Opportunity of Patterning in Chemistry.

Patterning offers an efficient way to quantitatively enhance and enlarge material properties and functionalities, offering unprecedented opportunities for innovation in various scientific domains. By precisely controlling the spatial arrangement of materials at the micro- and nanoscale, patterning enables the exploitation of inherent material properties in novel ways. In addition, it generates new properties, leading to the development of advanced devices and applications. This article highlights the significant contributions of spatially controlled patterning in chemistry, particularly in generating new functional properties and devices, discussing some representative articles. Examples include the use of unconventional patterning techniques for surface functionalization, as well as the application of spatial confinement in improving material properties and controlling crystallization processes. Furthermore, the discussion extends to creating new devices, such as optical storage media and sensors, through spatial organization of materials.

A nonionic microemulsion co-loaded with atorvastatin and quercetin: Simultaneous spectroscopic analysis and payload release kinetics.

In this study, we have co-loadedatorvastatin (ATR) and quercetin (QCT) in a nonionic microemulsion. After developing a derivative ratio spectrophotometric technique for simultaneous analysis of ATR and QCT, pseudoternary phase diagram was constructed utilizing1:4 d-α-tocopherol polyethylene glycol 1000 succinate (TPGS) and ethanol as surfactant and cosurfactant, respectively. Oleic acid was used as oil phase. Structural characterization of the formulation was carried out along a water dilution line created in monophasic region. Characterizations at these dilution points were performed using dynamic light scattering and polarized light microscopy. The average hydrodynamic size of the optimized formulation was found to be 18.9 nm and it did not change upon loading of ATR and QCT. In vitro release was assessed for the formulations loaded with different ratios of ATR and QCT, and the data were fitted to different mathematical models. Interestingly, we noticed differences in release kinetics during changes in dose ratios, particularly for QCT. Higuchi kinetics, observed at equal dose, shifted to Korsmeyer-Peppas model at higher QCT-ATR ratio (2:1 and 4:1). This difference is attributable to the ability of QCT molecules of overwhelming the interface at higher concentrations. Altogether, our observations highlight that the ratio of payloads should be selected carefully in order to avoid unpredictable release patterns.

The Spin-Orbit Effect on the Electronic Structures, Refractive Indices, and Birefringence of X2PO4I (X = Pb, Sn, Ba and Sr): A First-Principles Investigation.

Introducing post-transition metal cations is an excellent strategy for enhancing optical properties. This paper focuses on four isomers, namely the X2PO4I (X = Pb, Sn, Ba, and Sr) series. For the first time, the paper's attention is paid to the changes in electronic structure, as well as refractive indices and birefringence, with and without the inclusion of spin-orbit effects in this series. The first-principles results show that spin-orbit effects of the 5p and 6p states found in these compounds lead to splitting of the bands, narrowing of the band gap, enhancement of the lone-pair stereochemistry, and enhancement of the refractive indices and birefringence. Moreover, a comparison of the lone-pair electron phosphates, X2PO4I (X = Pb and Sn), and the isomeric alkaline earth metal phosphates, X2PO4I (X = Ba and Sr), reveals that changes in the band structure have a greater effect on the enhancement of the birefringence than the slight enhancement of the lone-pair stereochemical activity. This study has important implications for a deeper understanding of the optical properties of crystals and the design of novel optical materials.

Two Hydroxyfluorooxoborates Achieving Deep-ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi-anionic Groups.

Assembling multi-anionic groups is conducive to utilizing respective advantage to achieve the enhancement of optical performance. Two new hydroxyfluorooxoborates, Rb2B3O3F4(OH) and K8Cs2B15O14(OH)7F20·H2O with [B3O3F4(OH)] six-membered rings were synthesized for the first time. The title compounds exhibit short ultraviolet cutoff edges (< 200 nm) and K8Cs2B15O14(OH)7F20·H2O possesses a moderate experimental refractive index difference of 0.051@546.1 nm.

A Noncentrosymmetric Metal-Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent-Linkage.

Organic-inorganic hybrid linear and nonlinear optical (NLO) materials have received increasingly wide spread attention in recent years. Herein, the first hybrid noncentrosymmetric (NCS) borophosphate, (C5H6N)2B2O(HPO4)2 (4PBP), is rationally designed and synthesized by a covalent-linkage strategy. 4-pyridyl-boronic acid (4 PB) is considered as a bifunctional unit, which may effectively improve the optical properties and stability of the resultant material. On the one hand, 4 PB units are covalently linked with PO3(OH) groups via strong B-O-P connections, which significantly enhances the thermal stability of 4PBP (decomposition at 321, vs lower 200 °C of most of hybrid materials). On the other hand, the planar π-conjugated C5H6N units and their uniform layered arrangements represent large structural anisotropy and hyperpolarizability, achieving the largest birefringence (0.156 @ 546 nm) in the reported borophosphates and a second-harmonic generation response (0.7 × KDP). 4PBP also exhibits a wide transparency range (0.27-1.50 µm). This work not only provides a promising birefringent material, but also offers a practical covalent-attachment strategy for the rational design of new high-performance optical materials.

