We have developed a critical methodology for the evaluation of the quality of hybrid exchange-correlation (XC) density functional approximations (DFAs) based on very fundamental quantities, i.e., Kohn-Sham (KS) XC potentials, self-consistent electron densities, first ionization potentials (IPs), and total energies. Since the XC potentials, the primary objects in the current study, are not directly accessible for the hybrids, we calculate them by inverting the KS electron densities. Utilizing this methodology, we tested 155 hybrid DFAs available in the LIBXC library using FCI and CCSD(T) methods as a reference. We have found that a group of functionals produces very decent XC potentials, mainly those with a large mixture of Hartree-Fock exchange. Moreover, the value of IP strongly depends on the XC potential quality. On the other hand, we show that the XC energy is dominated by functional-driven error, which in some cases leads to substantial errors in electronic densities. The study shows new directions for constructing more accurate XC functionals within the KS-DFT framework.
{"title":"A Critical Evaluation of the Hybrid KS DFT Functionals Based on the KS Exchange-Correlation Potentials.","authors":"Vignesh Balaji Kumar, Szymon Śmiga, Ireneusz Grabowski","doi":"10.1021/acs.jpclett.4c01979","DOIUrl":"10.1021/acs.jpclett.4c01979","url":null,"abstract":"<p><p>We have developed a critical methodology for the evaluation of the quality of hybrid exchange-correlation (XC) density functional approximations (DFAs) based on very fundamental quantities, i.e., Kohn-Sham (KS) XC potentials, self-consistent electron densities, first ionization potentials (IPs), and total energies. Since the XC potentials, the primary objects in the current study, are not directly accessible for the hybrids, we calculate them by inverting the KS electron densities. Utilizing this methodology, we tested 155 hybrid DFAs available in the LIBXC library using FCI and CCSD(T) methods as a reference. We have found that a group of functionals produces very decent XC potentials, mainly those with a large mixture of Hartree-Fock exchange. Moreover, the value of IP strongly depends on the XC potential quality. On the other hand, we show that the XC energy is dominated by functional-driven error, which in some cases leads to substantial errors in electronic densities. The study shows new directions for constructing more accurate XC functionals within the KS-DFT framework.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11472381/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-10DOI: 10.1021/acs.jpclett.4c0203510.1021/acs.jpclett.4c02035
Rocco Martinazzo*, and , Irene Burghardt,
Geometric phases play a crucial role in diverse fields. In molecules, they appear when a reaction path encircles an intersection between adiabatic potential energy surfaces and the molecular wave function experiences quantum-mechanical interference effects. This intriguing effect, closely resembling the magnetic Aharonov–Bohm effect, crucially relies on the adiabatic description of the dynamics, and it is an open issue whether and how it persists in an exact quantum dynamical framework. Recent works suggest that the molecular geometric phase is an artifact of the adiabatic approximation, thereby challenging the entire concept. Here, building upon a recent investigation (Martinazzo, R.; Burghardt, I. Phys. Rev. Lett.2024, 132, 243002), we address this issue using the exact factorization of the total wave function. We introduce instantaneous gauge-invariant phases separately for the electrons and nuclei and use them to monitor the phase difference between the trailing edges of a wavepacket encircling a conical intersection between adiabatic surfaces. The transition from the time-dependent open-path phase differences to the closed-path limit is examined, revealing how the phase differences in the electronic and nuclear subspaces compensate for each other upon path closure. In this way, we unambiguously demonstrate the role of the geometric phase in the interference process and shed light on its persistence beyond the adiabatic approximation.
