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1.
Juices, wines, and extracts from plants contain high concentrations of various chiral compounds such as carboxylic acids or sugars. Several prior studies reported the synthesis of metallic and semiconducting nanoparticles relying on components of complex biological solutions. Herein, we present preparation of chiral CdS and CdSe quantum dots (QDs) using apple juice and red wine via phase transfer ligand exchange. Although both apple juice and red wine contain a complex mixture of chiral and achiral compounds, we have successfully used them for selective induction of predicted chiroptical properties and confirmed L-malic acid from the apple juice and L-tartaric acid from the red wine as the chiral inducers. This work illustrates the capability of using complex mixtures to construct chiral QDs with desired chiroptical properties as well as potential of QDs to selectively report a chiral molecule in a complex chiral mixture without the need for elaborate chiral recognition system. 相似文献
2.
Hydrodynamic forces are capable of inducing structural order in dispersed solid phases, and of causing symmetry-breaking when chiral crystals precipitate from an achiral liquid phase. Until it was observed upon vortex-assisted fibrillation of insulin, such behavior had been thought to be confined to few unbiological systems. In this paper we are discussing chiroptical properties of two chiral variants of insulin amyloid, termed +ICD and -ICD, which form during the process of chiral bifurcation in vortexed solutions of aggregating insulin. As conventional measurements of circular dichroism of solid, anisotropic substances are particularly vulnerable to overlapping influences of linear birefringence and linear dichroism, we have employed complementary tools including dedicated universal chiroptical spectrophotometer to rule out such artifacts. We propose that the strong chiroptical properties of +ICD and -ICD insulin fibrils are an aspect of genuine superstructural chirality of amyloid fibrils and of powerful excitonic couplings taking place within them. A comparison of thioflavin T complexes with fibrils formed by insulin and polyglutamic acid suggests that the extrinsic Cotton effect stemming from the level of single twisted dye molecules is weaker, although diagnostically useful, and cannot account for the overall magnitude of ICD of the dye bound to ±ICD insulin amyloid. 相似文献
3.
Over the past decades, chiroptical spectroscopy has proved its incomparable ability to elucidate the structure and spatial arrangement of chiral molecules. Systematic analysis of biomolecules in the natural environment of biofluids, however, remains challenging. In this study, we used chiroptical spectroscopy to monitor urinary levels of human serum albumin. Not only severe proteinuria but even just a slightly increased urinary excretion of albumin (microalbuminuria) may indicate serious health complications, especially for diabetic individuals. Given the chiral nature of albumin and its typical spectral pattern, it may be easily observable by chiroptical spectroscopy, particularly electronic circular dichroism. The performed chiroptical analysis of urine not only allowed the detection of clinically confirmed microalbuminuria but was also able to reveal this pathological condition in cases beyond the diagnostic capability of common clinical procedures. Thus, our approach suggests that electronic circular dichroism is a useful tool for the fast and reliable qualitative monitoring of microalbuminuria with the potential for a quantitative analysis in the future. 相似文献
4.
Several α-monoalkyl-α-aryloxyacetic acids have been synthesized and resolved into their optical antipodes; their absolute configuration was also established by chiroptical and chemical methods. The two enantiomers of a series of these compounds show opposite effects on skeletal muscle fibers chloride conductance. Therefore a HPLC procedure was developed for the direct determination of the optical purity of the antipodes before submitting them to biological tests. The chromatographic study was performed on DACH-DNB chiral stationary phase which shows a remarkable enantioselectivity for the considered compounds as free acids, esters and amides under different conditions with essentially the same chiral mechanism of separation. © 1992 Wiley-Liss, Inc. 相似文献
5.
We study the chiroptical properties of one‐dimensional photonic crystals supporting superchiral surface waves by introducing a simple formalism based on the Fresnel reflection matrix. We show that the proposed framework provides useful insights on the behavior of all the relevant chiroptical quantities, allowing for a deeper understanding of surface‐enhanced chiral sensing platforms based on one‐dimensional photonic crystals. Finally, we analyze and discuss the limitations of such platforms as the surface concentration of the target chiral analytes is gradually increased. 相似文献
6.
In recent years, four different chiroptical spectroscopic methods, namely vibrational circular dichroism, vibrational Raman optical activity, electronic circular dichroism, and optical rotatory dispersion, have become popular for establishing the absolute configuration and predominant conformations of chiral molecules in solution state. Many individual laboratories normally utilize only one of these methods to derive the molecular structural information. Although that approach may be satisfactory for most of the molecules studied, it is to be noted that in some instances a single method can give ambiguous conclusions or may not give complete structural information. This article summarizes the situations where simultaneous use of more than one chiroptical spectroscopic method is required to obtain molecular structural information and recommends the routine application of more than one chiroptical spectroscopic method for any given molecule. 相似文献
7.
