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This paper introduces the design concept of a dual-functional molecular dyad tailored specifically for solution-processable organic light-emitting diodes (OLEDs). Cy-tmCPBN, characterized by an asymmetric molecular dyad structure, integrates a host unit (tmCP) and a multiple-resonance (MR) emitter (CzBN) via a non-conjugated cyclohexane linker. Cy-tmCPBN exhibited efficient intramolecular energy transfers (EnTs) from tmCP to the CzBN unit, as confirmed by time-resolved fluorescence experiments. The fluorescence lifetime of the tmCP unit was approximately three times shorter in a highly diluted solution of Cy-tmCPBN than in a mixed solution of Cy-tmCP and Cy-CzBN. In addition, Cy-tmCPBN exhibited excellent solubility and film-forming ability, making it suitable for solution processing. Notably, OLEDs utilizing Cy-tmCPBN achieved over twice the brightness and improved external quantum efficiency of 12.3% compared to OLEDs using Cy-CzBN with the same concentration of CzBN in the emitting layer. The improved OLED performance can be explained by the increased EnT efficiency from Cy-tmCP to Cy-tmCPBN and the intramolecular EnT within Cy-tmCPBN. In our dual-functional dyad, incorporating both host and emitter units in an asymmetric molecular dyad structure, we induced a positive synergy effect with the host moiety, enhancing OLED performance through intramolecular EnT., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this study, two novel multiple resonance (MR) emitters, DtCzBN and Cy-DtCzBN, were designed based on the well-known BCzBN structure and synthesized for narrowband solution-processed organic light-emitting diodes (OLEDs). Cy-DtCzBN possesses a dimeric V-shaped structure formed by coupling two individual DtCzBN units via a nonconjugated cyclohexane linker. When compared with DtCzBN, Cy-DtCzBN, as a medium-sized molecule, was found to maintain the optical and photophysical properties of the corresponding monomeric unit, DtCzBN, but exhibits high thermal stability, excellent solubility, and good film-forming ability. Additionally, solution-processed OLEDs were fabricated by using two sets of molecules: one set of small molecular hosts and emitters (i.e., mCP and DtCzBN) and the other set of medium-sized molecular hosts and emitters (i.e., Cy-mCP and Cy-DtCzBN). Notably, devices using medium-sized molecular hosts and emitters exhibited similar optical and photophysical properties but showed significantly improved reproducibility and thermal stability compared with those based on small molecular hosts and emitters. Our current study provides some insights into molecular design strategies for thermally stable hosts and emitters, which are highly suitable for solution-processed OLEDs.

In solution-processed organic light-emitting diodes (OLEDs), achieving high color purity and efficiency is as important as that in vacuum processes. Emitters suitable for solution processing must have excellent solubility in organic solvents, high molecular weight, and compatibility with the host materials. In this study, we synthesized a deep-blue emitter that satisfies the above conditions by introducing a 1,4-bis(indolo[3,2,1- jk ]carbazol-2-yl)benzene-based planar emitting core (DICz) structure and four 3,6-di- tert -butyl-9-phenyl-9 H -carbazole ( t Cz) peripheral units, namely, 4 t Cz-DICz. A comparative compound, 4Hex-DICz, incorporating hexyl phenyl groups was synthesized. In contrast to 4Hex-DICz, 4 t Cz-DICz exhibited exceptional solubility in organic solvents and superior film-forming properties attributed to the presence of t Cz units. Additionally, in the film state, the effective encapsulation of the emitting core (DICz) by the t Cz units in 4 t Cz-DICz helps prevent undesirable molecular aggregation. The solution-processed OLEDs employing the CH-2D1 film, doped with 5 wt % 4 t Cz-DICz as the emitting layer, exhibited a deep-blue emission at 424 nm, characterized by a narrow bandwidth of 22 nm, and achieved a maximum external quantum efficiency (EQE) of approximately 4.0%. In contrast, the 4Hex-DICz-based device demonstrated an EQE of 2.91%. Consequently, we have successfully demonstrated that the introduction of four bulky t Cz units into the DICz core is a promising molecular design strategy for the development of soluble indolocarbazole-based emitters, especially those used in high-performance deep-blue fluorescent OLEDs.

Objectives: The COVID-19 is a global health issue with widespread impact around the world, and many countries initiated lockdowns as part of their preventive measures. We aim to quantify the duration of delay in discharge to community from Community Hospitals, as well as quantify adverse patient outcomes post discharge pre and during lockdown period., Design and Methods: We conducted a before-after study comparing the length of stay in Community Hospitals, unscheduled readmissions or Emergency Department attendance, patients' quality of life using EQ5D-5l, number and severity of falls, in patients admitted and discharged before and during lockdown period., Results: The average length of stay in the lockdown group (27.77 days) were significantly longer than that of the pre-lockdown group (23.76 days), p  = 0.003. There were similar proportions of patients with self-reported falls post discharge between both groups. Patients in the pre-lockdown group had slightly better EQ-5D-5l Index score at 0.55, compared to the lockdown study group at 0.49. Half of the patients in both groups were referred to Community Care Services on discharge., Conclusion: Our study would help in developing a future systematic preparedness guideline and contingency plans in times of disease outbreak and other similar public health emergencies., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (© 2023 Chia, Xia, Kwan, Lim, Tan, Low, Xu, Loo, Kong, Koh, Towle, Lim, Yoon, Seah and Low.)

