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A unique class of tridentate diaryltriazine ligand-containing gold(III) complexes with thermally activated delayed fluorescence (TADF) and/or thermally stimulated delayed phosphorescence (TSDP) properties has been designed and synthesized. With a simple structural modification on the coordination of carbazole moiety in the monodentate ligand, a large spectral shift of ∼160 nm (ca. 4900 cm -1 ) spanning from sky blue to red emissions has been demonstrated in solid-state thin films. Three-state or four-state models have been employed in fitting the emission lifetimes of the gold(III) complexes at various temperatures. The findings clearly indicate the presence of three emitting states, S 1 , T 1 , and T 1 ', suggesting the coexistence of TADF, phosphorescence, and TSDP. Notably, a minor structural change in the donor moiety between phenylcarbazolyl and diphenylaminoaryl has been demonstrated to turn on/off the TSDP, resulting in TADF-TSDP-phosphorescence or TADF-phosphorescence emitters. The TADF and/or TSDP properties have also been supported by temperature-dependent ultrafast transient absorption studies, with the direct observation of reverse intersystem crossing (RISC) and reverse internal conversion (RIC) and the determination of the activation parameters and excited state dynamics. Solution-processed and vacuum-deposited organic light-emitting devices (OLEDs) have been prepared, in which sky blue emitting devices based on 5 exhibit an operational lifetime LT 70 ∼ 5 times longer than the previously reported sky blue emitting analogue that shows only TSDP property. These results have provided valuable insights into the manipulation of the excited states via rational molecular design toward the realization of gold(III)-based TSDP and/or TADF materials with multiple radiative decay pathways that show enhanced radiative decay rate constants ( k r ) for practical OLED applications.

Photo-responsive malachite green moieties have been incorporated into an alkynylplatinum(II) bzimpy system. The photo-caged complexes in acetonitrile solutions exhibit self-assembly properties modulable by photo-removal of the cyano protecting group. Distinct aggregate morphologies, which are facilitated by the non-covalent metal-metal and π-π stacking interactions, have been observed before and after photo-irradiation.

Achieving both high efficiency and high stability in blue thermally activated delayed fluorescence organic light-emitting diodes (TADF-OLEDs) is challenging for practical displays and lighting. Here, we have successfully developed a series of sky-blue to pure-blue emitting donor-acceptor (D-A) type TADF materials featuring a four-coordinated boron with 2,2'-(pyridine-2,6-diyl)diphenolate (dppy) ligands, i.e. 1-8. Synergistic engineering of substituents on the phenyl bridge as well as the electronic properties and the attached positions of heteroatom N-donors not only enables fine-tuning of the emission colors, but also modulates the nature and energies of their triplet excited states that are important for the reverse intersystem crossing (RISC). Particularly for the compound with two methyl substituents on the phenyl bridge (compound 8), RISC is significantly facilitated through the vibronic coupling of the energetically close-lying triplet charge transfer ( 3 CT) and the triplet local excited ( 3 LE) states, when compared to analogue 7. Efficient sky-blue to pure-blue OLEDs with electroluminescence peaks ( λ EL ) at 460-492 nm have been obtained, in which ca . five-fold higher external quantum efficiencies (EQEs) of 18.9% have been demonstrated by 8 than that by 7. Moreover, ca . thirty times longer device operational half-lifetimes (LT 50 ) of 9113 hours for 8 than that for 7 as well as satisfactory LT 50 reaching 26 643 hours for 6 at an initial luminance of 100 cd m -2 have also been demonstrated. To the best of our knowledge, these results represent one of the best high-performance blue OLEDs based on tetracoordinated boron TADF emitters. Moreover, the design strategy presented here has provided an attractive strategy for enhancing the device performance of blue TADF-OLEDs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Strained carbon nanohoops exhibit attractive photophysical properties due to their unique π-conjugated structure. However, incorporation of such nanohoops into the pincer ligand of metal complexes has rarely been explored. Herein, a new family of highly strained cyclometalated platinum(II) nanohoops has been synthesized and characterized. Strain-promoted C-H bond activation has been observed during the metal coordination process, and Hückel-Möbius topology and random-columnar packing in the solid state are found. Transient absorption spectroscopy revealed the size-dependent excited state properties of the nanohoops. Moreover, the nanohoops have been successfully employed as active materials in the fabrication of solution-processable resistive memory devices, including the use of the smallest platinum(II) nanohoop for the fabrication of a binary memory, with low switching threshold voltages of ca. 1.5 V, high ON/OFF current ratios, and good stability. These results demonstrate that strain incorporation into the structure can be an effective strategy to fundamentally fine-tune the reactivity, optoelectronic, and resistive memory properties.

A new class of amphiphilic tetradentate platinum(ii) Schiff base complexes has been designed and synthesized. The self-assembly properties by exploiting the potential Pt⋯Pt interactions of amphiphilic platinum(ii) Schiff base complexes in the solution state have been systematically investigated. The presence of Pt⋯Pt interactions has further been supported by computational studies and non-covalent interaction (NCI) analysis of the dimer of the complex. The extent of the non-covalent Pt⋯Pt and π-π interactions could be regulated by a variation of the solvent compositions and the hydrophobicity of the complexes, which is accompanied by attractive spectroscopic and luminescence changes and leads to diverse morphological transformations. The present work represents a rare example of demonstration of directed cooperative assembly of amphiphilic platinum(ii) Schiff base complexes by intermolecular Pt⋯Pt interactions in solution with an in-depth mechanistic investigation, providing guiding principles for the construction of supramolecular structures with desirable properties using platinum(ii) Schiff base building blocks., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