Novel optically active oligothiophenes bearing electron-donating chiral side chains have been prepared by synthetic methods suitable to achieve regioregular head-to-tail and head-to-head/tail-to-tail derivatives. In particular, the chiral ( S)-(2-methyl)butyl moiety was linked at position 3 of the thiophene ring through heteroatoms, such as S or O, to evaluate its effect on the macro molecular aggregation and, consequently, on the chiroptical properties of the material in the solid state. The materials have been fully characterized and investigated by optical and chiroptical methods upon aggregation both from the solution and as cast films. Compared with the related head-to-tail and head-to-head/tail-to-tail poly(3-alkyl)thiophene derivatives, with the same optically active moiety directly linked to the ring and possessing a higher polymerization degree, the chiroptical properties of the newly synthesized oligomers were significant, or even better, and provided insight into the role of intrachain–interchain interactions between the heteroatom and the thienyl sulfur atom. 相似文献
8.
The development of chiral HPLC methods and isolation techniques within Zeneca Agrochemicals (formerly ICI Agrochemicals) is reviewed. The use of low temperature to improve chiral separations has been successfully applied to production analysis, but although useful for some compounds it is regrettably not a universal panacea for all poor separations. The need to isolate small quantities of individual enantiomers from new compounds for research evaluation has led us to devise a more universal and cheap chiral stationary phase (CSP) for Preparative-LC. Joint academic research produced a CSP based on tartaric acid which was made commercially available and it was gratifying to find it was the only phase able to resolve a novel insecticide. However, as new CSPs emerged almost every month, our attention turned to using a universal chiral detector for analysis, rather than via separation of individual enantiomers. Diode laser-based polarimeters offered the opportunity of cheap, sensitive chiroptical detectors for HPLC and the ability to move away from chiral columns in both research and production analysis. Jointly sponsored research with a university has successfully explored the versatility of chiroptical detectors in agrochemical and food analysis. Comparison of chiral SFC with chiral HPLC and an extensive evaluation of established and research agrochemicals on a wide range of commercial CSPs have led to a revised method development strategy. Current work with high load displacement chiral chromatography will be described as a potential means of isolating pure enantiomers from racemates. © 1994 Wiley-Liss, Inc. 相似文献
9.
Plasmonic nanoparticles (NPs) adsorbing onto helical bacteria can lead to formation of NP helicoids with micron scale pitch. Associated chiroptical effects can be utilized as bioanalytical tool for bacterial detection and better understanding of the spectral behavior of helical self-assembled structures with different scales. Here, we report that enantiomerically pure helices with micron scale of chirality can be assembled on Campylobacter jejuni, a helical bacterium known for severe stomach infections. These organisms have right-handed helical shapes with a pitch of 1–2 microns and can serve as versatile templates for a variety of NPs. The bacteria itself shows no observable rotatory activity in the visible, red, and near-IR ranges of electromagnetic spectrum. The bacterial dispersion acquires chiroptical activity at 500–750 nm upon plasmonic functionalization with Au NPs. Finite-difference time-domain simulations confirmed the attribution of the chiroptical activity to the helical assembly of gold nanoparticles. The position of the circular dichroism peaks observed for these chiral structures overlaps with those obtained before for Au NPs and their constructs with molecular and nanoscale chirality. This work provides an experimental and computational pathway to utilize chiroplasmonic particles assembled on bacteria for bioanalytical purposes. 相似文献
10.
The chiroptical response of plasmonic chiral nanostructures can be tuned by combining different structures. In this paper, an L-shaped metal strip is introduced into a rectangular metal nanohole to generate absorption circular dichroism (ACD). The results of a finite-element method calculation show that ACD effects result from contorted electrical oscillations in the L-shaped strip. Additional calculations show that the ACD effects of the proposed metasurface depend strongly on the structure parameters. These findings provide not only a mechanism for enhancing chiroptical responses in planar structures but also a general strategy for the chiral manipulation of light and creation of chiroptical devices. 相似文献
11.
Chiroptical materials have received much attention in diverse fields for applications such as displays, sensors, smart memory devices, and catalysis. Here, we develop a simple fabrication method for polymer films with tunable chiroptical properties using small amounts of self-assembling fluorescent dye as an additive. Both the circular dichroism and circularly polarized luminescence signals of the film can be tuned between positive and negative values by thermal treatment. The chiroptical properties can be varied by slight changes in the orientation of chiral pyrene moieties in self-assembled nanofibril networks. 相似文献
12.
Heterogeneous catalysis has vastly benefited from investigations performed on model systems under well‐controlled conditions. The application of most of the techniques utilized for such studies is not feasible for asymmetric reactions as enantiomers possess identical physical and chemical properties unless while interacting with polarized light and other chiral entities. A thorough investigation of a heterogeneous asymmetric catalytic process should include probing the catalyst prior to, during, and after the reaction as well as the analysis of reaction products to evaluate the achieved enantiomeric excess. I present recent studies that demonstrate the strength of chiroptical spectroscopic methods to tackle the challenges in investigating model heterogeneous asymmetric catalysis covering all the abovementioned aspects. 相似文献
13.
