High Optical Rotation Research Articles

Thermoresponsive behavior of polyrotaxanes based on α-cyclodextrins threaded on poly(2-alkyl-2-oxazoline)-poly(ethylene glycol)-poly(2-alkyl-2-oxazoline) triblock copolymers

Polyrotaxanes with poly-2-alkyl-2-oxazoline blocking moieties have been successfully synthesized. The structure of the synthesized samples was confirmed by NMR spectroscopy, and the molar masses were measured by light scattering and GPC. The density of cyclodextrin rings on polyethylene glycol did not depend on the structure of poly-2-alkyl-2-oxazoline chains and ranged from 2 to 5. A high specific optical rotation of the prepared polyrotaxanes is found which is caused by the formation of hydrogen bonds between neighboring macrocycles. The behavior of water-salt solutions of synthesized polyrotaxanes depended on the size of the poly-2-alkyl-2-oxazoline side groups. Only polymers with poly-2-isopropyl-2-oxazoline and poly-2-n-propyl-2-oxazoline blocking moieties were thermoresponsive in aqueous solutions, and the phase separation temperature decreased at passage from a polymer with poly-2-isopropyl-2-oxazoline to a sample with poly-2-n-propyl-2-oxazoline. Aqueous solutions of polyrotaxanes with smaller side groups were molecularly dispersed at all temperatures, and the polymer with poly-2-butyl-2-oxazoline blocking chains did not dissolve in water.

3D structured Bessel beam polarization and its application to imprint chiral optical properties in silica

Polarization plays a crucial role in light–matter interactions; hence its overall manipulation is an essential key to unlock the versatility of light manufacturing, especially in femtosecond laser direct writing. Existing polarization-shaping techniques, however, only focus on their manipulation in the transverse plane of light beams, i.e., two-dimensional control. In this paper, we propose a novel passive strategy that exploits a class of femtosecond laser written space varying birefringent elements to shape the polarization state along the optical path. As a demonstration, we generate a three-dimensional structured Bessel beam whose linear polarization state slowly evolves along the focus (typ. 90° within 60λ). Such a “helically polarized” Bessel beam allows imprinting “twisted nanogratings” in SiO2 glass which result in an extrinsic optical chirality at a micrometric scale and own a high optical rotation. Our work provides new perspectives for three-dimensional polarization manipulation and insights into applications in structured light, light–matter interaction, and chiral device fabrication.

On the Cation-π capabilities of infinitene (∞). Evaluation of bonding and circular dichroism properties for Infinitene-Ag(I)n (n = 1–4) complexes from relativistic DFT calculations

The helicoidal π-conjugated structure from helicenes is able to feature cation-π bonding towards Ag(I) atoms, resulting in the variation of their inherent high optical rotation values. Recently, the characterization of infinitene ([12]infinitene) as two fused [6]helicene structures with a central crossover section suggests the extension of such coordination characteristics to large and more complex structural landscapes. Herein, we evaluated the possible cation-π features of infinitene towards one to four silver cations from density functional calculations and their role in the optical rotation of the infinity-shaped backbone. The nature of the cation-π interaction for infinitene, shows a favorable formation of single and multiple Ag(I) aggregation, with a slight distortion of the structural backbone. Hence, the formation of cation- π complexes in infinitene is plausible, suggesting the expansion of its chemistry towards the formation of metal complexes in fused helicene species.

Optical Rotation—A Reliable Parameter for Authentication of Honey?

The controversial question of whether optical rotation data can be used to distinguish floral from honeydew honey was investigated. Specific optical rotation angles were determined for 41 honey samples, including floral, honeydew, and adulterated honey, indicating that moderate to high positive optical rotation angles were found for all adulterated samples measured. A strong correlation between the sugar profile and the specific optical rotation angle of honey was confirmed, and a method based on 13C NMR metabolomics was proposed to calculate specific optical rotation angles with good correlation with the experimental values. The results indicate that optical rotation is not a reliable method for distinguishing the origin of honey but could indicate adulteration.

