Solid State Research Articles

Review: Perovskite Nanostructures Materials Versatile Platform for Advance Biosensor Applications

The distinct presence of a central atom surrounded by eight ligands leads to higher light absorption and charge carrier mobility in perovskite materials. The peculiar nature of the structure inspires all the scientists and researchers to work more in sustainable applications, such as solar cells, light emitting diodes, transistor and biosensors. The capability of perovskite material in detecting smaller molecules such as O2, NO2 and CO2 is higher. Therefore, several biosensors are demonstrated based on the perovskite nanomaterial to various chemical and biological species with both solid and solution states. The immense sources of research articles thrived the author, to review the perovskite nanomaterials in the dimension of biosensor application extensively. This review covers major three areas of perovskite nanomaterial, such as components and characteristics of biosensors, properties and preparation of perovskite materials and application and research trends of perovskite nanostructure biosensor.

Fluorescent columnar liquid crystals based on BTD hexacatenars with salicylaldimine and benzaldimine core: Self-assembly and multifunctional properties

Two series of hexacatenars SB/n and BB/n containing a benzothiadiazole (BTD) central core with triple alkyl chains at both ends via salicylaldehyde or benzaldehyde derivated Schiff base links, respectively, were prepared. Different Schiff base links lead to different self-assembly and photophysical behaviors. Both series can self-assemble into columnar liquid crystal (LC) phases but with different lattices (p6mm for SB/n, p4mm for BB/n) in bulk states, and SB/n can additionally form gels in organic solution. Interestingly, SB/n series were characterized with excited state intramolecular proton transfer (ESIPT) and aggregation-induced emission enhancement (AIEE) effects, and displayed high fluorescence in their solid, LC and gel states with large Stokes shifts and environmental sensitive unique spectra patterns. The effect of photoisomerization driven by ESIPT process on LC state of SB/n was observed. The applications of SB/n as fingerprint imaging device, Al3+ fluorescence chemosensor, white light emitting diodes (WLED) as well as light-emitting liquid crystal displays (LE-LCD) have been successfully realized.

Deep Reinforcement Learning-Enabled Distributed Uniform Control for a DC Solid State Transformer in DC Microgrid

Deep Reinforcement Learning-Enabled Distributed Uniform Control for a DC Solid State Transformer in DC Microgrid

Hyperpolarizing Small Molecules using Parahydrogen and Solid-State Spin Diffusion.

Parahydrogen-induced polarization (PHIP) is an inexpensive way to produce hyperpolarized molecules with polarization levels of >10% in the solution-state, but is strongly limited in generality since it requires chemical reactions/interactions with H2. Here we report a new method to widen the scope of PHIP hyperpolarization: a source molecule is produced via PHIP with high 13C polarization, and precipitated out of solution together with a target species. Spin diffusion within the solid carries the polarization onto 13C spins of the target, which can then be dissolved for solution-state applications. We name this method PHIP-SSD (PHIP with solid-state spin diffusion) and demonstrate it using PHIP-polarized [1-13C]-fumarate as the source molecule, to polarize different 13C-labelled target molecules. 13C polarizations of between 0.01 and 3% were measured on [1-13C]-benzoic acid, depending on the molar ratio of fumarate:benzoate in the solid state. We also show that PHIP-SSD does not require specific co-crystallization conditions by grinding dry powders of target molecules together with solid fumarate crystals, and obtain 13C signal enhancements of between 100 and 200 on [13C,15N2]-urea, [1-13C]-pyruvate, and [1-13C]-benzoic acid. This approach appears to be a promising new strategy for facile hyperpolarization based on PHIP.

Synthesis of Molsidomine and Mesocarb Analog via Mechanochemistry

Iminosydnones (ImSyds) have renowned biological activities and attractive chemical properties for chemical biology. However, access to N6‐functionalized iminosydnones involves tricky and hazardous procedures. Thanks to an innovative mechanochemical strategy using 1,1’‐carbonyldiimidazole (CDI) as an activating agent, a straightforward synthesis of molsidomine and of a mesocarb analog, two bioactive iminosydnones, was achieved. The whole process, involving 4 linear steps, was carried out in the solid state by ball‐milling and with safe reagents, offering efficient and sustainable access to N‐carbonylated iminosydnones, in agreement with the principles of green chemistry.

