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Natural pyrethrins are one of the most used pesticides and insect repellents employed for domestic or agronomic use. However, they are highly hydrophobic and suffer from insolubility in water media and ready decomposition by photochemical, and oxidative actions. These aspects hamper their long-term storage and applicability. Herein, we report the synthesis and characterization of a nanomaterial based on the loading of pyrethrum extract (PE) into natural, low-cost, and eco-compatible halloysite nanotubes (Hal). The Hal/PE nanomaterial was thoroughly characterized, and the morphology was imaged by TEM and SEM investigations. Release experiments showed a slow release of pyrethrins from the carrier, and photodegradation studies, both in solution and in a solid state, highlighted that the pyrethrum extract in the Hal/PE nanomaterial showed high stability to UV irradiation, as proved by UPLC-ESI-MS, UV–vis, and circular dichroism measurements. Furthermore, to check if the obtained nanomaterial possesses the insecticidal activity of the pyrethrum, in vivo tests on two model insects, Galleria. mellonella and Tenebrio molitor, were performed. The pyrethrins loaded onto Hal showed the same activity as standard pyrethrins, at half dose compared to them.

CHIME, the Copernicus Hyperspectral Imaging Mission for the Environment, is one of the six High Priority Candidate Missions (HPCM) of the evolution in the Copernicus Space Component (CSC) foreseen in the mid-2020s that is proposed for further analysis. In this paper we summarize the results as retrieved by OHB (D) as part of the Phase A/B1. The contract was kicked off in 2018 and concluded in 2020 after finalisation of the Pre-development activities. The proposed instrument is a hyperspectral imager instrument with reflective telescope and grating-based spectrometer. The selected orbit is in the range of 625 ± 30 km, LTDN 10:45 – 11:15 am with a repeat cycle of 20 to 25 days for a single satellite and 10-12.5 days revisit for 2 satellites. The payload of each satellite records at a Spatial Sampling Distance (SSD) of 30m the full spectral range from 400 to 2500nm at a Spectral Sampling interval < 10nm with Low Keystone/Smile. On the front end a high performance TMA with wide-band coated optics collects the light from ground and feeds it to a highly linear almost distortion free spectrometer assembly attaining very good spectral stability. All units are integrated in an optical bench structure that offers excellent AIT access and provides a highly stable LOS. The electro-optical backend contains low-noise cold MCT detectors creating margin in the predicted NEDL performance. The instrument can be calibrated via on-board devices or using reference targets outside the spacecraft. We present the functional decomposition and the physical instrument architecture: the optical design and opto-mechanical layout, the electro-optical imaging chain ant thermal control system.

Due to be launched in late 2021, the Imaging X-Ray Polarimetry Explorer (IXPE) is a NASA Small Explorer mission designed to perform polarization measurements in the 2-8 keV band, complemented with imaging, spectroscopy and timing capabilities. At the heart of the focal plane is a set of three polarization-sensitive Gas Pixel Detectors (GPD), each based on a custom ASIC acting as a charge-collecting anode. In this paper we shall review the design, manufacturing, and test of the IXPE focal-plane detectors, with particular emphasis on the connection between the science drivers, the performance metrics and the operational aspects. We shall present a thorough characterization of the GPDs in terms of effective noise, trigger efficiency, dead time, uniformity of response, and spectral and polarimetric performance. In addition, we shall discuss in detail a number of instrumental effects that are relevant for high-level science analysis -- particularly as far as the response to unpolarized radiation and the stability in time are concerned., Comment: To be published in Astroparticle Physics

The cooperative effect of solvophobic interactions and hydrogen bonding has been exploited to self-assemble supramolecular helical architectures of 8-oxoguanosines in different environments. This self-assembly into helical structures is completely different from that of the parent guanosines which, in the same experimental conditions, form flat, ribbonlike structures. While optical microscopy and X-ray diffraction suggest a chiral columnar aggregate in the LC phase, NMR and Circular Dichroism reveal the presence of a helical structures in solution. Scanning Tunneling Microscopy made it possible to visualize hexagonally arranged G-quartets on graphite, which are sections of the helices packed with their long axis perpendicular to the basal plane of the substrate. Due to their rectifying electrical properties, such helices are interesting for fabricating (opto)electronic biodevices.