A new class of thermally activated delayed fluorescence (TADF) pyridine-/pyrazine-containing tetradentate C^C^N^N gold(III) complexes have been designed and synthesized. Displaying photoluminescence quantum yields (PLQYs) of up to 0.77 in solid-state thin films, these complexes showed at-least a six-fold increase in the radiative decay rate constant ( k r ) in toluene upon increasing temperature from 210 to 360 K. Using variable-temperature (VT) ultrafast transient absorption (TA) spectroscopy, the reverse intersystem crossing (RISC) processes were directly observed and the activation parameters were determined, in line with the results of the Boltzmann two-level model fittings, in which the energy separation values between the lowest-lying singlet excited state (S 1 ) and the lowest-lying triplet excited state (T 1 ), Δ E (S 1 -T 1 ), of these complexes were estimated to be in the range of 0.16-0.18 eV. Through strategic modification of the position of the electron-donating - t Bu substituent in the cyclometalating ligand, the permanent dipole moments (PDMs) of these tetradentate gold(III) emitters could be manipulated to enhance their horizontal alignment in the emitting layer of organic light-emitting devices (OLEDs). Consequently, the resulting vacuum-deposited OLEDs demonstrated a 30% increase in the theoretical out-coupling efficiency ( η out ), as well as promising electroluminescence (EL) performance with maximum external quantum efficiencies (EQEs) of up to 15.7%.

Both pillar[n]arenes (P[n]As) and [n]cycloparaphenylenes ([n]CPPs) play an important role in supramolecular chemistry. Herein, we report the precise synthesis of two multifunctional bismacrocycles [n]CPP-P[5]A by integrating P[5]A into the [n]CPP backbone. The photoluminescence quantum yield (Φ F ) of the bismacrocycles was found to show a dramatic increase relative to the corresponding [n]CPPs. The chiral enantiomers (pR)/(pS)-[8]CPP-P[5]A were successfully isolated by chiral HPLC, and showed promising properties of circularly polarized luminescence (g lum ≈0.02). In addition, [n]CPP-P[5]A bismacrocycles are capable of binding pyridinium salts and fullerene derivatives with high affinity and specificity within the two distinct cavities. Transient absorption studies showed that photo-induced electron transfer occurs in [10]CPP-P[5]A⊃C 60 complex. Our results suggest that [n]CPP-P[5]A are potentially useful in CPL-active materials, multiple guest recognition and supramolecular polymer preparation., (© 2023 Wiley-VCH GmbH.)

A new class of thermally activated delayed fluorescence (TADF) tetradentate C ∧ C ∧ N ∧ N ligand-containing gold(III) complexes containing acridinyl moieties has been designed and synthesized. These complexes exhibit orange-red to deep-red emission with photoluminescence quantum yields (PLQYs) of up to 0.76 in solid-state thin films. Short excited-state lifetimes of ≤2.0 μs and large radiative decay rate constants ( k r ) in the order of 10 5 s -1 have also been found in the complexes. High-performance solution-processed and vacuum-deposited organic light-emitting devices (OLEDs) based on these complexes have been fabricated, demonstrating high maximum external quantum efficiencies (EQEs) of 12.2 and 12.7%, respectively, which are among the best values ever reported for red-emitting gold(III)-based OLEDs. In addition, satisfactory operational half-lifetime (LT 50 ) values of up to 34,058 h have been attained in these red-emitting devices. It is found that the operational stability is strongly dependent on the choice of functional groups on the acridinyl moieties, of which the incorporation of -O- and -S- linkers can effectively prolong the LT 50 value by an order of magnitude. The TADF properties of the complexes are substantiated by the hypsochromic shift in emission energies and the remarkable enhancement in the emission intensity upon increasing temperature. The TADF properties have also been supported by temperature-dependent ultrafast transient absorption studies, with the direct observation of reverse intersystem crossing (RISC) and the determination of the activation parameters for the very first time, together with their excited-state dynamics.

Overactive Janus kinases (JAKs) are known to drive leukemia, making them well-suited targets for treatment. We sought to identify new JAK-activating mutations and instead found a JAK1-inactivating pseudokinase mutation, V666G. In contrast to other pseudokinase mutations that canonically lead to an active kinase, the JAK1 V666G mutation led to under-activation seen by reduced phosphorylation. To understand the functional role of JAK1 V666G in modifying kinase activity we investigated its influence on other JAK kinases and within the Interleukin-2 pathway. JAK1 V666G not only inhibited its own activity, but its presence could inhibit other JAK kinases. These findings provide new insights into the potential of JAK1 pseudokinase to modulate its own activity, as well as of other JAK kinases. Thus, the features of the JAK1 V666 region in modifying JAK kinases can be exploited to allosterically inhibit overactive JAKs.

A new series of robust C^C^N carbazolylgold(III) complexes is designed and synthesized through the introduction of inert and sterically bulky oligophenyl substituents on the pyridyl moiety of the cyclometalating ligand. High photoluminescence quantum yields of up to 96% are recorded with these complexes doped in solid-state thin films, and short excited-state lifetimes of 0.3 μs or less in the solid state at room temperature are found. Promising electroluminescence (EL) performances are shown by the vacuum-deposited organic light-emitting devices (OLEDs) based on this series of gold(III) complexes. High external quantum efficiencies of up to 19.5% with efficiency roll-offs of down to 10% at a practical luminance brightness level of 1000 cd m -2 are achieved. More importantly, record-long operational lifetimes (LT 50 ) of up to 470,700 h at 100 cd m -2 are realized, which is currently the highest value among all classes of gold(III) complexes with tridentate pincer ligands. Particularly, by introducing a sterically bulky terphenyl moiety on the reactive site of the pyridine ring, the LT 50 value is shown to attain ∼7 times longer half-lifetime than that based on the unsubstituted complex. These unprecedented EL performances and the simple synthetic route in a mercury-free fashion make them promising emitting materials for practical OLEDs toward commercialization.

