Tethered Helical Ladder-Type Aromatic Lactams.

Tethered nonplanar aromatics (TNAs) make up an important class of nonplanar aromatic compounds showing unique features. However, the knowledge on the synthesis, structures, and properties of TNAs remains insufficient. In this work, a new type of TNAs, the tethered aromatic lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess a helical ladder-type conjugated system of up to 13 fused rings. The overall yields ranged from 3.4 to 4.3%. The largest of the tethered aromatic lactams, 6L-Bu-C14, demonstrates a guest-adaptive hosting capability of TNAs for the first time. When binding fullerene guests, the cavity of 6L-Bu-C14 became more circular to better accommodate spherical fullerene molecules. The host-guest interaction is thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, and nuclear magnetic resonance (NMR) titration experiments. 6L-Bu-C14 shows stronger binding with C70 than with C60 due to the better convex-concave π-π interaction. P and M enantiomers of all tethered aromatic lactams show distinct and persistent chiroptical properties and demonstrate the potential of chiral TNAs as circularly polarized luminescence (CPL) emitters.

Asymmetric Π-Bridge Engineering Enables High-Permittivity Benzo[1,2-B:4,5-b']Difuran-Conjugated Polymer for Efficient Organic Solar Cells.

Organic solar cells (OSCs) exhibit complex charge dynamics, which are closely correlated with the dielectric constant (ɛr ) of photovoltaic materials. In this work, a series of novel conjugated copolymers based on benzo[1,2-b:4,5-b']difuran (BDF) and benzotriazole (BTz) is designed and synthesized, which differ by the nature of π-bridge from one another. The PBDF-TF-BTz with asymmetric furan and thiophene π-bridge demonstrates a larger ɛr of 4.22 than PBDF-dT-BTz with symmetric thiophene π-bridge (3.15) and PBDF-dF-BTz with symmetric furan π-bridge (3.90). The PBDF-TF-BTz also offers more favorable molecular packing and appropriate miscibility with non-fullerene acceptor Y6 than its counterparts. The corresponding PBDF-TF-BTz:Y6 OSCs display efficient exciton dissociation, fast charge transport and collection, and reduced charge recombination, eventually leading to a power conversion efficiency of 17.01%. When introducing a fullerene derivative (PCBO-12) as a third component, the PBDF-TF-BTz:Y6:PCBO-12 OSCs yield a remarkable FF of 80.11% with a high efficiency of 18.10%, the highest value among all reported BDF-polymer-based OSCs. This work provides an effective approach to developing high-permittivity photovoltaic materials, showcasing PBDF-TF-BTz as a promising polymer donor for constructing high-performance OSCs.

PDMS/magnetic lignin sponge for oil/water separation.

Recyclable, non-toxic, and degradable biological substrates contribute significantly to super-wetting surfaces. In this work, we prepared magnetic micro-nano super-hydrophobic surfaces through a robust solution with magnetic modified lignin particles as the supporting structure. A novel PDMS (polydimethylsiloxane)/magnetic lignin particle (lignin@Fe3O4)/PDA sponge composite was fabricated. Through dopamine (DA) self-polymerization, covalent deposition of magnetic lignin (ML), and PDMS silane modification, the magnetic super-hydrophobic polyurethane sponge composite (Sponge-P) was synthesized so that the Fe3O4 nanoscale microspheres wrapped with microscale lignin magnetic particles adhered to the sponge surface tighter and were barely dislodged. The as-prepared Sponge-P displayed excellent flexibility and a water contact angle of up to 152.2°. The super-hydrophobic sponge prepared with the proposed method was acid-base stable (pH = 2-12), self-cleaning, and suitable for high-salinity seawater. The magnetic super-hydrophobic sponge has good oil-water separation ability and can absorb 43 times its own weight of oil. In the meantime, due to the introduction of magnetic materials into lignin, we not only constructed micro-nanostructures to improve the surface super-hydrophobicity, but also made Sponge-P have the function of magnetic recovery, which has a unique advantage in treating oily wastewater.

