Structure-phase transformation of bismuth oxide to BiOCl/Bi24O31Cl10 shoulder-by-shoulder heterojunctions for efficient photocatalytic removal of antibiotic.

Developing heterojunction photocatalyst with well-matched interfaces and multiple charge transfer paths is vital to boost carrier separation efficiency for photocatalytic antibiotics removal, but still remains a great challenge. In present work, a new strategy of chloride anion intercalation in Bi2O3 via one-pot hydrothermal process is proposed. The as-prepared Ta-BiOCl/Bi24O31Cl10 (TBB) heterojunctions are featured with Ta-Bi24O31Cl10 and Ta-BiOCl lined shoulder-by-shouleder via semi-coherent interfaces. In this TBB heterojunctions, the well-matched semi-coherent interfaces and shoulder-by-shoulder structures provide fast electron transfer and multiple transfer paths, respectively, leading to enhanced visible light response and improved photogenerated charge separation. Meanwhile, a type-II heterojunction for photocharge separation has been obtained, in which photogenerated electrons are drove from the CB (conduction band) of Ta-Bi24O31Cl10 to the both of bilateral empty CB of Ta-BiOCl and gathered on the CB of Ta-BiOCl, while the photogenerated holes are left on the VB (valence band) of Ta-Bi24O31Cl10, effectively hindering the recombination of photogenerated electron-hole pairs. Furthermore, the separated electrons can effectively activate dissolved oxygen for the generation of reactive oxygen species (·O2-). Such TBB heterojunctions exhibit remarkably superior photocatalytic degradation activity for tetracycline hydrochloride (TCH) solution to Bi2O3, Ta-BiOCl and Ta-Bi24O31Cl10. This work not only proposes a Ta-BiOCl/Bi24O31Cl10 shoulder-by-shoulder micro-ribbon architectures with semi-coherent interfaces and successive type-II heterojunction for highly efficient photocatalytic activity, but offers a new insight into the design of highly efficient heterojunction through phase-structure synergistic transformation strategy.

Single-Particle Imaging Photoinduced Charge Transfer of Ferroelectric Polarized Heterostructures for Photocatalysis.

Piezoelectric-assisted photocatalysis has a huge potential in solving the energy shortage and environmental pollution problems, and imaging their detailed charge-transfer process can provide in-depth understanding for the development of high-active piezo-photocatalysts; however, it is still challenging. Herein, topotactic heterostructures of TiO2@BaTiO3 (TO@BTO-S) were constructed by the epitaxial growth of ferroelectric BaTiO3 mesocrystals on TiO2-{001} facets, resulting in a ferroelectric photocatalyst with a polarization orientation on the surface. Notably, the photoinduced charge transfer in ferroelectric TiO2@BaTiO3 was accurately monitored and directly visualized at the single-particle level by the advanced photoluminescence (PL) imaging microscopy systems. The longer PL lifetime of TO@BTO-S demonstrated the efficient charge separation caused by a built-in electric field, which is constructed by the polarization orientation of BaTiO3 mesocrystals. Therefore, the TO@BTO-S heterostructure exhibits efficient piezoelectric-assisted photocatalytic pure water splitting, which is 290 times higher than photocatalysis. This work revealed time/spatial-resolved photoinduced charge transfer in piezoelectric assistance photocatalysts at the single-particle level and demonstrated the great role of polarization orientation in promoting charge transfer for photocatalysis.

Experimental and theoretical structural investigation of an ionic Nd coordination polymer.

