Capacitive deionization (CDI) has emerged as a promising desalination technology for brackish water applications, distinguished by its exceptional recyclability and favorable energy consumption characteristics. The operational mechanism relies upon ion adsorption within electric double layers (EDLs) formed at the surface of active carbon materials, which enables reversible ion adsorption/desorption. However, the intrinsic disordered architecture of activated carbon, despite offering substantial specific surface area, simultaneously generates considerable ohmic resistance. Consequently, CDI systems utilizing activated carbon electrodes demonstrate restricted energy performance, proving economically viable exclusively for treating dilute saline solutions below 1000 mg L- 1 NaCl concentration. To address these conductivity limitations, researchers have incorporated antimony-doped tin oxide (ATO) nanoparticles onto ordered mesoporous carbon (OMC) substrates. Experimental results demonstrate that antimony incorporation substantially elevates the electronic conductivity of SnO2 nanoparticles deposited on OMCs. This enhancement facilitates NaCl removal primarily through EDL capacitive charging rather than Faradaic pseudocapacitive processes. ATO/OMC-1 achieved the salt adsorption capacity (SAC) of 29.28 mg g- 1, the salt adsorption rate (SAR) of 20.03 mg g- 1 min- 1, a charge efficiency of 61.79%, and repeated adsorption-desorption behavior over 20 cycles when tested at an applied potential of 1.1 V in 750 mg L -1 NaCl solution, while the highest charge efficiency reached 78.66% at 0.7 V. These outcomes validate that surface functionalization with ATO nanoparticles represents a viable strategy for advancing CDI electrode performance.
Designing RNA sequences that reliably adopt specified three-dimensional structures while maintaining thermodynamic stability remains challenging for synthetic biology and therapeutics. Current inverse folding approaches optimize for sequence recovery or single structural metrics, failing to simultaneously ensure global geometry, local accuracy, and ensemble stability-three interdependent requirements for functional RNA design. This gap becomes critical when designed sequences encounter dynamic biological environments. We introduce RiboPO, a Ribonucleic acid Preference Optimization framework that addresses this multi-objective challenge through reinforcement learning from physical feedback (RLPF). RiboPO fine-tunes gRNAde by constructing preference pairs from composite physical criteria that couple global 3D fidelity and thermodynamic stability. Preferences are formed using structural gates, PLDDT geometry assessments, and thermostability proxies with variability-aware margins, and the policy is updated with Direct Preference Optimization (DPO). On RNA inverse folding benchmarks, RiboPO demonstrates a superior balance of structural accuracy and stability. Compared to the best non-overlap baselines, our multi-round model improves Minimum Free Energy (MFE) by 12.3
Catheter-associated urinary tract infection (CAUTI) induced by rapid bacterial colonization and biofilm formation on urinary catheters is a key issue that urgently needs to be addressed. To prevent CAUTI, many contact-killing, non-leaching coatings have been developed for the surfaces of silicone catheters. However, due to the chemical inertness of the silicone substrate, most current coatings lack adhesion and are unstable under external forces. Thus, the aim of this study was to develop a surface coating that has both good antibacterial ability and a high affinity toward silicone substrates. To achieve high affinity, a pre-coating layer with abundant surface vinyl groups, named SI-vinyl, was prepared on the silicone substrate by moisture curing using a mixture of α,ω-dihydroxy polydimethylsiloxane and vinyltrimethoxysilane as the painting agent. To endow the surface with contact-killing ability, a series of polyurethanes with different contents of quaternary ammonium salt groups in their main chain and two vinyl end groups were synthesized and covalently grafted onto the surface of SI-vinyl, resulting in corresponding bactericidal coatings with different surface contents of quaternary ammonium salt groups (SI-QAS). Of these bactericidal coatings, SI-QAS-2, with a surface QAS content of 2.1 × 1016 N+ cm−2, was selected as the best coating based on the consideration of stability, compatibility, and antibacterial ability. The SI-QAS-2 coating demonstrated high contact-killing performance, rapidly inactivating 72.8%, 99.9%, and 98.9% of Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa within 30 min. Furthermore, even after being exposed to a high concentration of bacteria (106 CFU/mL) for 4 days, the SI-QAS-2 coating still maintained a high bactericidal ratio of over 80%. In summary, we developed a novel contact-killing coating that reduces the risk of bacterial infections caused by catheter implantation, demonstrating that it has high affinity toward silicone substrates, excellent contact-killing efficiency, a facile preparation method, and potential for further application.