Herein, a novel core molecule for V-shaped host molecules was synthesized, wherein two carbazoles were directly linked to cyclohexane. Cy-mCP and Cy-mCBP hosts were also successfully prepared for solution-processable thermally activated delayed fluorescence organic light-emitting diodes (TADF-OLEDs). The Cy-mCP and Cy-mCBP molecules contained a cyclohexane linker directly linked to two small molecular hosts (mCP and mCBP), exhibiting twice the molecular weight while maintaining the basic properties of a single host molecule with improved film-forming ability and solubility in organic solvents. These host materials showed superior thermal stability and high glass transition temperatures compared to lower molecular weight hosts. Green TADF-OLEDs were prepared using the two host materials and 2,4,5,6-tetra(3,6-di- tert -butylcarbazol-9-yl)-1,3-dicyanobenzene (t4CzIPN) emitter, achieving device efficiencies similar to that of a low-molecular-weight host. However, after the incorporation of a V-shaped host, superior characteristics were observed in terms of the thermal stability and operational stability of the device. The synthesis of V-shaped molecules by directly linking two carbazoles to a cyclohexane linker is promising for the development of different hosts for solution-processable OLEDs.

Two new Y6 derivatives of symmetrical YBO-2O and asymmetrical YBO-FO nonfullerene acceptors (NFAs) are prepared with a simplified synthetic procedure by incorporating octyl and fluorine substituents onto the terminal 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN) moiety. By moving the alkyl substituents on the Y6 core to the terminal INCN moiety, the lowest unoccupied molecular orbital of the YBO NFAs increases without decreasing solubility, resulting in high open-circuit voltages of the devices. Molecular dynamics simulation shows that YBO-2O/-FO preferentially form core-core and terminal-terminal dimeric interactions, demonstrating their tighter packing structure and higher electron mobility than Y6, which is consistent with 2D grazing incidence X-ray scattering and space charge limited current measurements. In blend films, the hole transfer (HT) from YBO-2O/-FO to the polymer donor PM6 is studied in detail by transient absorption spectroscopy, demonstrating efficient HT from YBO-FO to PM6 with their suitable energy level alignment. Despite the simplified synthesis, YBO-FO demonstrates photovoltaic performance similar to that of Y6, exhibiting a power conversion efficiency of 15.01%. Overall, this design strategy not only simplifies the synthetic procedures but also adjusts the electrical properties by modifying the intermolecular packing and energy level alignment, suggesting a novel simplified molecular design of Y6 derivatives., (© 2022 Wiley-VCH GmbH.)

One of the recent advances in medical nanotechnology has been the development of nanoformulations to overcome drug-resistant bacterial infections. Herein, we disclose a new nano-antibiotic formulation based on sceptrin-Au nano-aggregates (SANA), which are drug-metal ion multiple complexes. Sceptrin is a natural compound from a marine organism (sponge) and was reported as a potential compound with drug activities. SANA consists of a sceptrin-Au ion and is a self-assembled nano-formation with electrostatic interaction. Interestingly, SANA showed superior antibiotic/antibiofilm activity toward carbapenem-resistant Gram-negative bacteria with low toxicity to red blood cells and endothelial cells. The working mechanism of SANA was identified with analysis of the extracellular reactive oxygen species level and membrane depolarization of bacteria. The feasibility of SANA as a new nano-antibiotic was demonstrated in CRPA-contaminated medical supplies where SANA inhibited the formation of biofilms as well as the growth of CRPA. This work presents a new concept for the development of next-generation nano-antibiotics and a more feasible clinical translational pathway.

Introduction: The COVID-19 pandemic affects the process of care transition for patients with underlying chronic conditions. This study aims to explore the impact of the pandemic measures on discharge planning and continuum of care for vulnerable older patients from multi-stakeholder perspectives., Methods: We conducted focus group discussions and individual interviews with healthcare workers, community partners, government officials and family caregivers in Singapore. All interviews were audio-recorded, transcribed verbatim and thematically analysed., Results: A total of 53 individuals participated in the study. Discharge planning and care continuity in the community were affected primarily by the limited step-down care options and remote assessment of discharge needs. Participants felt a need to revisit the decision of 'essential' community services through engagement of all stakeholders to enhance care community.To improve better care transition, participants suggested the need for clearer communication of guidelines, improved intersectoral collaboration, shared responsibility of patient care through community engagement and employment of novel models of care., Conclusion: The pandemic measures generated challenges of safe discharge of patients and care continuity in the community. Findings shed light on the need to proactively assess care pathways and catalyse novel models to improve care transition beyond the pandemic., Competing Interests: The authors have no competing interests to declare., (Copyright: © 2022 The Author(s).)