Synthesis and characterization of aza[7]helicenes

Unsymmetrical aza[7]helicene is synthesized and its photophysical properties are studied. Its functionalization is carried out by Vilsmeier-Haack formylation, followed by its conversion to chiral amino derivative. The two formyl derivatives were characterized by single crystal X-ray diffraction analysis. The diastereomeric 2-aminomethyl aza[7]helicene was obtained in optically pure form, which shows high optical rotation values. Geometry optimization of aza[7]helicene was carried out using B3LYP/6–31G(d,p) level of theory and its HOMO-LUMO energy gap was calculated.

Asymmetric Synthesis and Chiroptical Properties of Enantiopure Helical Ferrocenes.

An enantiopure helical ferrocene ( Rp)-5 with five ortho-condensed aromatic rings was synthesized using a PtCl2-catalyzed cycloisomerization of planar-chiral 2-ethynyl-1-(4-phenanthrenyl)ferrocene ( Rp)-6f, prepared in 3 steps from known enantiopure sulfinyl ferrocenyl boronic acid ( SS, Sp)-7, as the source of planar chirality. This pentacyclic helical ferrocene showed a very high optical rotation value and strong circular dichroism (CD) signals.

Hypoglycemic triterpenes from Gynostemma pentaphyllum

To search for bioactive gypenosides and their analogues, a saponin enriched fraction and its hydrolyzate from Gynostemma pentaphyllum were phytochemically investigated. Fractionation by diverse chromatographic methods, including HPLC, Sephadex LH-20, silica gel, and C18 reverse phase silica gel, led to the isolation and purification of twelve triterpenes, including five undescribed and seven known. The chemical structures of all compounds were determined as analyzed by nuclear magnetic resonance (NMR), high resolution mass spectrometry (HR-MS), infrared spectrum (IR), optical rotation, and chemical transformations. Among all isolates, nine compounds possessed a rare dammarane triterpenoid framework with A-ring modified. The relative configurations of three compounds were determined by 2D NMR for the first time. The absolute configurations of four compounds were determined by the modified Mosher's method. Two of all isolated compounds significantly enhanced 2-deoxy-2-[(7-nitro-2,1,3-benzoxadiazol-4-yl)amino]-D-glucose (2-NBDG) uptake and Glucose Transporter 4 (GLUT4) translocation via activating the AMP-activated protein kinase (AMPK) and acetyl-CoA carboxylase (ACC) signaling pathway. This study provided the potential candidates for the development of antidiabetic agents.

Helicenes as Molecular Tweezers in the Formation of Cation-π Complexes. Bonding and Circular Dichroism Properties from Relativistic DFT Calculations.

Helicene ligands possess a unique helicoidal π-conjugated framework providing high optical rotation values. This has stimulated a growing interest in helicene derivatives as building blocks, which has triggered the development of simple strategies to tune their properties. In this context, we evaluated the formation of cation-π complexes derived from [6]- and [7]helicene, involving Sn2+ , Cd2+ , and In+ in addition of Ag+ , which appears as a plausible modification of such helicoidal structure. The nature of the cation-π interaction in the studied helicene complexes exhibits a covalent character, accounting for ligand π-donation to 5 s and 5p empty orbitals of the involved cations. Furthermore, the evaluation of their optical activity exhibits notorious modification patterns in the circular dichroism spectrum, suggesting that the modifications of the optical activity are dependent on the nature of the cation and its related charge state. Thus, the plausible formation of new cation-π complexes derived from helicene ligands, as discussed here, may lead to the characterization of novel species expanding the chemistry of helicene metal complexes to even to larger helicene units. We believe that the present study may open new avenues in the formation of cation-π helicene complexes.

Chiral exploration of 6,12-diphenyldibenzo[b,f][1,5]diazocine with stable conformation.

