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Conjugated block copolymers provide a pathway to achieve thermally stable nanostructured thin films for organic solar cells. We characterized the structural evolution of poly(3-hexylthiophene)-block-poly(diketopyrrolopyrrole-terthiophene) (P3HT-b-DPPT-T) from solution to nanostructured thin films. Aggregation of the DPPT-T block of P3HT-b-DPPT-T was found in solution by small-angle X-ray scattering with the P3HT block remaining well-solvated. The nanostructure in thin films was determined using a combination of wide and small-angle X-ray scattering techniques as a function of processing conditions. The structure in solution controlled the initial nanostructure in spin-cast thin films, allowing subsequent thermal annealing processes to further improve the ordering. In contrast to the results for thin films, nanostructural ordering was not observed in the bulk samples by small-angle X-ray scattering. These results suggest the importance of controlling solvent induced aggregation in forming nanostructured thin films of conjugated block copolymers.

The surface properties and self-adhesion mechanism of self-healing poly(butyl acrylate) (PBA) copolymers containing comonomers with 2-ureido-4[1H]-pyrimidinone quadruple hydrogen bonding groups (UPy) are investigated using a surface forces apparatus (SFA) coupled with a top-view optical microscope. The surface energies of PBA-UPy4.0 and PBA-UPy7.2 (with mole percentages of UPy 4.0% and 7.2%, respectively) are estimated to be 45-56 mJ m-2 under dry condition by contact angle measurements using a three probe liquid method and also by contact and adhesion mechanics tests, as compared to the reported literature value of 31-34 mJ m-2 for PBA, an increase that is attributed to the strong UPy-UPy H-bonding interactions. The adhesion strengths of PBA-UPy polymers depend on the UPy content, contact time, temperature and humidity level. Fractured PBA-UPy films can fully recover their self-adhesion strength to 40, 81, and 100% in 10 s, 3 h, and 50 h, respectively, under almost zero external load. The fracture patterns (i.e., viscous fingers and highly "self-organized" parallel stripe patterns) have implications for fabricating patterned surfaces in materials science and nanotechnology. These results provide new insights into the fundamental understanding of adhesive mechanisms of multiple hydrogen-bonding polymers and development of novel self-healing and stimuli-responsive materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Objectives: The aim of this prospective, multi-center, practice-based cohort study was to analyze factors associated with the success of implant supported all-ceramic single-unit crowns, made by computer-aided-design/computer-aided-manufacturing (CAD-CAM)., Methods: All-ceramic crowns placed in a private practice-based research network (Ceramic Success Analysis, AG Keramik) were analyzed. Data from 567patients with CAD-CAM implant supported all-ceramic crowns placed between 2008-2023 by 54dentists were evaluated. Firstly, all crowns with at least one follow-up control were included (n = 907). Secondly, all crowns being followed up for ≥ 5years and all failures were included (n = 151). At the latest follow-up visit, crowns were considered as successful (not failed) if they were still in function without the need for additional therapy. Multi-level Cox proportional hazards models were used to evaluate the association between a range of predictors and time of success., Results: Within a mean follow-up period (SD) of 2.5 (2)years (first scenario) and 6.2 (1.2)years (second scenario) [maximum:12years], 27crowns failed (annual failure rate [AFR]:0.74 %). The main failure types were decementation, (n = 11), fracture of the ceramic (n = 4) or Ti-Base (n = 4). In 5-year-scenario, crowns fabricated in the laboratory had 26times lower failure rate than those fabricated chairside (95 %CI:0.0-0.7;p = 0.038). Furthermore, the use of a silane (HR:0.051;95 %CI:0.0-0.5;p = 0.014) and etching of the ceramic (HR:0.053;95 %CI:0.0-0.8;p = 0.035) resulted in a significantly higher risk for failure than their non-use., Significance: For CAD-CAM manufactured implant supported all-ceramic crowns, high success rates were found in up to 12-year evaluation. Furthermore, after 5years, no patient-or implant-level factors, but operative-level factor (i.e.fabrication method, use of silane/etching) were significantly associated with failure. The study was registered in the German Clinical Trials Register (DRKS-ID: DRKS00020271)., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Objectives: This retrospective, single-center, practice-based cohort study aimed to analyze factors associated with the success of removable partial dentures retained by telescopic crowns (TRPD)., Materials and Methods: TRPD which were placed in a single practice of a practice-based research network were analyzed. Data from 139 patients (age (SD): 66 (11) years; 66 female) with 174 TRPD including 488 non-precious alloy telescopic crowns (TC) between 2004 and 2016 were included. TC without any technical complication were considered as successful, and as survived, if they were still in function at the last check-up. Multilevel Cox proportional hazard models were used to evaluate the association between clinical factors and time until failure., Results: Within a mean follow-up period (SD) of 4.2 (3.3) years (min-max: 1 day-12 years), 372 (76%) TC (AFR 5years,TC-level : 5.0%) as well as 136 (87%) TRPD (AFR 5years,TRPD-level : 5.1%) ("worst-case scenario") and 150 (86%) TRPD (AFR 5years,TRPD-level : 3.4%) ("best-case scenario") were considered as successful. The main failure types were recementation (n = 39), endodontic treatment (n = 36), and extraction (n = 35). TC in male patients showed 1.6 times higher risk for failure than in female patients (95%CI: 1.1-2.4; p = 0.023). TC on premolars showed 2.2 times higher risk for failure than on incisors (95%CI: 1.1-5.0; p = 0.023) and TC in dentures with ≤ 3TC showed 2.1 times higher risk for failure than TC in dentures with > 3TC (1.3-3.4; p = 0.042). Furthermore, TC on the most distal tooth in an arch showed 2.4 times higher risk for failure than TC on a more mesial tooth (1.5-3.8; p < 0.001)., Conclusion: For removable partial dentures retained by telescopic crowns, high success rates could be found after up to 12 years. Patient-level and tooth-level factors were significantly associated with failure., Clinical Relevance: For removable partial dentures retained by telescopic crowns, high success rates could be found after up to 12 years. Patient-level and tooth-level factors were significantly associated with failure., (© 2023. The Author(s).)

