SCARABAEID BEETLE EXOCUTICLE AS AN OPTICAL ANALOGUE OF CHOLESTERIC LIQUID CRYSTALS

1. A review is given of the optical and architectural analogies between cholesteric liquid crystals and certain insect cuticles (Coleoptera: Scarabaeidae). Earlier observations on the optical properties (reflexion of circularly polarized light and high form optical rotation) are confirmed and extended. Both cholesteric liquid crystals and lamellate cuticle have helicoidal structure (Fig. i). Even though their chemistry and physical states are very different, we are justified in making the analogy, since their optical properties depend primarily on the pitch of their helicoidal architecture. 2. The unusual optical properties were located for the first time in the outer 5 to 20 μ of the exocuticle. This layer is transparent and has regular spacings in the range required for interference colours according to Bragg's law. Among Scarabaeid beetles which show interference colours, we distinguish two types of outer exocuticle. (i) Optically active cuticles which reflect circularly polarized interference colours; show high angles of form optical rotation in transmitted light; and anomalous form birefringence perpendicular to the cuticle surface (reversible by deproteinization). (2) Optically inactive cuticles which show none of the above properties and in which the form birefringence is parallel to the cuticle surface. In the electron microscope the ultrastructure of these two types of outer exocuticle is clearly different. 3. All of the optically active species reflect left hand circularly polarized light, irrespective of the wavelength of the reflected colour. They therefore appear dark when viewed through a right hand circular analyser. The sense of reflected circularly polarized light does not reverse at higher wavelengths as recorded by previous workers. (A simple treatment is given for combinations of various wavelengths with retardation plates of varying values, as used in circular analysers.) We confirm earlier reports that the sense of reflected circularly polarized light is of the opposite sense to the transmitted light. 4. Using monochromatic light we have measured the anomalous dispersion with wavelength of the magnitude of optical rotation for various optically active cuticles. The dispersion curves change from negative values at lower wavelengths to positive values at higher wavelengths, and cross the zero optical rotation axis at a wavelength (AQ) corresponding to the interference colour of each sample. There is reasonable agreement between A₀ and the interference colour calculated from ultrastructural evidence and by comparison with interference filters of known wavelength. A dispersion curve measured for a combined sample of two cuticles with different dispersion curves showed that the resultant is an algebraic summation of the two component curves. 5. We present the first experimental verification of existing mathematical treatments of anomalous form optical rotatory dispersion curves. Although these treatments were derived for cholesteric liquid crystals, they give a reasonable fit to our measured curves for cuticle. We have confirmed from our cuticle dispersion curves that a second zero value for optical rotation occurs at a wavelength higher than A₀, as predicted by the theory of Chandrasekhar and Rao (1968). This has not yet been observed in any cholesteric liquid crystal system. 6. Our evidence shows that in optically active cuticle, interference colour is determined by helicoid pitch. In Lomaptera interference coloration follows the bilateral symmetry of the insect. Hence helicoidal pitch is controlled in a bilaterally symmetrical manner. However, the sense of helicoid rotation is the same all over the beetle and is therefore bilaterally asymmetrical. This supports the view that helicoid pitch is under the local control of the epidermal cells which secrete the cuticle, whereas its sense of rotation may be determined by an extracellular self-assembly process. In view of the self-assembling properties of cholesteric liquid crystals, it is tempting to suggest that helicoidal cuticle could be formed by the stabilization of a liquid crystal. 7. We discuss in detail the differences between optically active and inactive cuticles. The constructive interference colours arising from both types are then briefly compared with other multiple layer reflecting systems in other animals. 8. A detailed comparison is made between the optics of cuticle and cholesteric liquid crystals. The optical analogy provides a two-way contact between cuticle biophysicists and liquid crystal physical chemists.     