Decanuclear and pentanuclear gold(I) sulfido complexes of phenanthrene- and dibenzothiophene-based diphosphine ligands were synthesized and characterized. Unprecedented stimuli-induced reversible transformation between decanuclear and pentanuclear gold(I) sulfido complexes was observed, which could be readily monitored by NMR and UV-vis absorption spectroscopy in solution. Remarkably, the decanuclear gold(I) sulfido complex ( Au 10 -L Ph ) was found to show a highly reversible transformation process, which is stable for over 10 successive cycles in solution. The stimuli-induced reversible transformation behavior of the gold(I) sulfido complexes was found to depend on the P-P bite distance of the bidentate phosphine ligands.

A series of platinum(II) calix[4]arene-based molecular tweezers was synthesized. The studies of the host-guest association with a charge-neutral cyclometalated platinum(II) complex showed a drastic color change and the turning on of near-infrared emission resulting from Pt⋅⋅⋅Pt and π-π interactions. Control of the host-guest assembly process by varying the solvent composition can lead to a change from discrete host and guest molecules to high-ordered host-guest oligomers with the formation of sheet-like nanostructures, demonstrating a rare example of three-state supramolecular host-guest system with high solubility in solvents of diverse polarity. The change in host-guest assembly behaviors could be probed by drastic color changes from yellow to orange to green. The present study provides insights into the systematic design of solvent-responsive molecular materials using molecular tweezers-directed host-guest assembly, with potential applications in colorimetric sensing of changes in the micro-environment., (© 2022 Wiley-VCH GmbH.)

A series of carbazolyl ligands has been designed and synthesized through the integration of various electron-donating and electron-accepting motifs, including electron-donating 4-(diphenylamino)aryl and electron-accepting cyano and diphenylphosphine oxide moieties, for the development of a new class of gold(iii) complexes, where the energies of their triplet intraligand and ligand-to-ligand charge transfer excited states can be manipulated for the activation of thermally activated delayed fluorescence (TADF). Upon excitation, these complexes show high photoluminescence quantum yields of up to 80% in solid-state thin films, with short excited state lifetimes down to 1 μs. Vacuum-deposited and solution-processed organic light-emitting devices based on these complexes demonstrate promising electroluminescence (EL) performance with maximum external quantum efficiencies of 15.0% and 11.7%, respectively, and notably small efficiency roll-off values of less than 1% at the practical luminance brightness level of 1000 cd m -2 . These distinct EL performances are believed to be due to the occurrence of multichannel radiative decay pathways via both phosphorescence and TADF that significantly shorten the emission lifetimes and hence reduce the occurrence of the detrimental triplet-triplet annihilation in the gold(iii) complexes., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

G protein-coupled receptors (GPCRs) are the largest class of cell-surface receptor proteins with important functions in signal transduction and often serve as therapeutic drug targets. With the rapidly growing public data on three dimensional (3D) structures of GPCRs and GPCR-ligand interactions, computational prediction of GPCR ligand binding becomes a convincing option to high throughput screening and other experimental approaches during the beginning phases of ligand discovery. In this work, we set out to computationally uncover and understand the binding of a single ligand to GPCRs from several different families. Three-dimensional structural comparisons of the GPCRs that bind to the same ligand revealed local 3D structural similarities and often these regions overlap with locations of binding pockets. These pockets were found to be similar (based on backbone geometry and side-chain orientation using APoc), and they correlate positively with electrostatic properties of the pockets. Moreover, the more similar the pockets, the more likely a ligand binding to the pockets will interact with similar residues, have similar conformations, and produce similar binding affinities across the pockets. These findings can be exploited to improve protein function inference, drug repurposing and drug toxicity prediction, and accelerate the development of new drugs.

In order to improve the health and quality of life of older adults, the Chinese government is dedicated to establishing an equilibrium level of primary healthcare services for all communities. However, little attention has been paid to measuring the accessibility of primary hospitals to older adults, nor to understanding the seniors' satisfaction with and needs for primary healthcare services. Therefore, this study sought to investigate the spatial accessibility of primary hospitals to older adults, and also to examine the impact of walking distances on the seniors' satisfaction with their healthcare services. A two-step floating catchment area method was applied to measure the spatial accessibility of primary hospitals to older adults at the level of subdistricts. In order to investigate the actual opinions of older adults and verify the results of spatial analysis, a large-scale questionnaire survey was also conducted. The analyses found that (1) primary hospitals were not equally distributed; (2) most older adults did not have access to primary hospitals within a threshold walking distance of 1,000 m, but they usually could reach a hospital in their subdistrict within a threshold distance of 2,000 m; (3) older adults' satisfaction levels with primary hospitals were significantly different among subdistricts; (4) long walking distances negatively influenced older adults' satisfaction with primary hospitals; (5) the satisfaction of older adults was highest with a threshold distance of 500 m; and (6) a piecewise regression model indicated that older adults' satisfaction with primary hospitals would decrease with an increase in walking distance to the hospital. When the walking distances exceeded 1,000 m, the slope of the linear regression model increased significantly compared with the slope for walking distances less than 1,000 m. By adopting multiple research methods and capturing older adults' behaviors and satisfaction, our results provide (1) data on the importance of accessibility of primary hospitals to older adults, and (2) insights for future planning to achieve equity in primary healthcare and enhance the spatial distribution of primary hospitals., 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., (Copyright © 2022 Yu, Leung, Ma and Xia.)