Research concerning coordination polymers has been intense due to their significant variability and structural stability. With this in mind, an ionic neodymium coordination polymer was synthesized, composed of an anionic one-dimensional polymer interconnected to a cationic three-dimensional porous polymer, poly[dodecaaquabis(µ-pyridine-4-carbohydrazide-κ2N:O)bis(µ2-4-sulfobenzoato-κ2O:O')bis(µ3-4-sulfobenzoato-κ3O:O':O'')trineodymium(III)] catena-poly[aquabis(µ-pyridine-4-carbohydrazide-κ2N:O)bis(µ2-4-sulfobenzoato-κ2O:O')neodymium(III)] 4.33-hydrate, {[Nd3(C7H4O5S)4(C6H7N3O)2(H2O)12][Nd(C7H4O5S)2(C6H7N3O)2(H2O)]·4.33H2O}n. The ligands used were 4-sulfobenzoate (PSB) and pyridine-4-carbohydrazide, popularly known as isoniazid (INH), an antibiotic drug. The compound crystallizes in the monoclinic space group C2/c, with Z = 4. Solid-state calculations suggest that the crystal structure is mainly stabilized by hydrogen bonds, i.e. O-H...O and N-H...O interactions among the polymers, and by van der Waals interactions involving the organic side chains. This net is tetragonal, 2-nodal 3,4-connected, and can be described as the dmd (sqc 528) type.

Towards Stable Helical Structures with Enhanced Molecular Conductance by Strengthening Through-Space Conjugation.

Developing long-chain molecules with stable helical structures is of significant importance for understanding and modulating the properties and functions of helical biological macromolecules, but challenging. In this work, an effective and facile approach to stabilize folded helical structures by strengthening through-space conjugation is proposed, using new ortho-hexaphenylene (o-HP) derivatives as models. The structure-activity relationship between the through-space conjugation and charge transport behavior of the prepared folded helical o-HP derivatives is experimentally and theoretically investigated. It is demonstrated that the through-space conjugation within o-HP derivatives can be strengthened by introducing electron-withdrawing pyridine and pyrazine, which can effectively stabilize the helical structures of o-HP derivatives. Moreover, scanning tunneling microscopy-break junction measurements reveal that the stable regular helical structures of o-HP derivatives open up dominant through-space charge transport pathways, and the single-molecule conductance is enhanced by more than 70% by strengthening through-space conjugation with pyridine and pyrazine. But the through-bond charge transport pathways contribute much less to the conductance of o-HP derivatives. These results not only provide a new method for exploring stable helical molecules, but also pave a stepping stone for deciphering and modulating the charge transport behavior of helical systems at the single-molecule level.

Top-down mass spectrometry analysis of capsid proteins of recombinant adeno-associated virus using multiple ion activations and proton transfer charge reduction.

Adeno-associated viruses (AAVs) are common vectors for emerging gene therapies due to their lack of pathogenicity in humans. Here, we present our investigation of the viral proteins (i.e., VP1, VP2, and VP3) of the capsid of AAVs via top-down mass spectrometry (MS). These proteins, ranging from 59 to 81 kDa, were chromatographically separated using hydrophilic interaction liquid chromatography and characterized in the gas-phase by high-resolution Orbitrap Fourier transform MS. Complementary ion dissociation methods were utilized to improve the overall sequence coverage. By reducing the overlap of product ion signals via proton transfer charge reduction on the Orbitrap Ascend BioPharma Tribrid mass spectrometer, the sequence coverage of each VP was significantly increased, reaching up to ∼40% in the case of VP3. These results showcase the improvements in the sequencing of proteins >30 kDa that can be achieved by manipulating product ions via gas-phase reactions to obtain easy-to-interpret fragmentation mass spectra.

Improving Downstream Process Related Manufacturability Based on Protein Engineering-A Feasibility Study.

While bioactivity and a favorable safety profile for biotherapeutics is of utmost importance, manufacturability is also worth of consideration to ease the manufacturing process. Manufacturability in the scientific literature is mostly related to stability of formulated drug substances, with limited focus on downstream process-related manufacturability, that is, how easily can a protein be purified. Process-related impurities or biological impurities like viruses and host cell proteins (HCP) are present in the harvest which have mostly acid isoelectric points and need to be removed to ensure patient safety. Therefore, during molecule design, the surface charge of the target molecule should preferably differ sufficiently from the surface charge of the impurities to enable an efficient purification strategy. In this feasibility study, we evaluated the possibility of improving manufacturability by adapting the surface charge of the target protein. We generated several variants of a GLP1-receptor-agonist-Fc-domain-FGF21-fusion protein and demonstrated proof of concept exemplarily for an anion exchange chromatography step which then can be operated at high pH values with maximal product recovery allowing removal of HCP and viruses. Altering the surface charge distribution of biotherapeutic proteins can thus be useful allowing for an efficient manufacturing process for removing HCP and viruses, thereby reducing manufacturing costs.