几何相位在各个领域都发挥着至关重要的作用。在分子中,当反应路径环绕绝热势能面之间的交叉点,分子波函数经历量子力学干涉效应时,就会出现几何相。这种引人入胜的效应与磁性阿哈诺夫-玻姆效应十分相似,它主要依赖于对动力学的绝热描述,而在精确的量子动力学框架中,它是否以及如何持续存在是一个未决问题。最近的研究表明,分子几何相是绝热近似的产物,从而对整个概念提出了挑战。在此,我们以最近的一项研究(Martinazzo, R.; Burghardt, I. Phys. Rev. Lett. 2024, 132, 243002)为基础,利用总波函数的精确因子化来解决这一问题。我们分别为电子和原子核引入了瞬时量规不变相位,并利用它们来监测环绕绝热表面锥形交点的波包后缘之间的相位差。我们研究了从随时间变化的开放路径相位差到封闭路径极限的转变,揭示了电子子空间和核子空间的相位差如何在路径封闭时相互补偿。通过这种方法,我们明确地证明了几何相位在干涉过程中的作用,并揭示了其在绝热近似之外的持续性。
{"title":"Emergence of the Molecular Geometric Phase from Exact Electron–Nuclear Dynamics","authors":"Rocco Martinazzo*, and , Irene Burghardt, ","doi":"10.1021/acs.jpclett.4c0203510.1021/acs.jpclett.4c02035","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02035https://doi.org/10.1021/acs.jpclett.4c02035","url":null,"abstract":"<p >Geometric phases play a crucial role in diverse fields. In molecules, they appear when a reaction path encircles an intersection between adiabatic potential energy surfaces and the molecular wave function experiences quantum-mechanical interference effects. This intriguing effect, closely resembling the magnetic Aharonov–Bohm effect, crucially relies on the adiabatic description of the dynamics, and it is an open issue whether and how it persists in an exact quantum dynamical framework. Recent works suggest that the molecular geometric phase is an artifact of the adiabatic approximation, thereby challenging the entire concept. Here, building upon a recent investigation (Martinazzo, R.; Burghardt, I. <i>Phys. Rev. Lett.</i> <b>2024</b>, <i>132</i>, 243002), we address this issue using the exact factorization of the total wave function. We introduce instantaneous gauge-invariant phases separately for the electrons and nuclei and use them to monitor the phase difference between the trailing edges of a wavepacket encircling a conical intersection between adiabatic surfaces. The transition from the time-dependent open-path phase differences to the closed-path limit is examined, revealing how the phase differences in the electronic and nuclear subspaces compensate for each other upon path closure. In this way, we unambiguously demonstrate the role of the geometric phase in the interference process and shed light on its persistence beyond the adiabatic approximation.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450605","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}
Pub Date : 2024-10-10DOI: 10.1021/acs.jpclett.4c02022
Srestha Basu, Adi Hendler-Neumark, Gili Bisker
Ratiometric probing of analytes presents a substantial advancement in molecular recognition, offering self-calibrating signals that enhance the measurement accuracy and reliability. We present a dual-emitting probe based on (6,5) chirality-enriched single-walled carbon nanotubes (SWCNTs) with oxygen defects for cholesterol (Chol) detection using ratiometric fluorescence readouts. The interaction with Chol induced significant intensity variations in the E11 and E11* emission peaks of oxygen defect-induced SWCNTs, giving rise to ratiometric fluorescence changes. The sensitivity of these probes toward Chol in water and serum was 0.28 ± 0.01 and 0.72 ± 0.05 μM, respectively, which is comparable to that of common gold standards for cholesterol detection used in clinical samples. By utilizing ratiometric readouts, our approach enhanced selectivity over numerous competing analytes, including amino acids, sugars, cations, anions, proteins, steroid hormones, surfactants, and phospholipids. Mechanistic investigations revealed that Chol detection by defect-integrated SWCNTs was facilitated by Chol incorporation within micelles formed by sodium cholate, the surfactant dispersant used for the SWCNT suspension. Oxygen defects played a crucial role by directly interacting with Chol. This strategy employing defect-integrated dual-peak NIR-emitting SWCNTs as sensors for Chol in aqueous and serum environments not only enables background-free detection of biologically relevant analytes but also advances biosensing using SWCNTs through tailored surface functionalization and advanced read-out concepts.