铜绿丽金龟对圆偏振光的行为和视网膜电位反应

圆偏振光在地球环境中是很少见的, 来自珠宝金龟甲体壁反射圆偏振光是稀有的自然资源之一。铜绿丽金龟Anomala corpulenta Motschulsky与其他珠宝金龟甲一样其体壁能够反射左旋圆偏振光。为了解铜绿丽金龟对圆偏振光的感知能力, 本研究利用室内行为、 田间诱集与视网膜电位(electroretinogram, ERG)等方法研究了铜绿丽金龟对圆偏振光的响应。室内行为研究结果表明, 铜绿丽金龟对左旋圆偏振光与右旋圆偏振光的趋光反应明显低于非偏振光, 避光反应明显大于非偏振光, 且对左旋圆偏振光的趋、 避光反应均大于右旋圆偏振光。田间选择试验结果显示, 铜绿丽金龟对左旋和右旋圆偏振光的选择明显低于非偏振光, 且右旋大于左旋圆偏振光。电生理学研究结果表明, 左旋和右旋圆偏振光与非偏振光一样, 均能引发铜绿丽金龟的ERG反应, 且无明显差异。这些研究结果表明铜绿丽金龟体壁能够反射产生左旋圆偏振光, 且能够感知和区分左旋和右旋圆偏振光, 说明铜绿丽金龟存在偏振视觉, 具有圆偏振光敏感性。     

Circular Polarization of Transmitted Light by Sapphirinidae Copepods

Circularly polarized light, rare in the animal kingdom, has thus far been documented in only a handful of animals. Using a rotating circular polarization (CP) analyzer we detected CP in linearly polarized light transmitted through epipelagic free living Sapphirina metallina copepods. Both left and right handedness of CP was detected, generated from specific organs of the animal''s body, especially on the dorsal cephalosome and prosome. Such CP transmittance may be generated by phase retardance either in the muscle fibers or in the multilayer membrane structure found underneath the cuticle. Although the role, if any, played by circularly polarized light in Sapphirinidae has yet to be clarified, in other animals it was suggested to take part in mate choice, species recognition, and other forms of communication.

Highlights

Planktonic Sapphirinidae copepods were found to circularly polarize the light passing through them. Circular polarization may be created by unique, multilayered features of the membrane structure found under their cuticle or by organized muscle fibers.     

昆虫对偏振光的响应及感受机理研究进展

偏振光是不同于普通光源的一种光, 常指光矢量在某一个方向振动的光波, 可分为线性偏振光、 圆偏振光和椭圆偏振光等。目前已经发现自然界的偏振光影响许多昆虫的行为, 如西方蜜蜂Apis mellifera的飞行导航、 蛱蝶Heliconius cydno chioneus的觅偶、 凤蝶Papilio aegeus产卵场所的选择等。金龟子对圆偏振光的反射可以作为一种分类的性状。昆虫复眼背部边缘区域（dorsal rim area, DRA）小眼是感受偏振光的主要器官, 电生理学研究表明前视神经节是蝗虫偏振视觉通路的一部分。在匈牙利, 已经开始利用偏振光研制步甲等昆虫的诱捕器。     

Dendritic crystal growth, differential circular scattering, and the origin of biomolecular homochirality

Phthalic acid rapidly crystallizing in thin aqueous films is deposited radially and rhythmically as dendritic banded spherulites that have heterochiral meso-textures in hemi-circles. The chiral fields differentially scatter left and right circularly polarized light. A scenario for chiral amplification and the origin of biomolecular homochirality is thus proposed that combines the influences of crystals and light.     

Astronomical Sources of Circularly Polarized Light and the Origin of Homochirality

Possible astronomical sources of ultraviolet circularly polarized light(UVCPL) which might be responsible for enantiomeric selection in interstellarorganic molecules are considered, Synchrotron radiation from magnetic neutronstars has been suggested as a possible source of UVCPL. However, synchrotronradiation in these situations is not predicted to be strongly circularlypolarized. Very few such sources show optical synchrotron radiation and in thefew that do circular polarization has not been observed. Magnetic white dwarfsand white dwarf binaries (Polars) can be highly circularly polarized but anyeffect on molecular clouds and star formation regions must rely on rare chance encounters. Recent observations show that substantial levels of circularpolarization are present in reflection nebulae in star formation regions. Thismechanism produces polarized light exactly when and where it is needed inregions where star formation is occurring and organic molecules are known to be present.     