Hyperpolarizing Small Molecules using Parahydrogen and Solid‐State Spin Diffusion

Parahydrogen‐induced polarization (PHIP) is an inexpensive way to produce hyperpolarized molecules with polarization levels of >10% in the solution‐state, but is strongly limited in generality since it requires chemical reactions/interactions with H2. Here we report a new method to widen the scope of PHIP hyperpolarization: a source molecule is produced via PHIP with high 13C polarization, and precipitated out of solution together with a target species. Spin diffusion within the solid carries the polarization onto 13C spins of the target, which can then be dissolved for solution‐state applications. We name this method PHIP‐SSD (PHIP with solid‐state spin diffusion) and demonstrate it using PHIP‐polarized [1‐13C]‐fumarate as the source molecule, to polarize different 13C‐labelled target molecules. 13C polarizations of between 0.01 and 3% were measured on [1‐13C]‐benzoic acid, depending on the molar ratio of fumarate:benzoate in the solid state. We also show that PHIP‐SSD does not require specific co‐crystallization conditions by grinding dry powders of target molecules together with solid fumarate crystals, and obtain 13C signal enhancements of between 100 and 200 on [13C,15N2]‐urea, [1‐13C]‐pyruvate, and [1‐13C]‐benzoic acid. This approach appears to be a promising new strategy for facile hyperpolarization based on PHIP.

Experimental Simulation of Directional Crystallization of SiMo Cast Iron Alloyed with Al and Cr

SiMo ductile cast iron combines ease of part fabrication with good mechanical properties, including a usable plasticity range. Its poor corrosion resistance inherited from grey cast iron could be alleviated through alloying with Al or Cr additions capable of forming a dense oxide scale protecting the substrate. However, the presence of Al and Cr in cast iron tends to make the material brittle, and their optimum alloying additions need to be studied further. The present work was aimed at investigating the effect of crystallization rates on microstructure changes during directional crystallization of SiMo-type alloys with up to 3.5% Al and 2.4% Cr. The experiment was performed using the Bridgman–Stockbarger method. The tubular crucible was transferred from the hot section to cold section at rates ranging from 5 mm/h to 30 mm/h with a 4/5 crucible length and then quenched. The introduced Al promoted graphitization up to a point, wherein, at the highest applied addition, the graphite precipitation preceded crystallization of the rest of the melt. A rising level of Cr in these alloys from 1% to 2.4% resulted in the formation of low and high contents of pearlite, respectively. The higher crystallization rates proved effective in increasing the ferrite content at the expense of pearlite. In the investigated cast iron samples with smaller applied alloying additions, Widmanstätten ferrite or ausferrite, i.e., fine acircular phase, were often found. The switch from directional crystallization to quenching caused a transition from a liquid to solid state, which started with nucleation of islands of fine austenite dendrites with chunky graphite eutectic separating them. As these islands expanded, they pushed alloying additions to their sides, promoting carbide or pearlite formation in these places and forming a super-cell-like structure. The performed experiments helped gather information concerning the sensitivity of the microstructure of SiMo cast iron modified with Al and Cr to crystallization rates prevailing in heavy cast structures.

Uncovering Factors Controlling Reactivity of Metal-TEMPO Reaction Systems in the Solid State and Solution.

Nitroxides find application in various areas of chemistry, and a more in-depth understanding of factors controlling their reactivity with metal complexes is warranted to promote further developments. Here, we report on the effect of the metal centre Lewis acidity on both the distribution of the O- and N-centered spin density in 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and turning TEMPO from the O- to N-radical mode scavenger in metal-TEMPO systems. We use Et(Cl)Zn/TEMPO model reaction system with tuneable reactivity in the solid state and solution. Among various products, a unique Lewis acid-base adduct of Cl2Zn with the N-ethylated TEMPO was isolated and structurally characterised, and the so-called solid-state 'slow chemistry' reaction led to a higher yield of the N-alkylated product. The revealed structure-activity/selectivity correlations are exceptional yet are entirely rationalised by the mechanistic underpinning supported by theoretical calculations of studied model systems. This work lays a foundation and mechanistic blueprint for future metal/nitroxide systems exploration.

