End-extended Conjugation Strategy to Reduce the Efficiency-Stability-Mechanical Robustness Gap in Binary All-Polymer Solar Cells.

Concurrently achieving high efficiency, mechanical robustness and thermal stability is critical for the commercialization of all-polymer solar cells (APSCs). However, APSCs usually demonstrate complicated morphology, primarily attributed to the polymer chain entanglement which has a detrimental effect on their fill factors (FF) and morphology stability. To address these concerns, an end-group extended polymer acceptor, PY-NFT, was synthesized and studied. The morphology analysis showed a tightly ordered molecular packing mode and a favorable phase separation was formed. The PM6:PY-NFT-based device achieved an exceptional PCE of 19.12% (certified as 18.45%), outperforming the control PM6:PY-FT devices (17.14%). This significant improvement highlights the record-high PCE for binary APSCs. The thermal aging study revealed that the PM6:PY-NFT blend exhibited excellent morphological stability, thereby achieving superior device stability, retaining 90% of initial efficiency after enduring thermal stress (65 °C) for 1500 hours. More importantly, the PM6:PY-NFT blend film exhibited outstanding mechanical ductility with a crack onset strain of 24.1%. Overall, rational chemical structure innovation, especially the conjugation extension strategy to trigger appropriate phase separation and stable morphology, is the key to achieving high efficiency, improved thermal stability and robust mechanical stability of APSCs.

Recent Progress in All-Small-Molecule Organic Solar Cells.

Active layer material plays a critical role in promoting the performance of an organic solar cell (OSC). Small-molecule (SM) materials have the merits of well-defined chemical structures, few batch-to-batch variations, facile synthesis and purification procedures, and easily tuned properties. SM-donor and non-fullerene acceptor (NFA) innovations have recently produced all-small-molecule (ASM) devices with power conversion efficiencies that exceed 17% and approach those of their polymer-based counterparts, thereby demonstrating their great future commercialization potential. In this review, recent progress in both SM donors and NFAs to illustrate structure-property relationships and various morphology-regulation strategies are summarized. Finally, ASM-OSC challenges and outlook are discussed.

Structural Fusion Yields Guest Acceptors that Enable Ternary Organic Solar Cells with 18.77 % Efficiency.

The design and selection of a suitable guest acceptor are particularly important for improving the photovoltaic performance of ternary organic solar cells (OSCs). Herein, we designed and successfully synthesized two asymmetric silicon-oxygen bridged guest acceptors, which featured distinct blue-shifted absorption, upshifted lowest unoccupied molecular orbital energy levels, and larger dipole moments than symmetric silicon-oxygen-bridged acceptor. Ternary devices with the incorporation of 14.2 wt % these two asymmetric guest acceptors exhibited excellent performance with power conversion efficiencies (PCEs) of 18.22 % and 18.77 %, respectively. Our success in precise control of material properties via structural fusion of five-membered carbon linkages and six-membered silicon-oxygen connection at the central electron-donating core unit of fused-ring electron acceptors can attract considerable attention and bring new vigor and vitality for developing new materials toward more efficient OSCs.

Simultaneously Enhanced Efficiency and Mechanical Durability in Ternary Solar Cells Enabled by Low-Cost Incompletely Separated Fullerenes.

All-polymer solar cells (all-PSCs) are one of the most promising application-oriented organic photovoltaic technologies due to their excellent operational and mechanical stability. However, the power conversion efficiencies (PCEs) are mostly lower than 16%, restricting their core competitiveness. Furthermore, the improvement of mechanical durability is rarely paid attention to cutting-edge all-PSCs. This work deploys a low-cost "technical grade" PCBM (incompletely separated but pure mixtures containing ≥90% [70]PCBM or [60]PCBM), into the efficient PM6:PY-IT all-polymer blend, successfully yielding a high-performance ternary device with 16.16% PCE, among the highest PCE values for all-PSCs. Meanwhile, an excellent mechanical property (i.e., crack onset strain = 11.1%) promoted from 9.5% for the ternary system is also demonstrated. The "technical grade" PCBM slightly disrupts the crystallization of polymers, and disperses well into the amorphous polymer regions of the all-PSC blends, thus facilitating charge transport and improving film ductility simultaneously. All these results confirm introducing low-cost "technical grade" PCBM with high electron mobility into all-polymer blends can improve carrier mobility, reduce charge recombination, and optimize morphology of the amorphous polymer regions, thus yielding more efficient and mechanically durable all-PSCs.

