Nanostructured Polymer-Dispersed Liquid Crystals Using a Ferroelectric Smectic A Liquid Crystal.

Nanostructured polymer-dispersed liquid crystals (nano-PDLCs) are transparent and optically isotropic materials in which submicron-sized liquid crystal (LC) domains are dispersed within a polymer matrix. Nano-PDLCs can induce birefringence by applying an electric field (E-field) based on the reorientation of the LC molecules. If nano-PDLCs are utilized as light-scattering-less birefringence memory materials, it is necessary to suppress the relaxation of the LC molecule orientation after the removal of the E-field. We focused on the ferroelectric smectic A (SmA) phase to suppress the relaxation of LC molecules, owing to its layered structure and high viscosity. Although nano-PDLCs require a strong E-field to reorient their LC molecules because of the anchoring effect at the LC/polymer interface, the required field strength can be reduced using a ferroelectric smectic A (SmAF) LC with a large dielectric constant. In this study, we fabricated a nano-PDLC by shining an ultraviolet light on a mixture comprised an SmAF LC, photocurable monomers, and a photo-initiator. The electro-birefringence effect was evaluated using polarizing optical microscopy. After the removal of the E-field, an enhanced memory effect was observed in the sample using SmAF LC compared with nematic LC-based nano-PDLCs.

A review of ion scattering spectroscopy studies at liquid interfaces with noble gas ion projectiles.

Ion scattering spectroscopy (ISS) is an analytical tool that provides direct structural, topographical, and atomic compositional information at interfaces when ions are used as projectiles. Since its development in 1967, ISS is commonly used to obtain quantitative information about solid interfaces. Over the last couple of decades, ISS has emerged as an important technique to probe liquid interfaces and their studies employing ISS has become not uncommon, more so with Neutral impact collision ion scattering spectroscopy (NICISS). Therefore, here the principle of ISS with a particular focus on NICISS and its data evaluation are summarised while reviewing some important studies at vapor-liquid interfaces that provide direct information for molecular orientation of liquids (including ionic liquids), composition and distribution of atoms (or solutes) and charges as a function of depth to gain vast variety of thermodynamical information. Employing ISS such information can be achieved with high depth resolution of ∼1-2 Å (depending on the nature of the experiment). These examples highlight the significance of ISS and show potential for its application for studies related to specific ion effects, atmospheric reaction in aerosol and sea water droplets, and even determining the fate of environmental pollutants like heavy metal ions and per-fluoroalkyl substances (PFAS). Furthermore, some limitations of ISS are also discussed relating to investigation of high-vapor pressure liquids and probing buried interfaces like liquid-liquid interfaces while presenting progresses made in probing solid-liquid interfaces.

Enhanced Emitting Dipole Orientation Based on Asymmetric Iridium(III) Complexes for Efficient Saturated-Blue Phosphorescent OLEDs.

Three novel asymmetric Ir(III) complexes have been rationally designed to optimize their emitting dipole orientations (EDO) and enhance light outcoupling in blue phosphorescent organic light-emitting diodes (OLEDs), thereby boosting their external quantum efficiency (EQE). Bulky electron-donating groups (EDGs), namely: carbazole (Cz), di-tert-butyl carbazole (tBuCz), and phenoxazine (Pxz) are incorporated into the tridentate dicarbene pincer chelate to induce high degree of packing anisotropy, simultaneously enhancing their photophysical properties. Angle-dependent photoluminescence (ADPL) measurements indicate increased horizontal transition dipole ratios of 0.89 and 0.90 for the Ir(III) complexes Cz-dfppy-CN and tBuCz-dfppy-CN, respectively. Analysis of the single crystal structure and density functional theory (DFT) calculation results revealed an inherent correlation between molecular aspect ratio and EDO. Utilizing the newly obtained emitters, the blue OLED devices demonstrated exceptional performance, achieving a maximum EQE of 30.7% at a Commission International de l'Eclairage (CIE) coordinate of (0.140, 0.148). Optical transfer matrix-based simulations confirmed a maximum outcoupling efficiency of 35% due to improved EDO. Finally, the tandem OLED and hyper-OLED devices exhibited a maximum EQE of 44.2% and 31.6%, respectively, together with good device stability. This rational molecular design provides straightforward guidelines to reach highly efficient and stable saturated blue emission.

