Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy最新文献

英文中文

Ratiometric fluorescent probe for triphosgene detection and its application in electrospun fluorescent fibers

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-04-01 DOI: 10.1016/j.saa.2025.126149

Mengyu Chen , Cuibing Bai , Wenhui Xue, Xin Wang, Shizhen Wang, Qixiang Song, Xinyu Wang, Chenxu Liu, Lin Zhang, Biao Wei, Hui Miao, Rui Qiao

Triphosgene poses a potentially great threat to human health and safety. Therefore, it is of great significance to develop an effective method to realize the inexpensive, on-site, convenient, and rapid detection of triphosgene. Herein, based on the excited-state intramolecular proton transfer mechanism, a new fluorescent probe DPIM was designed and synthesized, which realized the rapid ratiometric identification and detection of triphosgene for the first time. Its limit of detection for triphosgene was 3.54 × 10⁻⁸ M, and it had a large Stokes shift of 198 nm. Its recognition mechanism was comprehensively analyzed. A smartphone detection platform and probe-loaded test paper were prepared to realize the inexpensive, on-site, and convenient detection of triphosgene. DPIM effectively enabled the ratiometric fluorescence “turn-on” for detecting residual triphosgene in the sand, showing its application practicality. Most importantly, the probe was incorporated into nanofibers and successfully used to monitor gaseous triphosgene with high specificity, showing its excellent application potential. This study provides a promising analytical tool for the rapid quantitative detection of triphosgene in solution and gaseous phases.

{"title":"Ratiometric fluorescent probe for triphosgene detection and its application in electrospun fluorescent fibers","authors":"Mengyu Chen , Cuibing Bai , Wenhui Xue, Xin Wang, Shizhen Wang, Qixiang Song, Xinyu Wang, Chenxu Liu, Lin Zhang, Biao Wei, Hui Miao, Rui Qiao","doi":"10.1016/j.saa.2025.126149","DOIUrl":"10.1016/j.saa.2025.126149","url":null,"abstract":"<div><div>Triphosgene poses a potentially great threat to human health and safety. Therefore, it is of great significance to develop an effective method to realize the inexpensive, on-site, convenient, and rapid detection of triphosgene. Herein, based on the excited-state intramolecular proton transfer mechanism, a new fluorescent probe <strong>DPIM</strong> was designed and synthesized, which realized the rapid ratiometric identification and detection of triphosgene for the first time. Its limit of detection for triphosgene was 3.54 × 10<sup>−8</sup> M, and it had a large Stokes shift of 198 nm. Its recognition mechanism was comprehensively analyzed. A smartphone detection platform and probe-loaded test paper were prepared to realize the inexpensive, on-site, and convenient detection of triphosgene. <strong>DPIM</strong> effectively enabled the ratiometric fluorescence “turn-on” for detecting residual triphosgene in the sand, showing its application practicality. Most importantly, the probe was incorporated into nanofibers and successfully used to monitor gaseous triphosgene with high specificity, showing its excellent application potential. This study provides a promising analytical tool for the rapid quantitative detection of triphosgene in solution and gaseous phases.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"337 ","pages":"Article 126149"},"PeriodicalIF":4.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760506","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}

引用次数: 0

A novel fluorescent sensor for imaging of viscosity and ClO− in plant cells and zebrafish

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-04-01 DOI: 10.1016/j.saa.2025.126162

Siyi Shen, Yuehua Yuan, Yuzhen Wang, Yongjun Zhu, Mengqing Du, Chaoyi Yue, Bing Pan, Shuai Ren, Feng Feng, Maozhong Tian