Atomically Precise Chiral Metal Nanoclusters for Circularly Polarized Light Detection

Circularly polarized light (CPL) detection is of great significance in various applications such as drug identification, sensing and imaging. Atomically precise chiral metal nanoclusters with intense circular dichroism (CD) signals are promising candidates for CPL detection, which can further facilitate device miniaturization and integration. Herein, we report the preparation of a pair of optically active chiral silver nanoclusters [Ag7(R/S‐DMA)2(dpppy)3] (BF4)3 (R/S‐Ag7) for direct CPL detection. The crystal structure and molecular formula of R/S‐Ag7 clusters are confirmed by single‐crystal x‐ray diffraction and high‐resolution mass spectrometry. R/S‐Ag7 clusters exhibit strong CD spectra and CPL luminescence both in solution and solid states. When used as the photoactive materials in photodetectors, R/S‐Ag7 enables effective discrimination between left‐handed circularly polarized and right‐handed circularly polarized light at 520 nm with short response time, high responsivity and considerable discrimination ratio. This study is the first report on using atomically precise chiral metal nanoclusters for CPL detection.

Atomically Precise Chiral Metal Nanoclusters for Circularly Polarized Light Detection.

Circularly polarized light (CPL) detection is of great significance in various applications such as drug identification, sensing and imaging. Atomically precise chiral metal nanoclusters with intense circular dichroism (CD) signals are promising candidates for CPL detection, which can further facilitate device miniaturization and integration. Herein, we report the preparation of a pair of optically active chiral silver nanoclusters [Ag7(R/S-DMA)2(dpppy)3] (BF4)3 (R/S-Ag7) for direct CPL detection. The crystal structure and molecular formula of R/S-Ag7 clusters are confirmed by single-crystal x-ray diffraction and high-resolution mass spectrometry. R/S-Ag7 clusters exhibit strong CD spectra and CPL luminescence both in solution and solid states. When used as the photoactive materials in photodetectors, R/S-Ag7 enables effective discrimination between left-handed circularly polarized and right-handed circularly polarized light at 520 nm with short response time, high responsivity and considerable discrimination ratio. This study is the first report on using atomically precise chiral metal nanoclusters for CPL detection.

Cellulose- and Saccharide-Based Orally Dispersible Thin Films Transform the Solid States and Dissolution Characteristics of Poorly Soluble Curcumin

Cellulose- and Saccharide-Based Orally Dispersible Thin Films Transform the Solid States and Dissolution Characteristics of Poorly Soluble Curcumin

Experimental Evidence of the Molecular and Macroscopic Origins of Circular Dichroism in Chiral Metal‐Halide Networks

AbstractClockwise or counter‐clockwise spin coating? In the current hot research topic of chiral metal‐halide semiconductors, several investigations have been undertaken in order to reveal their natural optical activity and have reported dissymmetry factors (gabs) for thin films of many hybrid compounds, usually without considering the macroscopic anisotropies inherent to solid‐state samples. Yet, CD in the solid state can be strongly modulated by the co‐existence of linear dichroism (LD) and linear birefringence (LB). Theoretical studies recently revealed the importance of such macroscopic interferences in the CD response of solid‐state samples, often referred as symmetric (sLDLB) and antisymmetric (aLDLB) effects. Based on the newly synthesized one‐dimensional lead‐halide networks of formula (S/R‐HP1A)PbBr3 and (S/R‐HP1A)PbI3, an experimental method to accurately discriminate between CD, sLDLB and aLDLB in chiral metal‐halide networks is here presented. The main experimental conditions influencing sLDLB and aLDLB amplitude are also highlighted, such as the concentration of the precursor solution and the spin‐coating rotation direction, finally providing a complete experimental guide for the forthcoming chiroptical investigations of such important family of chiral hybrid materials.

Telluronium-Catalyzed Halogenation Reactions: Chalcogen-Bond Activation of N-Halosuccinimides and Catalysis.

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and in solution is demonstrated herein. Cocrystals of the triaryltelluronium bearing two CF3 electron-withdrawing groups per aryl ring with N-chloro-, N-bromo- and N-iodosuccinimide (respectively NCS, NBS and NIS) were analyzed by X-ray diffraction, evidencing a ChB between tellurium and the carbonyl group of NXS. This ChB was confirmed in solution by NMR spectroscopy, especially by 125Te NMR titration experiment, which allowed the determination of the association constant (Ka) between the telluronium and NBS. The so-obtained Ka value of 17.3 ± 0.6 M-1 indicated a moderate interaction in solution because of the competitive role of the solvent. The strength of the Te---O ChB was however sufficient enough to promote the catalytic halofunctionalization of aromatics and of alkenes such as the intra- and intermolecular haloalkoxylation and haloesterification of alkenes.