Chronic low back pain (CLBP) is common among older adults. This systematic review aimed to summarize: (1) the prevalence and incidence of CLBP in older adults, and (2) demographic, psychological, and clinical factors positively/negatively associated with prevalence/incidence of CLBP among older adults. Four databases were searched to identify relevant publications. Ten studies (31,080 older adults) were included after being screened by 5 independent reviewers using predetermined criteria. The methodological quality of these studies was evaluated by standardized tools. The quality of evidence for all factors were appraised by modified GRADE for cohort studies. Twenty-eight and 1 factors were associated with a higher prevalence and a lower 5-year cumulative incidence of CLBP, respectively. No prognostic factor was identified. There was very limited to limited evidence that females, obesity, anxiety, depression, mental disorders, self-expectation of recovery, self-perceived health status, lifestyle (smoking, daily fluoride consumption), previous falls or lower body injury, retirement/disability due to ill health, family history of body pain, comorbidity (knee osteoarthritis, or chronic obstructive pulmonary disease with/without hypertension), weak abdominal muscles, leg pain, leg pain intensity, widespread pain, pain interference on functioning, use of pain medication, occupational exposure (driving for >20 years, or jobs involving bending/twisting for >10 years), disc space narrowing and severe facet osteoarthritis were significantly related to a higher prevalence of CLBP in older adults. However, very limited evidence suggested that intermediate level of leisure-time physical activity was associated with a lower prevalence of CLBP in older adults. Given the aging population and limited information regarding risk factors for CLBP in older adults, future high-quality prospective studies should identify relevant risk factors to help develop proper preventive and treatment strategies. PERSPECTIVE: Despite the high prevalence of non-specific chronic low back pain among older adults, there is only very limited to limited evidence regarding factors associated with a higher prevalence of chronic low back pain in this population. Given the aging population, high-quality prospective studies are warranted to address this gap., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

A new class of alkynylplatinum(II) bzimpy (bzimpy = bis(benzimidazol-2-yl)pyridine) double complex salts (DCSs) containing dialkoxynaphthalene or pyromellitic diimide moieties on the alkynyl ligand has been reported to display distinct morphological properties compared to their precursor alkynylplatinum(II) complexes, with the capability of being aligned by the directional Pt···Pt and/or π-π stacking interactions. The incorporation of donor and acceptor units on the alkynyl ligands has been found to significantly perturb the alignment of the oppositely charged complex ions in the DCSs to stack in a twisted head-to-head manner, attributed to the additional driving forces of electrostatic and donor-acceptor interactions. The modulation of the Pt···Pt distances and the extent of aggregate formation have been demonstrated by altering the charge matching between the platinum(II) bzimpy moieties and the donor or acceptor moieties on the alkynyl ligand.

A new series of four-coordinate boron compounds bearing a photochromic dithienylethene-containing C^C ligand and an ancillary N^C ligand have been successfully designed and synthesised. These compounds exhibit reversible photochromism upon photoexcitation with percentage conversions of 71-96% and readily tuneable photocycloreversion quantum yields by convenient modification of the ancillary ligand to turn on the thermally activated upconversion from the lower-lying unreactive excited state to the higher-lying photoreactive excited state.

A series of heteroleptic cyclometalated platinum(II) complexes, [Pt(C^N)(O^O)], (1-10) with various donors and acceptors has been synthesized and characterized by 1 H NMR spectroscopy, elemental analyses, infrared spectroscopy and mass spectrometry. The X-ray structure of 2 has also been determined. The electrochemical and photophysical properties of the platinum(II) complexes were studied. These experimental results have been supported by computational studies. Furthermore, two of the complexes have been employed as the active material in the fabrication of resistive memory devices, exhibiting stable binary memory performance with low operating voltage, high ON/OFF ratio and long retention time., (© 2021 Wiley-VCH GmbH.)

Colorectal cancer (CRC) is the third most common cancer that contributes to cancer-related morbidity. However, the differential expression of genes in different phases of CRC is largely unknown. Moreover, very little is known about the role of stress-survival pathways in CRC. We sought to discover the hub genes and identify their roles in several key pathways, including oxidative stress and apoptosis in the different stages of CRC. To identify the hub genes that may be involved in the different stages of CRC, gene expression datasets were obtained from the gene expression omnibus (GEO) database. The differentially expressed genes (DEGs) common among the different datasets for each group were obtained using the robust rank aggregation method. Then, gene enrichment analysis was carried out with Gene Ontology and Kyoto Encyclopedia of Genes and Genomes databases. Finally, the protein-protein interaction networks were constructed using the Cytoscape software. We identified 40 hub genes and performed enrichment analysis for each group. We also used the Oncomine database to identify the DEGs related to stress-survival and apoptosis pathways involved in different stages of CRC. In conclusion, the hub genes were found to be enriched in several key pathways, including the cell cycle and p53 signaling pathway. Some of the hub genes were also reported in the stress-survival and apoptosis pathways. The hub DEGs revealed from our study may be used as biomarkers and may explain CRC development and progression mechanisms.