Conducting Electrospun Poly(3-hexylthiophene-2,5-diyl) Nanofibers: New Strategies for Effective Chemical Doping and its Assessment Using Infrared Spectroscopy.

Vibrational spectroscopy allows the investigation of structural properties of pristine and doped poly(3-hexylthiophene-2,5-diyl) (P3HT) in highly anisotropic materials, such as electrospun micro- and nanofibers. Here, we compare several approaches for doping P3HT fibers. We have selected two different electron acceptor molecules as dopants, namely iodine and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). In the case of iodine, we have explored the doping of the fibers according to several different procedures, i.e., by sequential doping both in vapors and in solution, and with a novel promising one-step method, which exploits the mixing of the dopant to the electrospinning feed solution. Polarized infrared (IR) spectroscopy experiments prove the orientation of P3HT chains, with the polymer backbone mainly running parallel to the fiber axis. After doping, P3HT fibers show very strong and polarized doping-induced IR active vibrations (IRAVs), which are the spectroscopic signature of the structure relaxation induced by the charged defects (polarons), thus providing an unambiguous proof of the effective doping. Raman spectroscopy complements the IR evidence: The Raman spectrum shows a clearly recognizable shift of the main band, the so-called effective conjugation coordinate band, in the doped samples. A simple protocol, which quantifies the evolution of the IRAV bands with time, allows monitoring of the doping stability over time and confirms that F4TCNQ is by far superior to iodine.

Molecular Orientation Regulation of Hole Transport Semicrystalline-Polymer Enables High-Performance Carbon-Electrode Perovskite Solar Cells.

Carbon-based perovskite solar cells (PSCs) coupled with solution-processed hole transport layers (HTLs) have shown potential owing to their combination of low cost and high performance. However, the commonly used poly(3-hexylthiophene) (P3HT) semicrystalline-polymer HTL dominantly shows edge-on molecular orientation, in which the alkyl side chains directly contact the perovskite layer, resulting in an electronically poor contact at the perovskite/P3HT interface. The study adopts a synergetic strategy comprising of additive and solvent engineering to transfer the edge-on molecular orientation of P3HT HTL into 3D molecular orientation. The target P3HT HTL possesses improved charge transport as well as enhanced moisture-repelling capability. Moreover, energy level alignment between target P3HT HTL and perovskite layer is realized. As a result, the champion devices with small (0.04 cm2) and larger areas (1 cm2) deliver notable efficiencies of 20.55% and 18.32%, respectively, which are among the highest efficiency of carbon-electrode PSCs.

Nanostructured Molecular Packing of Polymer Films Formed on Water Surfaces.

In this study, we examined the nanostructured molecular packing and orientations of poly[[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)] (P(NDI2OD-T2)) films formed on water for the application of nanotechnology-based organic electronic devices. First, the nanoscale molecule-substrate interaction between the polymer and water was modulated by controlling the alkyl side chain length in NDI-based copolymers. Increasing alkyl side chain lengths induced a nanomorphological transition from face-on to edge-on orientation, confirmed by molecular dynamics simulations revealing nanostructural behavior. Second, the nanoscale intermolecular interactions of P(NDI2OD-T2) were controlled by varying the volume ratio of the high-boiling-point additive solvent in the binary solvent blends. As the additive solvent ratio increased, the nanostructured molecular orientation of the P(NDI2OD-T2) films on water changed remarkably from edge-on to bimodal with more face-on crystallites, thereby affecting charge transport. Our finding provides essential insights for precise nanoscale morphological control on water substrates, enabling the formation of high-performance polymer films for organic electronic devices.

A predicted model-aided reconstruction algorithm for X-ray free-electron laser single-particle imaging.