Mixed-charge hyperbranched polymer nanoparticles with selective antibacterial action for fighting antimicrobial resistance.

The escalating menace of antimicrobial resistance (AMR) presents a profound global threat to life and assets. However, the incapacity of metal ions/reactive oxygen species (ROS) or the indiscriminate intrinsic interaction of cationic groups to distinguish between bacteria and mammalian cells undermines the essential selectivity required in these nanomaterials for an ideal antimicrobial agent. Hence, we devised and synthesized a range of biocompatible mixed-charge hyperbranched polymer nanoparticles (MCHPNs) incorporating cationic, anionic, and neutral alkyl groups to effectively combat multidrug-resistant bacteria and mitigate AMR. This outcome stemmed from the structural, antibacterial activity, and biocompatibility analysis of seven MCHPNs, among which MCHPN7, with a ratio of cationic groups, anionic groups, and long alkyl chains at 27:59:14, emerged as the lead candidate. Importantly, owing to inherent differences in membrane potential among diverse species, alongside its nano-size (6 - 15 nm) and high hydrophilicity (Kow = 0.04), MCHPN7 exhibited exceptional selective bactericidal effects over mammalian cells (selectivity index > 564) in vitro and in vivo. By inducing physical membrane disruption, MCHPN7 effectively eradicated antibiotic-resistant bacteria and significantly delayed the emergence of bacterial resistance. Utilized as a coating, MCHPN7 endowed initially inert surfaces with the ability to impede biofilm formation and mitigate infection-related immune responses in mouse models. This research heralds the advent of biocompatible polymer nanoparticles and harbors significant implications in our ongoing combat against AMR. STATEMENT OF SIGNIFICANCE: The escalating prevalence of antimicrobial resistance (AMR) has been acknowledged as one of the most significant threats to global health. Therefore, a series of mixed-charge hyperbranched polymer nanoparticles (MCHPNs) with selective antibacterial action were designed and synthesized. Owing to inherent differences in membrane potential among diverse species and high hydrophilicity (Kow = 0.04), the optimal nanoparticles exhibited exceptional selective bactericidal effects over mammalian cells (selectivity index >564) and significantly delayed the emergence of bacterial resistance. Importantly, they endowed surfaces with the ability to impede biofilm formation and mitigate infection-related immune responses. Furthermore, the above findings focus on addressing the problem of AMR in Post-Pandemic, which will for sure attract attention from both academic and industry research.

Variations in objectively measured sleep parameters in patients with different premature ejaculation syndromes.