Serum TP53 Protein Level as a Sensitive Biomarker for the Diagnosis of Myocardial Damage in Children.

BACKGROUND High levels of TP53 protein can lead to apoptosis of myocardial cells. However, TP53 protein influence of myocardial damage remains unclear. This prospective study investigated the involvement of TP53 protein in secondary myocardial damage in children up to 18 years of age. MATERIAL AND METHODS Serum TP53 protein, N-terminal prohormone B-type natriuretic peptide (NT-ProBNP), cardiac troponin-I (cTnI), and creatine kinase isoenzyme MB (CK-MB) concentrations were measured in 50 hospitalized patients with secondary myocardial damage, 50 hospitalized patients without myocardial damage, and 50 healthy individuals (control). Cardiac damage was diagnosed based on cTnI, NT-ProBNP, and CK-MB levels, with electrocardiographic evidence as the reference. The appropriate cut-off value of TP53 protein for secondary myocardial damage was analyzed by receiver operating characteristic (ROC) curves. RESULTS The serum TP53 protein, NT-ProBNP, cTnI, and CK-MB concentrations of the patients with and without myocardial damage were 10.20±1.20 and 0.30±0.10 ng/L, 505.30 and 107.8 ng/L, 0.23±0.13 and 0.02±0.01 µg/L, and 28.30±5.13 and 12.24±4.29 IU/L, respectively. For the 50 patients with myocardial damage, the area under the ROC curve for serum TP53 protein, NT-ProBNP, cTnI, and CK-MB concentrations were 0.89 (95% CI: 0.81-0.95), 0.83 (95% CI: 0.77-0.91), 0.92 (95% CI: 0.84-0.97), and 0.85 (95% CI: 0.78-0.93), respectively, and the diagnostic cut-off values were 12.00 ng/L, 500.00 ng/L, 0.16 µg/L, and 27.00 IU/L, respectively, with positive likelihood ratios of 20.8, 13.2, 24.6, and 15.6. CONCLUSIONS TP53 protein is a valid biomarker of secondary myocardial damage in pediatric patients and can be diagnostic.

Age-Stratified Cut-Off Values for Serum Levels of N-Terminal ProB-Type Natriuretic Peptide and Mortality from Sepsis in Children Under Age 18 Years: A Retrospective Study from a Single Center.

BACKGROUND The N-terminal fragment of proB-type natriuretic peptide (NT-proBNP) is an established predictive marker for sepsis-related mortality in adult. This retrospective study aimed to determine age-stratified cut-off values for serum levels of NT-proBNP and mortality from sepsis in children under 18 years. MATERIAL AND METHODS Patients were stratified by age as follows: <1 year, 1-3 years, 4-6 years, and 7-18 years (age groups). The control group consisted of age- and sex-matched healthy children. Serum NT-proBNP levels were detected by laboratory assays in the participants. The appropriate serum NT-proBNP cut-off values for predicting short-term mortality of the sepsis patients were calculated via receiver operating characteristic (ROC) curve analyses. RESULTS Among 327 pediatric patients with sepsis, the serum NT-proBNP cut-off concentrations for predicting sepsis-related mortality in the <1 year, 1-3 years, 4-6 years, and 7-18 years age groups were 5000 ng/L, 4500 ng/L, 4100 ng/L, and 3800 ng/L, respectively (P<0.001). The area under the ROC curve (AUC) values for these were 0.815, 0.812, 0.806 and 0.725, respectively (P<0.001). CONCLUSIONS This retrospective study provided the age range-specific serum NT-proBNP cut- off concentrations for predicting short-term mortality in children. In children <1 year, 1-3 years, 4-6 years, and 7-18 years, age-stratified cut-off values that predicted sepsis-associated mortality were 5000 ng/L, 4500 ng/L, 4100 ng/L, and 3800 ng/L, respectively.

An αIIbß3- and phosphatidylserine (PS)-binding recombinant fusion protein promotes PS-dependent anticoagulation and integrin-dependent antithrombosis.