Child maltreatment is associated with significant negative long-term outcomes. Behaviors considered to be more serious and abusive are more likely identified as maltreatment and reported. Therefore, studying child maltreatment perceptions among professionals and the public who regularly work with children could inform practice. Existing studies examining professionals' and the public's perceptions of maltreatment have reported mixed findings, motivating a more comprehensive study of maltreatment perceptions. Our study compared perceived abusiveness and seriousness of behaviors (a) across professional groups (educators, counselors/social workers, nurses, doctors, and police officers), and (b) between professional groups and the public. We surveyed 1,022 professionals and 500 members of the public. Respondents completed an 18-item measure on their perceived abusiveness of potential maltreatment behaviors, and rated the seriousness of 21 vignettes depicting maltreatment behaviors. We found that educators surveyed in our study perceived all child maltreatment behaviors as more serious, and emotional maltreatment behaviors as more abusive, than other professional groups. Conversely, police officers in our sample perceived neglect/emotional maltreatment behaviors as less serious than other professionals. Police officers also perceived physical abuse and emotional maltreatment behaviors as less abusive than other professionals. In our sample, professionals perceived maltreatment behaviors as less serious than the public, while the public was more hesitant to label behaviors as constituting abuse than professionals. These findings highlight the need to address inconsistencies in maltreatment perceptions across professionals and the public, to ensure the provision of appropriate intervention in suspected maltreatment cases.

In this study, we demonstrated two deep-blue TADF emitters, BO-tCzPhICz and BO-tCzDICz, for solution-processable thermally activated delayed fluorescence organic light-emitting diodes (TADF-OLEDs). They were synthesized by employing an organoboron acceptor and 9-(3,6-di- tert -butyl-9 H -carbazol-9-yl)-5-phenyl-5,12-dihydroindolo[3,2- a ]carbazole (tCzPhICz) and 12-(3,6-di- tert -butyl-9 H -carbazol-9-yl)-15 H -diindolo[2,3- b :1',2',3'- lm ]carbazole (tCzDICz) as bulky aryl-annulated [3,2- a ] carbazole donors, respectively. Both emitters showed sufficient solubility in organic solvents, narrow deep-blue emission, and small energy difference (Δ E ST ) between singlet and triplet states, which can be applied to solution-processable deep-blue TADF-OLEDs. Solution-processed OLEDs exploiting these TADF emitters displayed deep-blue electroluminescence with CIE y <0.1, and high external quantum efficiencies of 17.8 and 14.8% were observed for BO-tCzPhICz and BO-tCzDICz, respectively. The emitter bearing bulky ICz-based donating units shows highly promising potential for high-efficiency solution-processable deep-blue TADF-OLEDs.

Sulfur-substituted biocompatible carbonyl fluorophores have been recognized as effective heavy-atom-free photosensitizers (PSs) for cancer therapy due to their remarkable phototherapeutic properties. However, guidelines on their molecular design are still a substantial challenge. Most of the existing thiocarbonyl-based PSs are nonemissive in both the solution and restricted states, which hinders their further biomedical applications. Herein, we report the interesting finding that sulfur-substituted coumarins exhibit an uncommon phenomenon, aggregation-induced emission. More intriguingly, we also found that the introduction of a strong electron-accepting trifluoromethyl group is crucial to facilitate the mitochondrial-targeting ability of neutral coumarin fluorophores. The resulting CMS-2 PS displayed selective imaging of mitochondria and exhibited much higher photodynamic therapy efficiency toward cancer cells than that of the commercial PS erythrosine B. This work provides deep insight into the molecular design of heavy-atom-free thiobase-based PSs and simultaneously offers a great opportunity to develop novel mitochondrial-targeting fluorescent indicators with neutral bioinspired platforms.

Background: The coronavirus disease-19 (COVID-19) pandemic has cost lives and economic hardships globally. Various studies have found a number of different factors, such as hyperinflammation and exhausted/suppressed T cell responses to the etiological SARS coronavirus-2 (SARS-CoV-2), being associated with severe COVID-19. However, sieving the causative from associative factors of respiratory dysfunction has remained rudimentary., Methods: We postulated that the host responses causative of respiratory dysfunction would track most closely with disease progression and resolution and thus be differentiated from other factors that are statistically associated with but not causative of severe COVID-19. To track the temporal dynamics of the host responses involved, we examined the changes in gene expression in whole blood of 6 severe and 4 non-severe COVID-19 patients across 15 different timepoints spanning the nadir of respiratory function., Findings: We found that neutrophil activation but not type I interferon signaling transcripts tracked most closely with disease progression and resolution. Moreover, transcripts encoding for protein phosphorylation, particularly the serine-threonine kinases, many of which have known T cell proliferation and activation functions, were increased after and may thus contribute to the upswing of respiratory function. Notably, these associative genes were targeted by dexamethasone, but not methylprednisolone, which is consistent with efficacy outcomes in clinical trials., Interpretation: Our findings suggest neutrophil activation as a critical factor of respiratory dysfunction in COVID-19. Drugs that target this pathway could be potentially repurposed for the treatment of severe COVID-19., Funding: This study was sponsored in part by a generous gift from The Hour Glass. EEO and JGL are funded by the National Medical Research Council of Singapore, through the Clinician Scientist Awards awarded by the National Research Foundation of Singapore., Competing Interests: Declaration of Competing Interests Dr Eng Eong Ooi reports grants from National Medical Research Council, Singapore, during the conduct of the study; personal fees from Tychan Private Limited, outside the submitted work; the other authors declare no competing interests., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Organic solar cells based on bulk heterojunctions (BHJs) are attractive energy-conversion devices that can generate electricity from absorbed sunlight by dissociating excitons and collecting charge carriers. Recent breakthroughs attained by development of nonfullerene acceptors result in significant enhancement in power conversion efficiency (PCEs) exceeding 17%. However, most of researches have focused on pursuing high efficiency of small-area (<1 cm 2 ) unit cells fabricated usually with spin coating. For practical application of organic photovoltaics (OPVs) from lab-scale unit cells to industrial products, it is essential to develop efficient technologies that can extend active area of devices with minimized loss of performance and ensured operational stability. In this progress report, an overview of recent advancements in materials and processing technologies is provided for transitioning from small-area laboratory-scale devices to large-area industrial scale modules. First, development of materials that satisfy requirements of high tolerability in active layer thickness and large-area adaptability is introduced. Second, morphology control using various coating techniques in a large active area is discussed. Third, the recent research progress is also underlined for understanding mechanisms of OPV degradation and studies for improving device long-term stability along with reliable evaluation procedures., (© 2020 Wiley-VCH GmbH.)