High-Yield Gold Nanohydrangeas on Three-Dimensional Carbon Nanotube Foams for Surface-Enhanced Raman Scattering Sensors.

Recently, carbon nanomaterial-supported plasmonic nanocrystals used as high-performance surface-enhanced Raman scattering (SERS) substrates have attracted increasing attention due to their ultra-high sensitivity of detection. However, most of the work focuses on the design of 2-D planar substrates with traditional plasmonic structures, such as nanoparticles, nanorods, nanowires, and so forth. Here, we report a novel strategy for the preparation of high-yield Au nanohydrangeas on three-dimensional porous polydopamine (PDA)/polyvinyl alcohol (PVA)/carbon nanotube (CNT) foams. The structures and growth mechanisms of these specific Au nanocrystals are systematically investigated. PDA plays the role of both a reducing agent as well as an anchoring site for Au nanohydrangeas' growth. We also show that the ratio of surfactant KBr to the gold precursor (HAuCl4) is key to obtain these structures in a manner of high production. Moreover, the substrate of the CNT foam-Au nanohydrangea hybrid can be employed as SERS sensors and can detect the analytes down to 10-9 M.

Self-Generated Buried Submicrocavities for High-Performance Near-Infrared Perovskite Light-Emitting Diode.

Embedding submicrocavities is an effective approach to improve the light out-coupling efficiency (LOCE) for planar perovskite light-emitting diodes (PeLEDs). In this work, we employ phenethylammonium iodide (PEAI) to trigger the Ostwald ripening for the downward recrystallization of perovskite, resulting in spontaneous formation of buried submicrocavities as light output coupler. The simulation suggests the buried submicrocavities can improve the LOCE from 26.8 to 36.2% for near-infrared light. Therefore, PeLED yields peak external quantum efficiency (EQE) increasing from 17.3% at current density of 114 mA cm-2 to 25.5% at current density of 109 mA cm-2 and a radiance increasing from 109 to 487 W sr-1 m-2 with low rolling-off. The turn-on voltage decreased from 1.25 to 1.15 V at 0.1 W sr-1 m-2. Besides, downward recrystallization process slightly reduces the trap density from 8.90 × 1015 to 7.27 × 1015 cm-3. This work provides a self-assembly method to integrate buried output coupler for boosting the performance of PeLEDs.

Solitary Scapular Metastasis as the First Presentation of Prostate Adenocarcinoma Identified on 99mTc-MDP SPECT/CT.

ABSTRACT: Metastases of prostate carcinoma in the skeleton are usually multiple. Solitary metastasis in appendicular skeleton is extremely rare. We present bone scan findings of solitary scapular metastasis from prostate adenocarcinoma as the initial presentation of his malignancy in a 62-year-old man. The 99mTc-MDP SPECT/CT demonstrated intense activity in the coracoid process of left scapula, whereas the tracer uptakes in other bones were not typical of metastases. The subsequent pathological results of the punctured left scapula confirmed as metastasis from prostate adenocarcinoma.

4-Terminal Inorganic Perovskite/Organic Tandem Solar Cells Offer 22% Efficiency.

After fast developing of single-junction perovskite solar cells and organic solar cells in the past 10 years, it is becoming harder and harder to improve their power conversion efficiencies. Tandem solar cells are receiving more and more attention because they have much higher theoretical efficiency than single-junction solar cells. Good device performance has been achieved for perovskite/silicon and perovskite/perovskite tandem solar cells, including 2-terminal and 4-terminal structures. However, very few studies have been done about 4-terminal inorganic perovskite/organic tandem solar cells. In this work, semi-transparent inorganic perovskite solar cells and organic solar cells are used to fabricate 4-terminal inorganic perovskite/organic tandem solar cells, achieving a power conversion efficiency of 21.25% for the tandem cells with spin-coated perovskite layer. By using drop-coating instead of spin-coating to make the inorganic perovskite films, 4-terminal tandem cells with an efficiency of 22.34% are made. The efficiency is higher than the reported 2-terminal and 4-terminal inorganic perovskite/organic tandem solar cells. In addition, equivalent 2-terminal tandem solar cells were fabricated by connecting the sub-cells in series. The stability of organic solar cells under continuous illumination is improved by using semi-transparent perovskite solar cells as filter.

