化学•材料最新文献

{"title":"Multiexciton Dynamics and Lattice Responses Associated with Amplified Spontaneous Emission in Metal Halide Perovskites","authors":"Hyeonji Lee,EunSeo Jang,Kwangdong Roh,JunWoo Kim","doi":"10.1021/acs.jpclett.6c02776","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02776","url":null,"abstract":"Amplified spontaneous emission (ASE) in metal halide perovskites occurs under intense photoexcitation, where multiexciton (ME) states contribute to population inversion. Here, we investigate how A-site compositional modification regulates ASE in FAPbBr3 films partially substituted with methylammonium (MA). The ASE threshold varies nonmonotonically with MACl additive concentration despite nearly linear bandgap shifts. Fluence-dependent transient absorption signals were decomposed into odd-order nonlinear responses, confirming that the picosecond component emerging at high fluence originates from ME states. The ME lifetime exhibits a pronounced MACl concentration dependence that closely follows the ASE threshold. Coherent phonon analysis reveals reduced phonon frequencies at intermediate MA concentrations, consistent with slower lattice modulation and prolonged ME lifetimes. MA substitution also modifies film morphology and reduces void-like features associated with optical scattering. These results show that ASE performance is jointly governed by ME relaxation dynamics and photon propagation losses.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"12 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226544","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":"Spontaneous Ether Hydrolysis on Cryogenic Water Ice Surfaces","authors":"Soham Chowdhury,Bijesh K. Malla,Thalappil Pradeep","doi":"10.1021/acs.jpclett.6c02695","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02695","url":null,"abstract":"We report the hydrolytic cleavage of C–O bonds in aliphatic ethers at cryogenic water ice surfaces under ultrahigh vacuum conditions. Ethers are conventionally resistant to hydrolysis, requiring strong Brønsted acids and elevated temperatures for C–O bond activation; their reactivity toward neutral water ice at temperatures as low as 10–50 K is therefore unexpected. Using Cs+ reactive ion scattering and low-energy sputtering in combination with isotopic labeling (H2O vs D2O), we demonstrate that dimethyl ether (DME), tert-butyl methyl ether (tBuOMe), and diethyl ether (DEE) undergo hydrolysis to form the corresponding deuterated alcohols upon contact with amorphous and crystalline D2O ice between 10 and 150 K. Isotopic incorporation establishes D2O ice as the source of the incorporated hydrogen. CH3OD was formed even at 10 K in codeposited DME-D2O films and it persisted on crystalline ice, while tBuOMe exhibited distinct product selectivity through the appearance of a tert-butyl carbocationic fragment in low-energy sputtering. These observations reveal an unexpected chemical reactivity of cryogenic water ice toward aliphatic ethers and establish ether hydrolysis as a previously unexplored low-temperature surface reaction.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221724","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":"Beyond Tumor Accumulation: Molecularly Targeted and Activatable Photoacoustic Contrast Agents","authors":"Dawei Zhou,&nbsp;Qing Dan,&nbsp;Lei Xi,&nbsp;Yunxue Xu,&nbsp;Zhifei Dai,&nbsp;Desheng Sun","doi":"10.1021/acs.bioconjchem.6c00386","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00386","url":null,"abstract":"<p>Photoacoustic imaging (PAI) combines optical absorption with ultrasonic detection and has emerged as a powerful platform for noninvasive molecular imaging. The clinical value of a photoacoustic contrast agent (PACA) is not only determined by tumoral accumulation, but also by whether it can generate sufficient target-to-background contrast. In practice, PACAs can be designed to detect tumor-associated biomarkers in two complementary strategies. Molecularly targeted PACAs rely on specific biological recognition to enhance probe localization or retention, whereas an activatable probe generates photoacoustic signals only in response to a disease-related biochemical trigger. Recent studies further show that molecular targeting and activatable sensing can be integrated within a single probe, for example, by combining receptor recognition with activatable, ratiometric, or photo switchable signal generation. We argue that next-generation PACAs should move beyond maximizing tumor uptake toward maximizing biologically informative target-to-background contrast under clinically realistic imaging conditions.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"1930–1934"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222044","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":"Atmospheric Observations Reveal the Spatial Influence of Inland Shipping Channels and Enhanced Emission Signals from AIS-Unmatched Vessels","authors":"Jiaqi Liu,Shanshan Wang,Yan Zhang,Xuejun Feng,Sheng Ye,Ruihua Wang,Yuxin Wang,Zimin Han,Bin Zhou","doi":"10.1021/acs.est.6c08667","DOIUrl":"https://doi.org/10.1021/acs.est.6c08667","url":null,"abstract":"Inland shipping is an important but poorly constrained source of urban air pollution, particularly in dense waterway networks, where vessel activity records are incomplete. Here, we integrate high-time-resolution differential optical absorption spectroscopy (DOAS), national air-quality observations, meteorological normalization, spatial exposure analysis, automatic identification system (AIS) records, and field photographs to evaluate inland shipping impacts in two representative channel environments in eastern China. SO2 showed stronger spatial heterogeneity than nitrogen-related pollutants and was more closely associated with the nearby shipping channels. After