Photostability of small-molecule (SM)-based organic photovoltaics (SM-OPVs) is greatly improved by utilizing a ternary photo-active layer incorporating a small amount of a conjugated polymer (CP). Semi-crystalline poly[(2,5-bis(2-hexyldecyloxy)phenylene)- alt -(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[ c ][1,2,5]thiadiazole)] (PPDT2FBT) and amorphous poly[(2,5-bis(2-decyltetradecyloxy)phenylene)- alt -(5,6-dicyano-4,7-di(thiophen-2-yl)benzo[ c ][1,2,5]thiadiazole)] (PPDT2CNBT) with similar chemical structures were used for preparing SM:fullerene:CP ternary photo-active layers. The power conversion efficiency (PCE) of the ternary device with PPDT2FBT (Ternary-F) was higher than those of the ternary device with PPDT2CNBT (Ternary-CN) and a binary SM-OPV device (Binary) by 15% and 17%, respectively. The photostability of the SM-OPV was considerably improved by the addition of the crystalline CP, PPDT2FBT. Ternary-F retained 76% of its initial PCE after 1500 h of light soaking, whereas Ternary-CN and Binary retained only 38% and 17% of their initial PCEs, respectively. The electrical and morphological analyses of the SM-OPV devices revealed that the addition of the semi-crystalline CP led to the formation of percolation pathways for charge transport without disturbing the optimized bulk heterojunction morphology. The CP also suppressed trap-assisted recombination and enhanced the hole mobility in Ternary-F. The percolation pathways enabled the hole mobility of Ternary-F to remain constant during the light-soaking test. The photostability of Ternary-CN did not improve because the addition of the amorphous CP inhibited the formation of ordered SM domains.

A new polymer acceptor poly{(N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl)-alt-5,5-(3,3'-didodecyl-2,2'-bifuran)} (NDI-BFR) made from naphthalenediimide (NDI) and furan-derived head-to-head-linked 3,3'-dialkyl-2,2'-bifuran (BFR) units is reported in this study. Compared to the benchmark polymer poly(naphthalenediimide-alt-bithiophene) (N2200), NDI-BFR exhibits a larger bathochromic shift of absorption maxima (842 nm) with a much higher absorption coefficient (7.2 × 10 4 m -1 cm -1 ), leading to an ultranarrow optical bandgap of 1.26 eV. Such properties ensure good harvesting of solar light from visible to the near-infrared region in solar cells. Density functional theory calculation reveals that the polymer acceptor NDI-BFR possesses a higher degree of backbone planarity versus the polymer N2200. The polymer NDI-BFR exhibits a decent electron mobility of 0.45 cm 2 V -1 s -1 in organic thin-film transistors (OTFTs), and NDI-BFR-based all-polymer solar cells (all-PSCs) achieve a power conversion efficiency (PCE) of 4.39% with a very small energy loss of 0.45 eV by using the environmentally friendly solvent 1,2,4-trimethylbenzene. These results demonstrate that incorporating head-to-head-linked BFR units in the polymer backbone can lead to increased planarity of the polymer backbone, reduced optical bandgap, and improved light absorbing. The study offers useful guidelines for constructing n-type polymers with narrow optical bandgaps., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Subwavelength gratings have been of great interest recently due to their ability to eliminate multiple orders. However, high index contrast ( Δ n ∼ 3 ) is typically achieved using metals or high-index dielectrics surrounded by vacuum in order to maintain good optical selectivity. Here, we theoretically propose and experimentally realize a selective subwavelength grating using an index contrast of Δ n ∼ 1.2 without vacuum. Despite its low index contrast, our simulation and experiments show that good optical selectivity is achieved using the same physics as subwavelength gratings made of high-index contrast. Such polymer-based encapsulated gratings are easier to scale up for use in large-area applications such as photovoltaics and lighting.