Controllable construction of multifunctional superhydrophobic coating with ultra-stable efficiency for oily water treatment.

Designing interfacial coating with tailored characteristics is a crucial step in regulating the wetting properties of oil/water separation materials; however, the controllable fabrication of multifunctional layer with long-term durability in harsh environments remains challenging. Fabrication of raised dots based on magnetic Fe3O4 particles on micro-nanometer units, inspired by mussel chemistry, under the adhesion behavior of dopamine (DA) self-polymerization covalent deposition of Fe3O4 particles and hydrophobic polydimethylsiloxane (PDMS) modification to synthesize magnetic superhydrophobic cotton composites (Cotton-P). Due to the unique magnetic and superhydrophobic surface composition, the synthetic Cotton-P possesses superhydrophobic (155.4°) and magnetic properties and still exhibits these excellent properties after 10 cycles. In addition, the hydrophobicity of magnetic monolithic cotton is virtually unaffected in harsh environments. The chemical/thermal stability of the Cotton-P composite is improved due to the rigid silane coating on the skeleton. Moreover, the Cotton-P revealed excellent oil/water separation efficiency of over 98 % after 10 cycles. Based on these outstanding properties, Cotton-P has the potential to develop in the treatment of oil-water mixtures.

A 4-Arm Small Molecule Acceptor with High Photovoltaic Performance.

Manipulating the backbone of small molecule acceptors (SMAs) is of particular importance in developing efficient organic solar cells (OSCs). The common design is constructing 2-arm SMAs with linear or curved backbones. Herein, we report an acceptor 4A-DFIC with a 4-arm backbone unexpectedly generated in the reaction of an electron-rich aromatic diamine and hexaketocyclohexane. Single-crystal X-ray diffraction analysis indicates the rigid and twisted molecular plane and the effective molecular stacking of 4A-DFIC in solid state. 4A-DFIC shows a low band gap of 1.40 eV and excellent light-harvesting capability from visible to near-infrared region. Binary and ternary OSCs based on 4A-DFIC gave power conversion efficiencies (PCEs) of 15.76 % and 18.60 % (certified 18.1 %), respectively, which are the highest PCEs for multi-arm SMA-based OSCs to date.

Folic Acid Rescues Valproic Acid-Induced Morphogenesis Inhibition in Neural Rosettes Derived From Human Pluripotent Stem Cells.

The ability of human pluripotent stem cells (hPSCs) to specialize in neuroepithelial tissue makes them ideal candidates for use in the disease models of neural tube defects. In this study, we cultured hPSCs in suspension with modified neural induction method, and immunostaining was applied to detect important markers associated with cell fate and morphogenesis to verify the establishment of the neural tube model in vitro. We carried out the drug experiments to further investigate the toxicity of valproic acid (VPA) exposure and the potential protective effect of folic acid (FA). The results demonstrated that neural rosette undergoes cell fate speciation and lumen formation accompanied by a spatiotemporal shift in the expression patterns of cadherin, indicating the model was successfully established. The results showed that VPA caused morphogenesis inhibition of lumen formation by altering cytoskeletal function and cell polarization, which could be rescued by FA supplement.

Rationally designed carboxymethylcellulose-based sorbents crosslinked by targeted ions for static and dynamic capture of heavy metals: Easy recovery and affinity mechanism.