BACKGROUND: Poor sleep quality is now a cause of sexual dysfunction. AIM: To investigate variations in sleep quality among patients with different types of premature ejaculation (PE) and a control group. METHODS: Patients with PE were categorized into groups according to 4 types: lifelong (LPE), acquired (APE), variable (VPE), and subjective (SPE). Basic demographic information about the participants was first collected, and then clinical data were obtained. OUTCOMES: Outcomes included the 5-item International Index of Erectile Function, Premature Ejaculation Diagnostic Tool, 7-item Generalized Anxiety Disorder, 9-item Patient Health Questionnaire, Pittsburgh Sleep Quality Index, self-estimated intravaginal ejaculation latency time (minutes), and sleep monitoring parameters obtained from a wearable device (Fitbit Charge 2). RESULTS: A total of 215 participants were enrolled in the study, of which 136 patients with PE were distributed as follows: LPE (31.62%), APE (42.65%), VPE (10.29%), and SPE (15.44%). Subjective scales showed that patients with APE were accompanied by a higher prevalence of erectile dysfunction, anxiety, and depression, as well as poorer sleep quality (assessed by the Pittsburgh Sleep Quality Index). The results of objective sleep parameters revealed that average durations of sleep onset latency (minutes) and wake after sleep onset (minutes) in patients with APE (mean ± SD; 20.03 ± 9.14, 55 ± 23.15) were significantly higher than those with LPE (15.07 ± 5.19, 45.09 ± 20.14), VPE (13.64 ± 3.73, 38.14 ± 11.53), and SPE (14.81 ± 4.33, 42.86 ± 13.14) and the control group (12.48 ± 3.45, 37.14 ± 15.01; P < .05). The average duration of rapid eye movement (REM; minutes) in patients with APE (71.34 ± 23.18) was significantly lower than that in patients with LPE (79.67 ± 21.53), VPE (85.93 ± 6.93), and SPE (80.86 ± 13.04) and the control group (86.56 ± 11.93; P < .05). Similarly, when compared with the control group, patients with LPE had significantly longer durations of sleep onset latency and wake after sleep onset and a significantly shorter duration of REM sleep. CLINICAL IMPLICATIONS: Our study suggests that clinicians should pay attention not only to male physical assessment but also to mental health and sleep quality. STRENGTHS AND LIMITATIONS: This study suggests that changes in sleep structure occur in patients with PE, which may provide some direction for future research. However, the cross-sectional study design does not allow us to conclude that sleep is a risk factor for PE. CONCLUSION: After controlling for traditional parameters such as age, erectile dysfunction, anxiety, and depression, sleep parameters are independently associated with PE. Patients with APE and LPE show significant alterations in sleep parameters, with patients with APE having notably poorer sleep quality, whereas patients with VPE and SPE have sleep parameters similar to controls.

[Effects of simulated gas of thermobaric bomb charge explosion on Tau protein phosphorylation and cognitive function in rats].

Objective: To explore the effect of simulated gas of thermobaric bomb charge explosion on cognitive function and the related mechanism of damage. Methods: In January 2022, thirty-two SPF rats were selected and randomly divided into control group, exposed group 1, 2 and 3 (the exposure time of the simulated gas of the explosion of the thermobaric bomb charge was 5 min, 10 min and 15 min, respectively) according to random number table method, with 8 rats in each group. The simulated gas of the explosion of the thermobaric bomb charge were CO 0.15%, CO(2) 3%, NO 0.1%, O(2) 15%, and the rest were N(2). After 30 days of exposure, water maze was used to detect the learning and memory function of rats. Golgi staining was used to observe the number distribution and morphological structure of hippocampal neurons in rats. Western blot was used to detect the expression of Tau-5, pSer262, pSer396, pThr181 and pThr231 proteins in rats. Repeated measure ANOVA was used to compare the design data of repeated measure, one-way ANOVA was used for multi-group mean comparison, and LSD method was used for pound-wise comparison. Results: There were significant differences in the results of repeated measurement ANOVA of the water maze localization navigation test (F=80.98, P<0.001), and there was an interaction between the group and the training days (F=2.16, P=0.022). There were significant differences in escape latency of rats at the 2nd, 3rd, 4th and 5th days among all groups (P<0.05). The results of spatial exploration showed that the frequency of rats crossing the platform was significantly different among all groups (F=4.49, P=0.011). The frequency of rats crossing the platform in exposed group 2 and exposed group 3 was lower than that in control group, and the frequency of rats crossing the platform in exposed group 3 was lower than that in exposed group 1 (P<0.05). With the increase of exposure time, the number of hippocampal neurons decreased, and the dendrite spine density of neurons in CA1 region decreased (P<0.05). Compared with the control group, there was no significant difference in the relative expression level of Tau-5 protein in all exposed groups (P>0.05), but the expression level of pSer262 protein was significantly increased (P<0.05). Compared with the control group, the protein expressions of pSer396, pThr181 and pThr231 in exposed group 2 and exposed group 3 were significantly increased (P<0.05) . Conclusion: The simulated gas of the explosion of the thermobaric bomb charge may contribute to the development of cognitive dysfunction by damaging hippocampal neurons with aberrant phosphorylation of Tau proteins.

Photomodulation of Charge Transfer through Excited-State Processes: Directing Donor-Acceptor Binding Dynamics.

