IF 2.8 4区化学

Chirality Pub Date : 2024-12-18 DOI: 10.1002/chir.70009

Camilla Ferrari, Alexandra Bogdan, Flavia Pop, Cosimo Curto, Alberta Carella, Francesco Rossella, Narcis Avarvari, Claudio Fontanesi

{"title":"Enantio-Recognition and Charge Transfer Complex Formation Involving Tetrathiafulvalene-Appended Chiral 1,2-Cyclohexane-Diamine: An Integrated Experimental and Theoretical Study","authors":"Camilla Ferrari, Alexandra Bogdan, Flavia Pop, Cosimo Curto, Alberta Carella, Francesco Rossella, Narcis Avarvari, Claudio Fontanesi","doi":"10.1002/chir.70009","DOIUrl":"10.1002/chir.70009","url":null,"abstract":"In this work, we exploit the electronic features of tetrathiafulvalene (TTF) as a backbone in synthesizing chiral derivatives. The aim is to make use of TTF's well-known and unique redox and semiconducting properties in the fields of enantio-selective recognition and chiral charge transfer (CT) complex preparation, with the ultimate objective of obtaining devices with various potential applications, ranging from plasmonics to quantum computing. In particular, both cyclohexane-bis (TTF-amide)–based enantiomers 1-(S,S) and 1-(R,R), stable under an oxidation regime, have been selected, and under these conditions, the electrochemical enantiospecific response of the four possible systems, coming from the combination with L- and D-tartaric acid, respectively, was tested. The 1:tartaric acid adducts show lower oxidation potentials than the pristine 1, together with clear enantio-discrimination demonstrated by sizeable potential differences in the range of 29–46 mV between the diastereomeric adducts. Because the oxidation potential of 1 suggests the possibility of the formation of CT complexes, impedance and FT-IR spectra were recorded to confirm this hypothesis in the case of the CT complex 1:I2. The experimental results obtained through the FT-IR analysis were also compared with the theoretical results deriving from the DFT-based calculations.","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 12","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.70009","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142852948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

On the Reactivity of (S)-Indoline-2-Carboxylic Acid 关于 (S)-吲哚啉-2-羧酸的反应性。

IF 2.8 4区化学

Chirality Pub Date : 2024-12-16 DOI: 10.1002/chir.70008

Fabiana Cordella, Sophie Faure, Claude Taillefumier, Gennaro Pescitelli, Elisa Martinelli, Giuseppe Alonci, Zhengming Liu, Gaetano Angelici

引用次数: 0

Highly Efficient Spectral Measurement Methods Using Newly Developed High-Throughput Magnetic Circularly Polarized Luminescence System

IF 2.8 4区化学

Chirality Pub Date : 2024-12-12 DOI: 10.1002/chir.70001

Satoko Suzuki, Akio Kaneta, Anas Santria, Taiji Oyama, Hiroyuki Nishikawa, Yoshitane Imai, Ken-ichi Akao, Naoto Ishikawa

{"title":"Highly Efficient Spectral Measurement Methods Using Newly Developed High-Throughput Magnetic Circularly Polarized Luminescence System","authors":"Satoko Suzuki, Akio Kaneta, Anas Santria, Taiji Oyama, Hiroyuki Nishikawa, Yoshitane Imai, Ken-ichi Akao, Naoto Ishikawa","doi":"10.1002/chir.70001","DOIUrl":"10.1002/chir.70001","url":null,"abstract":"<div>\u0000 \u0000 Magnetic circularly polarized luminescence (MCPL) spectroscopy is widely used to evaluate the luminescence dissymmetry factor (gMCPL) for compounds. However, even for the same instrument and operating conditions, the measured gMCPL is affected by errors associated with sources such as baseline drift and spectral noise, and so the range of variation of gMCPL must be considered when comparing values, which requires multiple measurements for the same sample. Also, because many samples undergo photodegradation under excitation light, it is difficult to accumulate and average spectra for samples with weak MCPL signals to improve the signal-to-noise ratio. Single measurements must therefore be performed on multiple samples and the results averaged. Furthermore, for samples with a small Stokes shift, spectral correction is required to compensate for the intensity reduction due to the inner-filter effect (IFE). Such measurements are generally performed manually and are therefore time consuming and prone to human error. Here, we demonstrate the use of a newly developed high-throughput MCPL system to automatically measure MCPL and fluorescence spectra of multiple samples of phthalocyanine complexes with high efficiency and reduced human errors. This system allows the incorporation of effective countermeasures to the issues of gMCPL variation, sample photodegradation, extremely weak MCPL signals, and the IFE.\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 12","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142812128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Chiral Differentiation of Chiral Lactides and Chiral Diketones on Native and Phenylcarbamoylated Cyclodextrin Chiral Stationary Phases 手性内酯和手性二酮在原生环糊精和苯基氨基甲酰化环糊精手性固定相上的手性分化。