Viscosity and hypochlorite (ClO⁻) are two crucial microenvironmental species that play significant roles in biological activities. Their abnormal levels are closely associated with numerous common diseases. Therefore, accurate and real-time detection of hypochlorite and viscosity related to inflammatory microenvironment conduces to elucidate the pathogenesis and further diagnose the disease. In this work, based on the strategy of the phenothiazine (PTZ)-dicyanoisophorone (DCO) dyad system, a new dual-response fluorescent sensor (PBI) was successfully constructed for the simultaneous detection and visualization of viscosity and hypochlorite (ClO⁻) both in vitro and in vivo. The free sensor emits weak fluorescence in aqueous solution thanks to twisted intramolecular charge transfer (TICT) and photoinduced electron transfer (PET). However, in a high-viscosity system, the fluorescence emission of the sensor at 459 nm was significantly enhanced. Upon introduction of ClO⁻ in aqueous buffer solution, the PBI exhibited apparent fluorescence enhancement at 577 nm, and showed large Stokes shift (177 nm). The fluorescence responsive mechanism was confirmed using HRMS, ¹H NMR and DFT calculation analysis. Onion and lotus root cells imaging of PBI towards ClO⁻ was implemented. Furthermore, PBI has been successfully applied to the fluorescence imaging of viscosity and exogenous/endogenous hypochlorite in zebrafish.

{"title":"A novel fluorescent sensor for imaging of viscosity and ClO− in plant cells and zebrafish","authors":"Siyi Shen, Yuehua Yuan, Yuzhen Wang, Yongjun Zhu, Mengqing Du, Chaoyi Yue, Bing Pan, Shuai Ren, Feng Feng, Maozhong Tian","doi":"10.1016/j.saa.2025.126162","DOIUrl":"10.1016/j.saa.2025.126162","url":null,"abstract":"<div><div>Viscosity and hypochlorite (ClO<sup>−</sup>) are two crucial microenvironmental species that play significant roles in biological activities. Their abnormal levels are closely associated with numerous common diseases. Therefore, accurate and real-time detection of hypochlorite and viscosity related to inflammatory microenvironment conduces to elucidate the pathogenesis and further diagnose the disease. In this work, based on the strategy of the phenothiazine (PTZ)-dicyanoisophorone (DCO) dyad system, a new dual-response fluorescent sensor (PBI) was successfully constructed for the simultaneous detection and visualization of viscosity and hypochlorite (ClO<sup>−</sup>) both <em>in vitro</em> and <em>in vivo</em>. The free sensor emits weak fluorescence in aqueous solution thanks to twisted intramolecular charge transfer (TICT) and photoinduced electron transfer (PET). However, in a high-viscosity system, the fluorescence emission of the sensor at 459 nm was significantly enhanced. Upon introduction of ClO<sup>−</sup> in aqueous buffer solution, the PBI exhibited apparent fluorescence enhancement at 577 nm, and showed large Stokes shift (177 nm). The fluorescence responsive mechanism was confirmed using HRMS, <sup>1</sup>H NMR and DFT calculation analysis. Onion and lotus root cells imaging of PBI towards ClO<sup>−</sup> was implemented. Furthermore, PBI has been successfully applied to the fluorescence imaging of viscosity and exogenous/endogenous hypochlorite in zebrafish.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"337 ","pages":"Article 126162"},"PeriodicalIF":4.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760504","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}

引用次数: 0

A smart photosensitive fluorescent probe for sensing Co2+ in extremely alkaline aqueous solution

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-31 DOI: 10.1016/j.saa.2025.126159

Yiming Zhang , Yujie Wang , Ruilin Shi , Bingxuan Huang , Shaoyin Wei , Yuji Wang , Nao Xiao

A novel pH-, viscosity-, and photo-sensitive polymorphic fluorescence probe NHP for sensing Co²⁺ has been developed. The hydrazone-based NHP can be synthesized by only one step of reflux reaction and purified by washing with poor solvents. Three single crystals of NHP-1, NHP-2, and NHP-3 with different conformations were resolved. As a photo acid generator (PAG), the hydrogen atom on the imino group of the probe NHP can be shed with 365 nm ultraviolet (UV) light illumination or in alkaline conditions. Due to the above two conditions, the negatively charged ligand obtained after dehydrogenation of NHP can accelerate its chelation with Co²⁺. When irradiated with 365 nm UV light, the product (NHP₂-Co²⁺ (I)) of NHP chelating with Co²⁺ appears yellowish in aqueous solution. In a strong alkali aqueous solution, the chelate product (NHP₂-Co²⁺ (II)) of NHP and Co²⁺ showed bright blue-green fluorescence. The formed divalent Co(II) complex NHP₂-Co²⁺ can be oxidized to trivalent Co(III) complex NHP₃-Co³⁺, as confirmed by the resolution of single crystals of NHP₃-Co³⁺.