G-quadruplex DNA (G4-DNA) structures are four-stranded helical DNA (or RNA) structures, comprising stacks of G-tetrads, which are the outcome of planar association of four guanines in a cyclic Hoogsteen hydrogen-bonding arrangement. In the last decade the number of publications where CD spectroscopy has been used to study G4-DNAs, is extremely high. However, with very few exceptions, these investigations use an empirical interpretation of CD spectra. In this interpretation two basic types of CD spectra have been associated to a single specific difference in the features of the strand folding, i.e. the relative orientation of the strands, "parallel" (all strands have the same 5′ to 3′ orientation) or "antiparallel". Different examples taken from the literature where the empirical interpretation is not followed or is meaningless are presented and discussed. Furthermore, the case of quadruplexes formed by monomeric guanosine derivatives, where there is no strand connecting the adjacent quartets and the definition parallel/antiparallel strands cannot apply, will be discussed. The different spectral features observed for different G-quadruplexes is rationalised in terms of chromophores responsible for the electronic transitions. A simplified exciton coupling approach or more refined QM calculations allow to interpret the different CD features in terms of different stacking orientation (head-to-tail, head-to-head, tail-to-tail) between adjacent G-quartets irrespectively of the relative orientation of the stands (parallel/antiparallel). © 2010 The Royal Society of Chemistry.

Molecular systems containing two or more azobenzene units are of interest for at least two reasons: (i) because of their multiphotochromic nature, such compounds can exist in a wealth of different states (up to 2n, where n is the number of photochromic units), a behaviour that may be useful for molecular-level information processing and storage; (ii) the cooperation of the different photoisomerizable units can produce an overall amplification of the geometrical changes related to the (E)-(Z) transformation, leading to new light-induced functions. In this work we have investigated the photophysical, photochemical and electrochemical properties of two bis(azo) derivatives, (E,E)-m-1 and (E,E)-p-1. The two compounds, that can be viewed as constituted of a pair of azobenzene units sharing one of their phenyl rings, differ only for the relative position of the two azo groups on the central phenyl ring – meta and para for m-1 and p-1, respectively. The UV-visible absorption spectra and photoisomerization properties are noticeably different for the two structural isomers; (E,E)-m-1 behaves similarly to (E)-azobenzene, while (E,E)-p-1 exhibits a substantial red shift in the absorption bands and a decreased photoreactivity. The three geometric isomers of m-1 – namely (E,E), (E,Z) and (Z,Z) – cannot be resolved in a mixture by absorption spectroscopy, while the presence of three distinct species can be revealed by analysis of the absorption changes observed upon photoisomerization of (E,E)-p-1. Quantum-chemical ZINDO/1 calculations of vertical excitation energies reproduce nicely the observed absorption changes and support the idea that, while the absorption spectra of the geometrical isomers of m-1 are approximately given by the sum of the spectra of the constituting azobenzene units in their relevant isomeric form, this is not the case for p-1. From a detailed study on the (E)→ (Z) photoisomerization reaction it was observed that the photoreactivity of an azo unit in m-1 is influenced by the isomeric state of the other one. Such observations indicate a different degree of electronic coupling and communication between the two azo units in m-1 and p-1, as confirmed by electrochemical experiments and quantum-chemical calculations. The decreased photoisomerization efficiency of (E,E)-p-1 compared to (E,E)-m-1 is rationalized by modelling the geometry relaxation of the lowest ππ* state at CIS/3-21G level of theory. These results are expected to be important for the design of novel oligomers and polymers, based on the azobenzene unit, having predetermined photoreactivity.

A radical-armed guanosine derivative shows drastic magnetic changes by addition (removal) of alkali metal cations corresponding to the reversible assembly (disassembly). In the presence of templating metal ions, the assembly is formed by 8 molecules and 16 open-shell moieties confined in a sphere with a diameter of ca. 30 A.

[reaction: see text] The tunable interconversion between two highly ordered supramolecular motifs (G-quartet K(+)-templated column and G-ribbon) of a lipophilic guanosine derivative fueled by cation complexation and release in a cryptand [2.2.2] containing guanosine solution is reported. The process is controlled by the sequential addition of acid and base.

[reaction: see text] Photoswitchable enantiopure sulfinyl azo compounds have been synthesized. A remarkable perturbation of the azo system by the stereogenic sulfinyl moiety has been observed by CD in both the trans and the cis azobenzenes resulting by photoisomerization. After five irradiation cycles, the configurational integrity of these chiral switches remains unchanged.