Hierarchically porous carbons (HPCs) were synthesized using a sodium ion (Na+)-Pluronic F127 coordination complex as a template for application in capacitive deionization (CDI). By incorporating NaCl into the Pluronic F127-glucose aqueous solution during hydrothermal carbonization, the HPC-8/12 exhibited the largest specific surface area (267.30 m2/g) and mesopore volume (85.7 %). Compared to HPC-0/12, HPC-8/12 demonstrated a specific capacitance of 94.22F/g in a 1 M NaCl aqueous electrolyte. The HPC-8/12 was subsequently mixed with graphene oxide and processed into non-woven fabrics via wet-spinning. These fabrics were then thermally annealed in an inert gas at 800 degrees C to produce CDI electrodes. The resulting HPC-8/12-graphene composite fibers achieved salt adsorption capacities (SAC) of 13.34 mg/g for KCl, 18.78 mg/g for NaCl, and 12.53 mg/g for LiCl at a working voltage of 1.2 V. The Na+-Pluronic F127 coordination complexes completely degrade during thermal annealing, resulting in enlarged mesopore sizes that reduce ion transport resistance. Additionally, they introduce specific adsorption sites for Na+. This study demonstrates the potential for selectively adsorbing Na+ using CDI technology.
Designing enzyme backbones with substrate-specific functionality is a critical challenge in computational protein engineering. Current generative models excel in protein design but face limitations in binding data, substrate-specific control, and flexibility for de novo enzyme backbone generation. To address this, we introduce EnzyBind, a dataset with 11,100 experimentally validated enzyme-substrate pairs specifically curated from PDBbind. Building on this, we propose EnzyControl, a method that enables functional and substrate-specific control in enzyme backbone generation. Our approach generates enzyme backbones conditioned on MSA-annotated catalytic sites and their corresponding substrates, which are automatically extracted from curated enzyme-substrate data. At the core of EnzyControl is EnzyAdapter, a lightweight, modular component integrated into a pretrained motif-scaffolding model, allowing it to become substrate-aware. A two-stage training paradigm further refines the model's ability to generate accurate and functional enzyme structures. Experiments show that our EnzyControl achieves the best performance across structural and functional metrics on EnzyBind and EnzyBench benchmarks, with particularly notable improvements of 13% in designability and 13% in catalytic efficiency compared to the baseline models. The code is released at https://github.com/Vecteur-libre/EnzyControl.
Polymeric acceptors are prone to over-aggregate in photovoltaic thin films due to the entanglement of their long macromolecular chains, which hampers the exciton dissociation during the power conversion process. Although high boiling point solvent can retard the over-aggregation of polymeric acceptors, the structural order is often suppressed which will limit the charge transport in all-polymer solar cells (all-PSCs). In this work, the solvent additive 1-CN and solid additive INMB-F are combined to overcome the above issue, realizing enhanced structural order with refined phase separation in a cutting-edge PM6:PY-IT all-PSC, with a remarkable power conversion efficiency of 19.1%, which is one of the highest efficiency reported for binary PY-IT based all-PSCs. Molecular dynamics simulations and X-ray diffraction indicate that 1-CN can facilitate the disentanglement of PY-IT chains, while INMB-F can interact with these disentangled chains to promote ordered molecular stacking, thereby enhancing exciton dissociation and charge transport simultaneously. (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic). (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(all-PSCs)(sic)(sic)(sic)(sic)(sic)(sic). (sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)1-CN(sic)(sic) (sic)(sic)(sic)(sic)INMB-F(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)PM6:PY-IT(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)19.1% (sic)(sic)(sic)(sic)(sic)(sic)(sic)(PCE), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)PY-IT(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic). (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)X(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic), 1-CN(sic)(sic)(sic)(sic)PY-IT(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)INMB-F(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic), (sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic)(sic) (sic)(sic)(sic)(sic)(sic)(sic).
