Circular polarization attachments for FTIR spectrometers

Two devices (retarders) for converting linearly polarized IR radiation into circularly polarized one, based on total internal reflection, are described. One of them uses two totally reflecting KBr prisms while the other one works with a single ZnSe prism. Tests for the quality of the circular polarization are given.     

Poly(β-amino acid)s. IV. Synthesis and conformational properties of poly(α-isobutyl-L-aspartate)

Poly(α-isobutyl-L -aspartate) was prepared by the polycondensation reaction of p-nitrophenyl ester of α-isobutyl-L -aspartate and the conformation of the poly(β-amino acid) was investigated by X-ray diffraction, polarized infrared, circular dichroism (CD), optical rotatory dispersion (ORD), and NMR spectroscopy. α-Isobutyl β-p-nitrophenyl-L -aspartate hydrochloride and hydrobromide were used as monomers and dimethylformamide, chloroform, and chlorobenzene, as solvents. A high-molecular-weight polymer with [η] 1.0 dl/g (dichloroacetic acid, 25°C) was formed in the polymerization of the hydrochloride in chloroform at 25°C. The X-ray diagram and polarized infrared spectrum of the stretched polymer film obtained from a chloroform solution suggested a cross-β-form as the most probable structure in the solid state. The CD spectra of the polymer in a 2,2,2-trifluoroethanol (TFE) solution and its film cast from the solution showed a peak at 205 nm and a trough at 190 nm which were assigned to a β-structure. The polymer was associated in chloroform. The NMR and ORD spectra in chloroform were similar to those in TFE, which suggests that the polymer also exists in the β-structure in chloroform. The addition of small amounts of dichloroacetic acid and sulfuric acid to chloroform and TFE solutions, respectively, destroyed the β-structure. A random copolymer of α-isobutyl-L -aspartate with β-alanine was also prepared by polycondensation reaction. The copolymer apparently did not form an ordered structure in the solid state or in solution.     

The thermotropic and lyotropic liquid-crystalline properties of acetoacetoxypropyl cellulose

Acetoacetoxypropyl cellulose, formed by the acetoacetylation of hydroxypropyl cellulose using a diketene/acetone adduct at elevated temperature, forms both thermotropic and lyotropic liquid-crystalline phases. DSC and hot-stage polarized light microscopy confirmed the thermotropic nature of the bulk polymer. Thin layers showed green reflection colors at room temperature. The wavelength λ₀ of selective reflection was measured spectrophotometrically. The crystalline structure of the polymer was investigated using x-ray diffraction. A lyotropic mesophase formed in acetic acid at ≥ 40 wt% polymer. The value of λ₀ for the lyotropic cholesteric mesophase was determined by optical rotatory dispersion (ORD) and circular dichroism (CD) of a thin layer of a wholly anisotropic solution.     

Calculation of circular dichroism spectra from optical rotatory dispersion, and vice versa, as complementary tools for theoretical studies of optical activity using time-dependent density functional theory

A comparison of two theoretical methods based on time-dependent density functional theory for the calculation of the linear dispersive and absorptive properties of chiral molecules has been made. For this purpose, a recently proposed computational method for the calculation of circular dichroism (CD) spectra from the imaginary part of the optical rotation parameter has been applied to six rigid organic molecules. The results have been compared to the CD spectra obtained from the rotatory strengths and from the Kramers-Kronig transformation of optical rotatory dispersion (ORD) curves. We have also investigated a criterion based on the Kramers-Kronig integration formula to determine a number of excitations in truncated CD spectra which may yield a reasonable low frequency resonant ORD. It has been tested by calculating the ORD from the sum-over-states formula both in the nonresonant and resonant regions. Finally, we have applied these methods to model the resonant optical activity of proline at low pH.     