A first optical resolution of 6,12-diphenyldibenzo[b,f][1,5]diazocine with stable boat conformation was achieved by chiral supercritical fluid chromatography (SFC). The absolute configurations of enantiomers were first assigned and determined by X-ray crystal structure based on CIP-rules. The high optical rotation and circular dichroism spectrum were well explained by electronic helix theory. Owing to the high stabilization of boat conformation, the chiral configuration could be maintained at very high temperature, more than 200°C, which was proved by Density Functional Theory calculations.

High efficiency broadband -90° to 90° arbitrary optical rotation realized with meta reflectarray.

We theoretically demonstrate high efficiency broadband -90° to 90° arbitrary optical rotation realized with meta reflectarray composed of a L-shaped silver antenna array, a silica spacer, and a silver ground plane. Co-polarized and cross-polarized components of reflected wave can be manipulated efficiently by adjusting arm length of the L-shaped antenna, and 0° to 90° arbitrary optical rotation with high degree of linear polarization (DoLP) over a broadband can be achieved readily. The phase of cross-polarized field component can be reversed by turning the L-shaped antennas upside down, and 0° to 90° optical rotation can be turned into 0° to -90° rotation. Reflected phase can be shift by π after a 90° rotation of the L-shaped or Γ-shaped antennas, while optical rotation angle remains the same. Thus, rotation angle θ is changed to 180° + θ after the rotation, and we realized 0° to 360° polarization rotation with a step of 60° with the combination of six discrete structure units. In addition, we proposed metamaterial structures for highly efficient generation of vector beams with these units. The high efficiency broadband arbitrary angle optical rotation will profoundly affect a wide range of applications involving optical polarization.

Synthesis, Structures, Resolution, and Chiroptical Properties of 1,16-Diaryl-Substituted Benzo[5]helicene Derivatives.

An efficient route to the synthesis of benzo[5]helicene derivatives functionalized on the interior side of the helix was developed, and resulted in a series of 1,16-diaryl-substituted benzo[5]helicene derivatives starting from easily available 7-methoxytetralone. X-ray crystal structures showed that the benzo[5]helicene derivatives had highly helical, twisted structures, and could all create hierarchical packing architectures with alternating P and M layers in the solid state. Moreover, seven pairs of enantiomers based on 1,16-diaryl-substituted benzo[5]helicene derivatives were also obtained by efficient resolution through HPLC with semipreparative chiral columns. The enantiomers all showed clear mirror-image circular dichroism (CD) spectra and high specific optical rotations, and their absolute configurations were determined by X-ray crystallography. Interestingly, a helical nanotubular structure was formed by the self-assembly of one enantiomer through halogen bonding. Furthermore, the enantiomers were found to have high racemization barriers and thermostability, which might be caused by the introduction of aryl substituents at the C1(C16) position.

π-Helicenes truncated to a minimum: access through a domino approach involving multiple carbopalladations and a Stille coupling.

A novel type of π-helicenes is reported, in which the π-system is truncated to an all-s-cis all-Z oligoene chain. A domino sequence was developed, consisting of up to four consecutive carbopalladation reactions and a terminal Stille cross-coupling, to generate these entities in one step from the respective linear oligoynes. Despite the minimal π-system, very high optical rotation values were encountered for the single enantiomers. X-ray crystallography confirmed their screw-shaped structure.

An arabino(glucurono)xylan isolated from immunomodulatory active hemicellulose fraction of Salvia officinalis L.

From the aerial parts of sage (Salvia officinalis L.) an arabino-(4-O-methyl-glucurono)-xylan (AGX) was isolated by alkaline extraction followed by precipitation with barium hydroxide solution. Polymer was isolated from sage as a light brown polysaccharide material of molecular mass (Mp) 84,000. Compositional analyses of sage AGX revealed xylose (81%), arabinose (10%), glucuronic acid (8%) and small amounts of hexoses (1%). Linkage sugar analyses showed the (1→4)-linked xylopyranosyl backbone with low degree of substitution (9–10%) at O-2 and O-3. Arabinofuranose residues were found as the terminal, 1,3-, 1,5- and 1,3,5-linked. NMR structural analyses of acidic oligomers, generated by partial acidic hydrolysis of AGX, confirmed a substitution of xylose residues by glucuronic acid and its 4-O-methyl derivate at O-2 at an average on every fourteenth xylose residue. NMR and FT-IR measurements, as well as a high negative optical rotation confirmed the β configuration of glycosidic linkages in AGX backbone.