Ultra-intense, ultra-fast X-ray free-electron lasers (XFELs) enable the imaging of single protein molecules under ambient temperature and pressure. A crucial aspect of structure reconstruction involves determining the relative orientations of each diffraction pattern and recovering the missing phase information. In this paper, we introduce a predicted model-aided algorithm for orientation determination and phase retrieval, which has been tested on various simulated datasets and has shown significant improvements in the success rate, accuracy and efficiency of XFEL data reconstruction.

Three-dimensional spatio-angular fluorescence microscopy with a polarized dual-view inverted selective-plane illumination microscope (pol-diSPIM).

Polarized fluorescence microscopy is a valuable tool for measuring molecular orientations, but techniques for recovering three-dimensional orientations and positions of fluorescent ensembles are limited. We report a polarized dual-view light-sheet system for determining the three-dimensional orientations and diffraction-limited positions of ensembles of fluorescent dipoles that label biological structures, and we share a set of visualization, histogram, and profiling tools for interpreting these positions and orientations. We model our samples, their excitation, and their detection using coarse-grained representations we call orientation distribution functions (ODFs). We apply ODFs to create physics-informed models of image formation with spatio-angular point-spread and transfer functions. We use theory and experiment to conclude that light-sheet tilting is a necessary part of our design for recovering all three-dimensional orientations. We use our system to extend known two-dimensional results to three dimensions in FM1-43-labelled giant unilamellar vesicles, fast-scarlet-labelled cellulose in xylem cells, and phalloidin-labelled actin in U2OS cells. Additionally, we observe phalloidin-labelled actin in mouse fibroblasts grown on grids of labelled nanowires and identify correlations between local actin alignment and global cell-scale orientation, indicating cellular coordination across length scales.

The Neglected Role of Asphaltene in the Synthesis of Mesophase Pitch.

This study investigates the synthesis of mesophase pitch using low-cost fluid catalytic cracking (FCC) slurry and waste fluid asphaltene (WFA) as raw materials through the co-carbonization method. The resulting mesophase pitch product and its formation mechanism were thoroughly analyzed. Various characterization techniques, including polarizing microscopy, softening point measurement, Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA), were employed to characterize and analyze the properties and structure of the mesophase pitch. The experimental results demonstrate that the optimal optical texture of the mesophase product is achieved under specific reaction conditions, including a temperature of 420 °C, pressure of 1 MPa, reaction time of 6 h, and the addition of 2% asphaltene. It was observed that a small amount of asphaltene contributes to the formation of mesophase pitch spheres, facilitating the development of the mesophase. However, excessive content of asphaltene may cover the surface of the mesophase spheres, impeding the contact between them and consequently compromising the optical texture of the mesophase pitch product. Furthermore, the inclusion of asphaltene promotes polymerization reactions in the system, leading to an increase in the average molecular weight of the mesophase pitch. Notably, when the amount of asphaltene added is 2%, the mesophase pitch demonstrates the lowest ID/IG value, indicating superior molecular orientation and larger graphite-like microcrystals. Additionally, researchers found that at this asphaltene concentration, the mesophase pitch exhibits the highest degree of order, as evidenced by the maximum diffraction angle (2θ) and stacking height (Lc) values, and the minimum d002 value. Moreover, the addition of asphaltene enhances the yield and aromaticity of the mesophase pitch and significantly improves the thermal stability of the resulting product.

A fully validated LC­MS/MS method for quantifying bevacizumab in plasma samples from patients with NSCLC and its implications in therapeutic drug monitoring.