A search for circular dichroism in the VUV photofragmentation mass spectra of 2-amino-1-butanol

The dissociative photoionization of a single-enantiomer chiral molecule by circularly polarized synchrotron radiation was investigated, for the first time, in the gas phase. Photoion mass spectra were produced by the interaction of (+)-(S)-, (-)-(R)- and rac-2-amino-l-butanol with circularly polarized light. Comparison of these spectra places an upper bound of approximately 2% on circular dichroism in the dissociative photoionization of 2-amino-l-butanol at 21 eV, which may have consequences for the theory that the origin of biological homochirality was predominantly enantioselective photofragmentation by circularly polarized light. We have also identified and elucidated many of the difficulties of performing gas phase CD measurements in crossed beam experiments.     

Differential light-scattering of granal and agranal chloroplasts and their fragments.

Intact (class-A) granal and agranal maize chloroplasts and chloroplast fragments were examined for differential scattering of circularly polarized light (measured at 90 degrees) and c.d. (circular dichroism) (measured at 0 degrees) by using a modified spectropolarimeter with a large acceptance angle. Useful c.d. information was obtained by making corrections for scattered light. Chloroplast fragments exhibited a large and characteristic differential scattering of circularly polarized light recognized in the presence of granal chloroplasts. It is confirmed that agranal chloroplasts do not have the intense 682 nm c.d. peak that is assigned to the presence of grana.     

Circular polarization vision in a stomatopod crustacean

We describe the addition of a fourth visual modality in the animal kingdom, the perception of circular polarized light. Animals are sensitive to various characteristics of light, such as intensity, color, and linear polarization [1, 2]. This latter capability can be used for object identification, contrast enhancement, navigation, and communication through polarizing reflections [2-4]. Circularly polarized reflections from a few animal species have also been known for some time [5, 6]. Although optically interesting [7, 8], their signal function or use (if any) was obscure because no visual system was known to detect circularly polarized light. Here, in stomatopod crustaceans, we describe for the first time a visual system capable of detecting and analyzing circularly polarized light. Four lines of evidence-behavior, electrophysiology, optical anatomy, and details of signal design-are presented to describe this new visual function. We suggest that this remarkable ability mediates sexual signaling and mate choice, although other potential functions of circular polarization vision, such as enhanced contrast in turbid environments, are also possible [7, 8]. The ability to differentiate the handedness of circularly polarized light, a visual feat never expected in the animal kingdom, is demonstrated behaviorally here for the first time.     

Investigation of locust cuticle using the insecticide diflubenzuron.

Diflubenzuron inhibits the synthesis of chitin (Verloop, in prep.). Some of the resulting possibilities for the investigation of cuticle are explored in this paper. The cuticle of locusts treated with DFB is prone to fracture in characteristic ways. This is of relevance in studying the function of the exoskeleton. Cuticle affected by DFB was examined by polarised light microscopy. Three contrasting regions were used; the prealar arm, the proximal end of the hind tibia and the mandibles. The action of a protease on these regions was studied. The residual chitin content was estimated by analysing hydrolysates of cuticle samples for glucosamine.The results show that chitin is removed to a sufficient extent for the structural coherence and optical properties of the cuticle to be dependent on the proteins. Only in some regions is a stable layer of cuticle formed after treatment with DFB. In these regions, new information about the proteins of cuticle can be obtained. Of particular significance is the observation of a protein helicoid in part of the tibia.     

