Ethylenedioxythiophene-Based Small Molecular Donor with Multiple Conformation Locks for Organic Solar Cells with Efficiency of 19.3 .

Ternary organic solar cells (T-OSCs) represent an efficient strategy for enhancing the performance of OSCs. Presently, the majority of high-performance T-OSCs incorporates well-established Y-acceptors or donor polymers as the third component. In this study, a novel class of conjugated small molecules has been introduced as the third component, demonstrating exceptional photovoltaic performance in T-OSCs. This innovative molecule comprises ethylenedioxythiophene (EDOT) bridge and 3-ethylrhodanine as the end group, with the EDOT unit facilitating the creation of multiple conformation locks. Consequently, the EDOT-based molecule exhibits two-dimensional charge transport, distinguishing it from the thiophene-bridged small molecule, which displays fewer conformation locks and provides one-dimensional charge transport. Furthermore, the robust electron-donating nature of EDOT imparts the small molecule with cascade energy levels relative to the electron donor and acceptor. As a result, OSCs incorporating the EDOT-based small molecule as the third component demonstrate enhanced mobilities, yielding a remarkable efficiency of 19.3 %, surpassing the efficiency of 18.7 % observed for OSCs incorporating thiophene-based small molecule as the third component. The investigations in this study underscore the excellence of EDOT as a building block for constructing conjugated materials with multiple conformation locks and high charge carrier mobilities, thereby contributing to elevated photovoltaic performance in OSCs.

Endoscopic Broad Palisade Cartilage Graft Without Raising a Tympanomeatal Flap in the Repair of Subtotal Perforation.

Objective: This study evaluated the outcome of a broad palisade cartilage graft in the repair of subtotal perforation. Study Design: Prospective case series. Materials and Methods: This was a prospective study of 43 patients with subtotal perforations who underwent an endoscopic broad palisade cartilage graft procedure that did not include raising a tympanomeatal flap. The patients were followed up for 6 months. Results: The 43 patients (43 ears) included in this study had a mean operation time of 38.6 ± 7.4 minutes. Five (11.6%) patients were lost to follow-up; 38 (88.4%) completed the 6 month follow-up. The graft success rate in the latter was 92.1% (35/38). Audiological testing showed no sensorineural threshold shift. The mean preoperative air-bone gap (ABG) was 28.4 ± 5.1 dB, while the mean ABG at 6 months postoperatively was 13.6 ± 3.1 dB; the difference between these values was significant (P < .05; paired samples t test). According to the audiometry assessment, the successful surgery rate (postoperative ABG ≤ 20 dB) was 89.5% (34/38). No graft-related complications (eg, graft lateralization, significant blunting, graft medialization) were encountered during the follow-up period. However, granular myringitis with minimal moistness but without infection was noted in 5.3% (2/38) of the patients. Conclusions: In the repair of subtotal perforation, an endoscopic broad palisade cartilage graft, performed without raising a tympanomeatal flap, is simple and feasible, resulting in a high graft success rate and good hearing restoration.

Carboxylating Elastomer via Thiol-Ene Click Reaction to Improve Miscibility with Conjugated Polymers for Mechanically Robust Organic Solar Cells with Efficiency of 19.

Incorporating flexible insulating polymers is a straightforward strategy to enhance the mechanical properties of rigid conjugated polymers, enabling their use in flexible electronic devices. However, maintaining electronic characteristics simultaneously is challenging due to the poor miscibility between insulating polymers and conjugated polymers. This study introduces the carboxylation of insulating polymers as an effective strategy to enhance miscibility with conjugated polymers via surface energy modulation and hydrogen bonding. The carboxylated elastomer, synthesized via a thiol-ene click reaction, closely matches the surface energy of the conjugated polymer. This significantly improves the mechanical properties, achieving a high crack-onset strain of 21.48%, surpassing that (5.93%) of the unmodified elastomer:conjugated polymer blend. Upon incorporating the carboxylated elastomer into PM6:L8-BO-based organic solar cells, an impressive power conversion efficiency of 19.04% is attained, which top-performs among insulating polymer-incorporated devices and outperforms devices with unmodified elastomer or neat PM6:L8-BO. The superior efficiency is attributed to the optimized microstructures and enhanced crystallinity for efficient and balanced charge transport, and suppressed charge recombination. Furthermore, flexible devices with 5% carboxylated elastomer exhibit superior mechanical stability, retaining ≈88.9% of the initial efficiency after 40 000 bending cycles at a 1 mm radius, surpassing ≈83.5% for devices with 5% unmodified elastomer.