Mucin-type O-glycosylation is one of the most common posttranslational modifications of proteins. The abnormal expression of various polypeptide GalNAc-transferases (GalNAc-Ts) which initiate and define sites of O-glycosylation are linked to many cancers and other diseases. Current O-glycosyation prediction programs utilize O-glycoproteomics data obtained without regard to the transferase isoform (s) responsible for the glycosylation. With 20 different GalNAc-Ts in humans, having an ability to predict and interpret O-glycosylation sites in terms of specific GalNAc-T isoforms is invaluable. To fill this gap, ISOGlyP (Isoform-Specific O-Glycosylation Prediction) has been developed. Using position-specific enhancement values generated based on GalNAc-T isoform-specific amino acid preferences, ISOGlyP predicts the propensity that a site would be glycosylated by a specific transferase. ISOGlyP gave an overall prediction accuracy of 70% against in vivo data, which is comparable to that of the NetOGlyc4.0 predictor. Additionally, ISOGlyP can identify the known effects of long- and short-range prior glycosylation and can generate potential peptide sequences selectively glycosylated by specific isoforms. ISOGlyP is freely available for use at ISOGlyP.utep.edu. The code is also available on GitHub (https://github.com/jonmohl/ISOGlyP)., (© The Author(s) 2020. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Here we report complex supramolecular tessellations achieved by the directed self-assembly of amphiphilic platinum(II) complexes. Despite the twofold symmetry, these geometrically simple molecules exhibit complicated structural hierarchy in a columnar manner. A possible key to such an order increase is the topological transition into circular trimers, which are noncovalently interlocked by metal···metal and π-π interactions, thereby allowing for cofacial stacking in a prismatic assembly. Another key to success is to use the immiscibility of the tailored hydrophobic and hydrophilic sidechains. Their phase separation leads to the formation of columnar crystalline nanostructures homogeneously oriented on the substrate, featuring an unusual geometry analogous to a rhombitrihexagonal Archimedean tiling. Furthermore, symmetry lowering of regular motifs by design results in an orthorhombic lattice obtained by the coassembly of two different platinum(II) amphiphiles. These findings illustrate the potentials of supramolecular engineering in creating complex self-assembled architectures of soft materials., Competing Interests: The authors declare no competing interest.

G protein-coupled receptors (GPCRs) constitute the largest group of membrane receptor proteins in eukaryotes. Due to their significant roles in various physiological processes such as vision, smell and inflammation, GPCRs are the targets of many prescription drugs. However, the functional and sequence diversity of GPCRs has kept their prediction and classification based on amino acid sequence data as a challenging bioinformatics problem. There are existing computational approaches, mainly using machine learning and statistical methods, to predict and classify GPCRs based on amino acid sequence and sequence derived features. In this paper, we describe a searchable MySQL database, named GPCR-PEnDB (GPCR Prediction Ensemble Database), of confirmed GPCRs and non-GPCRs. It was constructed with the goal of allowing users to conveniently access useful information of GPCRs in a wide range of organisms and to compile reliable training and testing datasets for different combinations of computational tools. This database currently contains 3129 confirmed GPCR and 3575 non-GPCR sequences collected from the UniProtKB/Swiss-Prot protein database, encompassing over 1200 species. The non-GPCR entries include transmembrane proteins for evaluating various prediction programs' abilities to distinguish GPCRs from other transmembrane proteins. Each protein is linked to information about its source organism, classification, sequence lengths and composition, and other derived sequence features. We present examples of using this database along with its graphical user interface, to query for GPCRs with specific sequence properties and to compare the accuracies of five tools for GPCR prediction. This initial version of GPCR-PEnDB will provide a framework for future extensions to include additional sequence and feature data to facilitate the design and assessment of software tools and experimental studies to help understand the functional roles of GPCRs. Database URL: gpcr.utep.edu/database., (© The Author(s) 2020. Published by Oxford University Press.)

A class of acceptor-donor-acceptor chromophoric small-molecule non-fullerene acceptors, 1-4 , with difluoroboron(iii) β-diketonate (BF 2 bdk) as the electron-accepting moiety has been developed. Through the variation of the central donor unit and the modification on the peripheral substituents of the terminal BF 2 bdk acceptor unit, their photophysical and electrochemical properties have been systematically studied. Taking advantage of their low-lying lowest unoccupied molecular orbital energy levels (from -3.65 to -3.72 eV) and relatively high electron mobility (7.49 × 10 -4 cm 2 V -1 s -1 ), these BF 2 bdk-based compounds have been employed as non-fullerene acceptors in organic solar cells with maximum power conversion efficiencies of up to 4.31%. Moreover, bistable resistive memory characteristics with charge-trapping mechanisms have been demonstrated in these BF 2 bdk-based compounds. This work not only demonstrates for the first time the use of a boron(iii) β-diketonate unit in constructing non-fullerene acceptors, but also provides more insights into designing organic materials with multi-functional properties., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The photophysical properties of a series of T-shaped coinage d 10 metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new example of a tridentate T-shaped Ag I complex. Post-complexation modification of the Au I complex provides access to a linear cationic Au I complex following ligand alkylation, or the first example of a cationic square planar Au III -F complex from electrophilic attack on the metal centre. Emissions ranging from blue (Cu I ) to orange (Ag I ) are obtained, with variable contributions of thermally-dependent fluorescence and phosphorescence to the observed photoluminescence. Green emissions are observed for all three gold complexes (neutral T-shaped Au I , cationic linear Au I and square planar cationic Au III ). The higher quantum yield and longer decay lifetime of the linear gold(I) complex are indicative of increased phosphorescence contribution., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Mucin-type O-glycosylation is one of the most common post-translational modifications of proteins. This glycosylation is initiated in the Golgi by the addition of the sugar N-acetylgalactosamine (GalNAc) onto protein Ser and Thr residues by a family of polypeptide GalNAc transferases. In humans there are 20 isoforms that are differentially expressed across tissues that serve multiple important biological roles. Using random peptide substrates, isoform specific amino acid preferences have been obtained in the form of enhancement values (EV). These EVs alone have previously been used to predict O-glycosylation sites via the web based ISOGlyP (Isoform Specific O-Glycosylation Prediction) tool. Here we explore additional protein features to determine whether these can complement the random peptide derived enhancement values and increase the predictive power of ISOGlyP. The inclusion of additional protein substrate features (such as secondary structure and surface accessibility) was found to increase sensitivity with minimal loss of specificity, when tested with three different published in vivo O-glycoproteomics data sets, thus increasing the overall accuracy of the ISOGlyP predictions.

