化学•材料最新文献

{"title":"Boosting Photovoltaic Efficiency: The Role of Longitudinal Carrier Transport in Carbon Dot-Modified Perovskite Films","authors":"Xinlei Zhang, Jing Leng, Shengli Zhao, Qing Yang, Peng Xu, Shiqi Rong, Yan Xu, Wenming Tian, Shengye Jin","doi":"10.1021/acs.jpclett.5c00637","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00637","url":null,"abstract":"Defect passivation engineering, an effective strategy to optimize grain boundaries and reduce defects in organic–inorganic hybrid perovskites, has been widely used to improve device performance; however, knowledge of its impact on the carrier transport property is still limited. Herein, we take carbon dot (CD) passivation as an example to explore the effect of surface modification on the longitudinal carrier diffusivity (D) in CH₃NH₃PbI₃ perovskite films by using transient reflection spectroscopy. The results show that the D value remarkably increases from 0.30 cm² s^–1 in unmodified film to 1.02 cm² s^–1 in CD-modified film due to their enhanced conductivity, where CDs act as a highly conductive interstitial medium to enhance intergrain contact. Benefiting from the increase in carrier diffusivity, the power conversion efficiency of CD-modified perovskite solar cells (PSCs) increased from 23.1% (unmodified) to 25.4%, strongly confirming the positive effect of CD passivation on the PSC performance. Our finding highlights a novel avenue for enhancing PSC performance through the improvement of longitudinal carrier diffusivity via high-conductivity nanomaterial doping.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"215 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of Substrate Roughness on the Thermal Boundary Conductance in 2D Materials","authors":"Sylvester W. Makumi, Zlatan Aksamija","doi":"10.1021/acs.jpcc.4c08172","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08172","url":null,"abstract":"Heat dissipation and thermal management are key challenges for further adopting two-dimensional (2D) materials in nanoelectronics. Due to their large aspect ratio, most heat removal is through the substrate. Atomic-scale roughness at the surface of the substrate, together with the mechanical properties and the adhesion of 2D materials to the substrate, dictates how well 2D sheets conform and transfer heat to the substrate. However, a complete understanding of the combined impact of these factors on the thermal boundary conductance (TBC) of 2D/substrate interfaces is lacking. Here, we have used a numerical model to explore the TBC of interfaces between single layers of graphene, hBN, and MoS₂ and rough a-SiO₂ substrate. Our study shows that the effect of roughness on TBC depends on the average surface slope, defined as the ratio of rms roughness height and correlation length (Δ_rms/<i>L</i>_cor), rather than Δ_rms alone. We find that 2D materials conform well to a rough substrate when the surface slope is small and that the effective TBC remains unchanged. However, steep surface slope (Δ_rms/<i>L</i>_cor &gt; 0.1), caused by large roughness or short lateral correlation length, makes the 2D material partially delaminate from the substrate, leading to variations in van der Waals (vdW) spring coupling constant (<i>K</i>_s). For interfaces with weak adhesion, outlier <i>K</i>_s values lead to an enhancement in the effective TBC by up to 12% compared to that of a flat interface, provided the in-plane thermal conductivity of the 2D sheet is sufficient (&gt;1 Wm^1– K^–1) to spread the heat effectively. For interfaces with strong adhesion, we show that it is necessary that the slope remains below 0.1. Beyond this, the 2D material gets delaminated and coupling is weakened, resulting in a lower effective TBC. Therefore, our work provides essential information that will contribute to designing electronic devices with more efficient thermal management.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"On the Mechanism and Productivity of Single-Pulse Laser Fragmentation of Organic Curcumin Dispersions in a Continuous Flat Jet Flow-Through Reactor","authors":"Tina Friedenauer, Maximilian Spellauge, Alexander Sommereyns, Christoph Rehbock, Heinz P. Huber, Stephan Barcikowski","doi":"10.1021/acs.jpcc.4c08643","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08643","url":null,"abstract":"Curcumin is a natural food additive (nutraceutical), whose bioavailability is impaired by low solubility, a drawback which may be overcome by particle size reduction. Microparticle (MP) laser fragmentation in liquids (LFL) is an emerging