Comparison of the Extended Perichondrium-Cartilage Butterfly Inlay Technique and Over-Underlay Technique for Repairing Subtotal Perforation: A 2-Year Follow-up Study.

OBJECTIVE: To compare graft outcomes and postoperative complications between the extended perichondrium-cartilage butterfly inlay (PCBI) technique and the perichondrium-cartilage over-underlay (PCOU) technique for repairing subtotal perforations over a 2-year follow-up period. METHODS AND MATERIALS: Patients with subtotal perforations were prospectively randomized to either the extended PCBI (n = 52) or PCOU (n = 51) group. Evaluation metrics included operation time, graft success rate, hearing gain, and complications at 24 months postoperatively. RESULTS: The study included 103 patients with 103 ears. Follow-up loss occurred in 11 of 52 patients (21.2%) in the PCBI group and 13 of 51 patients (25.5%) in the PCOU group (P = .773). The final analysis included 41 of 52 patients (78.9%) in the PCBI group and 38 of 51 patients (74.5%) in the PCOU group. The average operation time was significantly shorter in the PCBI group (31.2 ± 1.9 min) compared to the PCOU group (52.8 ± 6.3 min, P < .001). At 24 months postoperatively, the graft success rate was 82.9% (34 patients) in the PCBI group and 92.1% (35 patients) in the PCOU group (P = .374). No significant group difference was noted in mean air-bone gap (ABG) gain (P = .759). High-resolution computed tomography (HRCT) demonstrated well-pneumatized mastoids and middle ears in both groups. Altered taste was reported in no PCBI group patients and 23.7% (9 patients) of the PCOU group patients (P < .05). Graft cholesteatoma was found in 4.9% (two patients) in the PCBI group and 7.9% (three patients) in the PCOU group (P = .930). CONCLUSION: The endoscopic extended PCBI technique is safe and effective for repairing subtotal perforation. It avoids raising a tympanomeatal flap and demonstrates high long-term graft success with minimal complications.

Perichondrium-Cartilage Inlay Butterfly Myringoplasty: An Office-Based Procedure for Closing Small- to Medium-Sized Tympanic Membrane Perforations.

Objective: The objective of this study was to assess the graft and functional outcomes of inlay butterfly cartilage-perichondrium graft myringoplasty in an office setting. Material and Methods: Adult patients with chronic perforations underwent inlay butterfly cartilage-perichondrium graft myringoplasty under local and topical anesthesia. The graft and functional outcomes, intraoperative pain score, and complications were evaluated at 6 months postoperatively. Results: A total of 39 patients (39 ears) were included in this study. All patients completed 6 months of follow-up. The mean operation time was 26.5 ± 3.2 (ranged from 21 to 32) minutes. The intraoperative mean pain score was 0.61 ± 0.28. The graft success rate was 97.4% (38/39) at 6 months postoperatively. The mean preoperative air-bone gap (ABG) was 19.18 ± 4.01 dB, while the mean postoperative ABG at 6 months was 10.56 ± 2.27 dB (P < .05; Paired-Samples T Test). The functional success rate was 100.0% (38/38). Endoscopic examination showed that the transplanted perichondrium graft gradually atrophied, flattened, and became indistinguishable from the surrounding tympanic membrane 2 to 3 months following surgery, the superficial layer of perichondrium graft formed the crust and migrated into the external auditory canal at 3 to 6 months postoperatively. Conclusions: Perichondrium-cartilage inlay butterfly myringoplasty is a highly successful and minimally invasive procedure well tolerated by adults for closure of small- and medium-sized perforations in an office setting.