A new electron-rich spirothienoquinoline unit, t BuSAF-Th, has been developed via incorporation of a thienyl unit instead of a phenyl unit into the six-membered ring of the spiroacridine (SAF) and utilized for the first time as a building block for constructing small-molecule electron donors in organic solar cells (OSCs) and as active layers in organic resistive memory devices. The resulting three-dimensional spirothienoquinoline-containing 1 - 4 exhibit high-lying highest occupied molecular orbital (HOMO) energy levels. By the introduction of electron-deficient benzochalcogenodiazole linkers, with the chalcogen atoms being varied from O to S and Se, a progressively lower lowest unoccupied molecular orbital (LUMO) energy level has been achieved while keeping the HOMO energy levels similar. This strategy has allowed an enhanced light-harvesting ability without compromising open-circuit voltage ( V oc ) in vacuum-deposited bulk heterojunction OSCs using 1 - 4 as donors and C 70 as the acceptor. Good photovoltaic performances with power conversion efficiencies (PCEs) of up to 3.86% and high short-circuit current densities ( J sc ) of up to 10.84 mA cm -2 have been achieved. In addition, organic resistive memory devices fabricated with these donor-acceptor small molecules exhibit binary logic memory behaviors with long retention times and high on/off current ratios. This work indicates that the spirothienoquinoline moiety is a potential building block for constructing multifunctional organic electronic materials.

A new class of pyrazine-based carbazole-containing gold(III) complexes featuring thermally stimulated delayed phosphorescence (TSDP) properties has been designed and synthesized. The emission colors are found to be sensitive to the coordinating atom of the carbazolyl ligands at the gold(III) center, with emission energies spanning from green to red. The efficiency of TSDP can be enhanced by lowering the polarity of the solvent, as supported by the variable-temperature emission and computational studies. Interestingly, a significant spectral shift in electroluminescence with the change of Commission Internationale de L'Eclairage (CIE) coordinates from (0.35, 0.60) to (0.44, 0.54) has been achieved by simply changing the host material from CBP to TmPyPB. Solution-processable organic light-emitting devices (OLEDs) have also been fabricated, with maximum current efficiencies of up to 22.4 cd A -1 and maximum external quantum efficiencies (EQEs) approaching 7.0%. A higher current efficiency of 35.1 cd A -1 and EQE of 10.7% can be achieved for the vacuum-deposited device based on 1 , representing the first demonstration of pyrazine-based tridentate ligand-containing gold(III) complexes as phosphorescent material for OLED application.

A new class of amphiphilic tridentate cyclometalated gold(III) complexes has been designed and synthesized as luminescent supramolecular building blocks. Positively charged trimethylammonium (-CH 2 NMe 3 + ) containing alkynyl ligands have been incorporated to introduce the electrostatic interactions. The X-ray crystal structures of two of the complexes have been determined, and the existence of π-π interactions between molecules has been observed. Steady-state and time-resolved absorption and emission studies have been carried out to investigate the nature of the excited states. The complexes are found to exhibit self-assembly properties with the assistance of π-π stacking and hydrophobic interactions and possibly weak Au···Au interaction, resulting in notable emergence of low-energy absorption bands and luminescence changes. The presence of a large hydrophobic moiety is found to be crucial for the formation of aggregates, especially in polar media where hydrophobic interactions play an important role. The nature of the counterion has been shown to have a significant effect on the extent of self-assembly in different media. Upon aggregation, nanofibers are formed in polar media, while nanorods are observed in nonpolar media in one of the representative complexes. Interestingly, a small modification on the alkynyl ligand resulted in the formation of nanoribbons instead. Intriguing luminescence mechanochromic properties have also been observed. This orthogonal and rational molecular design strategy has been shown to be effective in the construction of gold(III)-based smart and multiresponsive materials.

A new class of bent amphiphilic alkynylplatinum(ii) terpyridine complexes was found to adopt different modes of molecular stacking to give diverse nanostructures. In chlorinated solvents, the complexes aggregate in the presence of water droplets and assist in the formation of porous networks, while in DMSO solutions, they self-assemble to give fibrous nanostructures. The complexes would adopt a head-to-tail tetragonal stacking arrangement, as revealed by X-ray crystallographic studies, computational studies and powder X-ray diffraction (PXRD) studies. Their self-assembly follows a cooperative growth mechanism in DMSO and an isodesmic growth mechanism in DMSO-H 2 O mixture. The balance between hydrophobic and hydrophilic components of the complex system, in conjunction with the nuclearity and the positioning of the substituents, are found to govern the mode of molecular stacking and the fabrication of precise functional nanostructures. This class of complexes serve as versatile building blocks to construct orderly packed molecular materials and functional materials in a well-controlled manner., (This journal is © The Royal Society of Chemistry 2020.)