{"title":"Ratiometric Normalization of Near-Infrared Fluorescence in Defect-Engineered Single-Walled Carbon Nanotubes for Cholesterol Detection","authors":"Srestha Basu, Adi Hendler-Neumark, Gili Bisker","doi":"10.1021/acs.jpclett.4c02022","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02022","url":null,"abstract":"Ratiometric probing of analytes presents a substantial advancement in molecular recognition, offering self-calibrating signals that enhance the measurement accuracy and reliability. We present a dual-emitting probe based on (6,5) chirality-enriched single-walled carbon nanotubes (SWCNTs) with oxygen defects for cholesterol (Chol) detection using ratiometric fluorescence readouts. The interaction with Chol induced significant intensity variations in the <i>E</i><sub>11</sub> and <i>E</i><sub>11</sub><sup>*</sup> emission peaks of oxygen defect-induced SWCNTs, giving rise to ratiometric fluorescence changes. The sensitivity of these probes toward Chol in water and serum was 0.28 ± 0.01 and 0.72 ± 0.05 μM, respectively, which is comparable to that of common gold standards for cholesterol detection used in clinical samples. By utilizing ratiometric readouts, our approach enhanced selectivity over numerous competing analytes, including amino acids, sugars, cations, anions, proteins, steroid hormones, surfactants, and phospholipids. Mechanistic investigations revealed that Chol detection by defect-integrated SWCNTs was facilitated by Chol incorporation within micelles formed by sodium cholate, the surfactant dispersant used for the SWCNT suspension. Oxygen defects played a crucial role by directly interacting with Chol. This strategy employing defect-integrated dual-peak NIR-emitting SWCNTs as sensors for Chol in aqueous and serum environments not only enables background-free detection of biologically relevant analytes but also advances biosensing using SWCNTs through tailored surface functionalization and advanced read-out concepts.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":6.475,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398430","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}
Pub Date : 2024-10-10Epub Date: 2024-10-01DOI: 10.1021/acs.jpclett.4c02002
Fabian Munkes, Matthew H Rayment, Alexander Trachtmann, Florian Anschütz, Ettore Eder, Philipp Hengel, Yannick Schellander, Patrick Schalberger, Norbert Fruehauf, Jens Anders, Robert Löw, Tilman Pfau, Stephen D Hogan, Harald Kübler
High-resolution continuous-wave (cw) laser spectroscopy of nitric oxide (NO) molecules has been performed to study and characterize the energy-level structure of and effects of electric fields on the high Rydberg states. The experiments were carried out with molecules flowing through a room temperature gas cell. Rydberg-state photoexcitation was implemented using the resonance enhanced three-color three-photon excitation scheme. Excited molecules were detected by high-sensitivity optogalvanic methods. Detailed measurements were made of Rydberg states with principal quantum numbers n = 22 and 32 in the series converging to the lowest rotational and vibrational state of the NO+ cation. The experimental data were compared with the results of numerical calculations which provided insight into the orbital angular momentum character of the intermediate H 2Σ+ state, improved determinations of the nf and ng quantum defects, a bound on the magnitude of the nh quantum defect, and information on the decay rates of the nf and ng Rydberg states. These measurements represent a step-change in laser spectroscopic studies of high Rydberg states in small atmospheric molecules. They open opportunities for more detailed studies of slow decay processes of Rydberg NO molecules confined in electrostatic traps, the synthesis of ultralong range Rydberg bimolecules, and the development of optical methods for trace gas detection.
对一氧化氮(NO)分子进行了高分辨率连续波(cw)激光光谱分析,以研究一氧化氮(NO)分子的能级结构以及电场对高雷德贝格态的影响。实验是在分子流经室温气室时进行的。利用共振增强 (nl)X+ Σ+1←H Σ+2←A Σ+2←XΠ3/22 三色三光子激发方案实现了雷德贝格态光激发。用高灵敏度光电法检测受激分子。对主量子数 n = 22 和 32 的雷德贝格态进行了详细测量,该系列收敛于 NO+ 阳离子的最低旋转态和振动态。实验数据与数值计算结果进行了比较,从而深入了解了中间 H 2Σ+ 态的轨道角动量特性,改进了 nf 和 ng 量子缺陷的测定,确定了 nh 量子缺陷的大小,并提供了 nf 和 ng Rydberg 态衰变速率的信息。这些测量结果代表了对大气小分子中高雷德贝格态的激光光谱研究的一个进步。它们为更详细地研究静电陷阱中限制的 Rydberg NO 分子的缓慢衰变过程、合成超远距离 Rydberg 双分子以及开发痕量气体探测的光学方法提供了机会。