production method for sensitive, organic submicron particles (SMPs) and nanoparticles (NPs), as it is characterized by processing at minimal chemical degradation. However, the fragmentation mechanisms need to be understood to tune the MP-LFL process toward a high SMP yield. Therefore, we used pump-probe microscopy (PPM) to elucidate the dynamics of shockwave formation and cavitation bubble growth on single-curcumin particles in correlation with laser fluence utilizing a ps-pulsed laser at 1040 nm. We observed LFL to occur at a threshold fluence of 60 mJ cm^–2. Furthermore, we found a pressure buildup of 308 MPa within the particle, which exceeds the material’s tensile strength by one order of magnitude, hinting at strong contributions of photomechanical effects during curcumin MP-LFL. Consecutively, we examined the transfer to MP dispersions where concentration effects during MP-LFL were studied using a ps-pulsed laser at 532 nm and an optimized continuous flat jet (FJ) reactor, which is characterized by the ability to process particularly high concentrations of up to 1000 mg L^–1 due to the low liquid layer thickness. An increased mass yield of SMP and NP (determined by UV–vis extinction spectroscopy and SEM) was found at high educt concentrations of 500 mg L^–1, which leads to a relative SMP mass yield of 62% and a productivity of 278 mg h^–1, with the potential for quantitative conversion of all MPs into SMPs at optimized illumination conditions (100% yield, 500 mg h^–1). The outstandingly low by-product fraction (&lt; 0.5%) by far surpasses the standard comminution processes applied today, rendering the MP-LFL technology even more relevant to the food or pharma sector.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"90 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Atomistic Insights into gp82 Binding: A Microsecond, Million-Atom Exploration of <i>Trypanosoma cruzi</i> Host-Cell Invasion.","authors":"Raissa S L Rosa, Manuela Leal da Silva, Rafael C Bernardi","doi":"10.1021/acs.biochem.4c00710","DOIUrl":"https://doi.org/10.1021/acs.biochem.4c00710","url":null,"abstract":"<p><p>Chagas disease, caused by the protozoan <i>Trypanosoma cruzi</i>, affects millions globally, leading to severe cardiac and gastrointestinal complications in its chronic phase. The invasion of host cells by <i>T. cruzi</i> is mediated by the interaction between the parasite's glycoprotein gp82 and the human receptor lysosome-associated membrane protein 2 (LAMP2). While experimental studies have identified a few residues involved in this interaction, a comprehensive molecular-level understanding has been lacking. In this study, we present a 1.44-million-atom computational model of the gp82 complex, including over 3300 lipids, glycosylation sites, and full molecular representations of gp82 and LAMP2, making it the most complete model of a parasite-host interaction to date. Using microsecond-long molecular dynamics simulations and dynamic network analysis, we identified critical residue interactions, including novel regions of contact that were previously uncharacterized. Our findings also highlight the significance of the transmembrane domain of LAMP2 in stabilizing the complex. These insights extend beyond traditional hydrogen bond interactions, revealing a complex network of cooperative motions that facilitate <i>T. cruzi</i> invasion. This study not only confirms key experimental observations but also uncovers new molecular targets for therapeutic intervention, offering a potential pathway to disrupt <i>T. cruzi</i> infection and combat Chagas disease.</p>","PeriodicalId":28,"journal":{"name":"Biochemistry Biochemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spin-Free Exact Two-Component Linear Response Coupled Cluster Theory for the Estimation of Frequency-Dependent Second-Order Properties.","authors":"Sudipta Chakraborty, Tamoghna Mukhopadhyay, Achintya Kumar Dutta","doi":"10.1021/acs.jpca.4c03584","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c03584","url":null,"abstract":"<p><p>We have presented the theory, implementation, and benchmark results for the one-electronic variant of spin-free exact two-component (SFX2C1e) linear response coupled cluster (LRCCSD) theory for static and dynamic polarizabilities of atoms and molecules in the spin-summed formulation. The resolution of identity (RI) approximation for two-electron integrals has been used to reduce the computational cost of the calculation and has been shown to have a negligible effect on accuracy. The calculated static and dynamic polarizability values agree very well with the more expensive X2C-LRCCSD and the experimental results. Our calculated results show that accurate predictions of polarizabilities of atoms and molecules containing heavy atoms require the use of a large basis set containing an adequate number of diffuse functions, in addition to accounting for electron correlation and relativistic effects.