Axially chiral alleno-acetylenes, modified with lateral aryl groups via short and convenient synthetic pathways, are presented as efficient chiral dopants for producing cholesteric liquid crystals.

Lipophilic guanilic derivatives (lipoGs) dissolved in organic solvents can undergo different self-assembly pathways based on different H-bonded motifs, e.g., the cyclic discrete G-quartet, which forms in the presence of alkali-metal ions, and the "infinite" tape-like G-ribbon observed in the absence of ions. Using in-solution small-angle X-ray scattering, we analyzed a series of lipoGs dissolved in cyclohexane in the presence of different salts. The formation of G-quartet based supramolecular aggregates has been confirmed, evidencing the coexistence equilibrium of octamers and noncovalent molecular nanowires (the so-called G-quadruplexes). By global fitting the scattering data, the concentration of the two kinds of particles as well as the nanowire length have been derived as a function of temperature for the different compounds and salts. The thermodynamic parameters show that the self-assembly aggregation process is enthalpy driven, while the observed enthalpy-entropy compensation suggests that similar stacking interactions control the self-assembly of the different compounds. However, the strength of the stacking interactions, and then the nanowire stability, depends on the nature of templating cations and on their capacity to fill the central cavity of quadruplexes, with the order Sr(+) < Na(+) ≲ K(+).

In 1910 Ivar Bang reported that concentrated solutions of guanylic acid formed a gel. It took half a century before Gellert et al. in 1962 discovered the structural motif, a guanine-quartet, to be the basis for guanylic acid gelation. This chapter starts with a historical overview and gives credit to Ivar Bang and several other pioneers in the field. Then the basic principles of guanine self-assembly are explored, either for individual molecules like guanosine and its derivatives, or for guanine-rich oligonucleotides and G-rich DNA-sequences. Finally, we show how these guanine-based nanoarchitectures are visualised by surface techniques like scanning tunnelling microscopy or atomic force microscopy

This chapter is organized in two main parts. In the first part the supramolecular architectures originated by LGs, both in the absence and in the presence of metal cations, will be described. The second part will deal with the use of these structures for obtaining functional materials or devices.Among nucleobases, guanine (G) (Fig. 4.1) is the most interesting and versatile one, as the presence of different donor (N1H and N2H)and acceptor sites (O6, N3 and N7) located in a self-complementary arrangement coupled with a polarized aromatic surface makes it a unit able to easily self-assemble by both multiple hydrogen bonding and π-π stacking.

A new class of enantiopure ortho,ortho-disubstituted azobenzene photoswitches has been synthesized from (S)-2-(p-tolylsulfinyl)benzoquinone and arylhydrazines. The sulfoxide acts as a unidirectional controller of the helical chirality that arises in the Z isomer after photoisomerization. Highly congested E-azobenzenes 5 c showed two atropisomeric diastereoconformers in the solid state that converged upon irradiation into a unique Z isomer with defined helicity (M), as evident in the X-ray structure. The chiroptical properties of this three-state enantiopure switch can be externally tuned both photochemically and/or thermally. Theoretical CD spectra calculated by using time-dependent DFT methods support the existence of two atropoisomeric E isomers and only one Z isomer with (M) helicity. Complementary to the classical azobenzene-based switches, the photoswiching event is promoted under green/blue light and do not occur under UV irradiation.

Two different lipophilic guanosine derivatives (LipoGs) have been used for the disaggregation of single walled carbon nanotubes (SWCNTs) in chloroform. UV–vis–NIR spectrophotometry, Raman spectroscopy and NIR-photoluminescence measurements as well as AFM and SEM highlight a well debundling of SWCNTs while fluorescence measurements show the adsorption of LipoGs onto SWCNT surface. The ability of LipoGs to disperse SWCNTs has been demonstrated to depend on their tendency to self-assemble into ribbon-like supramolecular structures. In turn, the super-organization of these supramolecular structures appears to control the homogeneity of the dispersion.