{"title":"High-Resolution Continuous-Wave Laser Spectroscopy of Long-Lived Rydberg States in NO.","authors":"Fabian Munkes, Matthew H Rayment, Alexander Trachtmann, Florian Anschütz, Ettore Eder, Philipp Hengel, Yannick Schellander, Patrick Schalberger, Norbert Fruehauf, Jens Anders, Robert Löw, Tilman Pfau, Stephen D Hogan, Harald Kübler","doi":"10.1021/acs.jpclett.4c02002","DOIUrl":"10.1021/acs.jpclett.4c02002","url":null,"abstract":"<p><p>High-resolution continuous-wave (cw) laser spectroscopy of nitric oxide (NO) molecules has been performed to study and characterize the energy-level structure of and effects of electric fields on the high Rydberg states. The experiments were carried out with molecules flowing through a room temperature gas cell. Rydberg-state photoexcitation was implemented using the resonance enhanced <math><mrow><mo>(</mo><mi>n</mi><mi>l</mi><mo>)</mo></mrow><msup><mrow><mi>X</mi></mrow><mrow><mo>+</mo></mrow></msup><mmultiscripts><mrow><msup><mrow><mtext> </mtext><mi>Σ</mi></mrow><mrow><mo>+</mo></mrow></msup></mrow><mprescripts></mprescripts><none></none><mrow><mn>1</mn></mrow></mmultiscripts><mo>←</mo><mi>H</mi><mmultiscripts><mrow><msup><mrow><mtext> </mtext><mi>Σ</mi></mrow><mrow><mo>+</mo></mrow></msup></mrow><mprescripts></mprescripts><none></none><mrow><mn>2</mn></mrow></mmultiscripts><mo>←</mo><mi>A</mi><mmultiscripts><mrow><msup><mrow><mtext> </mtext><mi>Σ</mi></mrow><mrow><mo>+</mo></mrow></msup></mrow><mprescripts></mprescripts><none></none><mrow><mn>2</mn></mrow></mmultiscripts><mo>←</mo><mi>X</mi><mmultiscripts><mrow><msub><mrow><mi>Π</mi></mrow><mrow><mn>3</mn><mo>/</mo><mn>2</mn></mrow></msub></mrow><mprescripts></mprescripts><none></none><mrow><mn>2</mn></mrow></mmultiscripts></math> three-color three-photon excitation scheme. Excited molecules were detected by high-sensitivity optogalvanic methods. Detailed measurements were made of Rydberg states with principal quantum numbers <i>n</i> = 22 and 32 in the series converging to the lowest rotational and vibrational state of the NO<sup>+</sup> cation. The experimental data were compared with the results of numerical calculations which provided insight into the orbital angular momentum character of the intermediate H <sup>2</sup>Σ<sup>+</sup> state, improved determinations of the <i>n</i>f and <i>n</i>g quantum defects, a bound on the magnitude of the <i>n</i>h quantum defect, and information on the decay rates of the <i>n</i>f and <i>n</i>g Rydberg states. These measurements represent a step-change in laser spectroscopic studies of high Rydberg states in small atmospheric molecules. They open opportunities for more detailed studies of slow decay processes of Rydberg NO molecules confined in electrostatic traps, the synthesis of ultralong range Rydberg bimolecules, and the development of optical methods for trace gas detection.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142337418","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}
Pub Date : 2024-10-10Epub Date: 2024-10-01DOI: 10.1021/acs.jpclett.4c02309
Yuhan Huang, Gary S Cooney, David Talaga, Renaud A L Vallée, Rossana Quinzi, Laurent Bouffier, Sophie Lecomte, Sébastien Bonhommeau
Total-internal-reflection tip-enhanced Raman spectroscopy (TIR-TERS) imaging of amyloid-β (Aβ1-42-L34T) fibrils is performed with nanoscale spatial resolution in water, using TERS tips fabricated by bipolar electrodeposition. Ideal experimental parameters are corroborated by both theoretical simulations and TIR-TERS measurements. TIR-TERS imaging reveals the predominant parallel β-sheet secondary structure of Aβ1-42-L34T fibrils as well as the nanoscale spatial distribution of tyrosine, histidine, and phenylalanine aromatic amino acids. Their proportion in TERS spectra can be qualitatively explained by the combined effect of their localization in the Aβ1-42-L34T fibril structure and their molecular orientation with respect to the excitation laser light polarization. Conclusions drawn from the TERS experiments in water corroborate and significantly enrich our previous study in ambient air, thus confirming that hydration has only a marginal impact on the structure of such amyloid fibrils. This first TIR-TERS study in liquid opens fascinating perspectives for future applications in biology.