Novel Solid‐state Fluorophores, a Series of Cyanostilbene‐based Amorphous Molecular Materials

We have designed and synthesized a novel series of cyanostilbene‐based amorphous molecular materials with different methylene chain lengths, BMAC‐n (n=3,4,5,6), and investigated their emitting properties in solution and various solid states. All BMAC‐n molecules showed solvatochromic fluorescence in solutions. Emission spectra of BMAC‐n molecules in the same solution were identical to one another irrespective of the methylene chain length while the spectra in crystalline states depended on their methylene chain length. As in solutions, emission spectra of their spin‐coated amorphous films were identical to each other irrespective of the methylene chain length. Emission spectra of rubbed amorphous films prepared by grinding their crystals were identical to those for spin‐coated amorphous films; however, comparative studies between spin‐coated and rubbed amorphous films indicated that fluorescence quantum yields and photochemical reactivity depend on the preparation method.

Loquat and its phytochemical potential: A promising application in food technology

AbstractThis review study highlights the importance of loquat (Eriobotrya japonica Lindl.) in terms of its nutritional, pharmaceutical, and nutraceutical value. The entire plant, including its seeds, leaves, flowers, fruits, and peel, contains a wide range of bioactive compounds, such as phenolics, carotenoids, triterpenic acids, and organic acids. These compounds exhibit a wide range of beneficial properties such as fighting cancer, reducing inflammation, managing diabetes, combating viruses, preventing mutations, inhibiting nitrosamine formation, killing harmful microorganisms, lowering blood sugar levels, inducing cell death, and protecting the liver. The extraction and separation of such compounds will greatly enhance and expand its potential. Furthermore, the waste generated from the seeds and peel can be effectively used for submerged and solid state biomass production.

Delocalizing Excitation for Highly‐Active Organic Photovoltaic Catalysts

AbstractLocalized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo‐induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation of small molecular photovoltaic catalysts by weakening their electron‐phonon coupling via rational fluoro‐substitution. The optimized 2FBP‐4F catalyst we develop here exhibits a minimized Huang–Rhys factor of 0.35 in solution, high dielectric constant and strong crystallization in the solid state. As a result, the energy barrier for exciton dissociation is decreased, and more importantly, polarons are unusually observed in 2FBP‐4F nanoparticles (NPs). With the increased hole transfer efficiency and prolonged charge carrier lifetime highly related to enhanced exciton delocalization, the PM6 : 2FBP‐4F heterojunction NPs at varied concentration exhibit much higher optimized photocatalytic activity (207.6–561.8 mmol h−1 g−1) for hydrogen evolution than the control PM6 : BP‐4F and PM6 : 2FBP‐6F NPs, as well as other reported photocatalysts under simulated solar light (AM 1.5G, 100 mW cm−2).

Direct observation of electron transfer in solids through X-ray crystallography

Nanoscale electron transfer (ET) in solids is fundamental to the design of multifunctional nanomaterials, yet its process is not fully understood. Herein, through X-ray crystallography, we directly observe solid-state ET via a crystal-to-crystal process. We first demonstrate the creation of a robust and flexible electron acceptor/acceptor (A/A) double-wall nanotube crystal ([(Zn2+)4(LA)4(LA=O)4]n) with a large window (0.90 nm × 0.92 nm) through the one-dimensional porous crystallization of heteroleptic Zn4 metallocycles ((Zn2+)4(LA)4(LA=O)4) with two different acceptor ligands (2,7-bis((1-ethyl-1H-imidazol-2-yl)ethynyl)acridine (LA) and 2,7-bis((1-ethyl-1H-imidazol-2-yl)ethynyl)acridin-9(10H)-one (LA=O)) in a slow-oxidation-associated crystallization procedure. We then achieve the bottom-up construction of the electron donor incorporated-A/A nanotube crystal ([(D)2⊂(Zn2+)4(LA)4(LA=O)4]n) through the subsequent absorption of electron donor guests (D = tetrathiafulvalene (TTF) and ferrocene (Fc)). Finally, we remove electrons from the electron donor guests inside the nanotube crystal through facile ET in the solid state to accumulate holes inside the nanotube crystal ([(D•+)2⊂(Zn2+)4(LA)4(LA=O)4]n), where the solid-state ET process (D – e– → D•+) is thus observed directly by X-ray crystallography.

Spectroscopic Evidence for Doubly Hydrogen-Bonded Cationic Dimers in the Solid, Liquid, and Gaseous Phases of Carboxyl-Functionalized Ionic Liquids.