By means of the (1)H chemical shifts and the proton-proton proximities as identified in (1)H double-quantum (DQ) combined rotation and multiple-pulse spectroscopy (CRAMPS) solid-state NMR correlation spectra, ribbon-like and quartet-like self-assembly can be identified for guanosine derivatives without isotopic labeling for which it was not possible to obtain single crystals suitable for diffraction. Specifically, characteristic spectral fingerprints are observed for dG(C10)(2) and dG(C3)(2) derivatives, for which quartet-like and ribbon-like self-assembly has been unambiguously identified by (15)N refocused INADEQUATE spectra in a previous study of (15)N-labeled derivatives (Pham, T. N.; et al. J. Am. Chem. Soc.2005, 127, 16018). The NH (1)H chemical shift is observed to be higher (13-15 ppm) for ribbon-like self-assembly as compared to 10-11 ppm for a quartet-like arrangement, corresponding to a change from NH···N to NH···O intermolecular hydrogen bonding. The order of the two NH(2)(1)H chemical shifts is also inverted, with the NH(2) proton closest in space to the NH proton having a higher or lower (1)H chemical shift than that of the other NH(2) proton for ribbon-like as opposed to quartet-like self-assembly. For the dG(C3)(2) derivative for which a single-crystal diffraction structure is available, the distinct resonances and DQ peaks are assigned by means of gauge-including projector-augmented wave (GIPAW) chemical shift calculations. In addition, (14)N-(1)H correlation spectra obtained at 850 MHz under fast (60 kHz) magic-angle spinning (MAS) confirm the assignment of the NH and NH(2) chemical shifts for the dG(C3)(2) derivative and allow longer range through-space N···H proximities to be identified, notably to the N7 nitrogens on the opposite hydrogen-bonding face.

When a chiral dopant is dissolved in an achiral liquid crystal medium, the whole sample organizes into a helical structure with a characteristic length-scale of the order of microns. The relation between chirality at these quite different length-scales can be rationalized by a relatively simple model, which retains the relevant factors coming into play: the molecular shape of the chiral dopant, which controls the chirality of short range intermolecular interactions, and the elastic properties of the nematic environment, which control the restoring torques opposing distortion of the director. In this tutorial review the relation between molecular and phase chirality will be reviewed and several applications of the chiral doping of nematic LCs will be discussed. These range from the exploitation of the amplified molecular chirality for stereochemical purposes (e.g., the determination of the absolute configuration or the enantiomeric excess), to newer applications in physico–chemical fields. The latter take advantage of the periodicity of the chiral field, with length-scales ranging from hundreds to thousands of nanometres, which characterise the cholesteric phase.

Depending on the experimental conditions, lipophilic guanosines (LipoG’s) can undergo different self-assembly pathways based on different H-bonded motifs, e.g. the cyclic discrete G-quartet and the “infinite” tape-like G-ribbon. The switching between different supramolecular motifs have been obtained by a variety of external stimuli. In this article we will discuss after a general presentation of the LipoG self-assembly, the case of three different stimuli. A first example is represented by chemical stimuli: addition of an alkali metal ion stabilizes the Gquartet while its removal shifts the equilibrium toward the G-ribbon. A second type of stimuli is represented by light: the photocontrolled self-assembly of a modified guanosine nucleobase with a photoactive unit at C8 is obtained selecting the appropriate wavelength. Finally, a lipoG armed with a terthiophene unit undergoes a pronounced variation of its supramolecular organisation by changing the polarity of the solvent: in chloroform the derivative assembles via H-bonding in a Guanosine directed structure, while in the more polar (and H-bond competing) acetonitrile different aggregates are observed, where the terthiophene chains are π-π stacked in a helicoidal arrangement.

The conversion into 6,7-dihydro-5H-dibenz[c,e]azepine (DAZ) N-protected amides is a viable route for the determination of the absolute configuration of chiral 2-substituted carboxylic acids. The biphenyl moiety of DAZ, besides being a probe of chirality for the electronic circular dichroism (ECD) spectroscopy, makes these systems suitable for configuration assignment by exploiting the chirality amplification which occurs in nematic liquid crystals. To assess the reliability of the liquid crystal method in detecting the absolute stereochemistry of chiral amides bound to a biphenyl group, we measured the helical twisting power of a series of DAZ-N-protected amides and compared these data with the results obtained from ECD measurements. We will show that the liquid crystal method, corroborated by HTP predictions, is trustworthy with our biphenyl derivatives, even when ECD spectra are ambiguous for the presence of aryl moieties displaying strong UV absorptions in the same range of the biphenyl chromophore. Chirality, 2011. © 2011 Wiley-Liss, Inc.