meteorological normalization, inland-waterway configuration explained 44% of the interstation variability in urban SO2, with the strongest association at an influence distance of approximately 4 km. Event-scale analysis revealed frequent short-term pollutant enhancements associated with the vessel passages. However, only 54.4% of plume events at the open-channel station and 44.8% at the lock-controlled site could be matched to AIS-recorded vessels. AIS-unmatched plume events were not negligible and, in the lock-controlled environment, were associated with SO2 signals higher than those of AIS-matched events. These results demonstrate that atmospheric observations provide an independent constraint on underdetected inland shipping emissions and suggest that inventories relying solely on vessel activity records may underestimate or mischaracterize sulfur-related emissions from inland waterways.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"56 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226058","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":"A Green and Scalable Protocol for Oxidative Cyclization of N-Acylamidines with Oxone-Halide","authors":"Shiji Chen,Shixiu Hu,Shujun You,Yuxiao Li,Lingli Wang,Rongbiao Tong,Lixin Liang","doi":"10.1021/acs.joc.6c02012","DOIUrl":"https://doi.org/10.1021/acs.joc.6c02012","url":null,"abstract":"Oxidative cyclization of N-acylamidines is one of the most widely used approaches to yield 1,2,4-oxadiazoles, which are prevalent in many bioactive molecules and drugs. Herein, we report a scalable and green protocol using oxone and halide to achieve this transformation, affording the desired 1,2,4-oxadiazoles (32 examples, up to 93% yield) with readily removable inorganic salts as byproducts. This method offers distinct advantages over previous procedures, including operational simplicity, tolerance to air and moisture, ambient temperature, and no requirement for specialized equipment or expensive reagents. Notably, three oxadiazole-based agents were efficiently synthesized from the corresponding N-acylamidines via this protocol. Given its practical scalability and environmental friendliness, this approach is expected to find broad applications in organic synthesis and process chemistry.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226578","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":"Cysteine/GSH-Responsive Lipid Switch Development for Liposome Triggered Cargo Release","authors":"Mahbub Ullah,&nbsp;Kazi R. Shahriar,&nbsp;Mayesha B. Mustafa,&nbsp;Michael D. Best","doi":"10.1021/acs.bioconjchem.6c00392","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00392","url":null,"abstract":"<p>Liposomal delivery has emerged as an effective way to transport a broad range of therapeutics due to the excellent biocompatibility of these nanocarriers and their capacity to encapsulate a wide variety of cargo. However, challenges still persist in controlled content release at diseased cells. Although several stimuli have been recently targeted to achieve effective liposomal triggered release at the target site, cysteine and glutathione (GSH), which are overabundant in cancer cells and play crucial roles by deterring oxidative stress and enhancing cell survival offer important targets. Here, we introduce a unique cysteine/GSH-responsive liposomal platform, which was achieved by incorporating a newly developed <strong>SLPC</strong> lipid containing a disulfide moiety inserted within the <em>sn</em>-2 acyl chain. Förster Resonance Energy Transfer (FRET)-based fluorescence assays, transmission electron microscopy, and dynamic light scattering studies confirmed the formation of stable spherical liposome vesicles containing our <strong>SLPC</strong> lipid switch and cysteine-responsive controlled cargo release. Selectivity screening with cysteine, GSH, homocysteine, dithiothreitol, methionine, serine, glutathione disulfide (GSSG), alanine, and glutamate demonstrated that <strong>SLPC</strong>-containing liposomes show a triggered response only in the presence of molecules containing active thiols. These findings demonstrate that <strong>SLPC</strong> can act as a potent liposomal platform to achieve cysteine/GSH-triggered controlled content release toward the goal of targeted drug delivery to diseased cells.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"2035–2042"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221999","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":"Broadening The View of Aryl Diazonium Ion Reactivity with Proteins and DNA","authors":"Natasha R. Cornejo,&nbsp;Elizabeth N. Browne,&nbsp;Anna Z. Ramsook,&nbsp;Keren Chávez Goraum,&nbsp;Austin Lipinski,&nbsp;Paul R. Langlais,&nbsp;John C. Jewett","doi":"10.1021/acs.bioconjchem.6c00316","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.6c00316","url":null,"abstract":"<p>Aryl diazonium ions (ADIs) are well established for their reaction with both proteins and DNA, and yet these reactions have been studied independently without systematic comparison. When electrophilic bioconjugation probes are introduced to environments containing multiple macromolecules, questions of selectivity and competitive reactivity become critical. Here, we establish a systematic method to evaluate the selectivity of a series of ADIs toward proteins, specifically tyrosine and histidine residues, across varying pH and solvent conditions, while also looking at the ADI reaction with DNA. Electron-deficient ADIs preferentially modified tyrosine over histidine, but all tested ADIs reacted with and degraded DNA. We also observed strong pH- and hydrophobicity-dependent effects on amino acid selectivity. These findings provide a framework for understanding and controlling ADI reactivity in complex biological environments, informing the design of selective bioconjugation strategies.