Birefringence mapping of biological tissues based on polarization sensitive non-interferometric quantitative phase imaging technique.

OBJECTIVE: Oral cancer is a leading cause of mortality globally, particularly affecting developing regions where oral hygiene is often overlooked. The optical properties of tissues are vital for diagnostics, with polarization imaging emerging as a label-free, contrast-enhancing technique widely employed in medical and scientific research over past few decades. MATERIALS AND METHODS: We present a novel polarization sensitive quantitative phase imaging of biological tissues by incorporating the conventional polarization microscope and transport of intensity equation-based phase retrieval algorithm. This integration provides access to the birefringence mapping of biological tissues. The inherent optical anisotropy in biological tissues induces the polarization dependent refractive index variations which can provide the detailed insights into the birefringence characteristics of their extracellular constituents. Experimental investigations were conducted on both normal and cancerous oral tissue samples by recording a set of three polarization intensity images for each case with a step size of 2 µm. RESULTS: A noteworthy increment in birefringence quantification was observed in cancerous as compared to the normal tissues, attributed to the proliferation of abnormal cells during cancer progression. The mean birefringence values were calculated for both normal and cancerous tissues, revealing a significant increase in birefringence of cancerous tissues (2.1±0.2) ×10-2 compared to normal tissues (0.8±0.2) ×10-2. Data were collected from 8 patients in each group under identical experimental conditions. CONCLUSION: This polarization sensitive non-interferometric optical approach demonstrated effective discrimination between cancerous and normal tissues, with various parameters indicating elevated values in cancerous tissues.

Rational Combination of π-Conjugated and Non-π-Conjugated Groups Achieving Strong Nonlinear Optical Response, Large Optical Anisotropy, and UV Light-Switchable Fluorescence.

Combining π-conjugated and non-π-conjugated groups is an important strategy for synthesizing new nonlinear optical (NLO) crystals. However, the second harmonic generation (SHG) response and optical anisotropy can be limited by improper spatial alignment of these functional groups in the crystal structure. In this work, it is revealed that non-π-conjugated [NH2 SO3 ] group acts as both hydrogen bond donor and acceptor, effectively regulating the 2D planar structure formed by π-conjugated [C4 N3 H6 ] groups. The resulting organic-inorganic hybrid crystal C4 N3 H6 SO3 NH2 exhibits a strong SHG response (2.5 × KDP), large optical anisotropy (0.233@546 nm), and blue-violet and green fluorescence near 360 and 520 nm, respectively. This work expands the methodology for creating new NLO crystals through organic-inorganic hybridization, while also showcasing the potential of C4 N3 H6 SO3 NH2 as a multifunctional optical material.

Molecular Design of Sexiphenyl-Based Liquid Crystals: Towards Temperature-Stable, Nematic Phases with Enhanced Optical Properties.

This research introduces a novel liquid crystal molecular design approach based on the para-sexiphenyl (6P) structure. Six new liquid crystalline materials were synthesized, incorporating an alkyl terminal and lateral substitutions of the sexiphenyl core to achieve temperature-stable and broad nematic phases. The synthetic pathway involved cross-coupling, resulting in derivatives with strong nematogenic characteristics. Optical investigations demonstrated that the tested material had high birefringence values, making it promising for optical and electronic applications. These results open up new avenues of research and offer potential practical applications in electronics, photonics, optoelectronics and beyond.

From Cd(SCN)2(CH4N2S)2 to Cd(SCN)2(C4H6N2)2: Controlling Sulfur Content in Thiocyanate Systems Significantly Improves the Overall Performance of UV Nonlinear Optical Materials.