Given the increasing use of bevacizumab in combinatorial drug therapy for a multitude of different cancer types, there is a need for therapeutic drug monitoring to analyze the possible correlation between drug trough concentration, and therapeutic effect and adverse reactions. An ultra-performance liquid chromatography tandem-mass spectrometry method was then developed and validated to determine bevacizumab levels in human plasma samples. Chromatographic separation was achieved on a Shimadzu InertSustainBio C18 HP column, whereas subsequent mass spectrometric analysis was performed using a Shimadzu 8050CL triple quadrupole mass spectrometer equipped with an electro-spray ionization source in the positive ion mode. In total, three multiple reaction monitoring transitions of each of the surrogate peptides were chosen with 'FTFSLDTSK' applied as the quantification peptide whereas 'VLIYFTSSLHSGVPSR' and 'STAYLQMNSLR' were designated as the verification peptides using the Skyline software. This analytical method was then fully validated, with specificity, linearity, lower limit of quantitation, accuracy, precision, stability, matrix effect and recovery calculated. The linearity of this method was developed to be within the concentration range 5-400 µg/ml for bevacizumab in human plasma. Subsequently, eight patients with non-small cell lung cancer (NSCLC) were recruited and injected with bevacizumab over three periods of treatment to analyze their steady-state trough concentration and differences. To conclude, the results of the present study suggest that bevacizumab can be monitored in a therapeutic setting in patients with NSCLC.

Effect of Aggregation Structure on Capacitive Energy Storage in Conducting Polymer Films.

Conducting polymers (CPs), a significant class of electrochemical capacitor electrode materials, exhibit exceptional capacitive energy storage performance in aqueous electrolytes. Current research primarily concentrates on enhancing the electrical conductivity and capacitive performance of CPs via molecular design and structural control. However, the absence of a comprehensive understanding of the impact of molecular chain spatial order on ion/electron transport and capacitive performance impedes the development and optimization of advanced electrode materials. Here, a solvent treatment strategy is employed to modulate the molecular chain spatial order of PEDOT : PSS films. The results of electrochemical performance tests and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) show that Poly(3,4-ethylenedioxythiophene) : poly(styrenesulfonic acid) (PEDOT : PSS) films with both face-on and edge-on orientations exhibit exceptional electronic conductivity and ion diffusion efficiency, with capacitive performance 1.33 times higher than that of PEDOT : PSS films with only edge-on orientation. Consequently, molecular chain orientations conducive to charge transport not only enhance inter-chain coupling, but also effectively reduce ion transport resistance, enabling efficient capacitive energy storage. This research provides novel insights for the design and development of higher performance CPs-based electrode materials.

Electrostatic Potential Design of Solid Additives for Enhanced Molecular Order of Polymer Donor in Efficient Organic Solar Cells.

Polymeric semiconducting materials struggle to achieve fast charge mobility due to low structural order. In this work, five 1H-indene-1,3(2H)dione-benzene structured halogenated solid additives namely INB-5F, INB-3F, INB-1F, INB-1Cl, and INB-1Br with gradually varied electrostatic potential are designed and utilized to regulate the structural order of polymer donor PM6. Molecular dynamics simulations demonstrate that although the dione unit of these additives tends to adsorb on the backbone of PM6, the reduced electrostatic potential of the halogen-substituted benzene can shift the benzene interacting site from alkyl side chains to the conjugated backbone of PM6, not only leading to enhanced π-π stacking in out-of-plane but also arising new π-π stacking in in-plane together with the appearance of multiple backbone stacking in out-of-plane, consequent to the co-existence of face-on and edge-on molecular orientations. This molecular packing transformation further translates to enhanced charge transport and suppressed carrier recombination in their photovoltaics, with a maximum power conversion efficiency of 19.4% received in PM6/L8-BO layer-by-layer deposited organic solar cells.

Effect of different screw speeds on the structure and properties of starch straws.

To illustrate the action mechanism of screw speed on the performance of starch-based straws during the extrusion process, starch-based straws at different screw speeds were prepared using a twin-screw extruder and the structures and characteristics were compared. The results indicated that as screw speeds improved from 3 Hz to 13 Hz, the A chain of amylopectin increased from 25.47 % to 28.87 %, and the B3 chain decreased from 6.34 % to 3.47 %. The absorption peak of hydroxyl group shifted from 3296 cm-1 to 3280 cm-1. The relative crystallinity reduced from 13.49 % to 9.89 % and the gelatinization enthalpy decreased from 3.5 J/g to 0.2 J/g. The performance of starch straws did not increase linearly with increasing screw speeds. The starch straw produced at screw speed of 7 Hz had the largest amylose content, the highest gelatinization temperature, the minimum bending strength, and the lowest water absorption rate in hot water (80 °C). Screw speed had a remarkable impact on the mechanical strength, toughness and hydrophobicity of starch-based straws. This study revealed the mechanism of screw speed on the mechanical strength and water resistance of starch straws in the thermoplastic extrusion process and created the theoretical basis for the industrial production of starch-based straws.