Complex Polarization Response in Plasmonic Nanospirals

Archimedean nanospirals exhibit many far-field resonances that result from the lack of symmetry and strong intra-spiral plasmonic interactions. Here, we present a computational study, with corroborating experimental results, on the plasmonic response of the 4π Archimedean spiral as a function of incident polarization, for spirals in which the largest linear dimension is less than 550 nm. We discuss the modulation of the near-field structure for linearly and circularly polarized light in typical nanospiral configurations. Computational studies of the near-field distributions excited by circularly polarized light illustrate the effects of chirality on plasmonic mechanisms, while rotation of linearly polarized light provides a detailed view of the effects of broken symmetry on nanospiral fields in any given direction in the plane of the spiral. The rotational geometry exhibits a preference for circular polarization that increases near-field enhancement compared to excitation with linearly polarized light and exchanges near-field configurations and resonant modes. By analyzing the effects of polarization and wavelength on the near-field configurations, we also show how the nanospiral could be deployed in applications such as tunable near-field enhancement of nonlinear optical signals from chiral molecules.     

A simple method for correction of circular dichroism spectra obtained from membrane-containing samples

Circular dichroism (CD) spectroscopy is an important technique in structural biology for examining folding and conformational changes of proteins in solution. However, the use of CD spectroscopy in a membrane medium (and also in a nonhomogeneous medium) is limited by (i) high light scattering and (ii) differential scattering of incident left and right circularly polarized light, especially at shorter wavelengths (<200 nm). We report a novel methodology for estimating the distortion of CD spectra caused by light scattering for membrane-bound peptides and proteins. The method is applied to three proteins with very different secondary structures to illustrate the limits of its capabilities when calibrated with a simple soluble peptide ([Ac]ANLKALEAQKQKEQRQAAEELANAK[OH], standard peptide) with a balanced secondary structure. The method with this calibration standard was quite successful in estimating α-helix but more limited when it comes to proteins with very high β-sheet or β-turn content.     

Homochirality of Biomolecules: Counter-Arguments Against Critical Notes

Three recently published critical papersby Bonner and coworkers on the extraterrestrial origin of thehomochirality of biomolecules and the amplification of tinyenantiomeric excess are discussed. The presented arguments showthe difficulties involved in circularly polarized u.v. andvisible synchrotron radiation from neutron stars, in their ratioto non circularly polarized light and in racemization of theproducts. Attention is called upon another mechanism forproduction of extraterrestrial handedness based on Salam'scondensation theory and on the recent experimental demonstrationof the enantioselective magnetochiral photochemistry. Arguments,as well as experiments, point out that tiny enantiomeric excessesmight be amplified via the Yamagata accumulation principlequestioned by Bonner.     

Patterns and properties of polarized light in air and water

Natural sources of light are at best weakly polarized, but polarization of light is common in natural scenes in the atmosphere, on the surface of the Earth, and underwater. We review the current state of knowledge concerning how polarization and polarization patterns are formed in nature, emphasizing linearly polarized light. Scattering of sunlight or moonlight in the sky often forms a strongly polarized, stable and predictable pattern used by many animals for orientation and navigation throughout the day, at twilight, and on moonlit nights. By contrast, polarization of light in water, while visible in most directions of view, is generally much weaker. In air, the surfaces of natural objects often reflect partially polarized light, but such reflections are rarer underwater, and multiple-path scattering degrades such polarization within metres. Because polarization in both air and water is produced by scattering, visibility through such media can be enhanced using straightforward polarization-based methods of image recovery, and some living visual systems may use similar methods to improve vision in haze or underwater. Although circularly polarized light is rare in nature, it is produced by the surfaces of some animals, where it may be used in specialized systems of communication.     

Circularly polarized light at the mirror: Caveats and opportunities

Moving from the simple concept that reflection onto a mirror surface changes the handedness of circularly polarized light, we describe what happens to the emergent polarization in two different cases after reflection on a back mirror. In the first case, a regular emitter is taken into account, where reflection has the effect to destroy the emergent polarization. In the second case, we show what could happen when a hypothetical apparently non-reciprocal emitting material undergoes a similar experiment. These simple concepts have important implications in the design of efficient circularly polarized emitting devices.     