STM study of the self-assembly at the solid-liquid interface of substituted guanines exposing in the N(9)-position alkyl side chains with different lengths revealed the formation of distinct crystalline nanopatterns.

The formation of Langmuir and Langmuir-Blodgett film from lipophilic guanosines and adenosines has been investigated

We report here our findings on a lipophilic guanosine derivative armed with a terthiophene unit that undergoes a pronounced variation of its supramolecular organisation by changing the polarity of the solvent. In chloroform the guanosine derivative, templated by alkali metal ions, assembles via H-bonding in G-quartet based D(4)-symmetric octamers; the polar guanine bases are located into the inner part of the assembly and act as a scaffold for the terthienyl pendants. On the other hand, in the more polar (and H-bond competing) acetonitrile, different aggregates are observed in which the terthiophene chains are pi-pi stacked in a helicoidal (left-handed) arrangement in the central core, and the guanine bases (free from hydrogen bonding) are located at the periphery and exposed to the solvent. The system can be switched back and forth by subsequent addition of chloroform and acetonitrile. The solvent-induced switching can be easily followed by circular dichroism spectroscopy: the CD exciton-couplet in the guanine chromophore absorption region observed in chloroform disappears after addition of acetonitrile, indicating the disassembly of the G-quartet based octameric structure, while an intense quasi-conservative exciton splitting in the 300-450 nm spectral region becomes predominant in the CD spectrum. This latter strong bisignate optical activity can be ascribed to the helical packing of conjugated terthiophene moieties stabilised by pi-pi interactions. NMR spectra and photophysical investigations confirm the structures of the guanine-directed and thiophene-directed assemblies in chloroform and acetonitrile, respectively.

Over the last two decades, guanosine-related molecules have been of interest in different areas, ranging from structural biology to medicinal chemistry, supramolecular chemistry and nanotechnology. The guanine base is a multiple hydrogen-bonding unit, capable also of binding to cations, and fits very well with contemporary studies in supramolecular chemistry, self-assembly and non-covalent synthesis. This Concepts article, after reviewing on the diversification of self-organised assemblies from guanosine-based low-molecular-weight molecules, will mainly focus on the use of guanine moiety as a potential scaffold for designing functional materials of tailored physical properties.

The addition of a chiral non-racemic dopant to a nematic liquid crystal (LC) has the effect of transferring the molecular chirality to the phase organization and a chiral nematic phase is formed. This molecular chirality amplification in the LC provides a unique possibility for investigating the relationship between molecular structure, intermolecular interactions, and mesoscale organization. It is known that axially chiral or helical-shaped molecules with reduced conformational disorder are good candidates for high helical twisting power derivatives. In particular, biaryl derivatives are known to be efficient chiral inducers in biaryl nematic mesophases. In this paper, we focus on a new series of helicene-like molecules of known absolute configuration. We have integrated cholesteric pitch measurements with geometry optimization by DFT calculations and analysis of the twisting ability by the Surface Chirality model to shed light on the structural features responsible for the analogies and differences exhibited by these derivatives. The investigation of these dopants with well-defined geometry, by virtue of the low conformational freedom, and the substituents variously distributed around the core, allows us to extend our knowledge of the molecular origin of the chirality amplification in liquid crystals and to confirm the simple relationship “molecular P-helicity” → “cholesteric P-handedness” for helical-shaped helicene-like derivatives.