{"title":"A smart photosensitive fluorescent probe for sensing Co2+ in extremely alkaline aqueous solution","authors":"Yiming Zhang , Yujie Wang , Ruilin Shi , Bingxuan Huang , Shaoyin Wei , Yuji Wang , Nao Xiao","doi":"10.1016/j.saa.2025.126159","DOIUrl":"10.1016/j.saa.2025.126159","url":null,"abstract":"<div><div>A novel pH-, viscosity-, and photo-sensitive polymorphic fluorescence probe <strong>NHP</strong> for sensing Co<sup>2+</sup> has been developed. The hydrazone-based <strong>NHP</strong> can be synthesized by only one step of reflux reaction and purified by washing with poor solvents. Three single crystals of <strong>NHP</strong>-1, <strong>NHP</strong>-2, and <strong>NHP</strong>-3 with different conformations were resolved. As a photo acid generator (PAG), the hydrogen atom on the imino group of the probe <strong>NHP</strong> can be shed with 365 nm ultraviolet (UV) light illumination or in alkaline conditions. Due to the above two conditions, the negatively charged ligand obtained after dehydrogenation of <strong>NHP</strong> can accelerate its chelation with Co<sup>2+</sup>. When irradiated with 365 nm UV light, the product (<strong>NHP<sub>2</sub>-Co<sup>2+</sup></strong> (I)) of <strong>NHP</strong> chelating with Co<sup>2+</sup> appears yellowish in aqueous solution. In a strong alkali aqueous solution, the chelate product (<strong>NHP<sub>2</sub>-Co<sup>2+</sup></strong> (II)) of <strong>NHP</strong> and Co<sup>2+</sup> showed bright blue-green fluorescence. The formed divalent Co(II) complex <strong>NHP<sub>2</sub>-Co<sup>2+</sup></strong> can be oxidized to trivalent Co(III) complex <strong>NHP<sub>3</sub>-Co<sup>3+</sup></strong>, as confirmed by the resolution of single crystals of <strong>NHP<sub>3</sub>-Co<sup>3+</sup></strong>.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"337 ","pages":"Article 126159"},"PeriodicalIF":4.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760503","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}

引用次数: 0

Confinement effect of zirconium metal–organic frameworks derived enhanced oxidase-like activity and stability of gold nanoclusters for biosensing

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-31 DOI: 10.1016/j.saa.2025.126153

Pin Bai , Aifang Zhou , Mingyue Xie , Xintong Dong , Qianqian Zhu , Hong-Min Meng , Zhaohui Li

Gold nanoclusters (AuNCs), as an attractive material in heterogeneous catalysis, exhibit great potential in biosensing and biomedicine. However, controllable regulation of catalytic activity and preferable stabilization of AuNCs remain challenging. Benefiting from porous structures and ultrahigh specific surfaces, metal–organic frameworks (MOFs) have shown promising potential in the tailoring of catalytic activity and improving the stability of AuNCs. However, preferable catalytic activity and excellent stability are still challenging, due to the easy leaching of AuNCs from MOFs. Enhancing the combination between AuNCs and MOFs is of great significance. Herein, biomimic nanozymes of AuNCs@UiO-68 were designed through strong coordination between Zr atoms of the MOFs and phosphonate O atoms of DNA backbones from the DNA-templated AuNCs. Compared with control materials of AuNCs and AuNCs/UiO-68, a significant enhancement of oxidase-mimicking activity was achieved in AuNCs@UiO-68, owing to the confinement effect of Zr-MOFs. Additionally, it was found that the catalytic activity of AuNCs could be regulated by altering ligands of the Zr-MOFs. Based on the favorable catalytic activity of AuNCs@UiO-68, a highly sensitive and selective detecting platform for small uremic toxin molecule of hydroquinone was established, with a low detection limit of 0.85 μM. The stability of AuNCs was greatly improved by the proposed synthetic strategy. Besides, preferable and controllable catalytic activity was also obtained, attributed to the confinement effect of MOFs. This work provides a new way for rational regulation of catalytic activity and ameliorating the stability of metal clusters based nanozymes.