Objectives: The aim of this prospective, multi-center, practice-based cohort study was to analyze factors associated with the success of all-ceramic crowns., Methods: All-ceramic crowns placed in a practice-based research network ([Ceramic Success Analysis, AG Keramik) were analyzed. Data from 1254 patients with (mostly in-office CAD/CAM) all-ceramic crowns placed by 101 dentists being followed up for more than 5 years were evaluated. At the last follow-up visit crowns were considered as successful (not failed) if they were sufficient, whereas crowns were considered as survived (not lost) if they were still in function. Multi-level Cox proportional hazards models were used to evaluate the association between a range of predictors and time of success or survival., Results: Within a mean follow-up period (SD) of 7.2(2)years [maximum:15years] 776 crowns were considered successful (annual failure rate[AFR]:8.4%) and 1041 crowns survived (AFR:4.9%). The presence of a post in endodontically treated teeth resulted in a risk for failure 2.7 times lower than that of restorations without a post (95%CI:1.4-5.0;p = 0.002). Regarding the restorative material and adhesive technique, hybrid composite ceramics and single-step adhesives showed a 3.4 and 2.2 times higher failure rate than feldspathic porcelain and multi-step adhesives, respectively (p < 0.001). Use of an oxygen-blocking gel as well as an EVA instrument resulted in a 1.5-1.8 times higher failure rate than their non-use (p ≤ 0.001)., Significance: After up to 15years AFR were rather high for all-ceramic crowns. Operative factors, but no patient- or tooth-level factors were significantly associated with failure. The study was registered in the German Clinical Trials Register (DRKS-ID: DRKS00020271)., (Copyright © 2021 The Author(s). Published by Elsevier Inc. All rights reserved.)

Background: Femur fracture patients require significant in-hospital care. The burden incurred by caregivers of such patients amplifies the direct costs of these injuries and remains unquantified., Aim: Here we aim to establish the in-hospital economic burden faced by informal caregivers of femur fracture patients., Methods: 70 unique caregivers for 46 femoral shaft fracture patients were interviewed. Incurred economic burden was determined by the Human Capital Approach, using standardized income data to quantify productivity loss (in $USD). Linear regression assessed the relationship between caregiver burden and patient time-in-hospital., Results: The average economic burden incurred was $149, 9% of a caregiver's annual income and positively correlated with patient time in hospital (p<0.01)., Conclusion: Caregivers of patients treated operatively for femur fractures lost a large portion of their annual income, and this loss increased with patient time in hospital. These indirect costs of femur fracture treatment constitute an important component of the total injury burden., (© 2021 The College of Medicine and the Medical Association of Malawi.)

Objectives: We evaluated the initial and follow-up treatment costs of different post-restorations in a practice-based German healthcare setting., Methods: A total of 139 incisors, canines, or premolars received post-restorations placed by eight general dental practitioners in Germany, and were followed over a mean ± SD 7.1 ± 4.5 years. Preformed metal (MP, n = 68), glass-fiber (GF, n = 28), or cast post-and-core buildups (MC, n = 23) had been used to retain crowns or bridge anchors. Preformed metal and glass-fiber had also been used to retain directly built up post-retained composite restorations (PC, n = 20). Material and treatment costs for the initial post-restorations as well as restorative, endodontic, or surgical re-treatments were estimated from a public-payer-perspective in Germany. Associations between total and annualized total costs and covariates were assessed using generalized linear modeling. The study was registered in the German Clinical Trials Register (DRKS-ID: DRKS00012938)., Results: MC showed highest initial treatment costs (557.23 Euro), but the least re-treatments (6/23, 26%), while PC showed lowest initial costs (203.52 Euro) but the most re-treatments (11/20, 55%). Costs for MP/GF post-crowns were initially similarly costly (496.47/496.87 Euro), and both also showed similar re-treatments (35%/36%). The overall annual failure rate was 5.2% (MC: 3.5%, MP: 4.6%, GF: 5.3%, PC: 10.3%). Including costs for the resulting re-treatments, mean total costs were 591.66 Euro (MC), 548.31 Euro (MP), 526.37 Euro (GF), and 361.81 Euro (PC). Annualized total costs were 171.36 Euro (MC), 141.75 Euro (MP), 146.12 Euro (GF), and 135.65 Euro (PC). Total and annualized total costs were highest for MC, with PC being the significantly less costly option (p < 0.001)., Conclusions: Within German healthcare, both initial and follow-up costs for post-restorations were considerable. Saving costs initially may, at least partially, be offset by more complications long-term., Clinical Relevance: Dentists need to be aware that the placement of posts is not only initially costly but also comes with significant long-term costs for treating occurring complications. This should be communicated with patients and considered during treatment planning.

Introduction: The aims of this multicenter, practice-based cohort study were to evaluate the success and survival of endodontically treated teeth with post restorations (ETT+Ps) and to analyze factors associated with the longevity of ETT+Ps., Methods: Eight general dental practitioners each placed up to 27 ETT+Ps without any restriction to post materials or dimensions. Only incisors, canines, and premolars were included. At the last follow-up visit, ETT+Ps were considered as successful if the post and the initially placed definitive restoration were sufficient, whereas ETT+Ps were considered as survived if the post was still in function. Multilevel Cox proportional hazards models were used to evaluate the association between a range of predictors and time until no success and no survival., Results: Overall, 195 endodontic posts in 195 patients were followed up for a mean (95% confidence interval) of 91 (81-101) months; the longest follow-up was 15 years. Of these, 122 ETT+Ps were considered successful (estimated success time = 110 [101-120] months), and 152 ETT+Ps survived [estimated survival time = 133 [124-141] months). Regarding the categories of success and survival, the annual failure rates were 6.0% and 3.3%, respectively. Recementation of old (telescopic) crowns after placing new posts was the only significant predictor for decreased time until failure for both success and survival analyses. By excluding recemented restorations, annual failure rates decreased to 3.5% and 2.1%, respectively., Conclusions: For EET+Ps placed in a private practice setting, high success and survival rates were observed. If old (telescopic) crowns were recemented after new posts were placed, the high risk of subsequent failure should be considered and communicated with patients., (Copyright © 2020 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.)

The aim of this retrospective noninterventional multicenter practice-based study was to analyze factors influencing the survival of direct restorations. Records from patients who visited 5 private practices regularly were searched for the presence of direct restorations. Data were recorded from 7,858 patients with 27,407 direct restorations being detected at least 6 mo before the last recall visit. Multilevel Cox proportional hazard models were used to evaluate the association between clinical factors and time until failure. Within 228 mo, 5,493 failures could be observed. Median survival time was 207 mo. The annual failure rates were 3.8%, 4.0%, 4.6%, 4.9%, and 3.9% for class I, II, III, IV, and V restorations, respectively. Class II and IV restorations showed a 1.1-times (95% CI, 1.0 to 1.2) and 1.2-times (95% CI, 1.1 to 1.2) higher failure rate than class I restorations ( P ≤ 0.029). Patients aged <20 y and >60 y showed up to a 1.4-times higher failure rate than patients aged 20 to 60 y ( P ≤ 0.015). Restorations that underwent check-up twice a year or more showed a significantly higher failure rate than those that did so less than twice a year ( P < 0.001). Furthermore, the dentists significantly influenced time until failure ( P < 0.001). Regarding the restorative material, composites showed up to a 2.1-times longer time until failure than GIC ( P ≤ 0.020). Moderate failure rates were observed for direct restorations in the private practice setting after up to 18.5 y. Within the limitations of the present study, several factors on the levels of practice (i.e., dentist), patient (i.e., age), and tooth (i.e., restorative material, restored surfaces according to the classification of Black) were significant predictors for the failure rate. Therefore, treatment decision should take into account most relevant factors (German Clinical Trials Register DRKS00015228).

