Core-shellchiralpolymeric-metallic particles obtained in a single step by concurrentlight induced processes.

Core-shell architecture enables to impart unique customized properties to microparticles, through the proper selection of composition and aggregation state of the inner and outer materials. Here, the synthesis of microparticles with a chiral dielectric core and a metallic shell of gold nanoparticles is demonstrated. The chiral core is obtained by UV induced polymerization of the self-organized droplets of a cholesteric reactive mesogen in a chloroauric acid aqueous solution. Gold nanoparticles precipitation contemporarily occurs upon UV irradiation, covering the microparticles surface. Electron microscopy and optical spectroscopy investigations give evidence that the degree of coverage of the core by gold nanoparticles, with size less than 100 nm, depends on the chloroauric acid concentration, while their aggregation is influenced by the polymeric surface morphology. The optical properties of the chiral microparticles are modified by the gold shell. Specifically, gold coating of dye doped chiral microparticles, working as Bragg onion resonators, clearly improves the stability of omnidirectional microlasers. The proposed strategy, due to the flexibility of the chiral material and of the method, opens a route toward fabrication of microdevices with wide control over light manipulation, in term of intensity, polarization, generation.

Correction: Collective motion of chiral Brownian particles controlled by a circularly-polarized laser beam.

Correction for 'Collective motion of chiral Brownian particles controlled by a circularly-polarized laser beam' by Raúl Josué Hernández et al., Soft Matter, 2020, 16, 7704-7714, DOI: .

Photopatterning of Azobenzene-Containing Liquid Crystalline Triblock Copolymers: Light-Induced Anisotropy and Photostabilization.

Photochromic liquid crystalline block copolymers (PLCBCs) are currently playing a significant role as light-responsive materials because of their light controllable features over multiple length scales. Herein, a study of the photoinduced optical anisotropy derived by the combination of orientation phenomena at molecular and supramolecular levels in a novel kind of side-chain PLCBCs with mesogenic phenyl benzoate groups and pyridine units that is hydrogen bonded with azobenzene-containing phenol is reported. Based on the polymeric architectures and composition, the supramolecular configuration self-organizes in different microphases that affect the material response to the external stimuli. Simple, 1D, polarization holograms are recorded to evaluate the photoinduced birefringence. The first step, light patterning, involves the orientation of the azobenzene units and precedes a thermal treatment that amplifies the induced anisotropy through the cooperative orientation of the mesogenic units. By selective extraction, the azobenzene units can be removed, making the material transparent to the visible light. Excellent photostability of the material birefringence is obtained, whose final value is strongly affected by the block copolymer's architecture. The versatility in the molecular design, the fine control of the photoinduced features by external parameters, and, finally, the possibility to achieve photostability make these materials of great potential for developing optical and photonic devices.

Collective motion of chiral Brownian particles controlled by a circularly-polarized laser beam.

We demonstrate the emergence of circular collective motion in a system of spherical light-propelled Brownian particles. Light-propulsion occurs as consequence of the coupling between the chirality of polymeric particles - left (L)- or right (R)-type - and the circularly-polarized light that irradiates them. Irradiation with light that has the same helicity as the particle material leads to a circular cooperative vortical motion between the chiral Brownian particles. In contrast, opposite circular-polarization does not induce such coupling among the particles but only affects their Brownian motion. The mean angular momentum of each particle has a value and sign that distinguishes between chiral activity dynamics and typical Brownian motion. These outcomes have relevant implications for chiral separation technologies and provide new strategies for optical torque tunability in mesoscopic optical array systems, micro- and nanofabrication of light-activated engines with selective control and collective motion.

Assessment of EtQxBox complexation in solution by steady-state and time-resolved fluorescence spectroscopy.

Reliable chemical sensors with high selectivity and sensitivity toward specific target molecules require rational synthesis of receptors, in-depth characterization of their complexation abilities and highly efficient transduction of the molecular recognition event. Here we report a steady-state and time-resolved fluorescence investigation of EtQxBox, a fluorescent conformationally blocked quinoxaline-based cavitand, aimed at assessing its selectivity toward aromatic versus non-aromatic analytes in solution. Fluorescence quenching of the EtQxBox in acetone is observed at increasing concentration of both aromatic (i.e. benzonitrile) and aliphatic (i.e. acetonitrile) compounds. The combination with fluorescence lifetime measurements permits to discriminate the predominantly static quenching of the aromatic analyte, due to non-fluorescent host-guest complex formation, from the mostly dynamic quenching of the non-aromatic compound, resulting from aspecific diffusive collisions between the fluorophore and the quencher. The equilibrium association constants for both the complexes have been estimated using Stern-Volmer model.