To address and overcome the difficulties associated with the increased reactivity and susceptibility of blue emitters to deactivation pathways arising from the high-lying triplet excited states, we have successfully demonstrated an innovative strategy of harvesting triplet emission via the "thermally stimulated delayed phosphorescence" mechanism, where thermal up-conversion of excitons from the lower-energy triplet excited states (T 1 ) to higher-energy triplet excited states (T 1 ') are observed to generate blue emission. The lower-lying T 1 excited state could serve as a mediator to populate the emissive T 1 ' state by up-conversion via reverse internal conversion, which could enhance the photoluminescence quantum yield by over 20-folds. Organic light-emitting devices with respectable external quantum efficiencies of up to 7.7% and sky-blue emission with CIE coordinates of (0.17, 0.37) have been realized. The operational stability for the device based on complex 1 has also been explored, and the device is found to show fairly respectable lifetime. This work opens up a new avenue to the design and synthesis of blue phosphorescent emitters.

While separated by large expanses of dry terrain unsuitable for aquatic biota, aridland waters possess high biodiversity. How aquatic micrometazoans disperse to, and colonize, these isolated ephemeral habitats are not well understood. We used a multi-faceted approach including wind tunnel and rehydration experiments, and next-generation sequencing to assess potential movement of diapausing propagules of aquatic invertebrates by anemochory across regional scales (10 2 -10 5 km). Wind tunnel experiments using dry playa sediments with added micrometazoan propagules demonstrated that after entrainment by saltation and downwind transport were subsequently recoverable as viable animals when rehydrated. Further, rehydration of fallen natural dust yielded micrometazoans, including rotifers, gastrotrichs, microcrustaceans, and nematodes. Using conserved DNA primers, we identified >3,300 eukaryotic Operational Taxonomic Units (excluding fungi) in the dust including some taxa found in rehydration experiments. Thus, we provide strong evidence that anemochory can disperse micrometazoans among isolated, ephemeral ecosystems in North American deserts and likely elsewhere.

Mandibular asymmetry is common among orthognathic patients and exhibits great variation. The aim of this study was to propose a new classification of mandibular asymmetry by anatomical regions; namely R (ramus), B (mandibular body) and C (chin), in conjunction with a corresponding 'RBC' three-dimensional (3D) cephalometric analysis. The cone beam computed tomography data of 65 patients with mandibular asymmetry was retrieved to perform the RBC 3D cephalometric analysis and to investigate the characteristics of mandibular asymmetry. It was found that the more posteriorly in mandible, the more pronounced was the vertical asymmetry. Significant transverse asymmetry was only noted in mandibular body. Both mandibular body and chin were significantly asymmetric in length. Seven significant morphologic predictors of menton deviation were identified, namely lower dental midline shift, difference in ramus height, difference in chin length, difference in body length, body height on contralateral side, coronoid height on deviated side and body width on contralateral side, confirming the complex nature of mandibular asymmetry. This simple and concise classification allows comprehensive assessment of mandible morphology by anatomical regions which also facilitates diagnosis, treatment planning and communication in both clinical and research settings., (Copyright © 2018 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.)

Driven by fast-growing economies worldwide, the number of international construction projects is booming, and employing expatriates has inevitably become a strategy used by construction firms. However, stress arising from expatriate assignments can lead to early return, assignment failure, and staff turnover, causing in significant losses to an organisation. Extensive research has focused on the effectiveness of coping behaviours in relation to stress. However, studies investigating the antecedents of coping are rare. The limited studies to date tend to focus on content-based motivations (identifying what), instead of on how coping behaviours can be motivated in the stress management process (identifying how). Focus on expatriate construction professionals (ECPs) is further limited. Hence, this study aims to investigate from a process theory perspective the role of motivation in the stress management process. Using a qualitative interview study approach, involving 22 in-depth interviews, this study first identifies the content of motivation, coping behaviours, performance, and stress in the context of Hong Kong ECPs working on cross-cultural projects in China; it then unveils and explains the associations between the identified variables. Based on the results, stakeholders are recommended to review pre-departure training, so as to ensure that key elements such as personal awareness of stress (cognitive, affective, and physical), expectancies of coping strategies on stress (adaptive or maladaptive), and expectancies of the influence of stress on performance are covered., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

The cattle tick of Australia, Rhipicephalus australis, is a vector for microbial parasites that cause serious bovine diseases. The Haller's organ, located in the tick's forelegs, is crucial for host detection and mating. To facilitate the development of new technologies for better control of this agricultural pest, we aimed to sequence and annotate the transcriptome of the R. australis forelegs and associated tissues, including the Haller's organ. As G protein-coupled receptors (GPCRs) are an important family of eukaryotic proteins studied as pharmaceutical targets in humans, we prioritized the identification and classification of the GPCRs expressed in the foreleg tissues. The two forelegs from adult R. australis were excised, RNA extracted, and pyrosequenced with 454 technology. Reads were assembled into unigenes and annotated by sequence similarity. Python scripts were written to find open reading frames (ORFs) from each unigene. These ORFs were analyzed by different GPCR prediction approaches based on sequence alignments, support vector machines, hidden Markov models, and principal component analysis. GPCRs consistently predicted by multiple methods were further studied by phylogenetic analysis and 3D homology modeling. From 4,782 assembled unigenes, 40,907 possible ORFs were predicted. Using Blastp, Pfam, GPCRpred, TMHMM, and PCA-GPCR, a basic set of 46 GPCR candidates were compiled and a phylogenetic tree was constructed. With further screening of tertiary structures predicted by RaptorX, 6 likely GPCRs emerged and the strongest candidate was classified by PCA-GPCR to be a GABAB receptor.