Background and Objective: During routine patient care practitioners have to document several aspects. However, currently it is difficult to methodically analyze the longevity of therapeutic concepts in dental private practice. Thus, the aim of the present paper was to introduce a software (Dentareport) to compare the success of different treatment options and to identify risk factors for failures in dental patient care., Methods: Dentareport has a digital interface to automatically collect data of electronic patient files of practice management programs. By using computer-aided routines descriptive analyses of the treatments can be visualized. Dentareport also visually displays a bivariate risk factor analysis of treatment options. For this, crude associations between baseline characteristics (e.g. age) and time until failure (e.g. tooth loss) are calculated for the chosen treatment option by fitting separate models for each baseline characteristic as the independent variable. Furthermore, annual failure rates and survival graphs can be displayed., Results: The software has already been used to self-analyze treatment decisions. It highlighted the most long-lasting treatments for specific indications. Risk factors on practice-, patient- and tooth-level were easily identified. Furthermore, the software has been used to collect data for analysis of retrospective practice-based, mono-as well as multi-center observational studies., Conclusions: By using Dentareport practitioners can easily and objectively self-analyze treatment successes and risk factors. Furthermore, for researchers the software easily generates huge data sets in different fields in dentistry and enables the analysis on a multi-center level. Most relevant factors can, thus, be taken into account for treatment decisions., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Aim: This prospective, noninterventional, multi-centre, practice-based study aimed to evaluate the longevity of endodontically treated teeth (ETT) restored with posts and to analyse factors influencing the success and survival of endodontic posts., Methodology: Eight general dental practitioners each placed up to 27 endodontic posts without any restriction to size and material. Teeth were restricted to incisors, canines and premolars. Multi-level Cox proportional hazards models were used to evaluate the association between clinical factors and time until failure., Results: A total of 195 endodontic posts were followed-up for up to 6.5 years in 195 patients. Of these, 140 posts were judged as successful [mean success time: 59 (55-63) months]; the mean annual failure rate was 8.6%. This decreased to 4.4% when excluding recementations. 152 posts survived [mean survival time: 64 (60-67) months]. Recemented restorations had an eight times higher failure rate compared with new restorations. Furthermore, restorations with glass fibre post had a significantly lower success rate compared with titanium posts., Conclusion: Relatively low success and survival rates occurred for restorations with posts after root canal treatment in a private practice setting after a follow-up of up to 6.5 years. Recemented crowns had a high risk of failure., (© 2018 International Endodontic Journal. Published by John Wiley & Sons Ltd.)

Aim: The aim of this prospective, non-interventional, multi-center, practice-based study was, firstly, to evaluate the longevity of composite build-ups in endodontically treated teeth (ETT) without post placement and, secondly, to analyze factors influencing the success of these composite build-ups., Methodology: Each of seven general dental practitioners placed up to 50 composite build-ups without additional posts in ETT. Teeth were restricted to incisors, canines, and premolars. Several clinical data were recorded for 192 coronal restorations on ETT in 192 patients. Cox proportional hazard models were applied to analyze associations between clinical factors and time until failure., Results: Within a follow-up period of 10 years, 167 restorations were judged as successful [mean success time, 110 (105-115) months] and 180 teeth survived [mean survival time, 114 (110-119) months]. The main failure type was fracture of the restoration (n = 15). The annual failure rate was 2.4%. In bivariate Cox regression, both factors such as number of restored tooth surfaces and adhesive were significantly associated with the failure rate. In multivariate Cox proportional hazards regression, none of the investigated factors were significantly associated with the failure rate., Conclusion: For composite build-ups in ETT without post placement, high success rates could be found after up to 10 years of observation time. Within the limitations of the present study, none of the analyzed factors such as "tooth type" or "number of restored tooth surfaces" was a significant predictor for the failure rate., Clinical Relevance: Endodontically treated teeth can be successfully directly restored with composite build-ups even when no additional post is inserted., Trial Registration: The study was registered in the German Clinical Trials Register (DRKS-ID: DRKS00012882).

Objectives: The aim of this retrospective, non-interventional, multi-center, practice-based study was to analyze factors influencing the survival of restorative treatments of one- and two-surface active cervical (root) caries lesions (CCLs)., Methods: Records from patients who visited five private practices regularly were searched for the presence of active one- and two-surface CCLs. Data from 1167 patients with 2070 CCLs being detected at least 6 months before the last recall visit were recorded. Kaplan-Meier-analyses were used to analyze time-to-failure. Cox proportional hazards models were used to evaluate the association between clinical factors and time until failure., Results: Within 120 months [mean (SD) follow-up period:50 (40) months] 219 failures could be observed. Median survival time was 120 months. The AFR was 1.82% for one-surface restorations (CCL 1 ) and 3.25% for two-surface restorations (CCL 2 ). In multivariate Cox regression two-surface cervical restorations showed 1.75 times higher failure rates than one-surface cervical restoration. Furthermore, CCL being checked up more than twice a year showed significantly higher failure rates than restorations being checked up less than twice a year (p < 0.001)., Conclusion: Low failure rates could be found for restorative treatment strategies of one- as well as for two-surface CCLs., Clinical Significance: Restorative treatment of CCLs is a viable way to manage one-surface CCLs. However, the proximal extension of the CCL significantly shortens the longevity of the restoration. The study was registered in the German Clinical Trials Register (DRKS-ID: DRKS00012510)., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Background: Violent injury is the second most common cause of death among 15- to 24-year olds in the US. Up to 58% of violently injured youth return to the hospital with a second violent injury. Hospital-based violence intervention programs (HVIPs) have been shown to reduce injury recidivism through intensive case management. However, no validated guidelines for risk assessment strategies in the HVIP setting have been reported. We aimed to use qualitative methods to investigate the key components of risk assessments employed by HVIP case managers and to propose a risk assessment model based on this qualitative analysis., Materials and Methods: An established academic hospital-affiliated HVIP served as the nexus for this research. Thematic saturation was reached with 11 semi-structured interviews and two focus groups conducted with HVIP case managers and key informants identified through snowball sampling. Interactions were analyzed by a four-member team using Nvivo 10, employing the constant comparison method. Risk factors identified were used to create a set of models presented in two follow-up HVIP case managers and leadership focus groups., Results: Eighteen key themes within seven domains (environment, identity, mental health, behavior, conflict, indicators of lower risk, and case management) and 141 potential risk factors for use in the risk assessment framework were identified. The most salient factors were incorporated into eight models that were presented to the HVIP case managers. A 29-item algorithmic structured professional judgment model was chosen., Conclusions: We identified four tiers of risk factors for violent reinjury that were incorporated into a proposed risk assessment instrument, VRRAI., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Objectives: The aim of this retrospective, non-interventional clinical study was to analyze factors influencing the survival of restorative treatments of active cervical (root) caries lesions (aCCLs) and the success of non-invasive treatment options of inactive cervical (root) caries lesions (iCCLs)., Material and Methods: Records from patients who visited a single private practice regularly were searched for the presence of solely buccal CCLs. Data from 345 aCCLs and 232 iCCLs being detected at least 6 months before the last recall visit in 295 patients were recorded. Kaplan-Meier analyses were used to analyze time to failure in both groups. Cox proportional hazards models were used to evaluate the association between clinical factors and time until failure., Results: Within 120 months, 20 aCCLs had received a second restorative follow-up treatment. For iCCLs, 35 lesions had to be restored within 120 months. Median survival/success time was 111 months for aCCLs (annual failure rate 1.7%) and 120 months for iCCLs (annual "restoration" rate 4.3%). In multivariate Cox regression, active and inactive CCLs being checked up more than twice a year showed significantly higher failure/restoration rates than CCLs being checked up less than twice a year (p < 0.001)., Conclusion: Low failure/restoration rates could be found for both treatment strategies for CCLs, and only the "number of check-ups per year" was significantly positively associated with failures., Clinical Relevance: Caries monitoring is a viable way to manage CCLs. However, individual check-up interval should be defined carefully, since higher rate of check-ups seems to lead to increased intervention rates in the management of CCLs. The study was registered in the German Clinical Trials Register (DRKS-ID: DRKS00010003).