The architectural configuration of an electrode material significantly impacts its capacitive deionization (CDI) performance, particularly due to the disparity in ion diffusion resistance between the surface and core. To mitigate this disparity, a hollowing methodology was employed to revamp conventional porous carbon spheres. Hierarchically porous hollow carbon spheres (HCSs) were synthesized by thermal annealing phenol formaldehyde resin-coated melamine formaldehyde resin spheres (MFSs) in an inert gas at 800 degrees C. The advantage of employing modified MFSs as templates lies in their complete degradation during thermal annealing, a feature not observed with commercial polystyrene microspheres. Unlike mesoporous SiO2 microspheres which require additional hydrofluoric acid treatment, these do not. HCS-100 exhibited exceptional NaCl adsorption capacity, achieving a salt adsorption capacity of 25.20 mg g(-1) and a salt adsorption rate of 2.78 mg g(-1) min(-1) under a working voltage of 1.2 V. This performance was demonstrated with an initial NaCl solution concentration of 500 mg L-1, and it maintained impressive stability over 70 cycles. The results demonstrate that the hollowing strategy is a direct yet powerful way to enhance the CDI performance of electrode materials. The utilization of the modified MFS template simplifies the fabrication process, contributing to the overall effectiveness of this approach.
All polymer solar cells (all-PSCs) promise mechanically-flexible and morphologically-stable organic photovoltaics and have aroused increased interests very recently. However, due to their disorderly conformation structures within the photoactive film, inefficient charge generation and carrier transport are observed which lead to inferior photovoltaic performance compared to smaller molecular acceptor-based photovoltaics. Here, by diluting PM6 with a cutting-edge polymeric acceptor PY-IT and diluting PY-IT with PM6 or D18, donor-dominating or acceptor-dominating heterojunctions were prepared. Synchrotron X-ray and multiple spectrometer techniques reveal that the diluted heterojunctions receive increased structural order, translating to enhanced carrier mobility, improved exciton diffusion length, and suppressed non-radiative recombination loss during the power conversion. As the results, the corresponding PM6+1%PY-IT/PY-IT+1%D18 and PM6+1%PY-IT/PY-IT+1%PM6 devices fabricated by layer-by-layer deposition received superior power conversion efficiency (PCE) of 19.4% and 18.8% respectively, along with enhanced operational lifetimes in air, outperforming the PCE of 17.5% in the PM6/PY-IT reference device.
UV-light illumination converts the aromatic conformation of polymer donors into a rigid quinone structure, resulting in compact fibrillar aggregation of the active layer to achieve a maximum efficiency of 19.9% of single-junction organic solar cells.
The nanoscale fibrillar morphology, featuring long-range structural order, provides abundant interfaces for efficient exciton dissociation and high-quality pathways for effective charge transport, is a promising morphology for high performance organic solar cells. Here, we synthesize a thiophene terminated non-fullerene acceptor, L8-ThCl, to induce the fibrillization of both polymer donor and host acceptor, that surpasses the 20% efficiency milestone of organic solar cells. After adding L8-ThCl, the original weak and less continuous nanofibrils of polymer donors, i.e. PM6 or D18, are well enlarged and refined, whilst the host acceptor L8-BO also assembles into nanofibrils with enhanced structural order. By adapting the layer-by-layer deposition method, the enhanced structural order can be retained to significantly boost the power conversion efficiency, with specific values of 19.4% and 20.1% for the PM6:L8-ThCl/L8-BO:L8-ThCl and D18:L8-ThCl/L8-BO:L8-ThCl devices, with the latter being certified 20.0%, which is the highest certified efficiency reported so far for single-junction organic solar cells. The nanoscale fibrillar morphology of the photoactive layer is critical to improve performance of organic solar cells. Here, the authors incorporate thiophene terminal groups in the non-fullerene acceptor, realizing nanofibrils with enhanced structural order and certified device efficiency of 20%.