{"title":"Confinement effect of zirconium metal–organic frameworks derived enhanced oxidase-like activity and stability of gold nanoclusters for biosensing","authors":"Pin Bai , Aifang Zhou , Mingyue Xie , Xintong Dong , Qianqian Zhu , Hong-Min Meng , Zhaohui Li","doi":"10.1016/j.saa.2025.126153","DOIUrl":"10.1016/j.saa.2025.126153","url":null,"abstract":"<div><div>Gold nanoclusters (AuNCs), as an attractive material in heterogeneous catalysis, exhibit great potential in biosensing and biomedicine. However, controllable regulation of catalytic activity and preferable stabilization of AuNCs remain challenging. Benefiting from porous structures and ultrahigh specific surfaces, metal–organic frameworks (MOFs) have shown promising potential in the tailoring of catalytic activity and improving the stability of AuNCs. However, preferable catalytic activity and excellent stability are still challenging, due to the easy leaching of AuNCs from MOFs. Enhancing the combination between AuNCs and MOFs is of great significance. Herein, biomimic nanozymes of AuNCs@UiO-68 were designed through strong coordination between Zr atoms of the MOFs and phosphonate O atoms of DNA backbones from the DNA-templated AuNCs. Compared with control materials of AuNCs and AuNCs/UiO-68, a significant enhancement of oxidase-mimicking activity was achieved in AuNCs@UiO-68, owing to the confinement effect of Zr-MOFs. Additionally, it was found that the catalytic activity of AuNCs could be regulated by altering ligands of the Zr-MOFs. Based on the favorable catalytic activity of AuNCs@UiO-68, a highly sensitive and selective detecting platform for small uremic toxin molecule of hydroquinone was established, with a low detection limit of 0.85 μM. The stability of AuNCs was greatly improved by the proposed synthetic strategy. Besides, preferable and controllable catalytic activity was also obtained, attributed to the confinement effect of MOFs. This work provides a new way for rational regulation of catalytic activity and ameliorating the stability of metal clusters based nanozymes.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"337 ","pages":"Article 126153"},"PeriodicalIF":4.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760505","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}

引用次数: 0

The enhanced excited-state intramolecular proton transfer energy barrier of flavonols induced by deprotonation

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-31 DOI: 10.1016/j.saa.2025.126146

Jian Luo, Zheng Li, Mengrong Hu, Yuhan Xia, Qin Yu, Siyu Hou

The barrierless excited-state intramolecular proton transfer (ESIPT) is believed to account for the non-radiative decays of flavonols composed of 5-hydroxyl group. However, the ESIPT mechanisms of flavonol anions have never been elucidated. In this work, by using the time-dependent density functional theory (TDDFT) calculations, we have determined the barrierless ESIPT in kaempferol and galangin, in agreement with their non-emissive properties. In contrast, deprotonation at the position 7 of them is demonstrated to decrease the basicity of proton acceptor and acidity of proton donor in the excited state, largely increasing the ESIPT barrier and leading to the fluorescence emission from the normal state. A further deprotonation of mono-deprotonated kaempferol is inferred to induce blue shifted emission. These results elucidate the nature of emissive flavonol anions and give a deep insight into the optical properties of flavonols in different matrices.