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nonlinear Metasurfaces: A New Paradigm for Short-Wavelength Generation and Modulation","authors":"Zhihui Wang, Rong Lin, Chen Chen, Jiajun Wu, Jin Yao, Din Ping Tsai","doi":"10.1021/acs.jpcc.5c01186","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01186","url":null,"abstract":"Ultraviolet (UV) light has a shorter wavelength and higher photon energy, making it critical for numerous applications such as spectroscopy, microscopy, and information processing. Compared with conventional approaches, nonlinear metasurfaces offer a compact and flexible platform for UV light generation and manipulation. They leverage the strong light–matter interactions and resonant effects to efficiently convert fundamental light into the UV region. In this perspective, we reveal the underlying principles of UV generation based on nonlinear metasurfaces and review the latest advances in ultraviolet light generation and manipulation by plasmonic and dielectric nonlinear metasurfaces. Finally, we discuss the current challenges and future directions. We believe that nonlinear metasurfaces hold great potential for advancing UV photonics.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"98 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Properties and Reactivity of Iron-Organic Matter-Arsenic Composites and their Influence on Arsenic Behavior in Microbial Reduction and Oxidation Processes","authors":"Ruixia Han, Zhe Wang, Jitao Lv, Kaiwen He, Siyao Liu, Zhe Zhu, Jerome Nriagu, H. Henry Teng, Yong-Guan Zhu, Gang Li","doi":"10.1021/acs.est.5c00696","DOIUrl":"https://doi.org/10.1021/acs.est.5c00696","url":null,"abstract":"The biogeochemistry of arsenic in soils is strongly controlled by iron oxides and soil organic matter (SOM). The present study intends to elucidate the behavior of arsenic in Fe-SOM-As composites formed through adsorption or coprecipitation under redox conditions. The X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) showed that crystalline minerals were generated during Fe-HA-As coprecipitation, while other composites exhibited an amorphous structure. In an anoxic environment, iron-reducing bacteria reduced Fe(III) and As(V) to Fe(II) and As(III), respectively, enhancing the mobility of arsenic. The presence of SOM increased the concentrations of dissolved Fe(II) and As(III) through complexation. Notably, elevated As(III) and reduced Fe(II) were observed in the HA-containing coprecipitation group due to the weak adsorption capacity of crystalline minerals, which released As(V) into solution and competed with Fe(III) for electrons. Under oxic conditions, superoxide, hydrogen peroxide, and hydroxyl radical (^•OH) were formed through the oxidation of Fe(II) and reduced SOM. As(III) was subsequently oxidized by superoxide and ^•OH, and the process was dominated by ^•OH. Substantial ^•OH in the HA-containing coprecipitation group mainly oxidized dissolved As(III), while limited ^•OH in other groups contributed greater to adsorbed As(III). These findings contribute substantially to understanding the mechanisms of the coupled transformation of iron and arsenic in soil under fluctuating redox conditions.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"12 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Magnetic Circular Dichroism of Chiral Quantum Rods","authors":"Rui Sun, Bolin Feng, Xiaoqing Gao","doi":"10.1021/acs.jpcc.4c08802","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08802","url":null,"abstract":"Circular dichroism (CD) and magnetic circular dichroism (MCD) are two distinct spectroscopic techniques that offer valuable insights into the properties of materials. Generally speaking, CD spectroscopy reveals information about the ground electronic states of chiral materials, while MCD spectroscopy is sensitive to the degeneracy splitting of energy states in achiral materials under an applied magnetic field. For typical chiral molecules, the measurement of their MCD spectra invariably involves an intrinsic CD signal, which arises from their chiral structure. Consequently, the MCD spectrum can be dissected into two components: one is the CD spectrum