IF 2.8 4区化学

Chirality Pub Date : 2024-11-22 DOI: 10.1002/chir.70007

Xiaoxuan Li, Xueyang Feng, Xiaoxuan Du, Yong Wang

{"title":"Chiral Differentiation of Chiral Lactides and Chiral Diketones on Native and Phenylcarbamoylated Cyclodextrin Chiral Stationary Phases","authors":"Xiaoxuan Li, Xueyang Feng, Xiaoxuan Du, Yong Wang","doi":"10.1002/chir.70007","DOIUrl":"10.1002/chir.70007","url":null,"abstract":"<div>\u0000 \u0000 Inclusion complexation, hydrogen bonds, π–π interaction, dipole–dipole interaction, and steric hindrance effect all contribute to the enantioseparation ability of cyclodextrin (CD) or CD derivatives. In this work, one native cationic CD chiral stationary phases (SHCDCSP) and four derivatized CD-CSPs, namely, per(4-trifluoromethyl) phenylcarbamoylated-β-CD CSP (SFPhCDCSP), per(4-chloro) phenylcarbamoylated-β-CD CSP (SCPhCDCSP), per(4-bromo) phenylcarbamoylated-β-CD CSP (SBPhCDCSP), and per(4-methyl) phenylcarbamoylated-β-CD CSP (SMPhCDCSP), were prepared via thioether linkage and applied for the enantioseparation of chiral lactides and chiral diketones in both reverse phase (RP) and normal phase (NP) modes. Most of the studied chiral lactides were found to be well resolved (Rs > 1.5) under RP mode, especially Met-Sty-Ibn (compound 11) is observed to display highest resolutions (Rs = 5.09, Rs = 3.17) among all the analytes on the SFPhCDCSP and SMPhCDCSP. In NP mode, SFPhCDCSP showed excellent chiral recognition ability towards chiral lactides. The comparison study of CD-CSPs reveals the structure of CSPs play a significant role on the enantioselectivities.\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 12","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142686245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Multiwavelength Optical Rotation Detection: An Effective Approach for the Recognition of Analytical and Semi-Preparative HPLC Enantioseparation of the Chiral Pheromone Olean and Its Stereochemical Characterization 多波长光学旋转检测：分析和半制备高效液相色谱手性信息素欧琳的对映体分离及其立体化学表征的有效方法。

IF 2.8 4区化学

Chirality Pub Date : 2024-11-12 DOI: 10.1002/chir.70006

Francesca Romana Mammone, Daniele Sadutto, Roberto Cirilli

{"title":"Multiwavelength Optical Rotation Detection: An Effective Approach for the Recognition of Analytical and Semi-Preparative HPLC Enantioseparation of the Chiral Pheromone Olean and Its Stereochemical Characterization","authors":"Francesca Romana Mammone, Daniele Sadutto, Roberto Cirilli","doi":"10.1002/chir.70006","DOIUrl":"10.1002/chir.70006","url":null,"abstract":"<div>\u0000 \u0000 Olean is the chiral spiroacetal sex pheromone of the female olive fruit fly Bactrocera oleae. Laboratory tests have demonstrated that the (R)-(−)-olean enantiomer is active on males, whereas females respond to (S)-(+)-olean. Here we present the first HPLC enantioseparation of olean using polysaccharide derivatives as chiral stationary phases and a polarimetric detector equipped with a micro-flow cell capable of detecting optical rotation at six different wavelengths. Unlike blind UV detection, the polarimetric detector allows the chiral spiroacetal, which lacks a chromophore, to be detected as bisegnate peaks, indicating the opposite sign of the optical rotation. The HPLC enantioseparation was optimized on the coated type amylose-based Chiralpak AS-H CSP using a mobile phase consisting of n-hexane-2-propanol 99.99:0.01 (v/v). These conditions were scaled up to a semi-preparative level and allowed resolution of 2.5 mg of racemic sample in 5 min. Multiwavelength optical rotation detection during HPLC enantioseparation of racemic samples provides a direct readout of the stereochemistry of olean and allows tracking of virtual optical rotation dispersion curves without the need for preliminary collection of enantiomeric samples by semi-preparative HPLC.\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 11","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142614426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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