Blood platelets are required for normal wound healing, but they are also involved in thrombotic diseases, which are usually managed with anticoagulant drugs. Here, using genetic engineering, we coupled the disintegrin protein echistatin, which specifically binds to the platelet integrin αIIbß3 receptor, to annexin V, which binds platelet membrane-associated phosphatidylserine (PS), to create the bifunctional antithrombotic molecule recombinant echistatin-annexin V fusion protein (r-EchAV). Lipid binding and plasma coagulation studies revealed that r-EchAV dose-dependently binds PS and delays plasma clotting time. Moreover, r-EchAV inhibited ADP-induced platelet aggregation in a dose-dependent manner and exhibited potent antiplatelet aggregation effects. r-EchAV significantly prolonged activated partial thromboplastin time, suggesting that it primarily affects the in vivo coagulation pathway. Flow cytometry results indicated that r-EchAV could effectively bind to the platelet αIIbß3 receptor, indicating that r-EchAV retains echistatin's receptor-recognition region. In vivo experiments in mice disclosed that r-EchAV significantly prolongs bleeding time, indicating a significant anticoagulant effect in vivo resulting from the joint binding of r-EchAV to both PS and the αIIbß3 receptor. We also report optimization of the r-EchAV production steps and its purification for high purity and yield. Our findings indicate that r-EchAV retains the active structural regions of echistatin and annexin V and that the whole molecule exhibits multitarget-binding ability arising from the dual functions of echistatin and annexin V. Therefore, r-EchAV represents a new class of anticoagulant that specifically targets the anionic membrane-associated coagulation enzyme complexes at thrombogenesis sites and may be a potentially useful antithrombotic agent.

Investigation of Two Kinds of Periodical Surface Structures Induced by Femtosecond Laser on the Surface of Titanium Plate.

Two kinds of laser-induced periodical structures observed on metal titanium plate irradiated by femtosecond laser (fs-laser) are reported, including the fs-laser-induced concentric rings and periodical subwavelength ripples. The rings can be produced only when the titanium target is located before the focal plane. The period and distribution of the rings stay almost fixable with the change of laser fluence and pulse number. The average cross section area (ACSA) is introduced to investigate the material removal behavior with the growth of the rings. The rings grow with the accumulation of laser pulses and the increase of the laser fluence, but the growth rate will be moderated with the increase of the pulse number. The ripples are obtained in an annular region when powerful multi-pulses irradiate on the target surface. The ripple period varies with laser fluence and location. And the annular region migrates outward when the laser fluence increases. We suggest that the formations of ripples are attributed to the propagation of the laser-stimulated surface plasma wave (SPW) on the air/ti interface. The dependence of the ripple period on the pulse fluence calculated by the SPW model agrees well with our experimental observation. The investigation improves the understanding of the two kinds of periodical surface structures both in their appearances and mechanisms.

Effects of insulin combined with idebenone on blood-brain barrier permeability in diabetic rats.

This study investigates the effect of insulin combined with idebenone on blood-brain barrier (BBB) permeability in experimental streptozotocin-induced diabetic rats as well as the underlying mechanisms. With a diabetic rat model, we show that insulin and idebenone normalize body weight and water intake and restore BBB permeability and that their combination displays a synergistic effect. The results from transmission electron microscopy show that the combination of insulin and idebenone significantly closed the tight junction (TJ) in diabetic rats. The results from Western blotting in diabetic rats show that the upregulation of TJ-associated proteins occludin, and zonula occludens (ZO)-1 caused by the combination of insulin and idebenone is more remarkable than that with either agent alone. In addition, the activations of reactive oxygen species (ROS) and advanced glycation end products (AGEs) and the expression levels of receptors for advanced glycation end-products (RAGE) and nuclear factor-κB (NF-κB) were significantly decreased after treatment with insulin and idebenone in diabetic rats. These results suggest that the combination of insulin and idebenone could decrease the BBB permeability in diabetic rats by upregulating the expression of occludin, claudin-5, and ZO-1 and that the ROS/AGE/RAGE/NF-κB signal pathway might be involved in the process.

Evaluation of dynamic control of continuous capture with periodic counter-current chromatography under feedstock variations.