Halogenated solvents are prevailingly used in the fabrication of nonfullerene organic solar cells (NF-OSCs) at the current stage, imposing significant restraints on their practical applications. By copolymerizing phthalimide or thieno[3,4- c ]pyrrole-4,6-dione (TPD) with 1,4-di(3-alkoxy-2-thienyl)-2,5-difluorophenylene (DOTFP), which features intramolecular noncovalent interactions, the backbone planarity of the resulting DOTFP-based polymers can be effectively tuned, yielding distinct solubilities, aggregation characters, and chain packing properties. Polymer DOTFP-PhI with a more twisted backbone showed a lower degree of aggregation in solution but an increased film crystallinity than polymer DOTFP-TPD. An organic thin-film transistor and NF-OSC based on DOTFP-PhI, processed with a nonhalogenated solvent, exhibited a high hole mobility up to 1.20 cm 2 V -1 s -1 and a promising power conversion efficiency up to 10.65%, respectively. The results demonstrate that DOTFP is a promising building block for constructing wide bandgap polymers and backbone coplanarity tuning is an effective strategy to develop high-performance organic semiconductors processable with a nonhalogenated solvent.

Hole-transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long-term stability, high-performance dopant-free small-molecule HTMs (SM-HTMs) are greatly desired. However, such dopant-free SM-HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor-acceptor-type SM-HTMs (MPA-BTI and MPA-BTTI) are devised, which synergistically integrate several design principles for high-performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant-free MPA-BTTI-based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long-term stability under illumination, which breaks the long-time standing bottleneck in the development of dopant-free SM-HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well-aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA-BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high-performance dopant-free SM-HTMs in PVSCs., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel imide-functionalized arene, di(fluorothienyl)thienothiophene diimide (f-FBTI2), featuring a fused backbone functionalized with electron-withdrawing F atoms, is designed, and the synthetic challenges associated with highly electron-deficient fluorinated imide are overcome. The incorporation of f-FBTI2 into polymer affords a high-performance n-type semiconductor f-FBTI2-T, which shows a reduced bandgap and lower-lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analog without F or with F-functionalization on the donor moiety. These optoelectronic properties reflect the distinctive advantages of fluorination of electron-deficient acceptors, yielding "stronger acceptors," which are desirable for n-type polymers. When used as a polymer acceptor in all-polymer solar cells, an excellent power conversion efficiency of 8.1% is achieved without any solvent additive or thermal treatment, which is the highest value reported for all-polymer solar cells except well-studied naphthalene diimide and perylene diimide-based n-type polymers. In addition, the solar cells show an energy loss of 0.53 eV, the smallest value reported to date for all-polymer solar cells with efficiency > 8%. These results demonstrate that fluorination of imide-functionalized arenes offers an effective approach for developing new electron-deficient building blocks with improved optoelectronic properties, and the emergence of f-FBTI2 will change the scenario in terms of developing n-type polymers for high-performance all-polymer solar cells., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Highly efficient nonfullerene polymer solar cells (PSCs) are developed based on two new phthalimide-based polymers phthalimide-difluorobenzothiadiazole (PhI-ffBT) and fluorinated phthalimide-ffBT (ffPhI-ffBT). Compared to all high-performance polymers reported, which are exclusively based on benzo[1,2- b :4,5- b ']dithiophene (BDT), both PhI-ffBT and ffPhI-ffBT are BDT-free and feature a D-A 1 -D-A 2 type backbone. Incorporating a second acceptor unit difluorobenzothiadiazole leads to polymers with low-lying highest occupied molecular orbital levels (≈-5.6 eV) and a complementary absorption with the narrow bandgap nonfullerene acceptor IT-4F. Moreover, these BDT-free polymers show substantially higher hole mobilities than BDT-based polymers, which are beneficial to charge transport and extraction in solar cells. The PSCs containing difluorinated phthalimide-based polymer ffPhI-ffBT achieve a substantial PCE of 12.74% and a large V oc of 0.94 V, and the PSCs containing phthalimide-based polymer PhI-ffBT show a further increased PCE of 13.31% with a higher J sc of 19.41 mA cm -2 and a larger fill factor of 0.76. The 13.31% PCE is the highest value except the widely studied BDT-based polymers and is also the highest among all benzothiadiazole-based polymers. The results demonstrate that phthalimides are excellent building blocks for enabling donor polymers with the state-of-the-art performance in nonfullerene PSCs and the BDT is not necessary for constructing such donor polymers.

In this study, we synthesized two acceptor-donor-acceptor (A-D-A)-type small molecules (SMs) (P3T4-VCN and P3T4-INCN) with different terminal end-groups (dicyanovinyl (VCN) and 2-methylene-3-(1,1-dicyanomethylene)indanone (INCN)) based on the 1,4-bis(thiophenylphenylthiophene)-2,5-difluorophenylene (P3T4) core that possesses high coplanarity because of intrachain noncovalent Coulombic interactions. We investigated the influence of terminal end-groups on intermolecular packing and the resulting electrical and photovoltaic characteristics. A small change in the end-group structure of the SMs induces a significant variation in the torsional structures, molecular packing, and pristine/blend film morphology. It is noteworthy that the less crystalline P3T4-INCN with tilted conformation is highly sensitive to post-treatments (i.e., additives and annealing) such that it permits facile morphological modulation. However, the highly planar and crystalline P3T4-VCN exhibits a strong tolerance toward processing treatments. After morphology optimization, the fullerene-based bulk-heterojunction solar cell of tilted P3T4-INCN exhibits a power conversion efficiency (PCE) of 5.68%, which is significantly superior to that of P3T4-VCN:PC 71 BM (PCE = 1.29%). Our results demonstrate the importance of the terminal end-group for the design of A-D-A-type SMs and their sensitivity toward the postprocessing treatments in optimizing their performance.