Dirhodium complexes bearing N-substituted chiral amino acid ligands are investigated. These complexes have an unusual twisted paddlewheel structure, showing inherent chirality. We would like to demonstrate that parallel application of chiroptical spectroscopic methods (ECD and VCD) and NMR spectroscopy combined with quantum chemical calculations constitutes a powerful tool to determine the configuration of the complexes unequivocally. Two chiroptical methods are needed to determine the absolute configuration: ECD for the coordinated nitrogen atom and VCD for the rhodium core. A quick to use NMR method is also presented: Upon the coordination of small molecules in the axial position, the relative configuration of both the rhodium core and the nitrogen atom can be determined simultaneously by studying spatial proximities provided by 1D NOE spectra. 相似文献
15.
The attempts of applying chiroptical spectroscopy to supramolecular chirality are reviewed with a focus on vibrational circular dichroism (VCD). Examples were taken from gels, solids, and monolayers formed by low‐molecular mass weight chiral gelators. Particular attention was paid to a group of gelators with perfluoroalkyl chains. The effects of the helical conformation of the perfluoroalkyl chains on the formation of chiral architectures are reported. It is described how the conformation of a chiral gelator was determined by comparing the experimental and theoretical VCD spectra together with a model proposed for the molecular aggregation in fibrils. The results demonstrate the potential utility of the chiroptical method in analyzing organized chiral aggregates. Chirality 27:659–666, 2015. © 2015 Wiley Periodicals, Inc. 相似文献
16.
Chiroptical spectroscopy has evolved into a promising tool for chiral molecular structural determination in the last four decades. Determination of the absolute configurations (ACs) of bromochlorofluoromethane and [ 2H 1, 2H 2, 2H 3]‐neopentane demonstrated the enviable advantages of chiroptical spectroscopy. Furthermore, uncovering the errors in the ACs reported in the literature established a glimpse of what can be accomplished with the modern chiroptical spectroscopic methods. Despite these triumphs, it is important to exercise caution in the practice of chiroptical spectroscopic methods, because certain widely practiced approaches can lead to erroneous conclusions. Selected major accomplishments and special precautions needed for future applications are emphasized. Chirality 28:445–452, 2016. © 2016 Wiley Periodicals, Inc. 相似文献
17.
In conglomerates, each single crystal contains only one of the two possible enantiomeric forms--either dextrorotatory or levorotatory. The analysis of a single crystal by liquid chromatography on chiral support associated with chiroptical detection is a very efficient tool to reveal the occurrence of a conglomerate. In terms of rapidity and easiness, this method compares favorably with the classical methods used to show this occurrence. Two examples are provided. 相似文献
18.
We present results of fluorescence excitation circular dichroism studies of the chiroptical response of single (bridged triarylamine) helicene molecules immobilized at a polymer interface. We extract directly dissymmetry parameters, and corresponding probability distributions, associated with the single-molecule fluorescence excitation associated with modulation of a circular polarized excitation field for three different excitation wavelengths (405, 440, 457 nm) showing circular dichroism in bulk films. The observed single molecule chiroptical response is anomalously large in comparison with the results of time-dependent density functional calculations, and the observed defocused emission patterns seem to indicate a higher multipole nature to the transition probed. Our results provide new insights into chiroptical properties of chiral fluorophores that are hidden under the extensive averaging associated with conventional chiroptical probes. 相似文献
19.
The chiral recognition phenomenon observed in enantioselective excited-state energy transfer processes currently requires the use of chiroptical spectroscopic techniques to probe the magnitude and sense of the discriminatory interactions. The use of chiroptical spectroscopic techniques limits the study of chiral recognition to those molecular species with strong absorption or emission dissymmetry factors. This study presents the theoretical and experimental methodology to determine the magnitude of chiral discriminatory interactions with unpolarized, steady-state luminescence measurements. Based on bimolecular luminescence quenching kinetics for a system containing chiral molecules, the Stern-Volmer equation is derived and contains a chiral discriminatory term for a system containing a chiral but racemic luminophore and an enantiomerically resolved quencher species. The utility of this methodology is confirmed by examining the enantioselective excited-state quenching between several Ln(dpa)(3)(3-) complexes (where Ln = Eu(3+), Tb(3+), or Dy(3+) and dpa = pyridine-2,6-dicarboxylate) acting as the energy donor and either racemic or enantiomerically resolved [Co(dach)(3)](3+) (where dach = trans-1R,2R (or 1S,2S)-diaminocyclohexane) acting as the energy acceptor in an aqueous solution. The results of this study confirm the utility of unpolarized, steady-state luminescence measurements as a probe of chiral discriminatory behavior. 相似文献
20.
The biodegradation of the chiral phenoxyalkanoic herbicides 2-(2,4-dichlorophenoxy)propionic aid (2,4-DP) and 2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) was investigated using enantioselective HPLC and chiroptical detection. Racemic mixtures of 2,4-DP and MCPP were applied to three species of turf grass, four species of broadleaf weeds, and soil. Preferential degradation of the S-(-) enantiomer of each herbicide was observed in most species of broadleaf weeds and soil, while the degradation in all species of grass occurred without enantioselectivity. The biodegradation in all systems appeared to follow pseudo first-order kinetics with the fastest degradation occurring in broadleaf weeds, followed by the grasses. The slowest degradation was observed in soil. The results of this work illustrate the need to characterize both enantiomers of chiral agrochemicals in order to have an accurate understanding of their distribution and fate in the environment. 相似文献
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