arising from the asymmetry of the geometric structure inherent to the chiral molecules; the other is the MCD spectrum associated with the corresponding racemic mixtures. This principle of spectral decomposition is well-established in molecular systems; however, a natural question arises: what is the situation like in inorganic nanosystems? To address this query, an in-depth analysis was conducted of the MCD spectra of chiral quantum rods (QRs) with the same diameter but varying lengths. Intriguingly, it was discovered that the analytical approach applicable to chiral molecules can also be extended to chiral quantum rods (QRs), especially when chiral molecules are present on the surfaces of these materials. This finding holds great significance, as it paves the way for a more accurate and comprehensive MCD analysis of inorganic nanoparticles, potentially enabling new insights and applications in nanomaterials research.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"4 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Monolithic Ceramic CoTiO3/TiO2 Membrane Balancing Catalytic Efficiency and Durability in Advanced Oxidation Processes","authors":"Yuyao Zhang, Kwan Lam Yip, Yonghyeon Kim, Claire Chouinard, James Licato, Jae-Hong Kim","doi":"10.1021/acs.est.4c12814","DOIUrl":"https://doi.org/10.1021/acs.est.4c12814","url":null,"abstract":"Membrane-based advanced oxidation processes (AOPs) have shown great promise in degrading persistent organic pollutants in wastewater. However, their long-term application is often limited by the trade-off between catalytic efficiency and durability. In this study, we present a stable monolithic ceramic membrane integrating a CoTiO₃/TiO₂ interface that successfully overcomes this trade-off. The CoTiO₃/TiO₂ interface enhances peroxymonosulfate (PMS) activation while preventing Co²⁺ leaching, ensuring both high catalytic efficiency and structural integrity under reactive conditions. Finite element analysis suggests that the optimized distribution of the catalyst across our membrane regulates PMS utilization and minimizes the corrosive effects of radicals, extending the membrane’s lifespan. The synthesized membrane demonstrated exceptional catalytic performance and stability, achieving fast bisphenol A removal (up to 99% within 25 s of reaction time) and maintaining structural integrity during 120 h of prolonged exposure to reactive PMS environments. This membrane design not only overcomes efficiency and durability but also offers a scalable solution for advanced water treatment applications.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"132 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exposure of Parental Zebrafish to Difenoconazole throughout Their Life Cycle May Lead to Developmental Toxicity in the F1 Generation through Epigenetic Changes in Gametes, Impaired Nutrient Supply from the Ovum, and Maternal Transfer of Difenoconazole","authors":"Xiangguang Chen, Junyue Zheng, Chengju Wang, Miaomiao Teng, Jiazhen Jiang, Fengchang Wu","doi":"10.1021/acs.est.4c13073","DOIUrl":"https://doi.org/10.1021/acs.est.4c13073","url":null,"abstract":"Difenoconazole is a widely used agricultural fungicide that has been frequently detected in aquatic environments. Given its stable presence in aquatic environments, long-term exposure of wild fish may pose a risk to offspring embryonic development. This study demonstrated that exposure of zebrafish to environmental concentrations of difenoconazole throughout their life cycle resulted in abnormal development of offspring embryos/larvae, including decreased heart rate, delayed hatching, increased malformation rate, shortened body length, and increased mortality. These changes were significantly correlated with the affected apoptosis, autophagy, energy metabolism and MAPK signaling pathways in F1 generation. This transgenerational toxic effect results from epigenetic alterations in gametes, impaired nutrient supply from the ovum, and maternal transfer of difenoconazole. After exposure to difenoconazole, the development of female fish offspring was affected more than that of male fish offspring, which was mainly caused by the impaired nutrient supply from the ovum and the maternal transfer of difenoconazole. Because this transgenerational developmental toxicity was observed at environmental levels, difenoconazole may pose a threat to the survival of wild larvae and therefore a risk to wild fish populations.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"31 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}