Background: Femoral shaft fractures are one of the most common injuries seen by surgeons in low- and middle-income countries (LMICs). Surgical repair in LMICs is often dismissed as not being cost-effective or unsafe, though little evidence exists to support this notion. Therefore, the goal of this study is to determine the cost of intramedullary nailing of femoral shaft fractures in Tanzania., Methods: We used micro-costing methods to estimate the fixed and variable costs of intramedullary nailing of femoral shaft fractures. Variable costs assessed included medical personnel costs, ward personnel costs, implants, medications, and single-use supplies. Fixed costs included costs for surgical instruments and administrative and ancillary staff., Results: 46 adult femoral shaft fracture patients admitted to Muhimbili Orthopaedic Institute between June and September 2014 were enrolled and treated with intramedullary fixation. The total cost per patient was $530.87 (SD $129.99). The mean variable cost per patient was $419.87 (SD $129.99), the largest portion coming from ward personnel $144.47 (SD $123.30), followed by implant $134.10 (SD $15.00) medical personnel $106.86 (SD $28.18), and medications/supplies $30.05 (SD $12.28). The mean fixed cost per patient was $111.00, consisting of support staff, $103.50, and surgical instruments, $7.50., Conclusions: Our study provides empirical information on the variable and fixed costs of intramedullary nailing of femoral shaft fractures in LMICs. Importantly, the lack of surgical capacity was the primary driver of the largest cost for this procedure, preoperative ward personnel time. Our results provide the cost data for a formal cost-effectiveness analysis on this intervention.

We present experimental and theoretical investigations of the order-disorder transition (ODT) in thin films of cylinder-forming diblock copolymers with asymmetric wetting conditions. Grazing incidence small-angle X-ray scattering (GISAXS) was implemented to determine the ODT temperatures (TODT) for poly(styrene-b-2-vinyl pyridine) (PS-P2VP) block copolymer thin films on a P2VP-preferential silicon substrate. Specifically, films consisting of multilayers of horizontally-oriented cylindrical structures (from 1- to 9-layers) were tested. We find that films with more than 2 cylindrical layers have a TODT comparable to the bulk case. However, TODT decreases as the film becomes thinner and the monolayer system has an ODT 30 °C below the bulk. Using self-consistent field theory (SCFT), we studied the ordering in corresponding thin films with asymmetric (top and bottom surface) wetting conditions. Surprisingly, SCFT is found to predict an opposite trend in TODT with film thickness than observed experimentally. Field-theoretic simulations with complex Langevin sampling were employed to resolve this discrepancy and demonstrate that thermal fluctuations in the PS-P2VP thin-film system dominate its ordering behavior in monolayer and bilayer films.

Purpose: The use of traction for treatment of femoral shaft fractures remains common in low- and middle-income countries (LMICs). The objective of this study is to systematically review the literature on outcomes of traction as definitive treatment for adult femoral shaft fractures in LMICs., Methods: Using the recommended PRISMA methods for systematic reviews, MEDLINE, EMBASE, LILACS, and AJOL were searched for relevant publications. Results were limited to studies occurring in LMICs as defined by the World Bank. Data on time spent in traction (TT), length of stay (LOS), time to partial weight bearing (PWB), complication incidences, and a total complication incidence were recorded., Results: Of the 693 initial results, nine were eligible for analysis giving a total of 455 unique patients with a mean age of 32.9 years (range: 0 to 96). The average time spent in traction was 52.8 days (range: 19.8 to 122.5), the average length of stay was 55.4 days (range: 45 to 140), and the average time to partial weight bearing was 52.2 days (range: 42 to 60 days). There were a total of 91 malunions, 25 un-united fractures, 60 infections, 45 other complications, giving a total of 221 complications in 455 patients., Conclusions: The use of traction in treating femoral shaft fractures is associated with a high incidence of complications and prolonged course of treatment. Although operative stabilization may be a better alternative, comparative studies are needed to assess whether this can be achieved in a safe and cost-effective manner for widespread application in LMICs.

Nanolayered lamellae are common structures in nanoscience and nanotechnology, but most are nearly symmetric in layer thickness. Here, we report on the structure and mechanics of highly asymmetric and thermodynamically stable soft-hard lamellar structures self-assembled from optimally designed PS1-(PI-b-PS2)3 miktoarm star block copolymers. The remarkable mechanical properties of these strong and ductile PS (polystyrene)-based nanomaterials can be tuned over a broad range by varying the hard layer thickness while maintaining the soft layer thickness constant at 13 nm. Upon deformation, thin PS lamellae (<100 nm) exhibited kinks and predamaged/damaged grains, as well as cavitation in the soft layers. In contrast, deformation of thick lamellae (>100 nm) manifests cavitation in both soft and hard nanolayers. In situ tensile-SAXS experiments revealed the evolution of cavities during deformation and confirmed that the damage in such systems reflects both plastic deformation by shear and residual cavities. The aspects of the mechanics should point to universal deformation behavior in broader classes of asymmetric hard-soft lamellar materials, whose properties are just being revealed for versatile applications.