利用双极电沉积法制造的 TERS 头,在水中对淀粉样蛋白-β(Aβ1-42-L34T)纤维进行了具有纳米级空间分辨率的全内反射尖端增强拉曼光谱(TIR-TERS)成像。理想的实验参数得到了理论模拟和 TIR-TERS 测量的证实。TIR-TERS 成像揭示了 Aβ1-42-L34T 纤维的主要平行 β 片二级结构,以及酪氨酸、组氨酸和苯丙氨酸芳香族氨基酸的纳米级空间分布。它们在 TERS 光谱中的比例可以通过它们在 Aβ1-42-L34T 纤维结构中的定位及其相对于激发激光偏振的分子取向的综合效应得到定性解释。在水中进行的 TERS 实验得出的结论证实并极大地丰富了我们之前在环境空气中进行的研究,从而证实了水合作用对这种淀粉样蛋白纤维结构的影响微乎其微。这项首次在液体中进行的 TIR-TERS 研究为未来在生物学中的应用开辟了迷人的前景。
{"title":"Nanoscale Chemical Imaging of Amyloid Fibrils in Water Using Total-Internal-Reflection Tip-Enhanced Raman Spectroscopy.","authors":"Yuhan Huang, Gary S Cooney, David Talaga, Renaud A L Vallée, Rossana Quinzi, Laurent Bouffier, Sophie Lecomte, Sébastien Bonhommeau","doi":"10.1021/acs.jpclett.4c02309","DOIUrl":"10.1021/acs.jpclett.4c02309","url":null,"abstract":"<p><p>Total-internal-reflection tip-enhanced Raman spectroscopy (TIR-TERS) imaging of amyloid-β (Aβ<sub>1-42</sub>-L34T) fibrils is performed with nanoscale spatial resolution in water, using TERS tips fabricated by bipolar electrodeposition. Ideal experimental parameters are corroborated by both theoretical simulations and TIR-TERS measurements. TIR-TERS imaging reveals the predominant parallel β-sheet secondary structure of Aβ<sub>1-42</sub>-L34T fibrils as well as the nanoscale spatial distribution of tyrosine, histidine, and phenylalanine aromatic amino acids. Their proportion in TERS spectra can be qualitatively explained by the combined effect of their localization in the Aβ<sub>1-42</sub>-L34T fibril structure and their molecular orientation with respect to the excitation laser light polarization. Conclusions drawn from the TERS experiments in water corroborate and significantly enrich our previous study in ambient air, thus confirming that hydration has only a marginal impact on the structure of such amyloid fibrils. This first TIR-TERS study in liquid opens fascinating perspectives for future applications in biology.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142337420","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}
Pub Date : 2024-10-10Epub Date: 2024-10-03DOI: 10.1021/acs.jpclett.4c01767
Sara Bobone, Claudia Storti, Chiara Fulci, Alessia Damiani, Chiara Innamorati, Daniela Roversi, Paolo Calligari, Luca Pannone, Simone Martinelli, Marco Tartaglia, Gianfranco Bocchinfuso, Fernando Formaggio, Cristina Peggion, Barbara Biondi, Lorenzo Stella
Peptide-based drugs are powerful inhibitors of therapeutically relevant protein-protein interactions. Their affinity and selectivity for target proteins are commonly assessed using fluorescence-based assays such as anisotropy/polarization or quantitative microarrays. This study reveals that labeling can perturb peptide/protein binding by more than 1 order of magnitude. We have recently developed inhibitors targeted to the N-terminal Src homology 2 (SH2) domain of oncogenic phosphatase SHP2. Despite their high activity and selectivity, these molecules demonstrated an undesired interaction with the SH2 domain of another protein, known as APS, in a fluorescence microarray assay. Fluorescence anisotropy measurement in solution showed that the dissociation constant was significantly influenced by labeling (∼10 times), and the effect depended on the specific fluorophore and SH2 domain. Notably, displacement assays performed with unlabeled peptides were successfully used to eliminate these artifacts, demonstrating that the inhibitors' affinity for their target is over 1,000 times higher than for APS.