A separable spherical bio-adsorbent (CMC-Cr) was prepared for capturing heavy metal ions by simple coordination and cross-linking between targeted ions of Cr3+ and carboxymethyl cellulose (CMC). A simple alternation of the CMC incorporation allowed the interconnected networks within the microspheres of preformed solid CMC to be adjusted. The excellent network structure could achieve the maximum collision between the adsorbent and the heavy metal cations in the wastewater. Through investigations, CMC-Cr-2 beads were determined as the optimal adsorbent. The adsorption performance of novel materials was evaluated by examining their adsorption behavior on Pb(II) and Co(II) under both static and dynamic conditions. The results showed that the adsorption behavior of CMC-Cr-2 beads on both two heavy metal cations could be fully reflected by the Freundlich model. Under the theoretical conditions, the maximum adsorption capacities were 97.26 and 144.74 mg/g. The kinetic results for the adsorption of two heavy metal cations on CMC-Cr-2 beads were consistent with the Pseudo-second-order kinetic model. Moreover, the correlation coefficient of the Thomas model was significant in the dynamic adsorption performance tests. Five regeneration cycle studies were successfully carried out on CMC-Cr-2 beads to evaluate reusability and stability. The applicability of CMC-Cr-2 beads in authentic aqueous solutions (both the single and binary pollutant systems) was also studied, and the results indicated that CMC-Cr-2 beads had a high potential for practical implementation. Furthermore, by analyzing the surface interactions of two heavy metal cations with the CMC-Cr-2 beads based on FTIR and XPS characterization, a basic understanding of the interaction between bio-sorbents and pollutants in wastewater can be obtained.

Bi-layered hollow amphoteric composites: Rational construction and ultra-efficient sorption performance for anionic Cr(VI) and cationic Cu(II) ions.

Here, we have developed a novel bilayer hollow amphiphilic biosorbent (BHAB-3) with large adsorption capacity, rapid adsorption kinetics, and cost-effective for the removal of Cr(VI) and Cu(II) from aqueous solutions. The synthesis was based on the clever use of freeze-drying to fix the structure, secondary modification of the carboxymethyl cellulose microspheres with polyethyleneimine and cross-linking by glutaraldehyde. The consequences of pH, initial concentration, contact time and temperature on adsorption were investigated. The Langmuir model fits showed that the maximum adsorption capacities of the two target heavy metal ions reached 835.91 and 294.79 mg/g, respectively. Moreover, BHAB-3 was characterized by SEM, FT-IR, TGA, and XPS synergistically, showing that it exhibits a strong complexation ability for Cu(II) and a strong electrostatic effect for Cr(VI). Adsorption and desorption experiments showed only a slight decrease in the adsorption capacity of the BHAB-3 for Cr(VI) and Cu(II) ions after 5 and 26 cycles, respectively. Given the excellent properties of this adsorbent, it is a promising candidate for heavy metal ion removal.

A Sagittal Patellar Angle Linear Equation Reflecting Patellofemoral Kinematics: Evaluation of Patellar Height at any Degree of Knee Flexion Angle.