引用次数: 0

Examining the adsorption and sensing characteristics of cytosine (CTE) on Y9N9 (Y = Al, B, Ga) nanorings using solvent effects, DFT, AIM and SERS analyses

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-31 DOI: 10.1016/j.saa.2025.126148

Jamelah S. Al-Otaibi , Y. Sheena Mary , Unnati Jethawa , Brahmananda Chakraborty , Maria Cristina Gamberini

Nucleobases are nitrogenous biological compounds that are more significant in a range of biological and in medical applications. They are constituents of nucleotides in deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). Therefore, we assessed the sensing applicability by studying the cytosine (CTE)-Y₉N₉ (Y = Al, B, Ga) nanoring interaction using density functional theory. It was evident that CTE interacted strongly with each ring. Due to charge transfer between the nanoring and CTE, a dipole moment (DM) is generated. All complexes have band gaps less than that of CTE. Complexes’ band gap energies are lower in aqueous phase and vacuum than they are in pristine rings. All complexes exhibit higher adsorption energies in solvent medium in comparison with that in vacuum. Changes in the frontier molecular orbitals (FMOs) energies of nanorings after interaction have a major impact on their electrical conductivity and work function. In addition to being an electrical sensor, the Y₉N₉ nanorings for CTE can also be utilized as a work function-based sensor. But Y₉N₉′s CTE recovery time indicates that it can be used to extract or store CTE depending on the environment. The current work can be expanded to examine the impact of Ag/Au/Cu doping using Y₉N₉ in order to examine the characteristics of drug delivery carriers and the consequence of doping. The interaction between the analyte and substrate was further studied using reduced density gradient (RDG) analysis, comparing the nature and strength of the interaction in both vacuum and aqueous medium. The observations revealed a stronger interaction in the presence of an aqueous medium, which aligns with the higher adsorption energy values.

{"title":"Examining the adsorption and sensing characteristics of cytosine (CTE) on Y9N9 (Y = Al, B, Ga) nanorings using solvent effects, DFT, AIM and SERS analyses","authors":"Jamelah S. Al-Otaibi , Y. Sheena Mary , Unnati Jethawa , Brahmananda Chakraborty , Maria Cristina Gamberini","doi":"10.1016/j.saa.2025.126148","DOIUrl":"10.1016/j.saa.2025.126148","url":null,"abstract":"<div><div>Nucleobases are nitrogenous biological compounds that are more significant in a range of biological and in medical applications. They are constituents of nucleotides in deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). Therefore, we assessed the sensing applicability by studying the cytosine (CTE)-Y<sub>9</sub>N<sub>9</sub> (Y = Al, B, Ga) nanoring interaction using density functional theory. It was evident that CTE interacted strongly with each ring. Due to charge transfer between the nanoring and CTE, a dipole moment (DM) is generated. All complexes have band gaps less than that of CTE. Complexes’ band gap energies are lower in aqueous phase and vacuum than they are in pristine rings. All complexes exhibit higher adsorption energies in solvent medium in comparison with that in vacuum. Changes in the frontier molecular orbitals (FMOs) energies of nanorings after interaction have a major impact on their electrical conductivity and work function. In addition to being an electrical sensor, the Y<sub>9</sub>N<sub>9</sub> nanorings for CTE can also be utilized as a work function-based sensor. But Y<sub>9</sub>N<sub>9</sub>′s CTE recovery time indicates that it can be used to extract or store CTE depending on the environment. The current work can be expanded to examine the impact of Ag/Au/Cu doping using Y<sub>9</sub>N<sub>9</sub> in order to examine the characteristics of drug delivery carriers and the consequence of doping. The interaction between the analyte and substrate was further studied using reduced density gradient (RDG) analysis, comparing the nature and strength of the interaction in both vacuum and aqueous medium. The observations revealed a stronger interaction in the presence of an aqueous medium, which aligns with the higher adsorption energy values.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"337 ","pages":"Article 126148"},"PeriodicalIF":4.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760502","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}