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":"37 10","pages":"2011–2019"},"PeriodicalIF":4.5,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222001","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":"Monitoring the Environmental Degradation of Biodegradable Mulch Films Using Py-GC-MS and a Multitechnique Analytical Approach","authors":"Francesca De Falco,Tommaso Nacci,Fannie Burgevin,Winnie Courtene-Jones,Allicia Fullarton,Rachel L. Coppock,Ilaria Degano,Francesca Modugno,Richard C. Thompson","doi":"10.1021/acs.est.6c11149","DOIUrl":"https://doi.org/10.1021/acs.est.6c11149","url":null,"abstract":"Biodegradable mulch films have been developed for use in agriculture to reduce costs incurred during the retrieval of conventional mulch films and to prevent plastic pollution of soil caused by their incomplete removal. However, there are knowledge gaps on their degradation rate and potential environmental impact of any residuals. This study investigated the degradation of three commercially available mulch films, one made of polyethylene and two labeled as “biodegradable”. These products were exposed to four conditions in the open environment. After 24 months in soil, air, and a combination of air pre-exposure for 3 months followed by soil burial, all samples retained their overall film structure and were still recoverable, although different levels of physical and chemical changes indicated ongoing degradation. In seawater, no residual fragments of the biodegradable mulch films remained after 3 months of exposure. Pyrolysis-gas chromatography-mass spectrometry detected leaching of a plasticizer from one of the biodegradable films in all environments and other degradation features. The outcome of this study highlights the potential for environmental accumulation of mulch films labeled as “biodegradable” and the need for the development of international environmental testing standards and associated labeling to guide users on appropriate use and disposal of mulch films.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"8 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226063","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":"Dynamic Reconstitution of Fe–In Dual-Atom Sites with Bridged Intermediate Adsorption for Selectively Electrochemical Oxygen Reduction to Hydroxyl Radicals","authors":"Liang She,Aiyang Xie,Yanbin Wang,Hongbao Jia,Zonglin Li,Hongying Zhao","doi":"10.1021/acs.est.6c11811","DOIUrl":"https://doi.org/10.1021/acs.est.6c11811","url":null,"abstract":"The three-electron (3e–) oxygen reduction reaction (ORR) to hydroxyl radicals (HO•) represents an emerging strategy for water purification, yet achieving high selectivity remains challenging due to the scaling relationships between oxygen-containing intermediates. Herein, we report a Fe–In dual-atom catalyst (FeIn-DAC) with unique d-p orbital hybridization to tailor the electronic structure of Fe–In pairs for triggering optimal oxygen-bridged adsorption. Operando XANES and in situ Raman spectroscopy reveal that the initial Fe–N4 motif dynamically reconstitutes into Fe–N3 as the genuine active site upon ORR initiation, exposing more unsaturated sites for Yeager-type bridge-adsorbed *O–O* species. DFT calculations confirm that charge rearrangement within Fe–In pairs avoids excessively strong or weak electronic coupling with oxygen intermediates for steering 3e– ORR to HO•. As expected, the FeIn-DAC electrocatalytic system achieves a high HO• generation rate of 6.02 μmol L–1 min–1 and delivers ∼90% TOC removal for various antibiotic pollutants across wide pH ranges. A pilot flow-through device further verifies its practical applicability for real pharmaceutical wastewater treatment with ∼75%–85% TOC/COD removal during 24 h continuous operation. This study highlights potential-driven dynamic reconstitution of dual-atom catalysts for steering selective multielectron ORR under real working conditions.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"62 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226067","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":"Effects of Fabrication Processes and Temperature on Exciton Diffusion in Non-Fullerene Acceptors","authors":"Jianbin Zhong,Junyi Feng,Chuangcheng Hong,Tengxiang Gao,Wei Zhang,Jianjun Jiang,Wei Li,Zhihai Liu,Xianshao Zou","doi":"10.1021/acs.jpclett.6c02713","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02713","url":null,"abstract":"Exciton diffusion to donor–acceptor interfaces plays a critical role in charge generation in organic solar cells, yet its dependence on film fabrication and operating temperature remains poorly understood for high-performance nonfullerene acceptors. Here, femtosecond transient absorption spectroscopy and exciton–exciton annihilation analysis quantify diffusion in Y6 and L8-BO. In Y6 films, processing changes the diffusion coefficient (D) from 0.4 × 10–2 to 1.3 × 10–2 cm2 s–1 and the diffusion length (Ld) from 16.9 to 37.4 nm, whereas L8-BO maintains substantially more stable exciton diffusion across processing conditions. Cooling markedly decreases D and Ld despite a prolonged exciton lifetime, consistent with reduced thermally assisted exciton hopping in an energetically disordered environment. In PM6:Y6 blends, processes related to bimolecular charge recombination slow down with decreasing temperature. These results highlight molecular packing, energetic disorder, and temperature as key factors controlling exciton diffusion and charge dynamics in Y-series acceptors, providing a mechanistic framework for optimizing exciton harvesting in nonfullerene organic solar cells.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"22 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149226502","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}