Co-La-Based Hole-Transporting Layers for Binary Organic Solar Cells with 18.82 % Efficiency.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a widely used hole transporting layer (HTL) in organic solar cells (OSCs), but its acidity severely reduces the stability of devices. Until now, very few HTLs were developed to replace PEDOT:PSS toward stable and high-performance OSCs. Herein, a new cobalt-lanthanum (Co-La) inorganic system was reported as HTL to show a high conversion efficiency (PCE) of 18.82 %, which is among the top PCEs in binary OSCs. Since electron-rich outer shell of La atom can interact with Co atom to form charge transfer complex, the work function and conductivity of the Co-La system could be simultaneously enhanced compared to Co or La-based HTLs. This Co-La system could also be applied into other OSCs to show high performance. All these results demonstrate that binary Co-La systems as HTL can efficiently tackle the issue in hole transporting and show powerful application in OSCs to replace PEDOT:PSS.

N-Annulated Perylene Bisimide-Based Double-Cable Polymers with Open-Circuit Voltage Approaching 1.20 V in Single-Component Organic Solar Cells.

In this work, we have introduced single/double-sided N-annulated perylene bisimide (PBI) with deep energy levels into double-cable polymers with poly[1-(5-(4,8-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)-6-methylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-5,7-bis(2-ethylhexyl)-3-(5-methylthiophen-2-yl)-4H,8H-benzo[1,2-c:4,5-c']dithiophene-4,8-dione] (PBDB-T-Cl) as a donor backbone, marking as s-PPNR and as-PPNR, according to the molecular symmetry. Both double-cable polymers displayed a high open-circuit voltage approaching 1.20 V in light of high energy level discrepancy between electron-donating and electron-withdrawing parts, which is the highest open-circuit voltage among double-cable-based single-component organic solar cell (SCOSC) devices. Additionally, the asymmetric polymer displayed improved absorption spectra, thereby promoting crystallization and phase separation. Consequently, the as-PPNR-based SCOSCs achieved a power conversion efficiency of 5.05% along with a higher short-circuit current density and fill factor than their s-PPNR-based counterparts. In this work, we have successfully incorporated N-annulated PBI into double-cable polymers and revealed the important effects on structural symmetry and phase separation of double-cable polymers for higher SCOSC performance.

Mechanically and Ultraviolet Light Stable Ultrathin Organic Solar Cell via Semi-Embedding Silver Nanowires in a Hydrogen Bonds-Based Polyimide.

Ultrathin organic solar cells (OSCs) with both high power conversion efficiency (PCE) and operational stability are of great significance for the industrial applications but still challenging. Here, a polyimide (PI) substrate for high-performance and stable ultrathin OSCs, which is physically crosslinked via strong hydrogen bonds (denoted as HB-PI) to enhance the mechanical, thermal, solvent-resistant, and UV filtering properties (with a cut-off wavelength of 376 nm), is synthesized. An ultrathin flexible transparent composite electrode (FTCE, ≈7 µm) is fabricated via semi-embedding AgNWs in the HB-PI substrate. The FTCE possesses excellent optoelectronic property, smooth surface, and high mechanical stability simultaneously. Based on this FTCE, an ultrathin OSC is constructed with a PCE of 13.52% (average of 13.22%). Moreover, the ultrathin OSC shows outstanding mechanical stability (PCE decreased by less than 4% after 1000 bending cycles at a small bending radius of 0.5 mm) and superior UV light stability (no evident PCE degradation after irradiation under UV light for 10 h). This work will provide a new avenue for fabricating high-performance and stable ultrathin OSCs.