Head-to-head linked bithiophenes with planar backbones hold distinctive advantages for constructing organic semiconductors, such as good solubilizing capability, enabling narrow bandgap, and effective tuning of frontier molecular orbital (FMO) levels using minimal thiophene numbers. In order to realize planar backbone, alkoxy chains are typically installed on thiophene head positions, owing to the small van der Waals radius of oxygen atom and accompanying noncovalent S⋯O interaction. However, the strong electron donating alkoxy chains on the electron-rich thiophenes lead to elevated FMO levels, which are detrimental to material stability and device performance. Thus, a new design approach is needed to counterbalance the strong electron donating property of alkoxy chains to bring down the FMOs. In this study, we designed and synthesized a new head-to-head linked building block, 4-alkoxy-5-(3-alkylthiophen-2-yl)thiazole (TRTzOR), using an electron-deficient thiazole to replace the electron-rich thiophene. Compared to previously reported 3-alkoxy-3'-alkyl-2,2'-bithiophene (TRTOR), TRTzOR is a weaker electron donor, which considerably lowers FMOs and maintains planar backbone through the noncovalent S⋯O interaction. The new TRTzOR was copolymerized with benzothiadiazoles with distinct F numbers to yield a series of polymer semiconductors. Compared to TRTOR-based analogous polymers, these TRTzOR-based polymers have broader absorption up to 950 nm with lower-lying FMOs by 0.2-0.3 eV, and blending these polymers with PC 71 BM leads to polymer solar cells (PSCs) with improved open-circuit voltage ( V oc ) by ca. 0.1 V and a much smaller energy loss ( E loss ) as low as 0.59 eV. These results demonstrate that thiazole substitution is an effective approach to tune FMO levels for realizing higher V oc s in PSCs and the small E loss renders TRTzOR a promising building block for developing high-performance organic semiconductors., Competing Interests: There are no conflicts of interest to declare, (This journal is © The Royal Society of Chemistry.)

A face-on oriented and p-doped semicrystalline conjugated polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]-thiadiazole)] (PPDT2FBT), was studied as a hole-transport layer (HTL) in methylammonium lead triiodide-based perovskite solar cells (PVSCs). PPDT2FBT exhibits a mid-band gap (1.7 eV), high vertical hole mobility (7.3 × 10 -3 cm 2 /V·s), and well-aligned frontier energy levels with a perovskite layer for efficient charge transfer/transport, showing a maximum power conversion efficiency (PCE) of 16.8%. Upon doping the PPDT2FBT HTL with a nonhygroscopic Lewis acid, tris(pentafluorophenyl)borane (BCF, 2-6 wt %), the vertical conductivity was improved by a factor of approximately 2, and the resulting PCE was further improved up to 17.7%, which is higher than that of standard PVSCs with 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) as an HTL. After BCF doping, the clearly enhanced carrier diffusion coefficient, diffusion length, and lifetime were measured using intensity-modulated photocurrent and photovoltage spectroscopy. Furthermore, compared to the standard PVSCs with spiro-OMeTAD, the temporal device stability was remarkably improved, preserving the ∼60% of the original PCE for 500 h without encapsulation under light-soaking condition (1 sun AM 1.5G) at 85 °C and 85% humidity, which is mainly due to the highly crystalline conjugated backbone of PPDT2FBT and nonhygroscopic nature of BCF. In addition, formamidinium lead iodide/bromide (FAPbI 3-x Br x )-based PVSCs with the BCF-doped PPDT2FBT as an HTL was also prepared to show 18.8% PCE, suggesting a wide applicability of PPDT2FBT HTL for different types of PVSCs.

p16 is a negative regulator of cell proliferation and is considered a tumor suppressor protein. Alterations in p16 protein expression are associated with tumor development and progression. However, the p16 expression status in the peritumoral stroma has not been investigated in the endometrium. Therefore, we evaluated stromal p16 expression in different types of endometrial lesions using immunohistochemistry. Differences in the p16 expression status according to the degree of malignancy and histological type were analyzed. This study included 62, 26, and 36 cases of benign, precancerous, and malignant endometrial lesions, respectively. Most benign lesions showed negative or weak expression, whereas precancerous lesions showed a variable degree of staining proportion and intensity. Atypical hyperplasia/endometrial intraepithelial neoplasia (AH/EIN) and serous endometrial intraepithelial carcinoma (SEIC) had significantly higher stromal p16 expression levels than benign lesions. Endometrioid carcinoma (EC), serous carcinoma (SC), and carcinosarcoma showed significantly elevated stromal p16 expression levels compared with benign and precancerous lesions. In addition, there were significant differences in stromal p16 expression between AH/EIN and SEIC and between EC and SC. In contrast, differences in stromal p16 expression among nonpathological endometrium, atrophic endometrium, endometrial polyp, and hyperplasia without atypia were not statistically significant. Our observations suggest that stromal p16 expression is involved in the development and progression of endometrial carcinoma, and raise the possibility that p16 overexpression in the peritumoral stroma is associated with aggressive oncogenic behavior of endometrial SC.