An optical rotation sensor based on dispersive slow-light medium

Slow light supported by electromagnetically induced transparency effect in dispersive medium is extremely susceptible with respect to Doppler detuning. In this paper, the Doppler effect induced by rotating dispersive medium was considered and the effect of the velocity of rotating dispersive medium on the group velocity was studied. Based on a dispersive slow-light medium, a high sensitive optical rotation sensor for measuring absolute rotation is proposed and analysed. The sensitivity of the rotation sensor is the group delay between the counterpropagationed wave packets in the device, and scales directly with square of the group index which can reach 102−108 orders of magnitude by selecting a proper dispersive medium.

Optical-activity anisotropy of ordered phases in cellulose acetates

The optical activity of anisotropic solutions of cellulose diacetate in nitromethane and dimethyl sulfoxide and of diand triacetate films with vitrified ordered structure has been studied. The systems under study are characterized by high specific optical rotation [α], suggesting formation of a cholesteric mesophase. The value of [α] is found to depend on the angle of rotation of the samples relative to the direction of the polarization vector of an incident light beam in the plane perpendicular to this beam (the anisotropy of optical activity). This dependence (indicatrix) shows an irregular pattern and, when plotted in Cartesian coordinates, can be described with a distorted sinusoid. The data on the resolution of indicatrices into harmonic constituents and isolation of contributions due to isotropic components and anisotropic components, each of which is determined by the structural element with the corresponding asymmetry, are analyzed.

Synthesis, chiroptical properties, and their theoretical simulation of some highly rotating benzotricamphor derivatives

The large molecules 1-3 (69, 90, and 102 atoms, respectively), prepared by cyclotrimerization of enantiomerically pure derivatives of (-)-bornyl acetate, show intense ECD spectra, high optical rotation (OR) values (200-1300, in absolute value) dominated in sign and order of magnitude by the lowest-energy Cotton effects, that is, they are the ideal candidates to test the reliability of our "approximate" (TDDFT/B3LYP/6-31G* or smaller basis set) approach to the calculation of chiroptical properties. As a matter of fact, a correct simulation of the OR values and ECD spectra of 1 and 2 can be obtained even using STO-3G basis set and semiempirical or molecular mechanics input geometries: for 1, at the TDDFT/B3LYP/STO-3G level, the OR values are of the order of 500-550, versus an experimental value ranging between 660 and 690, depending on the solvent. On the contrary, the case of 3 (exp. OR between -1330 and -1500) is really complex (for instance, the OR values range between -3216 and -729 (TDDFT/B3LYP/6-31G* calculations) or -1824 and -444 (TDDFT/B3LYP/STO-3G calculations)), making the comparison between calculated and experimental values more difficult. The behavior of 3 is due to its molecular flexibility, whereas 1 is a really rigid molecules and 2 behaves (vide infra) as it were a rigid system. These observations strongly indicate that the conformational freedom constitutes one of the major difficulties for a correct but simple simulation of the chiroptical properties.

Pure chiral organic thin films with high isotropic optical activity synthesized by UV pulsed laser deposition

We show that the pulsed laser deposition (PLD) technique allows us to elaborate pure molecular solid state thin films based on binaphthyl molecules featuring high isotropic optical rotation (HIOR). The transfer of chirality from the ablated target to the substrate was probed by polarimetry and circular dichroism (CD) measurements. A rotary power of 12° mm at 546 nm has been obtained. CD spectroscopy confirms both the chiral and the isotropical nature of the deposited thin films and put into evidence the disorder between the naphthyl chromophores inside the molecular material. Finally, we highlight three regimes for the deposition mechanism depending on the laser fluence: desorption without racemisation, desorption with racemisation, and ablation with degradation. These results demonstrate that, by properly adjusting the growth conditions, isotropic purely organic chiral films can be grown by PLD, thereby opening the prospect for the synthesis of high value organic materials for applications such as waveguiding.