Probing Molecular Recognition at the Solid-Gas Interface by Sum-Frequency Vibrational Spectroscopy.

Molecular recognition is among the most important chemical events in living systems and has been emulated in supramolecular chemistry, driven by chemical and biochemical sensing potential. Identifying host-guest association in situ at the interface, between the substrate-bound receptors and the analyte-containing media, is essential to predict complexation performances in term of the receptor conformation, orientation and organization. Herein, we report the first sum-frequency vibrational spectroscopy study of molecular recognition at the solid-gas interface. The binding capability of tetraquinoxaline cavitands toward volatile aromatic and aliphatic compounds, namely benzonitrile and acetonitrile, is investigated as test system. We prove the selective complexation of the receptors, organized in a solid-supported hybrid bilayer, toward aromatic compounds. Quantitative analysis allows to correlate the average orientations of the guest molecules and the host binding pockets, establishing "on-axis" complexation of benzonitrile within the cavitand cavity. The study is readily applicable to other receptors, molecular architectures, interfaces and analytes.

Liquid crystal microlens arrays recorded by polarization holography.

We report the characterization of diffractive microlens arrays (MAs) using a polarization holographic approach assisted by a spatial light modulator (SLM), in a nematic liquid crystal (NLC) cell. The MAs were recorded in the photoaligning substrates of the cell and then replicated in the NLC bulk, through the surface interactions. The transparency of the NLC on a wide range of wavelengths and the ability to tune its optical birefringence, through an external voltage, allowed us to create MAs with high efficiency. We have presented the results obtained for diverse MAs configurations, composed by spherical and cylindrical microlenses and characterized by different focal lengths. The efficiency reaches a value of 90%, at a wavelength of 633 nm.

A bifunctional amorphous polymer exhibiting equal linear and circular photoinduced birefringences.

The large and reversible photoinduced linear and circular birefringences in azo-compounds are at the basis of the interest in these materials, which are potentially useful for several applications. Since the onset of the linear and circular anisotropies relies on orientational processes, which typically occur on the molecular and supramolecular length scale, respectively, a circular birefringence at least one order of magnitude lower than the linear one is usually observed. Here, the synthesis and characterization of an amorphous polymer with a dimeric repeating unit containing a cyanoazobenzene and a cyanobiphenyl moiety are reported, in which identical optical linear and circular birefringences are induced for proper light dose and ellipticity. A pump-probe technique and an analytical method based on the Stokes-Mueller formalism are used to investigate the photoinduced effects and to evaluate the anisotropies. The peculiar photoresponse of the polymer makes it a good candidate for applications in smart functional devices.

Polarization holograms in a bifunctional amorphous polymer exhibiting equal values of photoinduced linear and circular birefringences.

Light-controlled molecular alignment is a flexible and useful strategy introducing novelty in the fields of mechanics, self-organized structuring, mass transport, optics, and photonics and addressing the development of smart optical devices. Azobenzene-containing polymers are well-known photocontrollable materials with large and reversible photoinduced optical anisotropies. The vectorial holography applied to these materials enables peculiar optical devices whose properties strongly depend on the relative values of the photoinduced birefringences. Here is reported a polarization holographic recording based on the interference of two waves with orthogonal linear polarization on a bifunctional amorphous polymer that, exceptionally, exhibits equal values of linear and circular birefringence. The peculiar photoresponse of the material coupled with the holographic technique demonstrates an optical device capable of decomposing the light into a set of orthogonally polarized linear components. The holographic structures are theoretically described by the Jones matrices method and experimentally investigated.

Single-step polarization holographic method for programmable microlens arrays.

Optical microsystems have become important tools for imaging, optofluidics, and sensor applications. Here we show a versatile method to create microlens arrays (MAs) exploiting spatial-light-modulator-assisted polarization holography, which enables an efficiency of diffraction up to 100%. We demonstrate the large flexibility of the proposed approach by codifying mixed MAs, i.e., composed of spherical and cylindrical lenses with different focal lengths, either positive or negative. Reconfigurable MAs with 70% total diffraction efficiency have been recorded on a photosensitive polymer that exhibits linear photoinduced birefringence with long time stability as well as optical and thermal reversibility. The good quality of the MA has been shown by a digital holographic test.