引用次数: 0

Carbazolylphenyl ethynyl anthracenes as TTA emitters with improved horizontal alignment for the applications in OLEDs and for optical detection of the nitroaromatic explosive compounds

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-29 DOI: 10.1016/j.saa.2025.126127

Oleksandr Bezvikonnyi , Pavel Arsenyan , Alla Petrenko , Ehsan Ullah Rashid , Audrius Bucinskas , Zheng-Yu Wei , Jiun-Haw Lee , Tien-Lung Chiu , Dmytro Volyniuk , Sergey Belyakov , Mariia Stanitska , Oleksandr Navozenko , Mykhaylo Losytskyy , Juozas V. Grazulevicius

Synthesis and properties of the carbazolylphenyl ethynyl anthracenes with tert-butyl, methoxy, and methoxyethoxy groups are reported. The compounds exhibit remarkably high thermal stability with the temperatures of the onsets of thermal degradation exceeding 407 °C. The ionization potentials of the compounds range from 5.38 to 5.65 eV. Hole mobilities of the derivatives exceed 1 × 10⁻⁴ cm² × V⁻¹s⁻¹ at high electric fields. The photoluminescence quantum yields of the toluene solutions of the compounds are in the range of 86–97 %. The low-lying triplet excited states with the energy of 1.98 eV are detected experimentally and confirmed by the theoretical calculations utilizing density-functional theory for all the studied compounds. The long-lived photoluminescence with a lifetime of up to 0.19 ms is detected for the film of tert-butylcarbazole-based emitter. Triplet-triplet annihilation as an emissive mechanism of the emitters was discussed. The solid samples of dimethoxycarbazolyl-containing derivative shows photoluminescence quantum yield of 36 %. The triplet–triplet fusion is manifested by the long-lived electroluminescence of organic light emitting diode (OLED) with this compound as the emitter and the slope of 2 of the linear plot of brightness versus current density in log–log scale. The considerable quenching of emission of the dispersions of the compounds in THF/water mixtures with a volume fraction of water of 99 % is observed after the addition of picric acid. The respective Stern-Volmer constants are in the range of 6.3 × 10⁴-1.1 × 10⁵ M⁻¹.

{"title":"Carbazolylphenyl ethynyl anthracenes as TTA emitters with improved horizontal alignment for the applications in OLEDs and for optical detection of the nitroaromatic explosive compounds","authors":"Oleksandr Bezvikonnyi , Pavel Arsenyan , Alla Petrenko , Ehsan Ullah Rashid , Audrius Bucinskas , Zheng-Yu Wei , Jiun-Haw Lee , Tien-Lung Chiu , Dmytro Volyniuk , Sergey Belyakov , Mariia Stanitska , Oleksandr Navozenko , Mykhaylo Losytskyy , Juozas V. Grazulevicius","doi":"10.1016/j.saa.2025.126127","DOIUrl":"10.1016/j.saa.2025.126127","url":null,"abstract":"<div><div>Synthesis and properties of the carbazolylphenyl ethynyl anthracenes with <em>tert</em>-butyl, methoxy, and methoxyethoxy groups are reported. The compounds exhibit remarkably high thermal stability with the temperatures of the onsets of thermal degradation exceeding 407 °C. The ionization potentials of the compounds range from 5.38 to 5.65 eV. Hole mobilities of the derivatives exceed 1 × 10<sup>−4</sup> cm<sup>2</sup> × V<sup>−1</sup>s<sup>−1</sup> at high electric fields. The photoluminescence quantum yields of the toluene solutions of the compounds are in the range of 86–97 %. The low-lying triplet excited states with the energy of 1.98 eV are detected experimentally and confirmed by the theoretical calculations utilizing density-functional theory for all the studied compounds. The long-lived photoluminescence with a lifetime of up to 0.19 ms is detected for the film of <em>tert</em>-butylcarbazole-based emitter. Triplet-triplet annihilation as an emissive mechanism of the emitters was discussed. The solid samples of dimethoxycarbazolyl-containing derivative shows photoluminescence quantum yield of 36 %. The triplet–triplet fusion is manifested by the long-lived electroluminescence of organic light emitting diode (OLED) with this compound as the emitter and the slope of 2 of the linear plot of brightness <em>versus</em> current density in log–log scale. The considerable quenching of emission of the dispersions of the compounds in THF/water mixtures with a volume fraction of water of 99 % is observed after the addition of picric acid. The respective Stern-Volmer constants are in the range of 6.3 × 10<sup>4</sup>-1.1 × 10<sup>5</sup> M<sup>−1</sup>.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"337 ","pages":"Article 126127"},"PeriodicalIF":4.3,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143760500","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}