A Study on the Optically Active Polymer Poly‐β‐pinene

Poly‐β‐pinene (PBP) was obtained by radiation‐induced polymerization of monomer with γ radiation. The polymerizations were conducted both in vacuum and in the presence of air at different radiation doses up to 1–3 MGy. It was found that the presence of oxygen retards the polymerization rate and reduces the polymer yields and the radiation chemical yield suggesting that the polymerization mechanism involves free radicals. It is shown that PBP can also be obtained in low yields from β‐(‐)pinene polymerization with a free radical initiator. The chemical structures of the PBP radiopolymer and PBP obtained by a free radical initiator were studied by FT‐IR and 13C CP‐MAS NMR spectroscopy. The data shows that the PBP obtained have highly ordered structures, which is manifested also by the very high specific optical rotation which is about 3 times that of the starting monomer in the case of the radiopolymer and about 5 times in the case of the PBP prepared with the free radical initiator. In contrast, PBP obtained in high yields by cationic polymerization shows a very low specific optical rotation, much lower than that of the starting monomer and low regularity in chemical structure has been attributed to this polymer by FT‐IR and 13C CP‐MAS NMR spectroscopy. It is shown that PBP with high optical activity racemizes over an acidic catalyst.

Absolute Configuration of Natural Cyclohexene Oxides by Time Dependent Density Functional Theory Calculation of the Optical Rotation: The Absolute Configuration of (−)-Sphaeropsidone and (−)-Episphaeropsidone Revised

The optical rotatory power of some natural cyclohexene oxides, such as (+)-chaloxone, 1, (+)-epiepoformine, 2, (+)-epoformine, 3, (+)-epoxidone, 5, (-)-sphaeropsidone, 6, (-)-episphaeropsidone, 7, and the synthetic compound (+)-epitheobroxide, 4, has been calculated by means of the TDDFT/B3LYP method using the 6-31G(d) and aug-cc-pVDZ basis sets, both in the gas phase and in solution by means of the polarizable continuum model. For compounds 1 and 2, which possess high (about 300 units) optical rotations, gas-phase calculations with the smaller basis set are able to reproduce the experimental values both in sign and order of magnitude. By contrast, a larger basis set is required to satisfactorily simulate the OR values of 3 and 4, which show smaller (about 100 units or less) rotations. The inclusion of the solvent effects is different for different compounds; for 1 and 2, it leads to a better agreement between experiment and prediction, while for 3 and 4, the presence of hydrogen bonding groups makes the application of continuum solvation models less satisfactory. For the flexible system 5, the absolute configuration could not be determined using gas-phase calculations and the smaller basis set, but both inclusion of solvent and larger basis set effects are compulsory. It is noteworthy that calculations both in the gas phase and in the solvent lead to a positive rotatory power for the laevorotatory natural compounds 6 and 7 if the ACs reported in the literature are employed to do the theoretical prediction. This strongly indicates that the ACs previously assigned to these compounds in the literature are not correct and that the TDDFT prediction of OR values has become by now a practicable tool for AC assignments.

A highly branched storage polyglucan in the thermoacidophilic red microalga Galdieria maxima cells

The thermoacidophilic red alga Galdieria maxima is capable of heterotrophic growth. The content of carbohydrates in H. maxima grown heterotrophically increases by a factor of 4, reaching as much as 60% of cell dry weight. The increase in the level of carbohydrates in cells is due to accumulation of a storage alpha-glycan. According to a specific cleavage to glucose catalyzed by amyloglucosidase and the high positive specific optical rotation characteristic of polyglucans, this polysaccharide can be classified as a floridean starch. The data of 1H NMR spectroscopy and the results of methylation showed that the average length of the unbranched regions of the polysaccharide molecule is six to seven glucose residues. The degree of branching of the starch molecule of G. maxima is greater than that of storage polysaccharides of other red algae, glycogens of yeast, and phytoglycogens of cyanobacteria.