Emergence of Optical Activity and Surface Morphology Changes in Racemic Amino Acid Films Under Circularly Polarized Lyman-α Light Irradiation 外消旋氨基酸薄膜在圆偏振莱曼-α光照射下出现的光学活性和表面形态变化

IF 2.8 4区化学

Chirality Pub Date : 2024-11-11 DOI: 10.1002/chir.70004

Masahiro Kobayashi, Jun-ichi Takahashi, Hiroshi Ota, Koichi Matsuo, Mohamed I. A. Ibrahim, Taketoshi Minato, Gen Fujimori, Masahiro Katoh, Kensei Kobayashi, Yoko Kebukawa, Hiroaki Nakamura

{"title":"Emergence of Optical Activity and Surface Morphology Changes in Racemic Amino Acid Films Under Circularly Polarized Lyman-α Light Irradiation","authors":"Masahiro Kobayashi, Jun-ichi Takahashi, Hiroshi Ota, Koichi Matsuo, Mohamed I. A. Ibrahim, Taketoshi Minato, Gen Fujimori, Masahiro Katoh, Kensei Kobayashi, Yoko Kebukawa, Hiroaki Nakamura","doi":"10.1002/chir.70004","DOIUrl":"10.1002/chir.70004","url":null,"abstract":"The homochirality of life remains one of the most enigmatic issues in the study of the origin of life. A proposed mechanism for symmetry breaking involves irradiation by circularly polarized light (CPL). To investigate the photoreaction of amino acids under CPL irradiation, a vacuum ultraviolet (VUV) CPL irradiation system was developed at the synchrotron light source UVSOR-III. Hydrogen Lyman-α CPL (121.6 nm) is considered a potential asymmetric source in space. Therefore, racemic alanine film samples were irradiated with Lyman-α CPL to explore the photoreaction of biomolecules. Circular dichroism (CD) spectra measurements revealed that irradiation with right- (left-) handed CPL induced a positive (negative) anisotropy factor g in the wavelength range of 180–240 nm. However, the spectra differed from those of enantiopure alanine, exhibiting broad wavelength ranges and no sign change. Liquid chromatography-mass spectrometry (LC–MS) measurements indicate formation of larger molecules, such as oligomeric alanine adducts or modified oligomers after the Lyman-α CPL irradiation. Additionally, CPL irradiation considerably changes the microstructure of the alanine film surface, leading to the formation of circular network aggregates on the scale of 100 nm. The morphology changes in the alanine film and/or the formation of the larger molecules could be possible causes of the modified anisotropy factor spectra compared to those of enantiopure alanine. These findings highlight the need for further research on the photoreaction of biomolecules in solid states under VUV CPL irradiation, particularly in the photoionization energy range, to validate the cosmic scenario of homochirality.","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"36 11","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.70004","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142614420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Proceedings From 33rd Symposium on Chirality 2023, Rome, Italy 第 33 届手性研讨会论文集 2023 年，意大利罗马。

IF 2.8 4区化学

Chirality Pub Date : 2024-11-08 DOI: 10.1002/chir.70005

Alessa Ciogli, Lorenzo Di Bari, Francesco Zinna, Nina Berova, Gennaro Pescitelli, Oliver Trapp, Simona Collina

引用次数: 0

Resolution and Absolute Configuration of Fargesin Enantiomers Fargesin 对映异构体的解析和绝对构型。

IF 2.8 4区化学

Chirality Pub Date : 2024-11-06 DOI: 10.1002/chir.70003

Eloá R. Mestriner, Eric Y. Lee, Camila L. Cunha, Victor M. S. Sousa, Isabele R. Nascimento, João M. Batista Jr

引用次数: 0

Chiroptical Sensing of Amines With Isatins 用异肽对胺进行光电传感