNT, Greenville and Howard University and other historically black schools had groups that came out as leaders. Newton believes that much has changed from 50 years ago. “I think we’ve certainly come a long way from what I’ve seen from the standpoint of growing up outside of Birmingham, Alabama,” Newton said. He believes that college campuses today are more organized in their approach to social causes. “The campus appears to be some more integrated amongst students in terms of organizations and friendships.” Barbara Flint Dr. Barbara Flint grew up in the southern part of Arkansas and came to Lincoln University in 1961. She describes her experience at Lincoln as “being at Lincoln when the world was changing.“ She was an active member of Lincoln’s History Club, which focused on current events and issues and influenced her decision to join the Selma march. “The first idea was to raise some money and then we started talking about ‘why can’t we go?’ I very much wanted to be a living witness in history.” Reflecting on the march and journey to Montgomery, Flint describes it as being filled with tension. “We were very conscious of the fact that once we got on the road past Tennessee we didn’t know what was going to happen,” said Flint during a February 2015 phone interview. “Many of the students had not been beyond Missouri, so they didn’t have that sense of what happens in the South. Having lived there you knew the balance as well as what is likely to happen and what is not likely to happen. As my father use to say, ‘you have to know how to stay on that line of balance.’” Upon arriving in Alabama she remembers the feeling of excitement and relief from everyone on the bus. “We were tired and very happy to be there and we were trying to figure out where we were going to join and get into the march,” Flint said. “There were so many people coming in and then we were also trying to stay together; that was one of the things that really stuck out for me, not just for us but the people who were coming in. You didn’t want to lose sight of the people you came with.” Flint says she was keenly aware of her surroundings. For her, it was more than just marching forward. “I can still hear those helicopters now,” Flint recalled. “Every time the helicopters would come over the sound would make people jump and look up - I think that demonstrated the extent of the tenseness that was there at the time because the helicopters kept coming over every few minutes.” She said that the marchers sang “we are not afraid,” but that fear remained with every step. “Just having been there and being a witness and marching you realize that I’m one of those drops that’s going to make up this flood and with this flood things will move,” said Flint. As a student at Lincoln in 1965, Flint says the Selma experience undoubtedly changed her life. “You can’t expect to do exactly what you came to Lincoln to do,” Flint says. “That march - along with all the other marchers and the action that was taking place - directly changed the paths that I and many other people at Lincoln would take.” She says current students and new generations need to reflect on their personal role in society. “Decide what needs to be done and ask yourself ‘how can I best contribute to it?’” Flint said. She notes technology and social media can be used to reach audiences in ways unavailable to her generation in 1965. “So you don’t always have to wait for someone else to step out there and say ‘let’s march,’ you can express your vision and your views and you have the means to do so (so) others can follow you. Jaci Newsom Jaci Newsom came to Lincoln in 1965 from Atlanta. She came to Lincoln to major in sociology and being in Jefferson City was largely different from what she had grown up with. “To be able to come into a restaurant, sit down and be served a nice meal was eye-opening to me,” said Newsom during a recent interview. She eventually became accustomed to the relaxed attitude of Missouri and was shocked by the situation she encountered on an out-of-town trip. “I took a bus trip from Atlanta to Pensacola and I encountered the worse racism that I have ever seen. I was at bus stop, I went in to be served and they would not serve me. There was a policeman sitting there at the table and he told me that privately owned places could select not to serve you.” Newsom describes her experience of marching in Montgomery as being one with a purpose. “We felt as though we achieved something - we felt a sense of unity,” Newsom said. “We were very excited (because) we were going to hear from Martin Luther King. To actually be in the presence of him and the other civil rights workers there was just such enthusiasm and excitement yet there was also some apprehension of what we might encounter.” Many of the marchers showed their inspiration and determination while pressing forward towards the grounds of the Alabama Capitol building. Newsom recalled that the marchers were singing the lyrics “ain’t gonna let nobody turn me around” and “we shall overcome.” “ I started seeing people just like me,” Newsom said. “I don’t recall any of the scowling, the hitting, the things I would see on TV later. I just saw a sea of humanity marching towards the Capitol. I don’t remember what Martin Luther King said but it was always the same message: keep the faith; we’re going to get where we’re going and let us remember what our purpose is.” Newsom offers advice on what individuals can do to make their society a more productive and peaceful place. “We have come a long way and we have ways to change things that we did not have before,” Newsom said. “You need to work in positive ways to change.” Referencing the recent unrest in Ferguson, Mo., she believes that people become destructive as a way to show and vent anger. Her generation, she says, was raised to react in lawful ways – and believe in hope. “We have faith to do things in a way that was lawful and it makes me sad what people do when they feel without hope, and there is hope,” Newsom says. “Non-violence does work - we need to include everyone to make this world a better place.” Newsom graduated from Lincoln in 1969 and describes her experience at Lincoln as, “I grew up and did more growing at Lincoln than I think I did for the rest of my life.”