Pure two-dimensional polarization patterns for holographic recording.

Two-dimensional (2D) polarization patterns are achieved by the interference of two pairs of beams with perpendicular planes of incidence and orthogonal polarizations (i.e. linear or circular). In both cases, imposing a phase shift of π/2 between consecutive beams contains the amplitude modulation of the optical field in the superposition region and, thus, pure 2D polarization patterns are created. The recording of these interference fields in a polarization-sensitive material, namely an amorphous azopolymer, creates reconfigurable 2D periodic microstructures with peculiar diffraction properties.

Method for artifact-free circular dichroism measurements based on polarization grating.

We propose a simple method to perform real-time measurements of circular dichroism (CD), which suppresses the artifacts introduced by anisotropic samples and nonideal optical elements in conventional spectrometers. A single polarization holographic grating is adopted, whose first orders of diffraction have amplitudes that are proportional to the right and left circular polarization component of the input light. We demonstrate that, exploiting unpolarized white light and the intrinsic spectral selectivity of the grating, the true CD spectrum is evaluated in parallel in the spectral range of interest from the intensities of the two diffraction orders, I(+1) and I(-1).

Polarization holographic recording in amorphous polymer with photoinduced linear and circular birefringence.

Polarization grating recording in an amorphous and nonchiral azo copolymer has been investigated. The reported study shows that the amorphous polymeric film undergoes a light-guided inhomogeneous supramolecular modification as a consequence of the illumination with proper polarized light patterns, acquiring new functionalities. Both linear and circular, spatially modulated, photoinduced birefringences occur, attaining their peak values in the linearly and circularly polarized regions of the light pattern, respectively. The photoinduced anisotropic structures strongly affect the polarization state of the light propagating through them, and the characterization of their optical diffraction enables measurement of the amplitude of the linear and circular birefringences. The recorded gratings show long-time stability and full reconfigurability functional to the multiple holographic recording.

Polarization gradient: exploring an original route for optical trapping and manipulation.

We report a study of the capabilities of an optical tweezer based on polarization gradient. We use a light polarization pattern that is able to simultaneously exert forces and torques in opposite directions depending on the particle's position. It allows to perform oscillatory displacements and control the sense of rotation of several particles inside a uniformly illuminated region. Unconventional trapping of spinning particles in circularly polarized fringes has been observed, which suggests the involvement of hydrodynamic forces.

Spectrograph based on a single diffractive element for real-time measurement of circular dichroism.

In this study, a novel and simple diffractive spectrographic method for real-time measurements of circular dichroism (CD) is considered from a theoretical and experimental approach. A demonstrator prototype of the CD spectrograph has been developed and its performance has been compared with a commercial phase-modulation CD spectrometer. The main element of the device is a polarization holographic grating, recorded in a thin photosensitive organic film, by two interfering opposite circularly polarized beams. A peculiarity of this grating is that the amplitude of the +1 (-1) order of diffraction is proportional to the right (left) circular polarization component of the incoming beam. Here we demonstrate that the CD spectrum of a specimen can be easily evaluated from the intensities of the diffracted beams. A white light beam passing through the specimen is diffracted from the grating and the intensities of the +/-1 orders of diffraction are measured. Due to the spectral selectivity of the grating, the CD at each wavelength can be evaluated at the same time using two linear array detectors.

Sensing vase-to-kite switching of cavitands by sum-frequency vibrational spectroscopy.

Vibrational sum frequency generation setup for the study of Langmuir film of cavitands molecules deposited at the water surface.

Optical two-beam coupling for a surface-induced photorefractive effect in undoped liquid crystals.

We report beam-coupling measurements of undoped nematic planar cells, for which the surface-induced photorefractive effect (SIPRE) has been confirmed to be due to photoelectric interface activation. We show that the energy transfer strongly depends on experimental geometry. Diffraction efficiency and beam-coupling analyses suggest that the unusual local and (or) nonlocal behavior can be ascribed to an additional in-phase-modulated longitudinal electric field component, unaccountable by standard photorefractivity. We consider a simple charge distribution model of the SIPRE, which produces a space-charge field having two orthogonal modulated components, in phase and pi/2 out of phase. Through the liquid crystal's electric response, the exploited geometries verify the presence of the two components.