The photoactive layer of organic solar cells consists of p-type electron donors and n-type electron acceptors, which phase separate to form fine and continuous networks for charge transport. The impact of the donor–acceptor interaction on the microstructure and optoelectronics of the photoactive layer remains unclear. In this work, a tiny amount (1 wt%) of donor PM6 is added into the non-fullerene acceptor (NFA) C8- R or L8-BO (or vice versa) to form a donor (or acceptor) diluted heterojunction. The structural order is improved through dipole–dipole interaction between the donor and the acceptor owing to their opposite electronegativity. We fabricate a pseudo-bilayer heterojunction solar cell based on NFA-diluted donor (that is, donor + 1% NFA) and donor-diluted NFA (that is, NFA + 1% donor) layers: the device exhibits superior power conversion efficiencies compared with their bulk heterojunction and conventional pseudo-bilayer counterparts. We demonstrate an efficiency of 19.4% (certified 19.1%) and 17.6% for 100 and 300 nm-thick PM6 + 1% L8-BO/L8-BO + 1% PM6 solar cells, respectively.
Insulating polymers are promising components for constructing high performance organic solar cells (OSCs) due to their advantages including low cost, excellent mechanical properties, and feasibility in morphology modulation. However, few studies have been conducted on the effect of molecular weight of insulating polymers on the performance of the corresponding OSCs. In this work, polymethyl methacrylate (PMMA) with different molecular weight (named as PMMAL and PMMAH) are incorporated into a range of polymer:nonfullerene photovoltaic systems. It is found that although both PMMAL and PMMAH can suppress the energetic disorder and the nonradiative energy loss, and lead to enhanced open‐circuit voltage in their corresponding OSCs, distinct mechanical property, operational stability as well as photovoltaic performance are observed. PMMAL can modulate the molecular packing of the host components more effectively due to its superior chain segment mobility during the film‐forming process, which can drive the host components to form more ordered molecular packing and therefore superior photovoltaic performance. On the other hand, due to the better miscibility of PMMAH with the host system, especially the C5‐16 acceptor, PMMAH can be well dispersed in the host and form a stable framework that provides superior mechanical properties and operational stability.
To avoid the undesired bacterial attachment on polyurethane-based biomedical devices, we designed a class of novel perfluoropolyether-incorporated polyurethanes (PFPU) containing different contents of perfluoropolyether (PFPE) segments. After blending with Ag nanoparticles (AgNPs), a series of bifunctional PFPU/AgNPs composites with bactericidal and anti-adhesion abilities were obtained and correspondingly made into PFPU/AgNPs films (PFPU/Ag-F) using a simple solvent-casting method. Due to its highest hydrophobicity and suitable mechanical properties, PFPU8/Ag-F containing 8 mol% of PFPE content was chosen as the optimized one for the next antibacterial assessment. The PFPU8/Ag-F can effectively deactivate over 99.9% of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) cells at 106 CFU mL-1 within 30 min. Furthermore, the PFPU8/AgNPs composite was used as painting material to form a protective coating for the commercial polyurethane (PU) catheter. The as-prepared PFPU8/Ag coating exhibits high resistance to bacterial adhesion in a continuous-flow artificial urine model in an 8 day exposure. Therefore, it can be expected that the proposed PFPE-containing films and coatings can effectively prevent bacterial colonization and biofilm formation on catheters or other implants, thereby reducing the risk of postoperative catheter-induced infection.