In addition to the traditional parameters of chi (χ) and degree of polymerization ( N ), we demonstrate that the segregation strength of a diblock copolymer can be increased by introduction of an ionic unit at the junction of the two blocks. Compared to neutral linking groups, the electrostatic interactions between counterions of adjacent domain junctions leads to increased enthalpy, segregation strength, and phase separation. As a result, the order disorder transition temperatures of block copolymers with a 1,2,3-triazolium ionic junction were observed to be significantly higher than the corresponding neutral block copolymers. To demonstrate the potential of block copolymers with ionic junctions for nanopatterning, block copolymers were prepared by click coupling of homopolymers and then used to fabricate well-defined sub-10 nm line features. We believe that the concept of improved thin-film assembly through the introduction of ionic junctions is a powerful tool for block copolymer lithography and complements chi (χ) and degree of polymerization ( N ) in the design of macromolecular systems with enhanced phase separation.

We demonstrate that small domain features (∼13 nm) can be obtained in a series of polystyrene (PS) and poly(lactic acid) (PLA) block copolymers, PS-(PLA) 2 and (PS) 2 -(PLA) 2 , that combine miktoarm molecular architectures with large interaction parameters. To supplement the experimental work, we used self-consistent field theory in tandem with the random phase approximation to explore and contrast the phase behavior of AB n and A n B n types of miktoarm block copolymers. Specifically, AB 2 and A 2 B 2 were found to be effective molecular architectures for inducing strong shifts in phase boundaries with copolymer composition and to simultaneously tune domain feature sizes. The performance of these systems is markedly different from the corresponding linear diblock copolymers and indicates the potential of macromolecular architecture control for future applications in lithography.

We report the creation of highly asymmetric lamellar structures with a well-designed miktoarm star block copolymer of the S(IS')3 type, where S and S' are polystyrenes of different lengths and I is poly(isoprene). The domain spacing can be tuned continuously from 37 nm to over 300 nm when the miktoarm star block copolymer is blended with suitable molecular weight polystyrene homopolymers. Beyond the unbinding transition of the lamellar phase, extremely asymmetric lamellar structures were obtained with up to 97 wt % polystyrene, remarkably leaving the poly(isoprene) layers intact at only 3 wt %!

We report an effective strategy for the synthesis of semi-crystalline block copolyethers with well-defined architecture and stereochemistry. As an exemplary system, triblock copolymers containing either atactic (racemic) or isotactic ( R or S ) poly(propylene oxide) end blocks with a central poly(ethylene oxide) mid-block were prepared by anionic ring-opening procedures. Stereochemical control was achieved by an initial hydrolytic kinetic resolution of racemic terminal epoxides followed by anionic ring-opening polymerization of the enantiopure monomer feedstock. The resultant triblock copolymers were highly isotactic (meso triads [ mm ]% ~ 90%) with optical microscopy, differential scanning calorimetry, wide angle x-ray scattering and small angle x-ray scattering being used to probe the impact of the isotacticity on the resultant polymer and hydrogel properties.

Nanostructured, responsive hydrogels formed due to electrostatic interactions have promise for applications such as drug delivery and tissue mimics. These physically cross-linked hydrogels are composed of an aqueous solution of oppositely charged triblocks with charged end-blocks and neutral, hydrophilic mid-blocks. Due to their electrostatic interactions, the end-blocks microphase separate and form physical cross-links that are bridged by the mid-blocks. The structure of this system was determined using a new, efficient embedded fluctuation (EF) model in conjunction with self-consistent field theory. The calculations using the EF model were validated against unapproximated field-theoretic simulations with complex Langevin sampling and were found consistent with small angle X-ray scattering (SAXS) measurements on an experimental system. Using both the EF model and SAXS, phase diagrams were generated as a function of end-block fraction and polymer concentration. Several structures were observed including a body-centered cubic sphere phase, a hexagonally packed cylinder phase, and a lamellar phase. Finally, the EF model was used to explore how parameters that directly relate to polymer chemistry can be tuned to modify the resulting phase diagram, which is of practical interest for the development of new hydrogels.

Side chain modification of a semiconducting polythiophene changes the resulting phase separation length scales when blended with a ferroelectric polymer for use in organic ferroelectric resistive switches. The domain size of the semiconducting portion of blends of poly[3-(ethyl- 5-pentanoate)thiophene-2,5-diyl] (P3EPT) and poly(vinylidene fluoride- co -trifluoroethylene) (PVDF-TrFE) in thin film blends are smaller than previously reported and easily controllable in size through simple tuning of the weight fraction of the semiconducting polymer. Furthermore, P3EPT has a relatively high degree of crystallinity and bimodal crystallite orientations, as probed by wide-angle X-ray scattering. Resistive switches fabricated from blends of P3EPT and PVDF-TrFE show memristive switching behavior over a wide range of polythiophene content and good ON/OFF ratios.

A complex coacervate is a fluid phase that results from the electrostatic interactions between two oppositely charged macromolecules. The nature of the coacervate core structure of hydrogels and micelles formed from complexation between pairs of diblock or triblock copolymers containing oppositely charged end-blocks as a function of polymer and salt concentration was investigated. Both ABA triblock copolymers of poly[(allyl glycidyl ether)-b-(ethylene oxide)-b-(allyl glycidyl ether)] and analogous poly[(allyl glycidyl ether)-b-(ethylene oxide)] diblock copolymers, which were synthesized to be nearly one-half of the symmetrical triblock copolymers, were studied. The poly(allyl glycidyl ether) blocks were functionalized with either guanidinium or sulfonate groups via postpolymerization modification. Mixing of oppositely charged block copolymers resulted in the formation of nanometer-scale coacervate domains. Small angle neutron scattering (SANS) experiments were used to investigate the size and spacing of the coacervate domains. The SANS patterns were fit using a previously vetted, detailed model consisting of polydisperse core-shell micelles with a randomly distributed sphere or body-centered cubic (BCC) structure factor. For increasing polymer concentration, the size of the coacervate domains remained constant while the spatial extent of the poly(ethylene oxide) (PEO) corona decreased. However, increasing salt concentration resulted in a decrease in both the coacervate domain size and the corona size due to a combination of the electrostatic interactions being screened and the shrinkage of the neutral PEO blocks. Additionally, for the triblock copolymers that formed BCC ordered domains, the water content in the coacervate domains was calculated to increase from approximately 16.8% to 27.5% as the polymer concentration decreased from 20 to 15 wt %.

We herein report a new facile strategy to ellipsoidal block copolymer nanoparticles that exhibit a pH-triggered anistropic swelling profile. In a first step, elongated particles with an axially stacked lamellae structure are selectively prepared by utilizing functional surfactants to control the phase separation of symmetric polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) in dispersed droplets. In a second step, the dynamic shape change is realized by cross-linking the P2VP domains, thereby connecting glassy PS discs with pH-sensitive hydrogel actuators., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The addition of small quantities of polystyrene (PS) is a simple and economically viable process that improves the power conversion efficiency of one of the most efficient small molecule donors. Addition of PS increases the solution viscosity, thereby providing thicker layers, and allows the formation of a desirable bulk heterojunction morphology. Moreover, the PS spontaneously accumulates as phase separated domains, away from the electrodes, so as not to interfere with charge extraction., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Many high-performance conjugated polymers for organic photovoltaics and transistors crystallize such that chains are parallel, resulting in significant anisotropy of the nanoscale charge transport properties. Here we demonstrate an unusual intercrystallite relationship where thin lamellae adopt a preferred epitaxial relationship with crossed-chains at the interface. The crossed-chains may allow either crystal to use the other as an "electronic shunt", creating efficient quasi-three-dimensional transport pathways that reduce the severity of grain boundaries and defects in limiting transport.