Modulating charge transfer (CT) interactions between donor and acceptor molecules may give rise to unique dynamic changes in physicochemical properties, exhibiting great importance in supramolecular chemistry and materials science. In this work, we demonstrate the first instance of reversible photomodulation of donor-acceptor (D-A) CT interaction in the solid state.Pyridinium-based chromophore featuring π-conjugated D-A structures can not only function as a good electron acceptor to undergo photoinduced electron transfer (ET) or engage in intermolecular CT interaction, but also exhibit unique dual emission depending on the excitation wavelengths. The rotatable C-C single bonds within D-A pairs enhance the tunability of molecular structure. Through the synergy of a photoinduced ET and an excited-state conformational change, the intermolecular CT interaction can be switched on and off by alternate light irradiation to enables reversibly modulation of the affinity between donor and acceptor molecules, accompanied by visual color switching and fluorescence on-off as feedback signals.

Coupling Between Electrons and Charge Density Wave Fluctuation and its Possible Role in Superconductivity.

In most charge density wave (CDW) systems of different material classes, ranging from traditional correlated systems in low-dimension to recent topological systems with Kagome lattice, superconductivity emerges when the system is driven toward the quantum critical point (QCP) of CDW via external parameters of doping and pressure. Despite this rather universal trend, the essential hinge between CDW and superconductivity has not been established yet. Here, the evidence of coupling between electron and CDW fluctuation is reported, based on a temperature- and intercalation-dependent kink in the angle-resolved photoemission spectra of 2H-PdxTaSe2. Kinks are observed only when the system is in the CDW phase, regardless of whether a long- or short-range order is established. Notably, the coupling strength is enhanced upon long-range CDW suppression, albeit the coupling energy scale is reduced. Interestingly, the estimation of the superconducting critical temperature by incorporating the observed coupling characteristics into McMillan's equation yields results closely resembling the known values of the superconducting dome. The results thus highlight a compelling possibility that this new coupling mediates Cooper pairs, which provides new insights into the competing relationship not only for CDW but also for other competing orders.

Fine-Tuning 2D Heterogeneous Channels for Charge-Lock Enhanced Lithium Separation from Brine.

The extraction of lithium (Li) from complex brines presents significant challenges due to the interference of competing ions, particularly magnesium (Mg2⁺), which complicates the selective separation process. Herein, a strategy is introduced employing charge-lock enhanced 2D heterogeneous channels for the rapid and selective uptake of Li⁺. This approach integrates porous ZnFe2O4/ZnO nanosheets into Ag+-modulated sub-nanometer interlayer channels, forming channels optimized for Li⁺ extraction. The novelty lies in the charge-lock mechanism, which selectively captures Mg2⁺ ions, thereby facilitating the effective separation of Li from Mg. This mechanism is driven by a charge transfer during the formation of ZnFe2O4/ZnO, rendering O atoms in Fe-O bonds more negatively charged. These negative charges strongly interact with the high charge density of Mg2⁺ ions, enabling the charge-locking mechanism and the targeted capture of Mg2⁺. Optimization with Ag⁺ further improves interlayer spacing, increasing ion transport rates and addressing the swelling issue typical of 2D membranes. The resultant membrane showcases high water flux (44.37 L m⁻2 h⁻¹ bar⁻¹) and an impressive 99.8% rejection of Mg2⁺ in real brine conditions, achieving a Li⁺/Mg2⁺ selectivity of 59.3, surpassing existing brine separation membranes. Additionally, this membrane demonstrates superior cyclic stability, highlighting its high potential for industrial applications.

Identifying Root Origin of Insulating Polymer Mediated Solar Water Oxidation.