Background: Diabetes is one of the most prevalent and costly chronic diseases in the United States., Objectives: To analyze the risk of developing diabetes and the annual cost of diabetes for a US general population., Methods: Data from the Medical Expenditure Panel Survey, 2008 to 2012, were used to analyze 1) probabilities of developing diabetes and 2) annual total health care expenditures for diabetics. The age-, sex-, race-, and body mass index (BMI)-specific risks of developing diabetes were estimated by fitting an exponential survival function to age at first diabetes diagnosis. Annual health care expenditures were estimated using a generalized linear model with log-link and gamma variance function. Complex sampling designs in the Medical Expenditure Panel Survey were adjusted for. All dollar values are presented in 2012 US dollars., Results: We observed a more than 6 times increase in diabetes risks for class III obese (BMI ≥ 40 kg/m 2 ) individuals compared with normal-weight individuals. Using age 50 years as an example, we found a more than 3 times increase in annual health care expenditures for those with diabetes ($13,581) compared with those without diabetes ($3,954). Compared with normal-weight (18.5 ≤ BMI < 25 kg/m 2 ) individuals, class II obese (35 ≤ BMI < 40 kg/m 2 ) and class III obese (BMI ≥ 40 kg/m 2 ) individuals incurred an annual marginal cost of $628 and $756, respectively. The annual health care expenditure differentials between those with and without diabetes of age 50 years were the highest for individuals with class II ($12,907) and class III ($9,703) obesity., Conclusions: This article highlights the importance of obesity on diabetes burden. Our results suggested that obesity, in particular, class II and class III (i.e., BMI ≥ 35 kg/m 2 ) obesity, is associated with a substantial increase in the risk of developing diabetes and imposes a large economic burden., (Copyright © 2017 International Society for Pharmacoeconomics and Outcomes Research (ISPOR). Published by Elsevier Inc. All rights reserved.)

In this study, the direct and indirect atmospheric responses over the Asian-Pacific-American region to the El Niño-Southern Oscillation (ENSO) are documented. Since ENSO is likely to induce the northward displacement of the East Asian trough (NDEAT), some of the influence of ENSO on the Asian-Pacific-American region is possibly indirect and acts by inducing NDEAT. To separate corresponding influences of ENSO and NDEAT, partial regression is utilized. It is noted that temperature variations in the East Asian-Western Pacific region are controlled mainly by NDEAT. In contrast, ENSO demonstrates a weak direct relation to the temperature variation over the East Asian-Western Pacific region. This suggests that the influence of ENSO on this region is indirect, through modulation of NDEAT. On the other hand, temperature variation over the tropical eastern Pacific is dominated by ENSO forcing. Finally, temperature variation over the eastern North American-Western Pacific region is controlled by both ENSO and NDEAT. Nevertheless, their influences on temperature and circulation over this region tend to offset each other. This implies that temperature variation is controlled by their relative strengths.

Purpose: Three-dimensional (3D) images are taken with positioning devices to ensure a patient's stability, which, however, place the patient's head into a random orientation. Reorientation of images to the natural head position (NHP) is necessary for appropriate assessment of dentofacial deformities before any surgical planning. The aim of this study was to review the literature systematically to identify and evaluate the various modalities available to record the NHP in 3 dimensions and to compare their accuracy., Materials and Methods: A systematic literature search of the PubMed, Cochrane Library and Embase databases, with no limitations on publication time or language, was performed in July 2015. The search and evaluations of articles were performed in 4 rounds. The methodologies, accuracies, advantages, and limitations of various modalities to record NHP were examined., Results: Eight articles were included in the final review. Six modalities to record NHP were identified, namely 1) stereophotogrammetry, 2) facial markings along laser lines, 3) clinical photographs and the pose from orthography and scaling with iterations (POSIT) algorithm, 4) digital orientation sensing, 5) handheld 3D camera measuring system, and 6) laser scanning. Digital orientation sensing had good accuracy, with mean angular differences from the reference within 1° (0.07 ± 0.49° and 0.12 ± 0.54°, respectively). Laser scanning was shown to be comparable to digital orientation sensing. The method involving clinical photographs and the POSIT algorithm was reported to have good accuracy, with mean angular differences for pitch, roll, and yaw within 1° (-0.17 ± 0.50°). Stereophotogrammetry was reported to have the highest reliability, with mean angular deviations in pitch, roll, and yaw for active and passive stereophotogrammetric devices within 0.1° (0.004771 ± 0.045645° and 0.007572 ± 0.079088°, respectively)., Conclusions: This systematic review showed that recording the NHP in 3 dimensions with a digital orientation sensor has good accuracy. Laser scanning was found to have comparable accuracy to digital orientation sensing, but routine clinical use was limited by its high cost and low portability. Stereophotogrammetry and the method using a single clinical photograph and the POSIT algorithm were potential alternatives. Nevertheless, clinical trials are needed to verify their applications in patients. Preferably, digital orientation sensor should be used as a reference for comparison with new proposed methods of recording the NHP in future research., (Copyright © 2016 American Association of Oral and Maxillofacial Surgeons. Published by Elsevier Inc. All rights reserved.)