Intermolecular interactions determine whether matter sticks together, gases condense into liquids, or liquids freeze into solids. The most prominent example is hydrogen bonding in water, responsible for the anomalous properties in the liquid phase and polymorphism in ice. The physical properties are also exceptional for ionic liquids (ILs), wherein a delicate balance of Coulomb interactions, hydrogen bonds, and dispersion interactions results in a broad liquid range and the vaporization of ILs as ion pairs. In this study, we show that strong, local, and directional hydrogen bonds govern the structures and arrangements in the solid, liquid, and gaseous phases of carboxyl-functionalized ILs. For that purpose, we explored the H-bonded motifs by X-ray diffraction and attenuated total reflection (ATR) infrared (IR) spectroscopy in the solid state, by ATR and transmission IR spectroscopy in the liquid phase, and by cryogenic ion vibrational predissociation spectroscopy (CIVPS) in the gaseous phase at low temperature. The analysis of the CO stretching bands reveals doubly hydrogen-bonded cationic dimers (c═c), resembling the archetype H-bond motif known for carboxylic acids. The like-charge doubly hydrogen-bonded ion pairs are present in the crystal structure of the IL, survive phase transition into the liquid state, and are still present in the gaseous phase even in (2,1) complexes wherein one counterion is removed and repulsive Coulomb interaction increased. The interpretation of the vibrational spectra is supported by quantum chemical methods. These observations have implications for the fundamental nature of the hydrogen bond between ions of like charge.

Immobilization of alkaline protease produced by Streptomyces rochei strain NAM-19 in solid state fermentation based on medium optimization using central composite design.

This study evaluated Streptomyces rochei strain NAM-19 solid-state fermentation of agricultural wastes to produce alkaline protease. Alkaline protease production increased with flaxseed, rice bran, and cheese whey fermentation reaching 147U/mL at 48h. Statistical optimization of alkaline protease production was performed using the central composite design (CDD). Results of CDD and the optimization plot showed that 4.59g/L flaxseed, 4.31g/L rice bran, 4.17mL cheese whey, and a vegetative inoculum size of 7.0% increased alkaline protease production by 27.2% reaching 186U/mL. Using the 20-70% ammonium sulfate fractionation method, the optimally produced enzyme was partially purified to fivefold. The partially purified alkaline protease was then covalently immobilized on a biopolymer carrier, glutaraldehyde-polyethylene-imine-κ-carrageenan (GA-PEI-Carr), with 90% immobilization efficiency. Characterizations revealed that immobilization improved thermostability, reusability, optimum temperature, and sensitivity towards metal ions of the free enzyme. The optimal temperature for free and immobilized enzymes was 40 and 50°C, respectively. Both enzymes had the same optimum pH of 10. Immobilization increased Km from 19.73 to 26.52mM and Vmax from 56.7 to 62.5mmolmin-1L-1. The immobilized enzyme retained 35% of its initial activity at 70°C, while the free enzyme retained only 5%. The immobilized enzyme kept 80% of its initial activity at the 20th cycle. After 7weeks of storage, the free enzyme lost all its initial activity, whereas the immobilized enzyme retained 50%. The free and immobilized enzymes were able to hydrolyze gelatin, and azo-casein demonstrating different relative activity, 85, 80, 90 and 95%, respectively, compared to casein (100%).

Helicene Appended Benzothiadiazoles as Chiral Emitters.

A homologous series of 4,7-bis(aryl) substituted benzothiadiazole (BTD) compounds, containing the helicenic derivatives bis([4]helicene), bis([5]helicene) and bis([6]helicene), have been prepared upon a double Suzuki coupling between 3,6-bis(pinacolyl-borane)-BTD and the corresponding bromo-aryl precursors. The single crystal X-ray structure of the bis([4]helicene) compound shows the existence of both helicities (M) and (P) on the same molecule. All the compounds of the series are highly emissive in solution, with quantum yields of the emission ranging from 50 to 91%. The enantiopure compounds (M,M) and (P,P) for the BTD-bis([6]helicene) have been prepared from the corresponding enantiopure 2-bromo-[6]helicene precursors. Their chiroptical properties have been investigated in correlation with density functional theory (DFT) calculations, which allowed to confidently assign the absolute configuration of the helicene arms and to characterize the different electronic transitions, including the low energy charge transfer excitation from helicenes to BTD. The enantiomerically pure fluorophores (M,M)- and (P,P)-BTD-bis([6]helicene), which exist in solution as two main conformers, according to the DFT calculations, show CPL activity in solution, with glum factors of ≈ 1.7×10-3 at lem = 525 nm, and also in the solid state, with glum factors of ≈ 1.2×10-3 in spite of the strong decrease of the quantum efficiency.