{"title":"Fluorescent Labeling Can Significantly Perturb Measured Binding Affinity and Selectivity of Peptide-Protein Interactions.","authors":"Sara Bobone, Claudia Storti, Chiara Fulci, Alessia Damiani, Chiara Innamorati, Daniela Roversi, Paolo Calligari, Luca Pannone, Simone Martinelli, Marco Tartaglia, Gianfranco Bocchinfuso, Fernando Formaggio, Cristina Peggion, Barbara Biondi, Lorenzo Stella","doi":"10.1021/acs.jpclett.4c01767","DOIUrl":"10.1021/acs.jpclett.4c01767","url":null,"abstract":"<p><p>Peptide-based drugs are powerful inhibitors of therapeutically relevant protein-protein interactions. Their affinity and selectivity for target proteins are commonly assessed using fluorescence-based assays such as anisotropy/polarization or quantitative microarrays. This study reveals that labeling can perturb peptide/protein binding by more than 1 order of magnitude. We have recently developed inhibitors targeted to the N-terminal Src homology 2 (SH2) domain of oncogenic phosphatase SHP2. Despite their high activity and selectivity, these molecules demonstrated an undesired interaction with the SH2 domain of another protein, known as APS, in a fluorescence microarray assay. Fluorescence anisotropy measurement in solution showed that the dissociation constant was significantly influenced by labeling (∼10 times), and the effect depended on the specific fluorophore and SH2 domain. Notably, displacement assays performed with unlabeled peptides were successfully used to eliminate these artifacts, demonstrating that the inhibitors' affinity for their target is over 1,000 times higher than for APS.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142363515","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}
Pub Date : 2024-10-10Epub Date: 2024-10-03DOI: 10.1021/acs.jpclett.4c02201
Jiae Jeong, Hyoungjin Park, Jihyun Kim, Hojin Moon, Hyeonsik Choi, Eunjin Kim, Seonuk Jeon, Yunsur Kim, Jiyong Woo
We investigate how the threshold voltage (VT) is adjusted to create a memory window (MW) in ferroelectric field-effect transistors (FeFETs) composed of ferroelectric Hf0.4Zr0.6O2 and InZnO (In2O3:ZnO = 9:1 wt %). Temperature-dependent polarization measurements reveal a dipole switching in Hf0.4Zr0.6O2. The properties of the n-type InZnO channel are examined by fabricating an oxide transistor with an HfO2 gate dielectric. Upon replacement of HfO2 with Hf0.4Zr0.6O2 in the oxide transistor, a counterclockwise MW is observed. Specifically, as the Hf0.4Zr0.6O2 thickness increases from 16 to 24 nm, the VT of the FeFET after a + gate voltage (VG) sweep remains nearly constant, while the VT after a -VG sweep shifts significantly from -0.9 to 0.5 V. The enlarged MW of approximately 2 V, which is proportional to the Hf0.4Zr0.6O2 thickness in the FeFET, can be explained by considering the balance between VG controllability across the gate stack and the ferroelectric switching of Hf0.4Zr0.6O2.