Ti-Oxo Clusters with Peripheral Alkyl Groups as Cathode Interlayers for Efficient Organic Solar Cells.

Three independent Ti-oxo clusters (TOCs) that contain 6, 8, and 12 Ti atoms in the cores and alkyl groups on the surface were developed as cathode interlayers in bulk-heterojunction organic solar cells (OSCs). These TOCs have precise chemical structures with a single crystal, excellent solubility in methanol, and well-aligned work function. Smooth films can be facilely obtained by spin-casting their solution on top of the active layer. Therefore, they can be used as an interlayer in OSCs to provide a high power conversion efficiency (17.29%). Further studies reveal that these TOCs can not only reduce the work function of the silver electrode to provide better energy level alignment but also exhibit a significant n-doping effect with the non-fullerene acceptors to facilitate efficient electron extraction and transport. Our results demonstrate that TOCs as semiconductors have great potential application in OSCs.

A metal-organic cage-based nanoagent for enhanced photodynamic antitumor therapy.

Herein, we report, for the first time, a Pd6L8(NO3)5.4(ICG)6.6 (ICG = indocyanine green) cage-based hexagonal nanoplate (3) via a combined nanoprecipitation and solid-state anion-exchange approach. Nanoplate 3 possesses enhanced near-infrared (NIR) light-triggered 1O2 generation, high cellular uptake selective lysosome-targeting ability, and, consequently, excellent antineoplastic activity.

Fullerene as an additive for increasing the efficiency of organic solar cells to more than 17.

In this work, we introduced a fullerene acceptor (PC71BM) into the binary photo-active layer based on a polymer donor (PM6) and a non-fullerene small molecular acceptor (BTP-BO-4Cl), and as a consequence, the ternary organic solar cells realized a high-power conversion efficiency of 17.39% compared to 16.65% in binary solar cells. The performance enhancement was found to be due to the optimized morphology and hence balanced hole and electron mobilities, which is responsible for the suppressed charge recombination and hence high photocurrent in solar cells. In addition, PC71BM shows the complementary absorption with PM6 and BTP-BO-4Cl, which can broaden the absorption range of the photo-active layer and hence more photons from the sunlight can be utilized. Besides, PC71BM shows the cascade energy level alignment between PM6 and BTP-BO-4Cl, which is helpful for charge transfer from donor to acceptor. All these merits explain the high performance in ternary solar cells, and also demonstrate that ternary photovoltaics adopting non-fullerene acceptor with the fullerene acceptor as small amount of additive is an efficient strategy to gain high performing organic solar cells.

An Organic-Inorganic Hybrid Electrolyte as a Cathode Interlayer for Efficient Organic Solar Cells.

An organic-inorganic hybrid electrolyte based on a cyclic Ti-oxo cluster as the inorganic core and naphthalene-based organic ammonium bromide salts as the electrolyte was developed with easy synthesis and low cost. The new hybrid electrolyte exhibits excellent solubility in methanol, aligned work function, good conductivity, and amorphous state in thin film, enabling its successful application as a cathode interlayer in organic solar cells with a high power conversion efficiency of 17.19 %. This work demonstrates that the hybrid electrolytes are a new kind of semiconductor, exhibiting promising applications in organic electronics.

Thieno[3,4-c]pyrrole-4,6-dione-based conjugated polymers for organic solar cells.