Impact of Intermittent Deposition on Spontaneous Orientation Polarization of Organic Amorphous Films Revealed by Rotary Kelvin Probe.

The control of the molecular orientation and resultant polarization is essential for improving the performance of organic optoelectronic devices. Conventionally, the substrate temperature and deposition rate are tuned to control the molecular orientation of vapor-deposited films. In this study, we proposed a novel method, referred to as "intermittent deposition", in which the polarization direction and magnitude are controlled by introducing intervals during physical vapor deposition. The rotary Kelvin probe measurement of the Alq3 and TPBi films clearly showed a time-dependent decrease in the surface potential owing to the surface relaxation of the molecular orientation immediately after deposition. Through a series of intermittent depositions, in which the deposition shutter is repeatedly opened and closed at certain intervals, a relaxed surface layer was built up, and we could control the polarization magnitude. For the Alq3 film, even the polarization direction was switched. The proposed new deposition method is applicable to general organic molecules, not limited to polar molecules, thereby potentially tuning the conduction properties of organic devices and fabricating novel devices.

Controlling Spontaneous Orientation Polarization in Organic Semiconductors─The Case of Phosphine Oxides.

Upon film growth by physical vapor deposition, the preferential orientation of polar organic molecules can result in a nonzero permanent dipole moment (PDM) alignment, causing a macroscopic film polarization. This effect, known as spontaneous orientation polarization (SOP), was studied in the case of different phosphine oxides (POs). We investigate the control of SOP by molecular design and film-growth conditions. Our results show that using less polar POs with just one phosphor-oxygen bond yields an exceptionally high degree of SOP with the so-called giant surface potential (slope), reaching more than 150 mV nm-1 in a neat bis-4-(N-carbazol(yl)phenyl)phenyl phosphine oxide (BCPO) film grown at room temperature. Additionally, by altering the evaporation rate and substrate temperature, we are able to control the SOP magnitude over a broad range from 0 to almost 300 mV nm-1. Diluting BCPO in a nonpolar host enhances the PDM alignment only marginally, but combining temperature control with dipolar doping can result in highly aligned molecules with more than 80% of their PDMs standing upright on the substrate on average.

Label-free detection of vitamin B by two-step enhanced Raman technique using dynamic borohydride-reduced silver nanoparticles.

A creatively designed novel two-step enhancement technique is presented in which B vitamin molecules are dynamically adsorbed onto the surface of silver nanoparticles by sodium borohydride, followed by local plasmon resonance in the presence of cations (calcium ions), ultimately achieving synergistic chemical and physical enhancement on the same molecule and constructing a "surface hot spots" two-step enhancement platform for vitamin detection. The Raman signal of the promoted vitamin molecule is enhanced by nine orders of magnitude. In a subsequent study it was observed that the vitamin B2 molecules were in a near-vertical image on the surface of the silver nanoparticles, which may also contribute to the Raman signal enhancement. Combined with deep learning techniques, the method has been successfully applied to the detection of B vitamins in body fluids. As an accurate, rapid, reproducible, non-invasive, and versatile assay platform, it holds great promise for the intelligent identification of trace B molecules in food, pharmaceuticals, and the human body.

Tuning Molecular Orientation Responses of Microfluidic Liquid Crystal Dispersions to Colloid and Polymer Flows.