{"title":"Hf<sub>0.4</sub>Zr<sub>0.6</sub>O<sub>2</sub> Thickness-Dependent Transfer Characteristics of In<sub><i>x</i></sub>Zn<sub>1-<i>x</i></sub>O<sub><i>y</i></sub> Channel Ferroelectric FETs.","authors":"Jiae Jeong, Hyoungjin Park, Jihyun Kim, Hojin Moon, Hyeonsik Choi, Eunjin Kim, Seonuk Jeon, Yunsur Kim, Jiyong Woo","doi":"10.1021/acs.jpclett.4c02201","DOIUrl":"10.1021/acs.jpclett.4c02201","url":null,"abstract":"<p><p>We investigate how the threshold voltage (<i>V</i><sub>T</sub>) is adjusted to create a memory window (MW) in ferroelectric field-effect transistors (FeFETs) composed of ferroelectric Hf<sub>0.4</sub>Zr<sub>0.6</sub>O<sub>2</sub> and InZnO (In<sub>2</sub>O<sub>3</sub>:ZnO = 9:1 wt %). Temperature-dependent polarization measurements reveal a dipole switching in Hf<sub>0.4</sub>Zr<sub>0.6</sub>O<sub>2</sub>. The properties of the n-type InZnO channel are examined by fabricating an oxide transistor with an HfO<sub>2</sub> gate dielectric. Upon replacement of HfO<sub>2</sub> with Hf<sub>0.4</sub>Zr<sub>0.6</sub>O<sub>2</sub> in the oxide transistor, a counterclockwise MW is observed. Specifically, as the Hf<sub>0.4</sub>Zr<sub>0.6</sub>O<sub>2</sub> thickness increases from 16 to 24 nm, the <i>V</i><sub>T</sub> of the FeFET after a + gate voltage (<i>V</i><sub>G</sub>) sweep remains nearly constant, while the <i>V</i><sub>T</sub> after a -<i>V</i><sub>G</sub> sweep shifts significantly from -0.9 to 0.5 V. The enlarged MW of approximately 2 V, which is proportional to the Hf<sub>0.4</sub>Zr<sub>0.6</sub>O<sub>2</sub> thickness in the FeFET, can be explained by considering the balance between <i>V</i><sub>G</sub> controllability across the gate stack and the ferroelectric switching of Hf<sub>0.4</sub>Zr<sub>0.6</sub>O<sub>2</sub>.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142363516","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}
Pub Date : 2024-10-09DOI: 10.1021/acs.jpclett.4c02619
Shixun Hu, Wenjia Zhang, Chi Yao, Shangshi Huang, Zhen Luo, Xiyu Zhang, Xinhua Dong, Xin Yu, Jun Hu, Qi Li, Xiangyang Peng, Jinliang He
How to fundamentally suppress charge transport is one of the essential issues in polymer dielectrics. This work reports significant charge transport suppression by glycidyl methacrylate (GMA) side group modification on polypropylene (PP). Experimental and computational investigations discover for the first time a quasi-hydrogen bond effect generated by carbonyl and epoxide of GMA in PP inter/intramolecular structure, while introducing trap energy levels within the HOMO–LUMO gap. These energy levels suppress the leakage current of GMA-modified PP thanks to the charge-trapping effect. The quasi-hydrogen bond originating from the interaction between the high-polar GMA group and flexible PP chain raises the thermostability while averaging the electron distribution between hydrogen and acceptor oxygen, which is conducive to lessening electric weak points, suppressing charge transport, and finally enhancing the electrical breakdown strength. This work provides new thinking on polymer dielectric design and charge transport regulation utilizing electron structure and weak interaction at the molecular scale.
{"title":"Quasi-Hydrogen Bond and Charge-Trapping Effect Originating from Polar Side Group Lead to Significantly Suppressed Charge Transport in Polypropylene","authors":"Shixun Hu, Wenjia Zhang, Chi Yao, Shangshi Huang, Zhen Luo, Xiyu Zhang, Xinhua Dong, Xin Yu, Jun Hu, Qi Li, Xiangyang Peng, Jinliang He","doi":"10.1021/acs.jpclett.4c02619","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02619","url":null,"abstract":"How to fundamentally suppress charge transport is one of the essential issues in polymer dielectrics. This work reports significant charge transport suppression by glycidyl methacrylate (GMA) side group modification on polypropylene (PP). Experimental and computational investigations discover for the first time a quasi-hydrogen bond effect generated by carbonyl and epoxide of GMA in PP inter/intramolecular structure, while introducing trap energy levels within the HOMO–LUMO gap. These energy levels suppress the leakage current of GMA-modified PP thanks to the charge-trapping effect. The quasi-hydrogen bond originating from the interaction between the high-polar GMA group and flexible PP chain raises the thermostability while averaging the electron distribution between hydrogen and acceptor oxygen, which is conducive to lessening electric weak points, suppressing charge transport, and finally enhancing the electrical breakdown strength. This work provides new thinking on polymer dielectric design and charge transport regulation utilizing electron structure and weak interaction at the molecular scale.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":6.475,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386133","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}
Pub Date : 2024-10-09DOI: 10.1021/acs.jpclett.4c02335
Surender Kumar, Torben Steenbock, Gabriel Bester
The origin of the high-frequency shoulder (HFS) observed above the longitudinal optical (LO) peak around 230 cm–1 in the Raman spectra of CdSe quantum dots (QDs) has been the subject of intense debate. We use state-of-the-art ab initio density functional theory applied to small CdSe QDs with various realistic surface passivations and find an intense Raman signal around 230 cm–1, which corresponds to a stretching vibration of a defective 2-fold coordinated Se atom. We interpret this signal as being the origin of the HFS. Since the signal disappears in fully passivated and defect-free (magic size cluster) structures, it can be used as a fingerprint to distinguish defective from nondefective structures.