Axially chiral, N-arylated 3,5-dihydro-4H-dinaphtho[2,1-c:1',2'-e]azepines have been prepared by short synthetic protocols from enantiopure 1,1'-bi(2,2'-naphthol) (BINOL) and anilines. Alkynes substituted with two N-phenyldinaphthazepine donors readily undergo a formal [2+2] cycloaddition, followed by retro-electrocyclization, with tetracyanoethene (TCNE) to yield donor-substituted 1,1,4,4-tetracyanobuta-1,3-dienes (TCBDs) featuring intense intramolecular charge-transfer (CT) interactions. A dicyanovinyl derivative substituted with one N-phenyldinaphthazepine donor was obtained by a "one-pot" oxidation/Knoevenagel condensation from the corresponding propargylic alcohol. Comparative electrochemical, X-ray crystallographic, and UV/Vis studies show that the electron-donor qualities of N-phenyldinaphthazepine are similar to those of N,N-dimethylanilino residues. The circular dichroism (CD) spectrum of a push-pull chromophore incorporating the chiral donor moiety features Cotton effects of exceptional intensity. With their elongated shape and the rigidity of the chiral N-aryldinaphthazepine donors, these chromophores are effective inducers of twist distortion in nematic liquid crystals (LCs). Thus, a series of the dinaphthazepine derivatives was used as dopants in the nematic LC E7 (Merck) and high helical twisting powers (beta) of the order of hundreds of microm(-1) were measured. Theoretical calculations were employed to elucidate the relation between the structure of the dopants and their helical twisting power. For the derivatives with two dinaphthazepine moieties, a strong dependence of the beta-values on the structure and conformation of the linker between them was found.

The guanosine derivative 1 functionalized with the persistent radical unit 4-carbonyl-2,2,6,6-tetramethylpiperidin-1-oxyl in solution has no particular intermolecular spin-spin interactions; however, in the presence of potassium ions this compound can form a D4-symmetric octameric assembly [1(8)K]+ in which the nitroxyl moieties show a weak electron spin-spin exchange interaction. Since the relative geometry of the radicals is the outcome of K+-directed self-assembly, the spin-spin interaction can be suppressed by removing the alkaline ion.

Self-assembly plays an important role in the formation of many chiral biological structures and in the preparation of chiral functional materials. Therefore the control of chirality in synthetic or biological self-assembled systems is important either for the comprehension of recognition phenomena or to obtain materials with predictable and controllable properties. Circular dichroism was developed to study molecular chirality, however, because of its outstanding sensitivity to chiral perturbations of the system under investigation; it has been extended more recently to supramolecular chemistry. In particular, self-assembly processes leading to the formation of chiral supramolecular architectures (and eventually to gels or liquid crystal phases) can be monitored by CD. Furthermore, CD spectroscopy often allows one to obtain structural information on the assembled structures. This review deals with representative contributions to the study of supramolecular chirality by means of circular dichroism.

We report on the synthesis and self-assembly of a guanosine derivative bearing an alkyloxy side group under different environmental conditions. This derivative was found to spontaneously form ordered supramolecular nanoribbons in which the individual nucleobases are interacting through H-bonds. In toluene and chloroform solutions the formation of gel-like liquid-crystalline phases was observed. Sub-molecularly resolved scanning tunneling microscopic imaging of monolayers physisorbed at the graphite-solution interface revealed highly ordered two-dimensional networks. The recorded intramolecular contrast can be ascribed to the electronic properties of the different moieties composing the molecule, as proven by quantum-chemical calculations. This self-assembly behavior is in excellent agreement with that of 5'-O-acylated guanosines, which are also characterized by a self-assembled motif of guanosines that resembles parallel ribbons. Therefore, for guanosine derivatives (without sterically demanding groups on the guanine base) the formation of supramolecular nanoribbons in solution, in the solid state, and on flat surfaces is universal. This result is truly important in view of the electronic properties of these supramolecular anisotropic architectures and thus for potential applications in the fields of nano- and opto-electronics.

Two series of enantiopure azobenzenes with a p-tolylsulfoxide at the ortho or meta position with respect to the azo group, have been regioselectively synthesized. Both can act as enantiopure molecular switches showing different structural features owing to the presence of the stereogenic sulfur. The photoisomerization process, studied by UV-vis, circular dichroism (CD), NMR, and chiral HPLC evidenced a double role of the sulfoxide. A transfer of chirality from the sulfoxide to the azo system was observed by CD in both cis and trans-isomers of the meta sulfinyl derivatives 3, whereas this perturbation was evident for the ortho sulfinyl series 7 only in the cis isomer. The NMR study evidenced that the s-cis rigid conformation of the bisaromatic sulfoxide was fixing a different orientation of the overall system in each series both in the trans and cis isomers, by forcing a final U-shaped structure in cis-3 and an S-shaped structure in cis-7. Very different values of specific optical rotations were measured in both trans and cis isomers, also reflecting the existence of distinct chiral entities in the photostationary states. The easy and reversible changes occurring between different conformational states could find applications in the photocontrol of several molecular switches.