引用次数: 0

Molecular level inelastic electron tunneling spectroscopy of protoporphyrin using scanning tunneling microscope

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-28 DOI: 10.1016/j.saa.2025.126126

Archana Thomas , S. Syamadas , K.B. Jinesh

Protoporphyrin IX (PPIX) is a crucial biomarker for tumor recurrence and to detect glioma at an early stage. Conventional optical detection methods for PPIX lack molecular-level sensitivity due to interference from its fluorescence. Inelastic electron tunneling spectroscopy (IETS) can be used as a probing technique to develop a hyper-sensitive biosensor for PPIX. We employ a scanning tunneling microscope (STM) to investigate the vibrational levels of single molecules at room temperature. The IETS-STM measurements of PPIX on highly oriented pyrolytic graphite (HOPG) showed the self-assembly of the molecules with a molecular array spacing of 1.71 ± 0.02 nm, and the spectra exhibited distinguishable peaks even at elevated temperatures. Analysis of peak broadening around 400 cm⁻¹ conducted at temperatures ranging from 77 K to 300 K showed deviation from the expected theoretical limit of thermal broadening. The impact of temperature and voltage on tunneling electrons were also analyzed to gain insight into the drift of the electrons through PPIX molecules.

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引用次数: 0

A multifunctional Tb-MOF constructed with triphenylamine-based hexacarboxylate ligands for highly luminescent sensing toward antibiotics and salicylaldehydes

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-28 DOI: 10.1016/j.saa.2025.126129

Zhihan Mao , Han Shi , Xuan Yu, Yuchen Liu, Fenglei Yang, Huiyan Liu, Haiying Wang

Antibiotics and salicylaldehydes are major organic pollutants in the environment, and their efficient selection and sensitive detection are of great significance but also challenging. A multifunctional terbium-organic framework (Tb-MOF) with multiple π-conjugated rings and basic sites decorated nanoporous channels was constructed with triphenylamine-based hexacarboxylate ligands. Structure analysis of Tb-MOF revealed that the six carboxyl groups on the skeleton of ligand exhibit considerable degree of distortion and can be regarded as three triangular nodes, which further combined the binuclear [Tb₂(COO)₆(H₂O)₄] nodes to form a new (3,3,3,6)-connected 3D net. Importantly, Tb-MOF provided the first example of luminescent MOFs constructed from triphenylamine-based hexacarboxylate ligands with multi-responsive behavior toward antibiotics and salicylaldehydes. Tb-MOF demonstrated excellent performance on the selection and recognition of two antibiotics, metronidazole (MDZ) and dimetridazole (DTZ), with the detection limit (LOD) of 0.60 and 0.95 μM, respectively. More importantly, Tb-MOF can achieve highly sensitive detection of three aldehydes, salicylaldehyde (SA), 5-methylsalicylaldehyde (5-MeSA) and 5-chlorsalicylaldehyde (5-ClSA), with LODs up to 0.58, 0.59 and 0.48 μM, respectively. Regenerated experiments indicated that Tb-MOF can be employed for the efficient detection of MDZ and SA at least five times. Thus, Tb-MOF can be potentially explored as a promising sensor to simultaneously identify antibiotics and salicylaldehydes in chemical detection and biologic environments with ultra-sensitivity, low LODs and extraordinary recycling capacity.