Background: Adults with intellectual disabilities (ID) face significant barriers to screening participation. We determined predictors for regular cardiovascular health screening at baseline among adults with ID in Singapore, and evaluated the effectiveness of a 3-month screening intervention., Methods: The study population involved all adults with ID aged ≥40 years receiving services from the Movement for the Intellectually Disabled of Singapore (MINDS), the largest such provider in Singapore. Over 3 months in 2011, adult clients not screened regularly at baseline for hypertension, diabetes and dyslipidaemia were offered free and convenient blood pressure, fasting blood glucose and lipid testing; data on other cardiovascular disease risk factors were also collected. Chi-square and logistic regression identified predictors of regular screening at baseline., Results: Participation was 95.0% (227/239). At baseline, among adults with ID, 61.8% (118/191), 24.8% (52/210) and 18.2% (34/187) had gone for regular hypertension, diabetes and dyslipidaemia screening respectively; post intervention, rates rose to 96.9%, 89.5% and 88.8% respectively. Prevalence of cardiovascular disease risk factors (22.5% with hypertension, 10.6% with diabetes, 34.8% with dyslipidaemia, 10.7% obese and 90.6% lacking regular exercise) was high compared against the general population. While receiving residential services was associated with regular hypertension screening, receiving non-residential services and being independently mobile were associated with regular participation in fasting blood tests (all P < 0.05)., Conclusion: Cardiovascular disease risk factors are common among adults with ID and clinicians should proactively screen such populations. Provision of free and convenient screening for cardiovascular disease risk improved screening participation., (© 2012 The Authors. Journal of Intellectual Disability Research © 2012 John Wiley & Sons Ltd, MENCAP & IASSIDD.)

Introduction: Little is known about the sociodemographic and clinical profile of older adults with intellectual disabilities (ID) in Singapore. We studied the sociodemographic and clinical profile of older adults with ID and investigated factors associated with caregiver availability and identity in this population., Materials and Methods: The study population involved all adults with ID aged ≥40 years receiving services from the Movement for the Intellectually Disabled of Singapore (MINDS), the largest such provider in Singapore. Information on sociodemographic and clinical profiles, functional status, and availability of caregivers were collected via interviewer-administered questionnaires from guardians of older adults with ID. Descriptive characteristics were computed and chi-square and logistic regression identifi ed predictors of caregiver availability and identity., Results: Participation was 95% (227/239). There were differences in client age, gender, and caregiver availability between recipients of residential and non-residential services (all P <0.05). Common comorbidities included hyperlipidaemia (17.6%), hypertension (15.9%), psychiatric diagnoses (16.3%) and epilepsy (10.6%). The majority were fully independent in basic activities of daily living, but only 21.1% were fully communicative. Only a small minority (9.4%) were exercising regularly. The majority (73.5%) of clients had a primary caregiver; almost equal proportions relied on either parents or siblings. Older client age was associated independently with the lack of a primary caregiver, independent of greater functional dependence and presence of medical comorbidities in the client., Conclusion: Older adults with ID have multiple medical, functional, and social issues. More can be done to support the care of this unique group of adults with special needs.

Determining the viral etiology of respiratory tract infections (RTI) has been limited for the most part to specific primer PCR-based methods due to their increased sensitivity and specificity compared to other methods, such as tissue culture. However, specific primer approaches have limited the ability to fully understand the diversity of infecting pathogens. A pathogen chip system (PathChip), developed at the Genome Institute of Singapore (GIS), using a random-tagged PCR coupled to a chip with over 170,000 probes, has the potential to recognize all known human viral pathogens. We tested 290 nasal wash specimens from Filipino children <2 years of age with respiratory tract infections using culture and 3 PCR methods-EraGen, Luminex, and the GIS PathChip. The PathChip had good diagnostic accuracy, ranging from 85.9% (95% confidence interval [CI], 81.3 to 89.7%) for rhinovirus/enteroviruses to 98.6% (95% CI, 96.5 to 99.6%) for PIV 2, compared to the other methods and additionally identified a number of viruses not detected by these methods.

In April 2009, a new influenza A (H1N1 2009) virus emerged that rapidly spread around the world. While current variants of this virus have caused widespread disease, particularly in vulnerable groups, there remains the possibility that future variants may cause increased virulence, drug resistance or vaccine escape. Early detection of these virus variants may offer the chance for increased containment and potentially prevention of the virus spread. We have developed and field-tested a resequencing kit that is capable of interrogating all eight segments of the 2009 influenza A(H1N1) virus genome and its variants, with added focus on critical regions such as drug-binding sites, structural components and mutation hotspots. The accompanying base-calling software (EvolSTAR) introduces novel methods that utilize neighbourhood hybridization intensity profiles and substitution bias of probes on the microarray for mutation confirmation and recovery of ambiguous base queries. Our results demonstrate that EvolSTAR is highly accurate and has a much improved call rate. The high throughput and short turn-around time from sample to sequence and analysis results (30 h for 24 samples) makes this kit an efficient large-scale evolutionary biosurveillance tool.