Optical rotatory dispersion and vacuum ultraviolet circular dichroism of poly[(R)-oxypropylene]

The circular dichroism (CD) spectrum of poly[(R)-oxypropylene] in a number of solvents has been measured in the vacuum ultraviolet region. Two CD bands were measured for cyclohexane, acetonitrile, and trifluoroethanol solutions. The CD spectrum was extended to 140 nm and three bands were measured in a 1,1,1,3,3,3-hexafluoro-2-propanol solution. The similarity of these four CD spectra in sign, shape, and intensity confirm that poly[(R)-oxypropylene] has similar conformations in all solvents studied, even though the optical rotatory dispersion (ORD) in the visible region is positive for the cyclohexane solution but negative for the alcohol solutions. A Kronig–Kramers transform of the two CD bands observed for the cyclohexane solution accounts for the observed positive ORD spectrum. In contrast, a third large and negative CD band centered below 160 nm is necessary to account for the negative ORD spectra observed for the alcohol solutions. Apparently the anomalous sign variation of the ORD curves observed in the visible region is due to subtle changes in the interplay of a large number of CD bands. Solvent interaction, observed as a blue shift of the first two CD bands for the alcohol solutions, could produce the subtle changes necessary to change the sign of the ORD curve in the visible region. The first two CD bands of poly[(R)-oxypropylene] are tentatively assigned as n? σ^* and the third as an n? 3s.     

Calculation of optical rotatory dispersion and electronic circular dichroism for tris-bidentate groups 8 and 9 metal complexes, with emphasis on exciton coupling

The optical rotatory dispersion (ORD, both non-resonant and resonant) and the electronic circular dichroism (CD) of tris-bidentate transition metal complexes of the form [M(L)(3)](n+) (M = Fe, Ru, Os, Co, Rh, Ir; n = 2, 3; L = 1,10-phenanthroline, 2,2'-bipyridine) are calculated using time-dependent density functional theory (TDDFT). The exciton CD band resulting from the coupling of ligand π-to-π* transitions is investigated in detail and analyzed in terms of exciton coupling of long-axis transitions using a dipole coupling model that takes TDDFT data for a single ligand as input. Results of the coupling model agree well with the full TDDFT CD spectra. The usefulness and reliability of this model is discussed. The resonant ORDs calculated directly from analytical damped linear TDDFT response compare well with Kramers-Kronig transformations of the calculated CD spectra. For comparisons of resonant ORD with experiment, one needs to consider wavelength shifts.     

Polarization fourier transform infrared spectroscopy

Some Fourier transform infrared spectroscopic studies with linearly and circularly polarized radiation are reported. They were all carried out by means of the differential technique, consisting in the comparison of two single-channel spectra of opposite polarization. Thus, linear dichroic or circular dichroic spectra with positive and negative bands were recorded. Typical application examples of both techniques are presented.     

Strukturanalyse organischer Verbindungen

Zusammenfassung Die Möglichkeit der Anwendung physikalischer Methoden für die Strukturanalyse organischer Verbindungen wird anhand von Beispielen besprochen. IR, NMR, MS und Raman gelten als allgemeine Methoden, die für alle organischen Verbindungen Aussagen ermöglichen, während andere Verfahren (UV, ESR, ORD, CD, Röntgendiffraktometrie an Einkristallen) nur für bestimmte Verbindungsklassen anwendbar sind. Zur Auswertung der Daten wird ein Schema zur teilautomatisierten Interpretation beschrieben.

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Summary The applicability of physical methods to the structure analysis of organic compounds is discussed and several examples are given. IR, NMR, MS and Raman are of general use for all organic compounds, whereas other methods (UV, ESR, ORD, CD, X-ray diffraction at single crystals) can be applied only to certain groups of compounds. A scheme for partly automatized interpretation is described for evaluation of the data obtained.

     

Theory of the absorption and circular dichroism spectra of helical molecular aggregates

A theory of the electronic circular dichroism (CD) and optical rotatory dispersion (ORD) of infinite aggregates exhibiting cylindrical symmetry is presented in which, to the authors' knowledge, for the first time vibrational structure is included explicitly. It is shown that, with the coherent exciton scattering approximation in the Green function approach, the detailed vibrational structure of the aggregate absorption. CD and ORD bands can be calculated from a knowledge of the electronic coupling and the monomer absorption line shape alone. Detailed model calculations for a single helix are made and the results are used to expose the origin of different spectral features. A good reproduction of experimental J-aggregate spectra is obtained, using the same electronic interaction to fit both absorption and CD spectral line shapes. The theory allows some prediction of aggregate geometry to be made, but it is shown that an unambiguous geometrical assignment can only be made where experimental spectra for light of different propagation directions with respect to the cylinder axis are available.     

Electron donor-acceptor complexes in polypeptides. 3. Optical activity of intra-and inter-molecular charge-transfer associated with absorption bands

Optical activity, i. e. circular dichroism (CD) and optical rotatory dispersion (ORD) associated with charge-transfer (CT) absorption bands were found for intra- and intermolecular electron-donor-acceptor (EDA)-complexes containing centers of configurational asymmetry.     