Conjugated polymers consisting of electron-rich and electron-deficient units as alternative structures have played important roles in the field of organic solar cells (OSCs). A thieno[3,4-c]pyrrole-4,6-dione (TPD) unit as an electron-deficient unit has been used to construct conjugated polymers for application in fullerene and non-fullerene based OSCs. TPD-based monomers can be simply prepared and TPD-polymers can be synthesized via environmentally friendly direct (hetero)arylation polymerization, providing a possibility for large quantity preparation. TPD-polymers usually have deep frontier energy levels, wide band gaps with absorption onset around 700 nm and good charge transport properties, showing the advantages of high open-circuit voltage, high fill-factor and excellent spectral matching with a small band gap non-fullerene acceptor. From the material design and synthesis and their optoelectrical properties, TPD-polymers have great potential applications in OSCs toward large-area devices. In this review, we provide an overview of TPD-polymers for OSCs in the last ten years, including the design and synthesis of TPD-polymers, and their application in fullerene and non-fullerene OSCs. We will also provide some perspective about the research of TPD-polymers that meet the requirement of OSCs. We hope that our universal summary can stimulate the study of TPD-polymers in the future, especially toward high performance, low cost and stable OSCs.

Atomically Precise, Thiolated Copper-Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions.

Copper-hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ketones to unsaturated alcohols. Stabilizing copper-based particles by ligand chemistry to nanometer scale is an appealing route to make active catalysts with optimized material economy; however, it has been long believed that the ligand-metal interface, particularly if sulfur-containing thiols are used as stabilizing agent, may poison the catalyst. We report here a discovery of an ambient-stable thiolate-protected copper-hydride nanocluster [Cu25H10(SPhCl2)18]3- that readily catalyzes hydrogenation of ketones to alcohols in mild conditions. A full experimental and theoretical characterization of its atomic and electronic structure shows that the 10 hydrides are instrumental for the stability of the nanocluster and are in an active role being continuously consumed and replenished in the hydrogenation reaction. Density functional theory computations suggest, backed up by the experimental evidence, that the hydrogenation takes place only around a single site of the 10 hydride locations, rendering the [Cu25H10(SPhCl2)18]3- one of the first nanocatalysts whose structure and catalytic functions are characterized fully to atomic precision. Understanding of a working catalyst at the atomistic level helps to optimize its properties and provides fundamental insights into the controversial issue of how a stable, ligand-passivated, metal-containing nanocluster can be at the same time an active catalyst.

IILS: Intelligent imaging layout system for automatic imaging report standardization and intra-interdisciplinary clinical workflow optimization.

BACKGROUND: To achieve imaging report standardization and improve the quality and efficiency of the intra-interdisciplinary clinical workflow, we proposed an intelligent imaging layout system (IILS) for a clinical decision support system-based ubiquitous healthcare service, which is a lung nodule management system using medical images. METHODS: We created a lung IILS based on deep learning for imaging report standardization and workflow optimization for the identification of nodules. Our IILS utilized a deep learning plus adaptive auto layout tool, which trained and tested a neural network with imaging data from all the main CT manufacturers from 11,205 patients. Model performance was evaluated by the receiver operating characteristic curve (ROC) and calculating the corresponding area under the curve (AUC). The clinical application value for our IILS was assessed by a comprehensive comparison of multiple aspects. FINDINGS: Our IILS is clinically applicable due to the consistency with nodules detected by IILS, with its highest consistency of 0·94 and an AUC of 90·6% for malignant pulmonary nodules versus benign nodules with a sensitivity of 76·5% and specificity of 89·1%. Applying this IILS to a dataset of chest CT images, we demonstrate performance comparable to that of human experts in providing a better layout and aiding in diagnosis in 100% valid images and nodule display. The IILS was superior to the traditional manual system in performance, such as reducing the number of clicks from 14·45 ±â€¯0·38 to 2, time consumed from 16·87 ±â€¯0·38 s to 6·92 ±â€¯0·10 s, number of invalid images from 7·06 ±â€¯0·24 to 0, and missing lung nodules from 46·8% to 0%. INTERPRETATION: This IILS might achieve imaging report standardization, and improve the clinical workflow therefore opening a new window for clinical application of artificial intelligence. FUND: The National Natural Science Foundation of China.

From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters.