Combining a strong second-order nonlinear optical (NLO) effect (>1×KH2PO4 (KDP)), a large band gap (>4.2 eV), and a moderate birefringence in ultraviolet (UV) NLO crystals remains a formidable challenge. Herein, Cd(SCN)2(C4H6N2)2, the first example of a thiocyanate capable of realizing a phase-matched UV NLO crystal material, is obtained by reducing the sulfur (S) content in the centrosymmetric (CS) structure of Cd(SCN)2(CH4N2S)2. Compared to the "shoulder-to-shoulder" one-dimensional (1D) chain of Cd(SCN)2(CH4N2S)2, Cd(SCN)2(C4H6N2)2 has a different sawtooth 1D chain structure. Cd(SCN)2(CH4N2S)2 has second harmonic generation (SHG) inertia with a band gap of 3.90 eV and a UV cutoff edge of 342 nm, however, it possesses a large birefringence (0.35@546 nm). In contrast, the symmetry center breaking of Cd(SCN)2(C4H6N2)2 leads to remarkably strong SHG intensity (10 times that of KDP). Furthermore, it has a wide band gap (4.74 eV), short UV cutoff edge (234 nm), and moderate birefringence capable of phase matching (0.17@546 nm). This research indicates that thiocyanates are a promising class of UV NLO crystal materials, and that modulation of the sulfur content of CS thiocyanates is an effective strategy for the development of UV NLO crystals with excellent overall performances.

Optical Anisotropy of Polyethylene Terephthalate Films Characterized by Spectral Means.

Polyethylene terephthalate (PET) films are the subject of intensive research because of great interest in using them in applications, especially in medicine. From an optical point of view, PET films with a low degree of stretching can be considered uniaxial materials, for which the determination of the linear birefringence and its dispersion is very important. Two methods were applied here for the estimation of these parameters: the ellipsometric method and the channeled spectra method. The ellipsometric method uses monochromatic radiation; therefore, the linear birefringence of the PET films is determined for a given value of the radiation wavelength. The channeled spectra method allows for the estimation of the linear birefringence and its dispersion for a large range of wavelengths in the visible spectrum. A decrease in both parameters with the increase in the wavelength was recorded. To evidence the microstructure of PET films and the conformational changes induced by elongation and to evaluate the degree of orientation, a polarized infrared spectral study in attenuated total reflection (ATR-FTIR) mode was performed. The dichroic ratio (between the absorbance measured with linearly polarized radiation parallel and orthogonal relative to the stretching direction, respectively) and the ATR absorbance ratio for the machine direction (MD) and transversal direction (TD) configurations both for the stretched and unstretched PET samples were measured.

Cardiac Pulsed Field Ablation Lesion Durability Assessed by Polarization-Sensitive Optical Coherence Reflectometry.

BACKGROUND: Pulsed field ablation uses electrical fields to cause nonthermal cell death over several hours. Polarization-sensitive optical coherence reflectometry is an optical imaging technique that can detect changes in the tissue ultrastructure in real time, which occurs when muscular tissue is damaged. The objective of this study was to evaluate the ability of a polarization-sensitive optical coherence reflectometry system to predict the development of chronic lesions based on acute changes in tissue birefringence during pulsed field ablation. METHODS: Superior vena cava isolation was performed in 30 swine using a biphasic, bipolar pulsed field ablation system delivered with a nonirrigated focal tip catheter. Acute changes in tissue birefringence and voltage abatement were analyzed for each individual lesion. A high-resolution electroanatomical map was performed at baseline and 4 to 12 weeks after ablation to locate electrical gaps in the ablated area. RESULTS: A total of 141 lesions were delivered and included in the analysis. Acute electrical isolation based on the electroanatomical map was achieved in 96% of the animals, but chronic isolation was only seen in 14 animals (46%). The mean voltage abatement of lesions that showed recovery was 82.8%±14.6% versus 84.4%±17.4% for those that showed fibrosis (P=0.7). The mean acute reduction in tissue birefringence in points demonstrating fibrosis was 63.8%±11.3% versus 9.1%±0.1% in the points that resulted in electrical gaps. A threshold of acute reduction of birefringence of ≥20% could predict chronic lesion formation with a sensitivity of 96% and a specificity of 83%. CONCLUSIONS: Acute tissue birefringence changes assessed with polarization-sensitive optical coherence reflectometry during pulsed field ablation can predict chronic lesion formation and guide the ablation procedure although limited by the tissue thickness.

Study on anisotropy orientation due to well-ordered fibrous biological microstructures.