Multi-column periodic counter-current chromatography is a promising technology for continuous antibody capture. However, dynamic changes due to disturbances and drifts pose some potential risks for continuous processes during long-term operation. In this study, a model-based approach was used to describe the changes in breakthrough curves with feedstock variations in target proteins and impurities. The performances of continuous capture of three-column periodic counter-current chromatography under ΔUV dynamic control were systematically evaluated with modeling to assess the risks under different feedstock variations. As the concentration of target protein decreased rapidly, the protein might not breakthrough from the first column, resulting in the failure of ΔUV control. Small reductions in the concentrations of target proteins or impurities would cause protein losses, which could be predicted by the modeling. The combination of target protein and impurity variations showed complicated effects on the process performance of continuous capture. A contour map was proposed to describe the comprehensive impacts under different situations, and nonoperation areas could be identified due to control failure or protein loss. With the model-based approach, after the model parameters are estimated from the breakthrough curves, it can rapidly predict the process stability under dynamic control and assess the risks under feedstock variations or UV signal drifts. In conclusion, the model-based approach is a powerful tool for continuous process evaluation under dynamic changes and would be useful for establishing a new real-time dynamic control strategy.

Amino-Functionalized Graphdiyne Derivative as a Cathode Interface Layer with High Thickness Tolerance for Highly Efficient Organic Solar Cells.

Efficient cathode interfacial materials (CIMs) are essential components for effectively enhancing the performance of organic solar cells (OSCs). Although high-performance CIMs are desired to meet the requirements of various OSCs, potential candidates for CIMs are scarce. Herein, an amino-functionalized graphdiyne derivative (GDY-N) is developed, which represents the first example of GDY that exhibits favorable solubility in alcohol. Utilizing GDY-N as the CIM, an outstanding champion PCE of 19.30% for devices based on the D18-Cl:L8-BO (certified result: 19.05%) is achieved, which is among the highest efficiencies reported to date in OSCs. Remarkably, the devices based on GDY-N exhibit a thickness-insensitive characteristic, maintaining 95% of their initial efficiency even with a film thickness of 25 nm. Moreover, the GDY-N displays wide universality and facilitates exceptional stability in OSCs. This work not only enriches the diversity of GDY derivatives, but also demonstrates the feasibility of GDY derivatives as CIMs with high thickness tolerance in OSCs.

An Unprecedented Efficiency with Approaching 21% Enabled by Additive-Assisted Layer-by-Layer Processing in Organic Solar Cells.

Recently published in Joule, Feng Liu and colleagues from Shanghai Jiaotong University reported a record-breaking 20.8% power conversion efficiency in organic solar cells (OSCs) with an interpenetrating fibril network active layer morphology, featuring a bulk p-i-n structure and proper vertical segregation achieved through additive-assisted layer-by-layer deposition. This optimized hierarchical gradient fibrillar morphology and optical management synergistically facilitates exciton diffusion, reduces recombination losses, and enhances light capture capability. This approach not only offers a solution to achieving high-efficiency devices but also demonstrates the potential for commercial applications of OSCs.

Isomerization Engineering of Solid Additives Enables Highly Efficient Organic Solar Cells via Manipulating Molecular Stacking and Aggregation of Active Layer.

Morphology control is crucial in achieving high-performance organic solar cells (OSCs) and remains a major challenge in the field of OSC. Solid additive is an effective strategy to fine-tune morphology, however, the mechanism underlying isomeric solid additives on blend morphology and OSC performance is still vague and urgently requires further investigation. Herein, two solid additives based on pyridazine or pyrimidine as core units, M1 and M2, are designed and synthesized to explore working mechanism of the isomeric solid additives in OSCs. The smaller steric hindrance and larger dipole moment facilitate better π-π stacking and aggregation in M1-based active layer. The M1-treated all-small-molecule OSCs (ASM OSCs) obtain an impressive efficiency of 17.57%, ranking among the highest values for binary ASM OSCs, with 16.70% for M2-treated counterparts. Moreover, it is imperative to investigate whether the isomerization engineering of solid additives works in state-of-the-art polymer OSCs. M1-treated D18-Cl:PM6:L8-BO-based devices achieve an exceptional efficiency of 19.70% (certified as 19.34%), among the highest values for OSCs. The work provides deep insights into the design of solid additives and clarifies the potential working mechanism for optimizing the morphology and device performance through isomerization engineering of solid additives.