The physical mechanism of cuticular color in Phelotrupes auratus (Coleoptera,Geotrupidae)

The physical mechanism of cuticular color in Phelotrupes auratus was investigated by polarized inspection, spectrophotometry and transmission electron microscopy (TEM). No color change was observed when viewed through either a right‐ or left‐handed circular polarizer. Further, under the incidence of linearly polarized light, the reflected intensity was markedly reduced when observed through a linear polarizer set with its optical axis perpendicular to that of the incident light. These results indicate that P. auratus does not possess any circularly polarizing reflectors. TEM observations revealed a total of ten or twelve thin layers (about 60–120 nm in thickness) of two types of material (electron‐dense and electron‐lucent) alternately stacked in the epicuticle. The thickness of the layers in the different color forms of the beetle corresponded to the peak wavelengths in the reflectance spectra, λmax(α), with thicker layers found in beetles exhibiting reflectance peaks at longer wavelengths and vice versa. Based on these findings, we concluded that all the cuticular color forms of P. auratus were not produced by a circularly polarizing reflector but by a simple multilayer reflector.     

Rapid identification of microorganisms by circular-intensity differential scattering.

There is a pressing need in clinical medicine for rapid identification of microorganisms. We describe a method that has the potential for such rapid identification: circular-intensity differential scattering, which is based on the differential scattering of left and right circularly polarized light. The scanning time required to obtain the spectral signature of an organism is about 4 min. Using a commercial circular dichrograph modified to measure circular intensity differential scattering at 90 degrees, we obtained significantly different spectra for five different crude influenza viruses. Salmonella typhimurium TA98 and TA100, and Escherichia coli HB101, HB101(pBR322), and HB101(pMB9). Purified supercoiled plasmid pBR322 DNA was readily distinguishable from linear pBR322 DNA; such differences in nucleic acid packaging may be significant factors in the discriminatory power of this technique.     

Rapid identification of microorganisms by circular-intensity differential scattering

There is a pressing need in clinical medicine for rapid identification of microorganisms. We describe a method that has the potential for such rapid identification: circular-intensity differential scattering, which is based on the differential scattering of left and right circularly polarized light. The scanning time required to obtain the spectral signature of an organism is about 4 min. Using a commercial circular dichrograph modified to measure circular intensity differential scattering at 90 degrees, we obtained significantly different spectra for five different crude influenza viruses. Salmonella typhimurium TA98 and TA100, and Escherichia coli HB101, HB101(pBR322), and HB101(pMB9). Purified supercoiled plasmid pBR322 DNA was readily distinguishable from linear pBR322 DNA; such differences in nucleic acid packaging may be significant factors in the discriminatory power of this technique.     

Angular optimization for cancer identification with circularly polarized light

Depolarization of circularly polarized light scattered from biological tissues depends on structural changes in cell nuclei, which can provide valuable information for differentiating cancer tissues concealed in healthy tissues. In this study, we experimentally verified the possibility of cancer identification using scattering of circularly polarized light. We investigated the polarization of light scattered from a sliced biological tissue with various optical configurations. A significant difference between circular polarizations of light scattered from cancerous and healthy tissues is observed, which is sufficient to distinguish a cancerous region. The line-scanning experiments along a region incorporating healthy and cancerous parts indicate step-like behaviors in the degree of circular polarization corresponding to the state of tissues, whether cancerous or normal. An oblique and perpendicular incidence induces different resolutions for identifying cancerous tissues, which indicates that the optical arrangement can be selected according to the priority of resolution.     

Photo-ionization spectroscopy and mass spectrometry of some molecular and supramolecular asymmetric systems in the isolated state

Asymmetric molecular and supramolecular systems are characterized by: i. the circular dicroism in the angular distribution of valence photoelectrons emitted from randomly oriented chiral molecules by their interaction with circularly polarized VUV light; ii. the different stability and reactivity of diastereomeric aggregates. Both these aspects may have some relationship with the "chiral enrichment mechanism" of chirogenesis, based on the preferential destruction of one enantiomer of a racemate by interaction with a chiral agent, whether a massive species or a circularly polarized photon. The most recent spectroscopic and mass spectrometric studies on this topic are reported in the present mini-review.