Significance: Most biological fibrous tissues have anisotropic optical characteristics, which originate from scattering by their fibrous microstructures and birefringence of biological macromolecules. The orientation-related anisotropic interpretation is of great value in biological tissue characterization and pathological diagnosis. Aim: We focus on intrinsic birefringence and form birefringence in biological tissue samples. By observing and comparing the forward Mueller matrix of typical samples, we can understand the interpretation ability of orientation-related polarization parameters and further distinguish the sources and trends of anisotropy in tissues. Approach: For glass fiber, silk fiber, skeletal muscle, and tendon, we construct a forward measuring device to obtain the Mueller matrix image and calculate the anisotropic parameters related to orientation. The statistical analysis method based on polar coordinates can effectively analyze the difference in anisotropic parameters. Results: For those birefringent fibers, the statistical distribution of fast-axis values derived from Mueller matrix polar decomposition was found to exhibit bimodal characteristics, which is a key point in distinguishing the single-layer birefringent fiber sample from a layered, multioriented fibrous sample. The application conditions and interference factors of anisotropic orientation parameters are analyzed. Based on the parameters extracted from the orientation bimodal distribution, we can evaluate the relative change trend of intrinsic birefringence and form birefringence in anisotropic samples. Conclusions: The cross-vertical bimodal distribution of the fast axis of anisotropic fibers is beneficial to accurately analyze the anisotropic changes in biological tissues. The results imply the potential of anisotropic orientation analysis for applications in pathological diagnosis.

Intraoperative collagen imaging of sutured cornea: A way towards managing post-penetrating keratoplasty astigmatism.

The birefringent nature of the human cornea plays an important role in comprehending its structural behavior in both diseased and surgical conditions. During corneal transplantation, irregular astigmatism is a common post-surgical complication that depends on the characteristics of suturing. Four human cadaver corneas are subjected to an in-vitro model of a typical full-thickness penetrating keratoplasty (PK) procedure using 16 simple interrupted 10-0 vicyrl sutures. The birefringence of these four corneas is analyzed using digital photoelasticity and compared with the control cornea (without PK). It is found that the sutures and their mutual interaction influence the morphology of the peripheral birefringence of the cornea. The findings of the present investigation are pertinent to intraoperative suture management during PK. Results suggest conserving the typical diamond-shaped morphology of peripheral birefringence would ensure uniform distribution of sutures. Therefore, birefringence imaging could be useful in suture management to ensure proper apposition of the graft-host junction, thus minimizing the risk of irregular astigmatism.

Exceptional Optical Anisotropy Enhancement Achieved Through Dual-Ions Cosubstitution Strategy in Novel Hybrid Bismuth Halides.

Guided by a superb dual-ions cosubstitution strategy, two novel, highly optically anisotropic hybrid bismuth halides are designed and synthesized. The first compound, Gu3 Bi2 NO3 Cl8 (Gu = C(NH2 )3 ), is developed using the 2D perovskite halide Cs3 Bi2 Cl9 as the maternal structure. This involved substituting all Cs+ cations with organic Gu+ and replacing some Cl- anions with [NO3 ]- . Further substitution of Cl- with additional [NO3 ]- resulted in the formation of nitrate-rich Gu2 Bi(NO3 )3 Cl2 crystal, exhibiting a 3.4-fold increase in [NO3 ]- per unit volume. Both compounds have a structurally 0D nature, comprising bismuth-centered polyhedra formed by coordinated chlorides and monodentate/bidentate nitrate moieties, with Gu+ serving as a separator and linker. Notably, the presence of superb optically anisotropic dual-ions, i.e., planar Gu+ and [NO3 ]- , enables these crystals to possess sharply enhanced optical anisotropy, with birefringence values more than 1 order of magnitude higher than that of the initial crystal Cs3 Bi2 Cl9 (0.162/0.186vs 0.011 at 546 nm). The discovery and characterization of Gu3 Bi2 NO3 Cl8 and Gu2 Bi(NO3 )3 Cl2 crystals provide new insights into achieving expected modifications in optical properties through the utilization of a dual-ions cosubstitution strategy.

Birefringence in Injection-Molded Cyclic Olefin Copolymer Substrates and Its Impact on Integrated Photonic Structures.

This contribution quantifies the birefringence within injection-molded cyclic olefin copolymer plates and discusses its impact on the mechanical properties of the plates. It also focuses on the impact of birefringence on integrated waveguides and Bragg gratings and provides fabrication guidelines for such structures. The anisotropy in all three dimensions of the workpiece is examined by means of polarimetry and a prism coupler. It is found that the birefringence is inhomogenously distributed within the workpieces, whereas the maximum birefringence not only varies locally, but also depends on the observation direction. Overall, a maximum birefringence of 10 × 10-4 is found at the plate's surface near the injection gate. The anisotropy then reduces exponentially towards the center of the workpiece and saturates at 1.8 × 10-4, in a depth of 0.4 mm. Thus, the birefringence strongly affects near-surface photonic structures. It is found that, depending on their orientation and the local birefringence of the substrate, waveguides and Bragg gratings fabricated with comparable parameters behave completely differently in terms of polarization-dependent optical attenuation, cross-sectional intensity distribution and Bragg reflection signal. For example, the support of the TM mode can vary between total loss and an optical attenuation of 0.9 dB × cm-1. In consequence, this study underlines the importance of quantifying the birefringent state of an injection-molded cyclic olefin copolymer workpiece if it is supposed to serve as a substrate for integrated photonic structures. The study furthermore demonstrates that birefringence effects can be omitted by burying the photonic structures deeper into the volume of the thermoplastic.