Model-assisted process development, characterization and design of continuous chromatography for antibody separation.

Continuous manufacturing in monoclonal antibody production has generated increased interest due to its consistent quality, high productivity, high equipment utilization, and low cost. One of the major challenges in realizing continuous biological manufacturing lies in implementing continuous chromatography. Given the complex operation mode and various operation parameters, it is challenging to develop a continuous process. Due to the process parameters being mainly determined by the breakthrough curves and elution behaviors, chromatographic modeling has gradually been used to assist in process development and characterization. Model-assisted approaches could realize multi-parameter interaction investigation and multi-objective optimization by integrating continuous process models. These approaches could reduce time and resource consumption while achieving a comprehensive and systematic understanding of the process. This paper reviews the application of modeling tools in continuous chromatography process development, characterization and design. Model-assisted process development approaches for continuous capture and polishing steps are introduced and summarized. The challenges and potential of model-assisted process characterization are discussed, emphasizing the need for further research on the design space determination strategy and parameter robustness analysis method. Additionally, some model applications for process design were highlighted to promote the establishment of the process optimization and process simulation platform.

Model-based evaluation and model-free strategy for process development of three-column periodic counter-current chromatography.

Multi-column counter-current chromatography is an advanced technology used for continuous capture processes to improve process productivity, resin capacity utilization and product consistency. However, process development is difficult due to process complexity. In this work, some general and convenient guidances for three-column periodic counter-current chromatography (3C-PCC) were developed. Boundaries and distributions of operating windows of 3C-PCC processes were clarified by model-based predictions. Interactive effects of feed concentration (c0), resin properties (qmax and De), recovery and regeneration times (tRR) were evaluated over a wide range for maximum productivity (Pmax). Furthermore, variation of Pmax was analyzed considering the constraint factors (capacity utilization target and flow rate limitation). The plateau value of Pmax was determined by qmax and tRR. The operating conditions for Pmax were controlled by qmax, tRR and c0 interactively, and a critical concentration existed to judge whether the operating conditions of Pmax under constraints. Based on the comprehensive understanding on 3C-PCC processes, a model-free strategy was proposed for process development. The optimal operating conditions could be determined based on a set of breakthrough curves, which was used to optimize process performance and screen resins. The approach proposed was validated using monoclonal antibody (mAb) capture with a 3C-PCC system under various mAb and feed concentrations. The results demonstrated that a thorough model-based process understanding on multi-column counter-current chromatography is important and could improve process development and establish a model-free strategy for more convenient applications.

Comparison of Protein A affinity resins for twin-column continuous capture processes: Process performance and resin characteristics.

Continuous chromatography is a promising technology for downstream processing of biopharmaceuticals. The operation of continuous processes is significantly different to batch-mode chromatography and needs comprehensive evaluation. In this work, the performances of four Protein A affinity resins were studied systematically for twin-column continuous capture processes. A model-based approach was used to evaluate the process performance (productivity and capacity utilization) under varying operation conditions, and the objective was to reveal the crucial resin properties for continuous capture. The trade-off between productivity and capacity utilization was found, and it is necessary to select appropriate resins for different feedstock and operation conditions. The capacity utilization heavily depends on mass transfer, and steep breakthrough curves are favorable for high capacity utilization. The productivity is determined by both equilibrium binding capacity and mass transfer, and the balance of feed amount and feed time is critical. Moreover, the influence of binding capacity and mass transfer on process productivity and parameter sensitivity with two important resin properties (equilibrium binding capacity qmax and effective pore diffusion coefficient De) were assessed by the model, and suitable resin parameter ranges for twin-column continuous capture were determined. The model-based approach is an effective and useful tool to evaluate the complex performance of different resins and guide the design of next-generation resins for continuous processes.

Synergy ascension of SnS/MoS2 binary metal sulfides on initial coulombic efficiency and stable capacity for lithium storage.