Rational construction of high-efficiency photoelectrodes with optimized carrier migration to the ideal active sites, is crucial for enhancing solar water oxidation. However, complexity in precisely modulating interface configuration and directional charge transfer pathways retards the design of robust and stable artificial photosystems. Herein, a straightforward yet effective strategy is developed for compact encapsulation of metal oxides (MOs) with an ultrathin non-conjugated polymer layer to modulate interfacial charge migration and separation. By periodically coating highly ordered TiO2 nanoarrays with oppositely charged polyelectrolyte of poly(dimethyl diallyl ammonium chloride) (PDDA), MOs/polymer composite photoanodes are readily fabricated under ambient conditions. It is verified that electrons photogenerated from the MOs substrate can be efficiently extracted by the ultrathin solid insulating PDDA layer, significantly boosting the carrier transport kinetics and enhancing charge separation of MOs, and thus triggering a remarkable enhancement in the solar water oxidation performance. The origins of the unexpected electron-withdrawing capability of such non-conjugated insulating polymer are unambiguously uncovered, and the scenario occurring at the interface of hybrid photoelectrodes is elucidated. The work would reinforce the fundamental understanding on the origins of generic charge transport capability of insulating polymer and benefit potential wide-spread utilization of insulating polymers as co-catalysts for solar energy conversion.

Precisely Tunable Instantaneous Carbon Rearrangement Enables Low-Working-Potential Hard Carbon Toward Sodium-Ion Batteries with Enhanced Energy Density.

As the preferred anode material for sodium-ion batteries, hard carbon (HC) confronts significant obstacles in providing a long and dominant low-voltage plateau to boost the output energy density of full batteries. The critical challenge lies in precisely enhancing the local graphitization degree to minimize Na+ ad-/chemisorption, while effectively controlling the growth of internal closed nanopores to maximize Na+ filling. Unfortunately, traditional high-temperature preparation methods struggle to achieve both objectives simultaneously. Herein, a transient sintering-involved kinetically-controlled synthesis strategy is proposed that enables the creation of metastable HCs with precisely tunable carbon phases and low discharge/charge voltage plateaus. By optimizing the temperature and width of thermal pulses, the high-throughput screened HCs are characterized by short-range ordered graphitic micro-domains that possess accurate crystallite width and height, as well as appropriately-sized closed nanopores. This advancement realizes HC anodes with significantly prolonged low-voltage plateaus below 0.1 V, with the best sample exhibiting a high plateau capacity of up to 325 mAh g-1. The energy density of the HC||Na3V2(PO4)3 full battery can therefore be increased by 20.7%. Machine learning study explicitly unveils the "carbon phase evolution-electrochemistry" relationship. This work promises disruptive changes to the synthesis, optimization, and commercialization of HC anodes for high-energy-density sodium-ion batteries.

Perpendicular crossing chains enable high mobility in a noncrystalline conjugated polymer.

The nature of interchain π-system contacts, and their relationship to hole transport, are elucidated for the high-mobility, noncrystalline conjugated polymer C16-IDTBT by the application of scanning tunneling microscopy, molecular dynamics, and quantum chemical calculations. The microstructure is shown to favor an unusual packing motif in which paired chains cross-over one another at near-perpendicular angles. By linking to mesoscale microstructural features, revealed by coarse-grained molecular dynamics and previous studies, and performing simulations of charge transport, it is demonstrated that the high mobility of C16-IDTBT can be explained by the promotion of a highly interconnected transport network, stemming from the adoption of perpendicular contacts at the nanoscale, in combination with fast intrachain transport.

On the importance of crystal structures for organic thin film transistors.

Historically, knowledge of the molecular packing within the crystal structures of organic semiconductors has been instrumental in understanding their solid-state electronic properties. Nowadays, crystal structures are thus becoming increasingly important for enabling engineering properties, understanding polymorphism in bulk and in thin films, exploring dynamics and elucidating phase-transition mechanisms. This review article introduces the most salient and recent results of the field.

Regulation of organic solar cells performance through external electric field: From charge transfer mechanisms to photovoltaic properties.

In organic solar cells (OSCs), comprehending the charge transfer mechanism at D/A interfaces is crucial for photoinduced charge generation and enhancing power conversion efficiency (PCE). The charge transfer mechanism and photovoltaic performance of the parallel stacking interface configuration of the PTQ10 polymer donor and T2EH non-fullerene acceptor (NFA) are systematically studied at the microscopic scale. The analysis of the electron-hole distribution of the PTQ10/T2EH excited states revealed the presence of multiple charge excitation modes and charge transfer pathways. Using Marcus theory, we examine the charge separation rate (KCS) of PTQ10/T2EH under external electric field (Fext) modulation, and it is clarified that reorganization energy (λ) is the main factor that affects the KCS. Our results show that Fext has a positive impact on the photovoltaic properties of PTQ10/T2EH thin films, as evidenced by the modulation of the open circuit voltage (VOC), voltage loss (VLOSS) and fill factor (FF). Overall, this study provides valuable theoretical insights for Fext to accelerate the charge separation process and enhance photovoltaic efficiency.