Interlayer engineering is crucial for achieving efficient and stable organic solar cells (OSCs). Herein, by introducing a commercialized brominated quaternary ammonium salt, hexamethonium bromide (HB), into a perylene diimide (PDI)-structured electron transport layer (ETL), a PDINN:HB hybrid ETL with enhanced charge collection ability and environmental/operational stability is realized. Molecular dynamics simulations and Kelvin probe force microscopy indicate that strong polar bromine and amine groups can form extra interfacial dipoles in the hybrid interlayer, while X-ray photoelectron spectroscopy and electron paramagnetic resonance suggest the hybrid ETL can interact with the Ag cathode, thereby regulating the energy level arrangement at the interface. As for the results, the PDINN:HB hybrid ETL enables improved power conversion efficiency (PCE) from 17.8 to 18.4% and 18.8 to 19.4% in PM6:C5-16 bulk heterojunction- and PM6/L8-BO pseudobulk heterojunction-based OSCs, respectively. The versatility of this method is further verified by introducing a range of brominated quaternary ammonium salts into PDINN, in which a superior PCE and stability are all obtained compared to the reference device.
The efficiency and stability of organic solar cells (OSCs) is often restricted by the metastable photoactive and charge transport layers. Here, we report the acquiring of stable photovoltaics via vacuum-assisted thermal annealing (VTA), which not only enhances the molecular packing of donor and acceptor but also restrains the overgrowth of photovoltaic molecules and leads to a slender fibrillar network, resulting in enhanced charge transport and suppressed carrier recombination. In situ ellipsometry measurements reveal that VTA can remove the trapped solvents and reduce the free volume of the photoactive layer, leading to slower structural relaxation during operation and therefore superior morphological and operational stability. As a result, the VTA-treated D18:L8-BO and PM6:L8-BO OSCs exhibit superior PCEs of 19.7% and 19.2%, respectively, with an ITO/PEDOT:PSS/active layer/PDINN/Ag structure, and a PCE of 18.0% with a T 80 lifetime of 45,200 h for the ITO/ MoO3/PM6:L8-BO/C60/BCP/Ag-structured 3 /PM6:L8-BO/C 60 /BCP/Ag-structured device, corresponding to an unprecedented lifetime of 30 years.
Ternary strategy is demonstrated as an efficient approach to achieve high short-circuit current and open-circuit voltage to boost the performance of organic solar cells (OSCs), however, the realization of high fill-factor (FF) in ternary OSCs has been rare. In this study, three thiophene terminated non-fullerene acceptors (NFAs) with methyl or chlorine substitutions on their end-groups are designed and synthesized, and further incorporated into the state-of-the-art PM6:L8-BO system to construct ternary OSCs. Subtle changes in their chemical structures significantly modify the molecular packings of these thiophene terminated NFAs. While BTP-ThMe and BTP-ThCl have limited forms of dimer, versatile molecular dimers, including "Z" shaped D-D, "S" shaped A-A, and "F" shaped A-D packings exist in BTP-ThMeCl, which lead to the formation of compact 3D honey-comb network and this is analogous to the host acceptor L8-BO. This synergetic molecular packing between BTP-ThMeCl and L8-BO contributes to maintain the 3D charge transport network in the ternary system via the formation of NFA co-crystals at the molecular level, and consequently realizing a maximum power conversion efficiency of 19.1% with a superior FF of 82.2%, which is the highest FF reported so far for OSCs.