A record high OFET hole mobility, as high as 23.7 cm(2) /Vs, is achieved in macroscopic aligned semiconducting polymers. The high mobility is insensitive to the polymer molecular weight. Polymer chains are aligned along the fiber to facilitate intrachain charge transport., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Solution processable semiconducting polymers with excellent film forming capacity and mechanical flexibility are considered among the most progressive alternatives to conventional inorganic semiconductors. However, the random packing of polymer chains and the disorder of the polymer matrix typically result in low charge transport mobilities (10(-5)-10(-2) cm(2) V(-1) s(-1)). These low mobilities compromise their performance and development. Here, we present a strategy, by utilizing capillary action, to mediate polymer chain self-assembly and unidirectional alignment on nanogrooved substrates. We designed a sandwich tunnel system separated by functionalized glass spacers to induce capillary action for controlling the polymer nanostructure, crystallinity, and charge transport. Using capillary action, we demonstrate saturation mobilities with average values of 21.3 and 18.5 cm(2) V(-1 )s(-1) on two different semiconducting polymers at a transistor channel length of 80 μm. These values are limited by the source-drain contact resistance, Rc. Using a longer channel length of 140 μm where the contact resistance is less important, we measured μh = 36.3 cm(2) v(-1) s(-1). Extrapolating to infinite channel length where Rc is unimportant, the intrinsic mobility for poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-alt-[1,2,5]thiadiazolo[3,4-c]pyridine] (Mn = 140 kDa) at this degree of chain alignment and structural order is μh ≈ 47 cm(2 )v(-1) s(-1). Our results create a promising pathway toward high performance, solution processable, and low-cost organic electronics.

Amphiphilic polymers, specifically combinations of hydrophilic and hydrophobic residues, have been shown to be effective as antifouling materials against the algae Ulva linza and Navicula diatoms. Here we use the inherent sequence specificity of polypeptoids made by solid-phase synthesis to show that the sequence of hydrophilic (methoxy) and hydrophobic (fluorinated) moieties affects both antifouling and fouling release of U. linza . The platform used to test these sequences was a polystyrene- b -poly(ethylene oxide- co -allyl glycidyl ether) (PS- b -P(EO- co -AGE)) scaffold, where the polypeptoids are attached to the scaffold using thiol-ene click chemistry. The fluorinated moiety is very surface active and directs the surface composition of the polymer thin film. The position and number of fluorinated groups in the polypeptoid are shown to affect both the surface composition and antifouling properties of the film. Specifically, the position of the fluorinated units in the peptoid chain changes the surface chemistry and the antifouling behavior, while the number of fluorinated residues affects the fouling-release properties.

A novel solution-processable small molecule, namely, benzo[1,2-b:4,5-b]bis(4,4'-dihexyl-4H-silolo[3,2-b]thiophene-2,2'-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole (p-SIDT(FBTTh2)2), was designed and synthesized by utilizing the silaindacenodithiophene (SIDT) framework as the central D(2) donor unit within the D(1)AD(2)AD(1) chromophore configuration. Relative to the widely studied 7,7'-[4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl]bis[6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole] (p-DTS(FBTTh2)2), which contains the stronger donor fragment dithienosilole (DTS) as D(2), one finds that p-SIDT(FBTTh2)2 exhibits a wider band gap and can be used to fabricate bulk heterojunction solar cells with higher open circuit voltage (0.91 V). Most remarkably, thin films comprising p-SIDT(FBTTh2)2 can achieve exceptional levels of self-organization directly via solution deposition. For example, high-resolution transmission electron microscopy analysis shows that p-SIDT(FBTTh2)2 spin-cast from chlorobenzene organizes into crystalline domains with lattice planes that extend over length scales on the order of hundreds of nanometers. Such features suggest liquid crystalline properties during the evolution of the film. Moreover, grazing incidence wide-angle X-ray scattering analysis shows a strong tendency for the molecules to exist with a strong "face-on" orientation relative to the substrate plane. Similar structural features, albeit of more restricted dimensions, can be observed within p-SIDT(FBTTh2)2:PC71BM bulk heterojunction thin films when the films are processed with 0.4% diiodooctane (DIO) solvent additive. DIO use also increases the solar cell power conversion efficiencies (PCEs) from 1.7% to 6.4%. Of significance from a practical device fabrication perspective is that, for p-SIDT(FBTTh2)2:PC71BM blends, there is a wide range of compositions (from 20:80 to 70:30 p-SIDT(FBTTh2)2:PC71BM) that provide good photovoltaic response, i.e., PCE = 4-6%, indicating a robust tendency to form the necessary continuous phases for charge carrier collection. Light intensity photocurrent measurements, charge selective diode fabrication, and internal quantum efficiency determinations were carried out to obtain insight into the mechanism of device operation. Inclusion of DIO in the casting solution results in films that exhibit much lower photocurrent dependence on voltage and a concomitant increase in fill factor. At the optimum blend ratio, devices show high charge carrier mobilities, while mismatched hole and electron mobilities in blends with high or low donor content result in reduced fill factors and device performance.

The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (Mw = 350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS8 K-b-P(E/B)25 K-b-PI10 K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (Mw = 550 g mol(-1)) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings.

Background and Hypothesis: Rotator cuff tears are the most common injury seen by shoulder surgeons. Glenohumeral osteoarthritis develops in many late-stage rotator cuff tear patients as a result of torn cuff tendons, termed "cuff tear arthropathy." However, the mechanisms of cuff tear arthropathy have not been fully established. It has been hypothesized that a combination of synovial and mechanical factors contribute equally to the development of cuff tear arthropathy. The goal of this study was to assess the utility of this model in investigating cuff tear arthropathy., Materials and Methods: We used a rat model that accurately reflects rotator cuff muscle degradation after massive rotator cuff tears through either infraspinatus and supraspinatus tenotomy or suprascapular nerve transection. Using a modified Mankin scoring system, we found significant glenohumeral cartilage damage after both rotator cuff tenotomy and suprascapular nerve transection after only 12 weeks., Results: Cartilage degeneration was similar between groups and was present on both the humeral head and the glenoid. Denervation of the supraspinatus and infraspinatus muscles without opening the joint capsule caused cartilage degeneration similar to that found in the tendon transection group., Conclusions: Our results suggest that altered mechanical loading after rotator cuff tears is the primary factor in cartilage degeneration after rotator cuff tears. Clinically, understanding the process of cartilage degeneration after rotator cuff injury will help guide treatment decisions in the setting of rotator cuff tears., Level of Evidence: Basic science study, animal model., (Copyright © 2013 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Mosby, Inc. All rights reserved.)