Designing Sulfate Crystals with Strong Optical Anisotropy through π-Conjugated Tailoring.

Sulfate crystals typically exhibit minimal optical anisotropy due to the near-zero polarizability anisotropy (δ) of [SO4 ]2- tetrahedra, arising from highly symmetrical electron clouds. Recent research sought to enhance δ via chemical modifications, such as fluorination. However, the resultant crystals often maintain subpar optical anisotropy, frequently with birefringence values below 0.1. In this study, we have uncovered that δ can be significantly strengthened by chemically tailoring the tetrahedral [SO4 ]2- with anisotropic π-conjugated modules. This has been demonstrated by several newly proposed S-O-Org (Org: π-conjugated organic species) moieties, which show a sharp increase in δ based on theoretical computations. To further validate this experimentally, we synthesized and characterized six new 3-pyridinesulfonate crystals with the formula A(3-C5 H4 NSO3 ) ⋅ xH2 O (A=Li, Ag, K, Rb, Cs, and NH4 ; x=0 and 1). Notably, these materials exhibit strong optical anisotropy, with birefringence values ranging from 0.240 to 0.312 at 546 nm. These values are approximately 23 to 145.5 times greater than those of corresponding sulfates, and they outperform a vast number of sulfate-related optical materials, thus verifying the effectiveness of the proposed strategy. Furthermore, the title compounds exhibit diverse microstructure peculiarities influenced by the size and binding natures of the counter cations.

Surface-Guided Crystallization of Xanthine Derivatives for Optical Metamaterial Applications.

Numerous bio-organisms employ template-assisted crystallization of molecular solids to yield crystal morphologies with unique optical properties that are difficult to reproduce synthetically. Here, a facile procedure is presented to deposit bio-inspired birefringent crystals of xanthine derivatives on a template of single-crystal quartz. Crystalline sheets that are several millimeters in length, several hundred micrometers in width, and 300-600 nm thick, are obtained. The crystal sheets are characterized with a well-defined orientation both in and out of the substrate plane, giving rise to high optical anisotropy in the plane parallel to the quartz surface, with a refractive index difference Δn ≈ 0.25 and a refractive index along the slow axis of n ≈ 1.7. It is further shown that patterning of the crystalline stripes with a tailored periodic grating leads to a thin organic polarization-dependent diffractive meta-surface, opening the door to the fabrication of various optical devices from a platform of small-molecule based organic dielectric crystals.

Multispectral polarization microscopy of different stages of human oral tissue: A polarization study.

Many optical techniques have been used in various diagnostics and biomedical applications since a decade and polarization imaging is one of the non-invasive and label free optical technique to investigate biological samples making it an important tool in diagnostics, biomedical applications. We report a multispectral polarization-based imaging of oral tissue by utilizing a polarization microscope system with a broadband-light source. Experiments were performed on oral tissue samples and multispectral Stokes mapping was done by recording a set of intensity images. Polarization-based parameters like degree of polarization, angle of fast axis, retardation and linear birefringence have been retrieved. The statistical moments of these polarization components have also been reported at multiples wavelengths. The polarimetric properties of oral tissue at different stages of cancer have been analyzed and significant changes from normal to pre-cancerous lesions to the cancerous are observed in linear birefringence quantification as (1.7 ± 0.1) × 10-3 , (2.5 ± 0.2) × 10-3 and (3.3 ± 0.2) × 10-3 respectively.

Electro-optics of confined systems.

Confinement in microenvironments occurs in many natural systems and technological applications. However, little is known about the behaviour of the immersed nanoparticles. In this work we show that their diffusion, electro-orientation and electric field induced polarization can be determined through electric birefringence experiments. We analyze aqueous dispersions of silver nanowires and clay particles confined inside microdroplets. We have observed that confinement reduces the amount of particles that can be oriented by the external electric field. However, the polarizability of the oriented particles is not affected by the presence of the oil/water boundary, and it is the same as in unbounded media, which agrees with the fact that the electric polarization and related phenomena are short-ranged.