Augmented Extraction Efficiency of a Hot D Exciton in MoS2 via Intervalley Scattering.

Prolonging hot carrier cooling, a crucial factor in optoelectronic applications, including hot carrier photovoltaics, presents a significant challenge. High-energy band-nesting excitons within parallel bands offer a promising and underexplored avenue for addressing this issue. Here, we exploit an exceptional D exciton cooling prolongation of 2 to 3 orders of magnitude compared to sub-picosecond in typical transition metal dichalcogenides (TMDs) owing to the complex Coulomb environment and the sequential and mismatch-valley relaxation. Simultaneously, the intervalley scattering upconversion of band-edge excitons with the slow D exciton formation in the metastable Γ valley/hill also reduces the cooling rate. We successfully extract D and C excitons as hot carriers through integrating with various thicknesses of TiOx, achieving the highest efficiency of 98% and 85% at a Ti thickness of 2 nm. Our findings highlight the potential of band-nesting excitons for extending hot carrier cooling time, paving the way for advancements in hot carrier-based optoelectronic devices.

Organic-Inorganic Interfacial Dipole Induced by Energy Level Alignment for Efficient Photocatalytic Sterilization.

Photocatalytic molecules are considered to be one of the most promising substitutions of antibiotics against multidrug-resistant bacterial infections. However, the strong excitonic effect greatly restricts their efficiency in antibacterial performance. Inspired by the interfacial dipole effect, a Ti3C2 MXene modified photocatalytic molecule (MTTTPyB) is designed and synthesized to enhance the yield of photogenerated carriers under light irradiation. The alignment of the energy level between Ti3C2 and MTTTPyB results in the formation of an interfacial dipole, which can provide an impetus for the separation of carriers. Under the role of a dipole electric field, these photogenerated electrons can rapidly migrate to the side of Ti3C2 for improving the separation efficiency of photogenerated electrons and holes. Thus, more electrons can be utilized to produce reactive oxygen species (ROS) under light irradiation. As a result, over 97.04% killing efficiency can be reached for Staphylococcus aureus (S. aureus) when the concentration of MTTTPyB/Ti3C2 was 50 ppm under 660 nm irradiation for 15 min. A microneedle (MN) patch made from MTTTPyB/Ti3C2 was used to treat the subcutaneous bacterial infection. This design of an organic-inorganic interface provides an effective method to minimize the excitonic effect of molecules, further expanding the platform of inorganic/organic hybrid materials for efficient phototherapy.

Distinct chemical degradation pathways of AAV1 and AAV8 under thermal stress conditions revealed by analytical anion exchange chromatography and LC-MS-based peptide mapping.

Adeno-associated virus (AAV)-based gene therapy is experiencing a rapid growth in the field of medicine and holds great promise in combating a wide range of human diseases. For successful development of AAV-based products, comprehensive thermal stability studies are often required to establish storage conditions and shelf life. However, as a relatively new modality, limited studies have been reported to elucidate the chemical degradation pathways of AAV products under thermal stress conditions. In this study, we first presented an intriguing difference in charge profile shift between thermally stressed AAV8 and AAV1 capsids when analyzed by anion exchange chromatography. Subsequently, a novel and robust peptide mapping protocol was developed and applied to elucidate the underlying chemical degradation pathways of thermally stressed AAV8 and AAV1. Compared to the conventional therapeutic proteins, the unique structure of AAV capsids also led to some key differences in how modifications at specific sites may impact the overall charge properties. Finally, despite the high sequency identity, the analysis revealed that the opposite charge profile shifts between thermally stressed AAV8 and AAV1 could be mainly attributed to a single modification unique to each serotype.