OBJECTIVE: To confirm whether a novel sagittal patellar angle linear equation used for evaluating patellar height by calculating expected sagittal patellar angle (SPA) at any degree of knee flexion angle is suitable for patients older than 17 years and its reliability compared with other commonly used methods. METHODS: From September 2016 to September 2019, a total number of 202 consecutive outpatients' knee lateral X-ray radiographs were retrospectively measured and evaluated using a recently proposed linear equation Y = 1.94 + 0.74 × knee flexion(KF) angle. Patients were divided by ages into ayounger group, whose ages were between 17-49 years, and an older group, whose ages were older than 49 years, which has not been validated in the original study. Parameters such as KF, SPA, patella and patella tendon length and so on were measured on computer with picture archiving and communication system by two independent observers at an interval of 1 month. Insall-Salvati (IS) index, Caton-Deschamps (CD) index and Y value, correlation coefficients were calculated and compared using SPSS 22.0 software. RESULTS: In the younger group, 143 patients (165 knees) were included, ages were 17-49 (31.62 ± 11.38) years, males/females were 70 (48.95%)/73 (51.05%), left knees/right knees were 83 (50.30%)/82 (49.70%), mean value of Y was 31.50° ± 10.07°, and SPA was 34.38° ± 12.38°, mean value of IS was 1.06 ± 0.17, mean value of CD was 1.04 ± 0.18. While in older group, 59 patients (78 knees) were included, ages were 50-60 (mean 54.61 ± 2.99) years, there were 32 males (54.24%) and 27 females (45.76%), 42 knees were left (53.85%) and 36 knees were right (46.15%), mean values of Y and SPA were 25.90° ± 11.55° and 29.36° ± 14.22°, mean IS index in older group was 1.06 ± 0.18, mean CD index was 1.00 ± 0.16. Intra- and inter-observer reliabilities of Y in younger and older groups were 0.999, 0.999, 1.000 and 0.999, meaning high reliability and reproducibility, but low Pearson's correlation coefficients with IS and CD index were showed as -0.213 and - 0.216 in younger group and - 0.113 and - 0.316 in older group. CONCLUSIONS: In patients older than 17 years, the linear equation Y = 1.94 + 0.74 × KF is a reliable and practical method to evaluate SPA regardless of age and knee flexion angle, but has weak correlation coefficients with the IS and CD index.

HPV-Related Promoter Methylation-Based Gene Signature Predicts Clinical Prognosis of Patients With Cervical Cancer.

Persistent high-risk HPV infection drives tumorigenesis in various human malignancies, including cervical, oropharyngeal, anal, and vulvar carcinomas. Although HPV-related tumors arise in several different sites, they share many common genetic and epigenetic events. Complex and heterogeneous genomic aberrations and mutations induced by high-risk HPV contribute to the initiation and progression of cervical cancer (CC). However, the associations between high-risk HPV infection and DNA methylation have not been clearly investigated. In the present study, HPV-related gene promoter methylation signature was comprehensively analyzed using multiple interactive platforms. CC patients were successfully classified into high-risk and low-risk groups with significant differences in clinical outcomes based on the HPV-related gene promoter methylation signature. Moreover, the protein levels of ALDH1A2 and clinical prognostic value were confirmed in the CC patients cohort. In summary, our study provides compelling evidence that HPV-related gene promoter methylation signature serves as a strong prognostic signature for CC patients. Clinical investigations in large CC patient cohorts are greatly needed to pave the way to implement epigenetic biomarkers into better clinical management.

Facile transformation of carboxymethyl cellulose beads into hollow composites for dye adsorption.

Novel millimeter hollow microspheres were fabricated from carboxymethyl cellulose microspheres and polyethyleneimine using glutaraldehyde as a crosslinking agent. The hollow microspheres prepared with different polyethyleneimine usages and different polyethyleneimine treatment time were investigated deeply and characterized via SEM-EDX, FT-IR, and BET surface area analysis. It was shown that polyethyleneimine could break the coordination bonds between the carboxyl and Al (III) in carboxymethyl cellulose microspheres, leading to the formation of hollow structures. Most importantly, the usage and treatment time of polyethyleneimine can distinctly tailor the structure of the carboxymethyl cellulose microspheres, resulting in the formation of different hollow microspheres with varied shell thickness and size. Most importantly, we found that the prepared hollow microspheres have excellent adsorption performance toward targeted methyl blue under testing conditions. By virtue of the large accessible amount of -NH2 groups and its unique hollow structure, this type of millimeter hollow microspheres have broad application prospects in the treatment of emerging contaminants in wastewater.

Nano-Aromatic Drugs Based on Mesoporous Silica Nanoparticles and Bergamot Essential Oil for Anti-Depression.