在硒化镉量子点(CdSe quantum dots,QDs)的拉曼光谱中,在纵向光学峰(LO)上方约 230 cm-1 处观察到的高频肩(HFS)的起源一直是激烈争论的主题。我们将最先进的 ab initio 密度泛函理论应用于具有各种现实表面钝化的小型硒化镉量子点,发现 230 cm-1 附近有一个强烈的拉曼信号,它对应于一个有缺陷的 2 倍配位硒原子的伸缩振动。我们将这一信号解释为 HFS 的起源。由于该信号在完全钝化和无缺陷(神奇尺寸簇)结构中消失,因此可将其用作区分缺陷和非缺陷结构的指纹。
{"title":"Origin of the High-Frequency Shoulder in the Raman Spectra of CdSe Quantum Dots","authors":"Surender Kumar, Torben Steenbock, Gabriel Bester","doi":"10.1021/acs.jpclett.4c02335","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02335","url":null,"abstract":"The origin of the high-frequency shoulder (HFS) observed above the longitudinal optical (LO) peak around 230 cm<sup>–1</sup> in the Raman spectra of CdSe quantum dots (QDs) has been the subject of intense debate. We use state-of-the-art <i>ab initio</i> density functional theory applied to small CdSe QDs with various realistic surface passivations and find an intense Raman signal around 230 cm<sup>–1</sup>, which corresponds to a stretching vibration of a defective 2-fold coordinated Se atom. We interpret this signal as being the origin of the HFS. Since the signal disappears in fully passivated and defect-free (magic size cluster) structures, it can be used as a fingerprint to distinguish defective from nondefective structures.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":6.475,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386128","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}
Pub Date : 2024-10-09DOI: 10.1021/acs.jpclett.4c02476
Piotr Łaski, Lerato Bosman, Jakub Drapała, Radosław Kamiński, Dariusz Szarejko, Patryk Borowski, Andreas Roodt, Robert Henning, Alice Brink, Katarzyna N. Jarzembska
The rare observation of transient Rh···Rh excimer formation in a single crystal is reported. The estimated excited-state lifetime at 100 K is 2 ns, which makes it the shortest-lived small-molecule species caught experimentally using the laser-pump/X-ray-probe time-resolved Laue method. Upon excitation with 390 nm laser light, the intermolecular Rh···Rh distance decreases from 3.379(4) to 3.19(1) Å, and the metal–metal contact gains more bonding character. On the basis of the experimental results and theoretical modeling, the structural changes determined with 100 ps time resolution reflect principally the S0 → S1 electronic transition.
{"title":"Nanosecond-Lived Excimer Observation in a Crystal of a Rhodium(I) Complex via Time-Resolved X-ray Laue Diffraction","authors":"Piotr Łaski, Lerato Bosman, Jakub Drapała, Radosław Kamiński, Dariusz Szarejko, Patryk Borowski, Andreas Roodt, Robert Henning, Alice Brink, Katarzyna N. Jarzembska","doi":"10.1021/acs.jpclett.4c02476","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02476","url":null,"abstract":"The rare observation of transient Rh···Rh excimer formation in a single crystal is reported. The estimated excited-state lifetime at 100 K is 2 ns, which makes it the shortest-lived small-molecule species caught experimentally using the laser-pump/X-ray-probe time-resolved Laue method. Upon excitation with 390 nm laser light, the intermolecular Rh···Rh distance decreases from 3.379(4) to 3.19(1) Å, and the metal–metal contact gains more bonding character. On the basis of the experimental results and theoretical modeling, the structural changes determined with 100 ps time resolution reflect principally the S<sub>0</sub> → S<sub>1</sub> electronic transition.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":6.475,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386132","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}