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引用次数: 0

An airborne CH4 sensor with temperature compensation based on a miniature optical structure for natural gas pipeline leakage analysis

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Pub Date : 2025-03-28 DOI: 10.1016/j.saa.2025.126130

Guolin Li, Haoran Yuan, Yingjie Zhao, Guangzhao Cui, Ruixiang Sun, Longju Li, Jianyu Gu, Wenxuan Zhao, Jinxu Yang

Pipeline transport plays an important role in the exploration and transmission of natural gas. An airborne near-infrared (NIR) methane (CH₄) sensor has been developed to analyze CH₄ leakage in the pipeline transport process based on the tunable diode laser absorption spectroscopy combined with wavelength modulation spectroscopy (WMS-TDLAS) technology relying on the high efficiency and convenience of unmanned aerial vehicles (UAVs). A laser diode in the form of an ultra-compact 8-pin package with a center wavelength of 1653.7 nm and an independently-designed miniature optical structure with an optical path length of 36 cm are adopted, which greatly reduces the size of the sensor. In order to improve the measurement accuracy, a temperature compensation link is designed to minimize the influence of temperature changes on the measured value. The original second harmonic signal is denoised by the variational mode decomposition algorithm optimized by Genghis Khan shark optimizer algorithm (GKSO-VMD), and the Bi-directional long short-term memory GKSO-BiLSTM algorithm is used for CH₄ concentration inversion. The measured and real concentration values of the sensor are closely related, with a correlation coefficient (R²) of 0.9996. The response time experiment demonstrates that the response time is approximately 6 s. The great stability of the sensor is confirmed by the long-term stability experiment. According to the Allan–Werle deviation, it is estimated that the sensor has a limit of detection (LoD) 613 ppb with an integration time of 230 s. Therefore, an effective analysis method is proposed for CH₄ leakage analysis during natural gas pipeline transport.

{"title":"An airborne CH4 sensor with temperature compensation based on a miniature optical structure for natural gas pipeline leakage analysis","authors":"Guolin Li, Haoran Yuan, Yingjie Zhao, Guangzhao Cui, Ruixiang Sun, Longju Li, Jianyu Gu, Wenxuan Zhao, Jinxu Yang","doi":"10.1016/j.saa.2025.126130","DOIUrl":"10.1016/j.saa.2025.126130","url":null,"abstract":"<div><div>Pipeline transport plays an important role in the exploration and transmission of natural gas. An airborne near-infrared (NIR) methane (CH<sub>4</sub>) sensor has been developed to analyze CH<sub>4</sub> leakage in the pipeline transport process based on the tunable diode laser absorption spectroscopy combined with wavelength modulation spectroscopy (WMS-TDLAS) technology relying on the high efficiency and convenience of unmanned aerial vehicles (UAVs). A laser diode in the form of an ultra-compact 8-pin package with a center wavelength of 1653.7 nm and an independently-designed miniature optical structure with an optical path length of 36 cm are adopted, which greatly reduces the size of the sensor. In order to improve the measurement accuracy, a temperature compensation link is designed to minimize the influence of temperature changes on the measured value. The original second harmonic signal is denoised by the variational mode decomposition algorithm optimized by Genghis Khan shark optimizer algorithm (GKSO-VMD), and the Bi-directional long short-term memory GKSO-BiLSTM algorithm is used for CH<sub>4</sub> concentration inversion. The measured and real concentration values of the sensor are closely related, with a correlation coefficient (R<sup>2</sup>) of 0.9996. The response time experiment demonstrates that the response time is approximately 6 s. The great stability of the sensor is confirmed by the long-term stability experiment. According to the Allan–Werle deviation, it is estimated that the sensor has a limit of detection (LoD) 613 ppb with an integration time of 230 s. Therefore, an effective analysis method is proposed for CH<sub>4</sub> leakage analysis during natural gas pipeline transport.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"337 ","pages":"Article 126130"},"PeriodicalIF":4.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746180","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}

引用次数: 0

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