We report the preparation of mesoporous titania thin films with the R$\bar 3$m pore structure derived from the Im$\bar 3$m self-assembled ordering of the titania species and an EO(106)PO(70)EO(106) triblock copolymer. The films were spin-cast and then aged at 18 degrees C at a relative humidity of 70 %, which led to the orientation of the Im$\bar 3$m structure with the [111] direction perpendicular to the substrates. The [111] body-diagonal channels became vertical channels upon calcination at 400 degrees C, thus leading to thin films with vertical channels. The pores are ordered over a large area of up to 1 mum(2). The titania films can be formed on various types of substrates. By using a titania film formed on a Pt-coated Si wafer as a template, we produced by an electrochemical-deposition technique arrays of gold nanowires, whose morphology suggests that most of the pores of the titania thin films are accessible. The pore structure of vertical channels is stable up to 600 degrees C, at which temperature the wall materials crystallize into anatase.

Objective: To investigate the effect of psychological arousal on pain ratings and the R2 component of the electrically evoked blink reflex to a 'pure' noiciceptive stimulus., Methods: Pain ratings and R2 to a noiciceptive stimulus (pulse width 0.3ms, 2mA, delivered from a concentric electrode attached to the supraorbital region of the forehead) were investigated in 16 healthy participants before and during a serial subtraction task, and in 16 control participants who sat quietly during nociceptive stimulation., Results: Pain ratings decreased whereas R2 amplitude increased during the serial subtraction task., Conclusions: Supra-spinal rather than spinal mechanisms inhibited pain perception during psychological arousal. Moreover, psychological arousal facilitated the R2 component of the blink reflex to a nociception-specific stimulus., Significance: Supra-spinal influences need to be considered during clinical evaluation of the trigeminal nociceptive blink reflex.

The gastroprotective activity of phytosphingosine hydrochloride (PS-HCl, CAS 554-62-1) was assessed in four different rat models of experimentally induced gastric ulcer. Various doses (2.5-10 mg/kg) of PS-HCI were orally administered to rats 30 min before the treatment with HCl/ethanol, indometacin, cysteamine, or to rats with ligated pylorus. Oral administration of PS-HCl (2.5-10 mg/kg) to rats prevented the acute ulcer formation in 4 different types of ulcer in a dose-dependent manner as follows: (1) HCl/ethanol-induced gastric mucosal membrane lesions (20.1-47.8% inhibition), (2) indometacin-induced gastric mucosal membrane lesions (4.6-31.9% inhibition), (3) duodenal ulcer induced by cysteamine (10-20% inhibition), (4) gastric secretion and ulceration following pylorus ligation (33.3-61.9% inhibition). These results indicate that PS-HCI may be useful for the prevention of gastric ulcer.

Severe mental illnesses cause their sufferers dismal functional impairment. The Global Burden of Disease lists schizophrenia among the top 10 contributors to health burden and disability around the world. In the Institute of Mental Health (IMH) of Singapore, 9 out of 10 Class-C beds are occupied by patients whose hospitalisation periods last 300 days on average. Whilst de-institutionalisation has not seen its expected level of success overseas, the provision of community-based psychiatric care has been shown to be more cost-effective than hospital-based inpatient care. As such, there is a need for increased emphasis on community psychiatric services, both to provide and to effectively utilise available resources to assist patients with severe mental illnesses in living and functioning within the community. In line with several other efforts, a pilot Assertive Community Treatment or ACT Programme was launched by IMH in November 2003. This article details the aims, set-up and services of this pilot project funded by the Health Service Development Programme (HSDP) for 3 years, which receives referrals from IMH psychiatrists. With the services provided by the ACT team including psychosocial rehabilitation, it is hoped that patients will continue to receive adequate psychiatric care as well as maintain sufficient skills for self-care and independent living within the community despite the well-documented deteriorating course of psychotic illnesses like schizophrenia.

Background: While the eradication of Helicobacter pylori in patients with bleeding peptic ulcer disease (PUD) decreases the rate of ulcer re-bleeding, the sensitivity of the rapid urease test (RUT) for H. pylori diagnosis is lower in this setting. The aim of this study was therefore to determine if exposing a gastric biopsy specimen to blood before its use in the RUT (CLOtest) could account for these findings., Methods: In patients undergoing endoscopy for the evaluation of dyspepsia gastric mucosal biopsies were obtained for H. pylori diagnosis (RUT, microbiology, and histology). Mucosal biopsies from each patient were also exposed to blood for 15, 30 and 45 minutes before use in the RUT., Results: Using a combination of diagnostic tests (histology, microbiology and routine CLOtest) as the 'gold standard', the sensitivity, specificity, positive predictive value and negative predictive value of the CLOtest remained above 90% despite prior exposure of the gastric biopsy specimen to blood, and these values were not significantly different from the performance characteristics of the CLOtest processed in a routine manner., Conclusion: The exposure of gastric mucosal biopsy specimens to blood alone is not the explanation for the reduced sensitivity of the RUT in patients with bleeding peptic ulcers.