An important approach to molecular diagnostics is integrating organized substances that provide complex molecular level responses to introduced chemical and biological agents with conditions that optimize and distinguish such responses. In this respect, liquid crystal dispersions are attractive components of molecular diagnostic tools. This paper analyzes a colloid system, containing a nematic liquid crystal as a dispersed phase, and aqueous surfactant and polymer solutions as the continuous phases. We applied a microfluidic approach for tuning orientation of liquid crystal molecules in picoliter droplets immobilized on microchannel walls. Introduction of surfactant to the aqueous phase was found to proportionally increase the order parameter of liquid crystal molecules in microdroplets. Infusion of polymer solutions into surfactant-mediated microfluidic liquid crystal dispersions increased the order parameter at much lower surfactant concentrations, while further infusion of surfactant solutions randomized the orientation of liquid crystal molecules. These effects were correlated with the adsorption of surfactant molecules on surfaces of microdroplets, stabilizing the effect of a polymer matrix on bound surfactant ions and the formation of insoluble polymer-colloid aggregates, respectively. The revealed molecular behavior of liquid crystal dispersions may contribute to optimized synthesis of responsive liquid crystal dispersions for in-flow molecular diagnostics of polymers and colloids, and the development of functional laboratory-on-chip prototypes.

Linearly Polarized Infrared Spectroscopy for the Analysis of Biological Materials.

The analysis of biological samples with polarized infrared spectroscopy (p-IR) has long been a widely practiced method for the determination of sample orientation and structural properties. In contrast to earlier works, which employed this method to investigate the fundamental chemistry of biological systems, recent interests are moving toward "real-world" applications for the evaluation and diagnosis of pathological states. This focal point review provides an up-to-date synopsis of the knowledge of biological materials garnered through linearly p-IR on biomolecules, cells, and tissues. An overview of the theory with special consideration to biological samples is provided. Different modalities which can be employed along with their capabilities and limitations are outlined. Furthermore, an in-depth discussion of factors regarding sample preparation, sample properties, and instrumentation, which can affect p-IR analysis is provided. Additionally, attention is drawn to the potential impacts of analysis of biological samples with inherently polarized light sources, such as synchrotron light and quantum cascade lasers. The vast applications of p-IR for the determination of the structure and orientation of biological samples are given. In conclusion, with considerations to emerging instrumentation, findings by other techniques, and the shift of focus toward clinical applications, we speculate on the future directions of this methodology.

Stacking Arrangement and Orientation of Aromatic Cations Tune Bandgap and Charge Transport of 2D Organic-Inorganic Hybrid Perovskites.

Chemical modifications on aromatic spacers of 2D perovskites have been demonstrated to be an effective strategy to simultaneously improve optoelectronic properties and stability. However, its underlying mechanism is poorly understood. By using 2D phenyl-based perovskites ([C6 H5 (CH2 )m NH3 ]2 PbI4 ) as models, the authors have revealed how the chemical nature of aromatic cations tunes the bandgap and charge transport of 2D perovskites by utilizing sum-frequency generation vibrational spectroscopy to determine the stacking arrangement and orientation of aromatic cations. It is found that the antiparallel slip-stack arrangement of phenyl rings between adjacent layers induces an indirect band gap, resulting in anomalous carrier dynamics. Incorporation of the CH2 moiety causes stacking rearrangement of the phenyl ring and thus promotes an indirect to direct bandgap transition. In direct-bandgap perovskites, higher carrier mobility correlates with a larger orientation angle of the phenyl ring. Further optimizing the orientation angle by introducing a para-substituted element in a phenyl ring, higher carrier mobility is obtained. This work highlights the importance of leveraging stacking arrangement and orientation of the aromatic cations to tune the photophysical properties, which opens up an avenue for advancing high-performance 2D perovskites optoelectronics via molecular engineering.

Instantaneous mapping of liquid crystal orientation using a polychromatic polarizing microscope.

Polarizing microscopy brought about many advancements in the science of liquid crystals and other soft materials, including those of biological origin. Recent developments in optics and computer-based analysis enabled a new generation of quantitative polarizing microscopy which produces spatial maps of the optic axis. Unfortunately, most of the available approaches require a long acquisition time of multiple images which are then analyzed to produce the map. We describe a polychromatic polarizing microscope, which allows one to map the patterns of the optical axis in a single-shot exposure, thus enabling a fast temporal resolution. We present a comparative analysis of the new microscope with alternative techniques such as a conventional polarizing optical microscope and MicroImager of Hinds Instruments.