Numerous efforts have been devoted to capability improvement and cycling stability in the past decades, and these performances have been significantly enhanced. Low initial coulombic efficiency is still a problem in the metal sulfide-based anode materials. This study developed a strategy to achieve high initial coulombic efficiency and superior capacity retention by interpenetrating binary metal sulfides of SnS and MoS2 in a conductive carbon matrix. The synergy ascension of electrochemical performances for the metal sulfides is attributed to their mutual impeding effects on coarsening of metal grains and the capsule-shaped coating structure embedded in the carbon sheet architecture. The SnS/MoS2/C composite was prepared by a simple NaCl template-assisted ball milling method, and showed excellent electrochemical performances in terms of a high initial coulombic efficiency up to 90.2% and highly stable reversibility with a specific capacity of 515.4 mA h g-1 after 300 cycles at 1.0 A g-1. All of these characteristics suggest that the proposed materials are superior among the previously reported metal sulfide-based anode materials for lithium-ion batteries.

Concurrently Improved Jsc, Fill Factor, and Stability in a Ternary Organic Solar Cell Enabled by a C-Shaped Non-fullerene Acceptor and Its Structurally Similar Third Component.

A ternary strategy is recognized as a promising approach that enjoys both the simplicity of fabrication conditions and potential to improve performance in organic solar cells. Herein, a C-shaped narrow band gap non-fullerene acceptor GL1 with a C2v symmetry based on a new core was designed and synthesized. A power conversion efficiency (PCE) of 11.43% was achieved by employing PBDB-T:GL1 as an active layer to fabricate photovoltaic devices. To further promote photovoltaic performance, following a similar-structure prescreen principle, a middle band gap acceptor F-2Cl with the same backbone shape, side-chain distribution, and dipole moment orientation as GL1 was introduced as the guest acceptor into the active layer. Thus, benefiting from the collaboration of complementary absorption, cascade energy levels, and well-modified microstructure of the active layer, a 13.17% PCE was obtained with concurrently elevated Jsc, fill factor, and stability for the optimized ternary device. This work presents a successful example of prescreening the third component to simplify the workload for a high-performance ternary device.

Model-based process development and evaluation of twin-column continuous capture processes with Protein A affinity resin.

Multi-column continuous chromatography has advantages of high resin capacity utilization and productivity, low buffer consumption and small footprint. Experimental optimization is often time-consuming and inefficient due to the complexity of continuous processes. In this study, a model-based approach was investigated to improve process development of twin-column continuous capture with Protein A affinity resin MabSelect PrismA. Breakthrough curves under various conditions, productivity and capacity utilization (CU) of the continuous processes under varying operating conditions were predicted. Effects of three key operating parameters (feed concentration (c0), interconnected feed residence time (RT) and breakthrough percentage control of the first column during interconnected feeding (s)) on the productivity and CU were evaluated. A recommended working window can be determined directly from contour maps to balance the trade-off between productivity and CU. The model-optimized operating conditions at varying feed concentrations were verified by experiments, which indicated that the model-based approach was feasible and reliable. The results showed that the suitable RT was 1~2 min and suitable s was 0.6~0.75 for the continuous IgG capture with MabSelect PrismA. The maximum productivity varied from 14 to 47 g/L/h with the feed IgG concentrations at the range of 1 to 10 mg/mL. The results indicated that model-based approach could assist process development efficiently and promote target-orientated process design for continuous processes.

All-Small-Molecule Organic Solar Cells Based on a Fluorinated Small Molecule Donor With High Open-Circuit Voltage of 1.07 V.

A new small molecule donor with an acceptor-donor-acceptor (A-D-A) structure, namely DRTB-FT, has been designed and synthesized for all-small-molecule organic solar cells (ASM-OSCs). By introducing fluorine atoms on the thienyl substituent of the central benzodithiophene unit, DRTB-FT shows a low-lying highest occupied molecular orbital (HOMO) energy level of -5.64 eV. Blending with an A-D-A type acceptor F-2Cl, DRTB-FT based ASM-OSCs gave a power conversion efficiency (PCE) of 7.66% with a high open-circuit voltage (V oc) of 1.070 V and a low energy loss of 0.47 eV. The results indicate that high V oc of ASM-OSC devices can be obtained through careful donor molecular optimization.