Solvent additive processing can lead to drastic improvements in the power conversion efficiency (PCE) in solution processable small molecule (SPSM) bulk heterojunction solar cells. In situ grazing incidence wide-angle X-ray scattering is used to investigate the kinetics of crystallite formation during and shortly after spin casting. The additive is shown to have a complex effect on structural evolution invoking polymorphism and enhanced crystalline quality of the donor SPSM., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Thermally convertible organic materials are useful for the fabrication of multilayered thin film electronic devices such as solar cells. However, substantial changes in molecular ordering can occur during the conversion process that may lead to multiple polymorphs having differing electronic properties. In-situ grazing incidence wide-angle X-ray scattering with 2-D detection (2-D GIWAXS) was used to study the changes in the thin film crystal structure, texture, and crystallite size of a convertible small-molecule electron donor, tetrabenzoporphyrin (BP), during thermal conversion from the precursor bicycloporphyrin (CP) and the resulting crystal-crystal phase transition from a metastable phase (phase I) to a stable phase (phase II). The annealing temperature and the presence of an underlying BP layer both affect the phase-transition behavior. Phase II has a much weaker degree of crystalline texture than phase I, attributed to changes in molecular packing to achieve a herringbone arrangement. The unit cell for phase I was determined by electron diffraction and GIWAXS, and the thin film structure of phase II matched the previously determined bulk structure. The texture of crystallites in phase II was characterized by the simulation of the GIWAXS pattern. Transmission electron microscopy revealed differences in the morphology, grain size, and film coverage of the two polymorphs. Peak shape analysis with corrections for geometric smearing and paracrystalline disorder showed an increase in crystallite size from phase I to phase II. These results demonstrate the utility of in-situ 2-D GIWAXS in revealing polymorphic phases during the structural transition of thermally convertible organic semiconductors, the presence of which may impact the performance of solar cells.

Hierarchical self-assembly has been demonstrated with diblock copolymers comprising poly(dimethylsiloxane) (PDMS) and poly(lactide) (PLA) with supramolecular, 4-fold hydrogen-bonding junctions. PDMS with a single ureidoguanosine unit at the end was synthesized by a postpolymerization strategy. PLA with a single 1,7-diamidonaphthyridine was synthesized by ring-opening polymerization from the appropriate functional initiator. Selective association of the end groups to form distinct, noncovalent connections between the respective homopolymers in blends was established by 1 H NMR spectroscopy. The orthogonal self-assembly of the resulting pseudoblock copolymer, driven by immiscibility between the polymer constituents was demonstrated. Bulk polymer blends were prepared that have approximately symmetric composition and a 1:1 end-group stoichiometry. Small angle X-ray scattering combined with differential scanning calorimetry and transmission electron microscopy provide unambiguous evidence for the adoption of a lamellar morphology having long-range order, nanoscopic domain dimensions (20 nm pitch), and a sharp domain interface defined by the supramolecular building blocks.

Control of interfacial interactions leads to a dramatic change in shape and morphology for particles based on poly(styrene-b-2-vinylpyridine) diblock copolymers. Key to these changes is the addition of Au-based surfactant nanoparticles (SNPs) which are adsorbed at the interface between block copolymer-containing emulsion droplets and the surrounding amphiphilic surfactant to afford asymmetric, ellipsoid particles. The mechanism of formation for these novel nanostructures was investigated by systematically varying the volume fraction of SNPs, with the results showing the critical nature that the segregation of SNPs to specific interfaces plays in controlling structure. A theoretical description of the system allows the size distribution and aspect ratio of the asymmetric block copolymer colloidal particles to be correlated with the experimental results.

Rotator cuff pathology is the most common shoulder problem seen by orthopedic surgeons. Rotator cuff muscle fatty infiltration and muscle atrophy are common in larger tears and are considered predicting factors for the prognosis of cuff repair. Clinically, MRI is the gold standard in determining fatty infiltration and muscle atrophy; however, analysis for MRI imaging is primarily qualitative in nature with the results lacking further validation. We have recently developed a mouse model of rotator cuff tears. The goal of this study is to quantify and verify rotator cuff muscle atrophy and fatty infiltration using high-resolution MRI in our mouse model. The rotator cuff muscles were analyzed for fat using a triglyceride quantification assay (TQA), muscle volume was measured through water displacement (WD), and histology. The study revealed that MRI had a high correlation with fat as measured with histology and TQA (R(2)  =098). MRI also correlated well with atrophy measured with WD and wet weight. This suggests that MRI is a reliable modality in evaluating the progression of fatty infiltration and muscle atrophy following rotator cuff tears in a small animal model., (Copyright © 2012 Orthopaedic Research Society.)

The thermotropic behavior of [6,6]-phenyl-C(61)-butyric acid n-butyl ester (PCBNB) in powder and thin film form was investigated using X-ray diffraction and transmission electron microscopy. Upon heating PCBNB powder above its glass-transition temperature, an amorphous-to-crystalline transition (i.e., cold crystallization) and a subsequent melting of these crystals were observed. A thin film of PCBNB was observed to order on a simple hexagonal lattice (HEX) with the c axis preferentially oriented normal to film at an annealing temperature of 180 °C but became disordered above 200 °C, consistent with the powder results. However, when annealed at 160 °C, the PCBNB thin film ordered on a superlattice of the HEX as indicated both by electron diffraction and high-angle annular dark field scanning TEM (HAADF-STEM) images. The formation of the HEX superlattice polymorph was independent of both solvent and substrate and could be formed both on heating from the amorphous as cast state and by cooling from the HEX structure formed at a higher temperature. HAADF-STEM shows that the superlattice corresponds to a regular deficiency of PCBNB molecules on every fifth (1 1[combining overline] 0 0) plane of the HEX structure.

A novel strategy for the synthesis of fully conjugated donor-acceptor block copolymers, in a single reaction step employing Stille coupling polymerization of end-functional polythiophene and AA + BB monomers, is presented. The unique donor-acceptor structure of these block copolymers provides a rich self-assembly behavior, with the first example of a fully conjugated donor-acceptor block copolymer having two separate crystalline domains being obtained.