A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13 Cu2 , into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13 Cu2 (DPPP)3 (SPy)6 ]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13 Cu2 ((2r,4r)/(2s,4s)-BDPP)3 (SPy)6 ]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images in the range of 250-500 nm with maximum anisotropy factors of 1.2×10-3 . DFT calculations provided good correlations with the observed CD spectra of the enantiomers and, more importantly, revealed the origin of the chirality. Racemization studies show high stability (no racemization at 70 °C) of these chiral nanoclusters, which hold great promise in applications such as asymmetry catalysis.

Microporous Cyclic Titanium-Oxo Clusters with Labile Surface Ligands.

By using ethylene glycol and monocarboxylic acid as surface ligands, a series of cyclic Ti-oxo clusters (CTOC) with permanent microporosity are successfully synthesized. With a cyclic {Ti32 O16 } backbone made of eight connected Ti4 tetrahedral cages that are arranged in a zigzag fashion, the clusters have a "donut" shape with an inner diameter of 8.3 Å, outer diameter of 26.9 Šand height of 10.4 Å. While both inner and outer walls of the "donut" clusters are modified by double-deprotonated ethylene glycolates, their upper and lower surfaces are bound by carboxylates and mono-deprotonated ethylene glycolates. The clusters are readily packed into one-dimensional tubes which are further arranged in two different modes into crystalline microporous solids with surface areas over 660 m2 g-1 , depending on the surface carboxylates. The solid with olefin-bearing carboxylates exhibits a superior CO2 adsorption capacity of 40 cm3 g-1 at 273 K under 1 atm. Moreover, the mono-deprotonated ethylene glycolates on the clusters are demonstrated to be highly exchangeable by other alcohols, providing a nice platform for creating microporous solids or films with a wide variety of surface functionalities.

Micro-Cu4I4-MOF: reversible iodine adsorption and catalytic properties for tandem reaction of Friedel-Crafts alkylation of indoles with acetals.

We report a convenient approach, the first of its kind, to construct a microscale non-metal@MOF composite catalytic host-guest system for an organic tandem reaction. The reported porous Cu4I4-MOF is able to reversibly adsorb molecular iodine at room temperature. The obtained I2@Cu4I4-MOF host-guest system can be a highly heterogeneous catalyst to promote the Friedel-Crafts alkylation of indoles with acetals in a one-pot two-step fashion under solvent-free conditions at room temperature.

Pd@Cu(II)-MOF-Catalyzed Aerobic Oxidation of Benzylic Alcohols in Air with High Conversion and Selectivity.

A new 3D porous Cu(II)-MOF (1) was synthesized based on a ditopic pyridyl substituted diketonate ligand and Cu(OAc)2 in solution, and it features a 3D NbO motif which is determined by the X-ray crystallography. Furthermore, the Pd NPs-loaded hybrid material Pd@Cu(II)-MOF (2) was prepared based on 1 via solution impregnation, and its structure was confirmed by HRTEM, SEM, XRPD, gas adsorption-desorption, and ICP measurement. 2 exhibits excellent catalytic activity (conversion, 93% to >99%) and selectivity (>99% to benzaldehydes) for various benzyl alcohol substrates (benzyl alcohol and its derivatives with electron-withdrawing and electron-donating groups) oxidation reactions in air. In addition, 2 is a typical heterogeneous catalyst, which was confirmed by hot solution leaching experiment, and it can be recycled at least six times without significant loss of its catalytic activity and selectivity.

An in situ self-assembled Cu4I4-MOF-based mixed matrix membrane: a highly sensitive and selective naked-eye sensor for gaseous HCl.

The Cu4I4-MOF-based mixed matrix membranes (MMMs) can be readily prepared by one-step in situ self-assembly of a tri-armed oxadiazole-bridged ligand and CuI in polymer binder solution under ambient conditions. The visual and luminescent HCl(g) sensing detecting limits of the resulting Cu4I4-MOF-based MMMs are 3.2 and 1.6 ppb, respectively, and the response time is less than 1 min.