An ATR method for measurement of IR circular dichroic spectra

The present study is an attempt to obtain circular dichroic IR spectra using a conventional ATR attachment provided with a hemicylinder of a high enough refractive index. The measurement is carried out by means of FTIR spectrometers taking a difference spectrum from two ATR experiments. The first one is performed with linearly polarized light of a suitable azimuth while the same azimuth but of opposite sign is used for the second experiment. A theoretical treatment is presented.     

Magneto-chiral Nonlinear Optical Effect with Large Anisotropic Response in Two-Dimensional Halide Perovskite

The chiral organic–inorganic halide perovskites (OIHPs) are vital candidates for superior nonlinear optical (NLO) effects associated with circularly polarized (CP) light. NLO in chiral materials often couples with magnetic dipole (MD) transition, as well as the conventional electric dipole (ED) transition. However, the importance of MD transition in NLO process of chiral OIHPs has not yet been well recognized. Here, the circular polarized probe analysis of second harmonic generation circular dichroism (SHG-CD) provides the direct evidence that the contribution of MD leads to a large anisotropic response to CP lights in chiral OIHPs, (R-/S-MBACl)₂PbI₄. The thin films exhibit great sensitivity to CP lights over a wide wavelength range, and the g-value reaches up to 1.57 at the wavelength where the contribution of MD is maximized. Furthermore, it is also effective as CP light generator, outputting CP-SHG with maximum g-factor of 1.76 upon the stimulation of linearly polarized light. This study deepens the understanding of relation between chirality and magneto-optical effect, and such an efficient discrimination and generation of CP light signal is highly applicable for chirality-based sensor and optical communication devices.     

Synthesis and chiroptical properties of optically active polymer liquid crystals containing azobenzene chromophores

A series of optically active methacrylic homopolymers, poly[(4‐{4′‐[(S)‐2‐methyl‐1‐butyloxycarbonyl]phenylazo}phenoxyl)x‐methylene methacrylate] (x = 0, 2, 6, or 11), were synthesized. The structures of the polymers were characterized by IR, ¹H NMR, UV, differential scanning calorimetry, and gel permeation chromatography. The chiroptical properties of the polymers in films were investigated with circular dichroism (CD) measurements. The CD and UV spectra of the films suggested that CD absorptions occurred in the films of the polymers with long spacers (x = 6 or 11) but not in the films of the polymers with short spacers (x = 0 or 2). After irradiation with linearly polarized light at 442 nm, the CD values were amplified in all the polymeric films. The amplificatory values of the CD bands in the absorption region (260–360 nm) of azobenzene chromophores suggested that the spacer length had an effect on both the transfer of chirality and photoinduced chirality in the polymeric films. The largest level of photoinduced chirality was induced in the polymer containing six methylene units. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3210–3219, 2006     

Kramers-Kronig transformation for optical rotatory dispersion studies

The Kramers-Kronig (KK) transform method for deriving optical rotatory dispersion (ORD) from electronic circular dichroism (ECD) has been analyzed. Three different numerical integration methods for the KK transform have been evaluated, and the method proposed by Ohta and Ishida has been used for further calculations. Using this method, the quantum mechanical predictions of electronic circular dichroism (ECD) have been converted to corresponding ORD and compared with that derived from the linear response method. For three molecules exhibiting monosignate ORD in the nonresonant long wavelength region, the KK transform of ECD associated with the lowest energy electronic transition is found to give ORD values close to those obtained with the linear response method. For molecules exhibiting bisignate ORD in the nonresonant long wavelength region, the KK transform method may not provide the correct results. In the resonant region, the KK transform method provides a computationally economical alternative for predicting ORD. While the KK transform method works much like sum-over-states method for ORD, the former offers convenience in transforming the experimental ECD spectrum without the need for spectral curve fitting.     