Coatings derived from surface active block copolymers (SABCs) having a combination of hydrophobic aliphatic (linear hydrocarbon or propylene oxide-derived groups) and hydrophilic poly(ethlyene glycol) (PEG) side chains have been developed. The coatings demonstrate superior performance against protein adsorption as well as resistance to biofouling, providing an alternative to coatings containing fluorinated side chains as the hydrophobe, thus reducing the potential environmental impact. The surfaces were examined using dynamic water contact angle, captive air-bubble contact angle, atomic force microscopy, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure analysis. The PS(8K)-b-P(E/B)(25K)-b-PI(10K) triblock copolymer precursor (K3) initially dominated the dry surface. In contrast to previous studies with mixed fluorinated/PEG surfaces, these new materials displayed significant surface changes after exposure to water that allowed fouling resistant behavior. PEG groups buried several nanometers below the surface in the dry state were able to occupy the coating surface after placement in water. The resulting surface exhibits a very low contact angle and good antifouling properties that are very different from those of K3. The surfaces are strongly resistant to protein adsorption using bovine serum albumin as a standard protein challenge. Biofouling assays with sporelings of the green alga Ulva and cells of the diatom Navicula showed the level of adhesion was significantly reduced relative to that of a PDMS standard and that of the triblock copolymer precursor of the SABCs.

Directed assembly of block copolymer thin films is recognized as a high-throughput, low-cost complement to optical lithography with the ability to overcome the 32 nm natural resolution limit of conventional lithographic techniques. For bulk block copolymer systems, desired feature sizes ranging from 5 to 100 nm can be obtained by controlling the molecular weight and composition of a block copolymer, as long as the bulk order-disorder temperature (ODT) is such that the copolymer is well-segregated at the processing conditions. However, our studies on graphoepitaxially aligned cylindrical morphology block copolymer monolayer and bilayer films demonstrate that, as domain sizes are reduced, the block copolymer becomes increasingly susceptible to an unacceptably high density of thermally generated defects, resulting in a significant reduction of the ODT. Thus, in thin films, the minimum feature spacing accessible is limited by thermal defect generation and not by the bulk ODT. Our experimental studies on monolayer films of cylindrical morphology polystyrene-b-poly(2-vinyl pyridine) with microdomain spacings approaching 20 nm reveal that defect densities and the ODT are surprisingly sensitive to variations as small as 2 nm in the microdomain spacing. Additionally, the monolayer and bilayer ODT differ by nearly 100 °C when the monolayer domain spacing is 20 nm, while the difference is only 20 °C when the monolayer domain spacing is 22 nm. We explain this behavior using a quantitative estimation of the energetic cost of defect production in terms of the domain spacing, χN, and block copolymer composition. These studies reveal unexpected consequences on the equilibrium defect densities of thin film block copolymers which must be accounted for when designing a block-copolymer-based directed-assembly process., (© 2012 American Chemical Society)

Solution deposition using high-boiling-point additives such as octanedithiol (ODT) provides a simple and widely used fabrication option for improving the power conversion efficiencies of solar cells composed of narrow-band-gap conjugated polymer donor/fullerene acceptor blends. Previous examination of the resulting device active layers has shown that the use of additives influences the degree of phase segregation within the bulk heterojunction (BHJ) blend and also improves ordering within the polymeric domains. In this work, in situ grazing-incidence wide-angle X-ray scattering as a function of time was used to explore the dynamics of the BHJ evolution. These studies showed that a small percentage of ODT in chlorobenzene (CB) induced the nucleation of polymeric crystallites within 2 min of deposition, increased the orientational order of specific polymorphs, and promoted further crystallite nucleation over a period longer than 40 min after casting. Similar structural changes did not occur when the same BHJ blend was cast from pure CB.

π-Conjugated, narrow band gap copolymers containing pyridal[2,1,3]thiadiazole (PT) were synthesized via starting materials that prevent random incorporation of the PT heterocycles relative to the backbone vector. Two regioregular structures could be obtained: in one the PTs are oriented in the same direction, and in the other the orientation of the PTs alternates every other repeat unit. Compared to their regiorandom counterparts, the regioregular polymers exhibit a 2 orders of magnitude increase of the hole mobilites, from 0.005 to 0.6 cm(2) V(-1) s(-1), as determined by field-effect transistor measurements.

To control the surface properties of a polystyrene-block-poly(ethylene oxide) diblock copolymer, perfluorinated chemical moieties were specifically incorporated into the block copolymer backbone. A polystyrene-block-poly[(ethylene oxide)-stat-(allyl glycidyl ether)] [PS-b-P(EO-stat-AGE)] statistical diblock terpolymer was synthesized with varying incorporations of allyl glycidyl ether (AGE) in the poly(ethylene oxide) block from 0 to 17 mol %. The pendant alkenes of the AGE repeat units were subsequently functionalized by thiol-ene chemistry with 1H,1H,2H,2H-perfluorooctanethiol, yielding fluorocarbon-functionalized AGE (fAGE) repeat units. (1)H NMR spectroscopy and size-exclusion chromatography indicated well-defined structures with complete functionalization of the pendant alkenes. The surfaces of the polymer films were characterized after spray coating by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS), showing that the P(EO-stat-fAGE) block starts to compete with polystyrene to populate the surface after only 1 mol % incorporation of fAGE. Increasing the incorporation of fAGE led to an increased amount of perfluorocarbons on the surface and a decrease in the concentration of PS. At a fAGE incorporation of 8 mol %, PS was not detected at the surface, as measured by NEXAFS spectroscopy. Water contact angles measured by the captive-air-bubble technique showed the underwater surfaces to be dynamic, with advancing and receding contact angles varying by >20°. Protein adsorption studies demonstrated that the fluorinated surfaces effectively prevent nonspecific binding of proteins relative to an unmodified PS-b-PEO diblock copolymer. In biological systems, settlement of spores of the green macroalga Ulva was significantly lower for the fAGE-incorporated polymers compared to the unmodified diblock and a polydimethylsiloxane elastomer standard. Furthermore, the attachment strength of sporelings (young plants) of Ulva was also reduced for the fAGE-containing polymers, affirming their potential as fouling-release coatings.

We report a facile strategy to synthesize amphiphilic gold (Au) nanoparticles functionalized with a multilayer, micelle-like structure consisting of a Au core, an inner hydroxylated polyisoprene (PIOH) layer, and an outer polystyrene shell (PS). Careful control of enthalpic interactions via a systematic variation of structural parameters, such as number of hydroxyl groups per ligand (N(OH)) and styrene repeating units (N(PS)) as well as areal chain density of ligands on the Au-core surface (Σ), enables precise control of the spatial distribution of these nanoparticles. This control was demonstrated in a lamellae-forming poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) diblock copolymer matrix, where the favorable hydrogen-bonding interaction between hydroxyl groups in the PIOH inner shell and P2VP chains in the PS-b-P2VP diblock copolymer matrix, driving the nanoparticles to be segregated in P2VP domains, could be counter balanced by the enthalphic penalty of mixing of the PS outer brush with the P2VP domains. By varying N(OH), N(PS), and Σ, the nanoparticles could be positioned in the PS or P2VP domains or at the PS/P2VP interface. In addition, the effect of additives interfering with the hydrogen-bond formation between hydroxyl groups on Au nanoparticles and P2VP chains in a diblock copolymer matrix was investigated, and an interesting pea-pod-like segregation of Au nanoparticles in PS domains was observed.