Organic semiconductors based upon conjugated frameworksare oftenisomeric and display distinct optoelectronic properties within minorstructural variation. In this work, two isomeric nonfullerene acceptors(NFAs) ThMeCl-1 and ThMeCl-2, having the methyl and chlorine atomsattached on different positions of the electron-withdrawing end group,are synthesized and incorporated as the third component in ternarysolar cells. Although these NFA isomers exhibit a similar bandgap,energy levels, and energy loss in their PM6 based binary devices,the efficiency enhancements in ternary devices differ significantly.Compared to ThMeCl-1, the incorporation of ThMeCl-2 in PM6:C5-16 solarcells enables less energy loss, leading to an extra 0.03 eV open-circuitvoltage gain and a maximum efficiency increase from 17.8 to 18.9%.Grazing-incidence X-ray diffraction and molecular dynamics simulationsreveal that this is attributed to the versatile intermolecular pi-pi stacking forms between ThMeCl-2 and the host NFA, which result inimproved charge transport and suppressed recombination. This workprovides a rational guidance for controlling the molecular packingin ternary systems to prepare high performance organic photovoltaics.
Realizing fibrillar molecular framework is highly encouraged in organic solar cells (OSCs) due to the merit of efficient charge carrier transport. This is however mainly achieved via the chemical structural design of photovoltaic semiconductors. In this work, through the utilization of three alkoxythiophene additives, T-2OMe, T-OEH, and T-2OEH, the intermolecular interactions among a series of BDT-type polymer donors, i.e., PM6, D18, PBDB-T, and PTB7-Th, are tuned to self-assemble into nanofibrils during solution casting. X-ray technique and molecular dynamics simulation reveal that the alkoxythiophene with (2-ethylhexyl)oxy (─OEH) chains can attach on the 2-ethylhexyl (EH) chains of these polymer donors and promote their self-assembly into 1D nanofibrils, in their neat films as well as photovoltaic blends with L8-BO. By adapting these fibrillar polymer donors to construct pseudo-bulk heterojunction (P-BHJ) OSCs via layer-by-layer deposition, generally improved device performance is seen, with power conversion efficiencies enhanced from 18.2% to 19.2% (certified 18.96%) and from 17.9% to 18.7% for the PM6/L8-BO and D18/L8-BO devices, respectively. This work provides a physical approach to promote the fibrillar charge transport channels for efficient photovoltaics.
Organic semiconductors are generally featured with low structure order in solid-state films, which leads to low charge-transport mobility and strong charge recombination in their photovoltaic devices. In this work, a "polycrystal-induced aggregation" strategy orders the polymer donor (PM6) and non-fullerene acceptor (L8-BO) molecules during solution casting with the assistance of PM6 polycrystals that are incubated through a vapor diffusion method, toward improved solar cell efficiency with either thin or thick photoactive layers. These PM6 polycrystals are redissolved in chloroform to prepare PM6 pre-aggregates (PM6-PA), and further incorporated into the conventional PM6:L8-BO blend solutions, which is found to prolong the molecular organization process and enhance the aggregation of both the PM6 and the L8-BO components. As the results, with the assistance of 10% PM6-PA, PM6:L8-BO solar cell devices obtain power conversion efficiencies (PCEs) from 18.0% and 16.2% to 19.3% and 17.2% with a 100 nm-thick and 300 nm-thick photoactive layer, respectively.
Interfacial modification is crucial for achieving efficient and stable organic solar cells (OSCs). Herein, an N,N-dimethylformamide (DMF) solution-cast poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) interlayer was applied to enhance the efficiency and stability of a range of OSCs, and the underlying mechanism was revealed via morphological and device physics studies. DMF rinse during the P(VDF-TrFE) interlayer casting process strengthens π-π stacking of the active layer with fibril aggregation, optimized phase separation, and vertical component distribution, while the P(VDF-TrFE) interlayer with rich diploes contributes to increased surface potential and internal electric field. The synergistic effect of the P(VDF-TrFE) interlayer and DMF rinse increases the PCEs of PM6:IT-4F, PM6:C5-16, and PM6:L8-BO OSCs from 12.7, 17.9, and 18.2% to 13.1, 18.7, and 18.8%, respectively. Additionally, OSCs containing the P(VDF-TrFE) interlayer also showed improved storage stability.