Determining the absolute configuration of (+)-mefloquine HCl, the side-effect-reducing enantiomer of the antimalaria drug Lariam

Even though the important antimalaria drug rac-erythro-mefloquine HCl has been on the market as Lariam for decades, the absolute configurations of its enantiomers have not been determined conclusively. This is needed, since the (-) enantiomer is believed to cause adverse side effects in malaria treatment resulting from binding to the adenosine receptor in the human brain. Since there are conflicting assignments based on enantioselective synthesis and anomalous X-ray diffraction, we determined the absolute configuration using a combination of NMR, optical rotatory dispersion (ORD), and circular dichroism (CD) spectroscopy together with density functional theory calculations. First, structural models of erythro-mefloquine HCl compatible with NMR-derived (3)J(HH) scalar couplings, (15)N chemical shifts, rotational Overhauser effects, and residual dipolar couplings were constructed. Second, we calculated ORD and CD spectra of the structural models and compared the calculated data with the experimental values. The experimental results for (-)-erythro-mefloquine HCl matched our calculated chiroptical data for the 11R,12S model. Accordingly, we conclude that the assignment of 11R,12S to (-)-erythro-mefloquine HCl is correct.     

Modeling the solvation of peptides. The case of (s)-N-acetylproline amide in liquid water

The structure and properties of (s)-N-acetylproline amide (NAP) in aqueous solution are studied by exploiting a continuum solvation model. The conformational preference of NAP as a function of the environment is discussed as well as data for a number of chiral and non-chiral spectroscopic and response properties (IR/VCD, Raman/VROA, UV/CD, ORD, NMR), whose calculation with the accounting of solvent effects is now possible due to recent developments introduced in the PCM approach. When available, calculated results are compared with experimental data, so as to evaluate the quality of the continuum approach to the solvation of this system.     

A single chiroptical spectroscopic method may not be able to establish the absolute configurations of diastereomers: dimethylesters of hibiscus and garcinia acids

Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), and vibrational circular dichroism (VCD) spectra of hibiscus acid dimethyl ester have been measured and analyzed in combination with quantum chemical calculations of corresponding spectra. These results, along with those reported previously for garcinia acid dimethyl ester, reveal that none of these three (ECD, ORD, or VCD) spectroscopic methods, in isolation, can unequivocally establish the absolute configurations of diastereomers. This deficiency is eliminated when a combined spectral analysis of either ECD and VCD or ORD and VCD methods is used. It is also found that the ambiguities in the assignment of absolute configurations of diastereomers may also be overcome when unpolarized vibrational absorption is included in the spectral analysis.     

Quantitative analysis of polymers by attenuated total reflectance fourier-transform infrared spectroscopy: Vinyl acetate and methyl content of polyethylenes

A comparison was made between the transmission and attenuated total reflectance (ATR) infrared spectroscopic techniques for the determination of the vinyl acetate content of poly(ethylene–vinyl acetate) copolymers and methyl content of polyethylene. It was demonstrated that the transmission and ATR calibration curves for ratios of absorbances of bands with maxima at very similar wavelength were coincident, while those for ratios of absorbances of bands with maxima at significantly dissimilar wavelength were shifted apart. The explanation of this behavior is based on the wavelength dependence of the interaction of the IR radiation in ATR, compared to the wavelength independence of the interaction in transmission IR. The effect of polarized radiation was investigated in each type of analysis with the ATR technique. It was found that essentially the same results were obtained with the IR radiation polarized at 0° or 90°, relative to the plane of incidence, as compared to spectra obtained with unpolarized radiation. However, larger scatter was observed with polarized radiation. The effect of clamping pressure was also investigated. It was found that a minimum clamping torque of 5 in. lb is necessary to assure good physical contact in ATR work.     

Time dependent density functional theory modeling of specific rotation and optical rotatory dispersion of the aromatic amino acids in solution

Time Dependent Density Functional Theory (TDDFT) along with the COnductor-like Screening MOdel (COSMO) has been applied to model the specific rotation at 589.3 nm and the optical rotatory dispersion (ORD) of the aromatic amino acids phenylalanine, tyrosine, histidine, and tryptophan. Solution structures at low, neutral, and high pH were determined. Both the anomalous dispersion absorbing (resonance) region and the lower energy (transparent) region of the ORD of the compounds were modeled. Linear response calculation of the specific rotation and ORD as well as Kramers-Kronig transformations of calculated circular dichroism spectra to model resonant ORD were compared with experimental data from the literature.     

圆偏振发光高分子的研究

综合评述了近年来有关圆偏振发光高分子的研究，包括圆偏振发光高分子的潜在应用及其在发光高分子理论研究上的意义，圆偏振发光高分子的类型与性能表征等。并提出了三条获得高度圆偏振发光高分子的可能途径。