Depression is a mental disorder characterized by low mood as the main pathological feature. Current medications for depression have long treatment cycles and serious side effects. Aromatherapy can alleviate depression in a "moistening things silently" way, but the fast evaporation rate of aromatic drugs weakens the effect of aromatherapy. In this study, we designed and prepared nano-aromatic drugs with slow release for anti-depressant application. We first synthesized rod-shaped mesoporous silica nanoparticles (MSNs) and encapsulated bergamot essential oil. These nanoaromatic drugs were named BEO@MSNs. Subsequently, we analyzed the pore properties of MSNs and BEO@MSNs. Further, we explored the thermal stability, encapsulation efficiency, and slow-release properties of bergamot essential oil in BEO@MSNs. Finally, we used BEO@MSNs to alleviate depression in mice while constructing depression model mice via corticosterone. The results showed that BEO@MSNs had excellent anti-depressant effects and biosafety.

Synergistic preparation of modified alginate aerogel with melamine/chitosan for efficiently selective adsorption of lead ions.

Superior mechanical properties, high adsorption capacity, and excellent regeneration property are crucial design criterions to develop a new-type aerogel for adsorptive applications towards heavy metal removal from water. Herein, chitosan and melamine not only introduced abundant functional groups to increase adsorbing sites for lead ions, but also reinforced the three-dimensional network skeleton structure of absorbents to improve the service life in adsorption applications. As-fabricated alginate/melamine/chitosan aerogel can extract Pb (II) from aqueous solution efficiently, i.e., the optimum adsorption quantity of 1331.6 mg/g at pH 5.5, which exhibited excellent and selective adsorption capacity for Pb (II) against the competition of coexisting divalent metal ions. More importantly, alginate/melamine/chitosan aerogel could be regenerated using dilute acidic solution and recovered well after eight adsorption-desorption cycles. This work might offer a new idea for design and preparation of biomass-based aerogel sorbents with promising prospect in the remediation of Pb (II)-contaminated wastewater.

Promotional effect of embedded Ni NPs in alginate-based carbon toward Pd NPs efficiency for high-concentration p-nitrophenol reduction.

Noble metal-based catalytic material with maximum utilization is of prime attraction for conserving rare metal resources. Herein, highly dispersion Ni nanoparticles (NPs)-modified N-doped mesoporous carbon material (Ni-N@C) was fabricated by pyrolysis of Ni2+/Histidine cross-linked alginate hydrogels. In a step forward, the obtained Ni-N@C nanocatalyst was treated by the solution of Pd2+, and tiny amount of Pd NPs were deposited on the surface of Ni via the reducibility of Ni to achieve the high dispersion of precious metals material. In the degradation of highly-concentration p-nitrophenol, the catalyst presents excellent performance which could completely degrade pollutants within a very short period. It was demonstrated that pre-embedded Ni NPs could not only increase the efficiency of Pd NPs but also endow the facile separation characteristic to the catalyst. Besides, the catalyst maintained favorable catalytic capacity even after five reaction cycles. In brief, this work may provide novel guidance for the maximum utilization of noble metal-modified mesoporous N-doped carbon-supported catalysts in practical applications of industrial and the treatment highly-concentration p-nitrophenol.

Perovskite-based tandem solar cells.

The power conversion efficiency for single-junction solar cells is limited by the Shockley-Quiesser limit. An effective approach to realize high efficiency is to develop multi-junction cells. These years have witnessed the rapid development of organic-inorganic perovskite solar cells. The excellent optoelectronic properties and tunable bandgaps of perovskite materials make them potential candidates for developing tandem solar cells, by combining with silicon, Cu(In,Ga)Se2 and organic solar cells. In this review, we present the recent progress of perovskite-based tandem solar cells, including perovskite/silicon, perovskite/perovskite, perovskite/Cu(In,Ga)Se2, and perovskite/organic cells. Finally, the challenges and opportunities for perovskite-based tandem solar cells are discussed.