Organic-inorganic Materials Research Articles

Nonenzymatic Potentiometric Detection of Ascorbic Acid with Porphyrin/ZnO-Functionalized Laser-Induced Graphene as an Electrode of EGFET Sensors.

Laser-induced graphene (LIG) has emerged as a highly versatile material with significant potential in the development of electrochemical sensors. In this paper, we investigate the use of LIG and LIG functionalized with ZnO and porphyrins-ZnO as the gate electrodes of the extended gate field effect transistors (EGFETs). The resultant sensors exhibit remarkable sensitivity and selectivity, particularly toward ascorbic acid. The intrinsic sensitivity of LIG undergoes a notable enhancement through the incorporation of hybrid organic-inorganic materials. Among the variations tested, the LIG electrode coated with zinc tetraphenylporphyrin-capped ZnO nanoparticles demonstrates superior performance, reaching a limit of detection of approximately 3 nM. Furthermore, the signal ratio for 5 μM ascorbic acid relative to the same concentration of dopamine exceeds 250. The practical applicability of these sensors is demonstrated through the detection of ascorbic acid in real-world samples, specifically in a commercially available food supplement containing l-arginine. Notably, formulations with added vitamin C exhibit signals at least 25 times larger than those without, underscoring the sensors' capability to discern and quantify the presence of ascorbic acid in complex matrices. This research not only highlights the enhanced performance of LIG-based sensors through functionalization but also underscores their potential for practical applications in the analysis of vitamin-rich supplements.

A 1D Sb-containing hybrid organic-inorganic material: Synthesis, structural characterization, hirshfeld surface, thermal behavior, vibrational and optical properties

A novel interesting hybrid organic-inorganic material of Bis (2-amino-3-nitropyridinuim) pentachloroantimoinates (III) with the formula [C5H6N3O2]2SbCl5 was elaborated by slow evaporation at room temperature. This compound was crystallized in the monoclinic system with the P 21/c space group, as shown using the X-ray diffraction results. The parameters are the following: a = 16.484(6) Å, b = 7.7170 (19) Å, c = 16.159 (7) Å, β= 109.26(5)°, Z = 4 and V = 1940,5(14) Å3. The asymmetric unit consists of one Sb (III) cation surrounded by five Cl− and two protonated cations 2-amino-3-nitropyridinuim. The crystal packing cohesion was maintained by NH…Cl and NH…O hydrogen bonds to form a three- dimensional network. The infrared IR and Raman studies which were recorded at room temperature in the 4000–400 cm−1 and 0–4000 cm−1 frequency regions, respectively, confirmed the existence of vibrational modes that correspond to the organic and inorganic groups. The Hirshfeld analysis results show that the predominate interactions were H…Cl and O…H contacts (39.9, 14.5 % respectively). The Thermogravimetric analysis TGA shows that this compound remains stable up to about 150 °C. The optical properties were characterized experimentally by UV–visible absorption studies and photoluminescence measurements. The Photoluminescence spectrum manifests a broad and strong band of luminescence around 454 nm (2.73 eV), which can be even observed with the naked eye at room temperature and is due to exciton emission.

Improve the Charge Carrier Transporting in Two-Dimensional Ruddlesden-Popper Perovskite Solar Cells.

Conventional 3D organic-inorganic halide perovskite materials have shown substantial potential in the field of optoelectronics, enabling the power conversation efficiency of solar cells beyond 26%. A key challenge limiting the further commercial application of 3D perovskite solar cells is their inherent instability over outer oxygen, humidity, light, and heat. By contrast, 2D Ruddlesden-Popper (2DRP) perovskites with bulky organic cations can effectively stabilize the inorganic slabs, yielding excellent environmental stability. However, the efficiencies of 2DRP perovskite solar cells are much lower than those of the 3D counterparts due to poor charge carrier transporting property of insulating bulky organic cations. Their inner structural, dielectric, optical, and excitonic properties remain to be primarily studied. In this review, the main reasons for the low efficiency of 2DRP perovskite solar cells are first analyzed. Next, a detailed description of various strategies for improving the charge carrier transporting of 2DRP perovskites is provided, such as bandgap regulation, perovskite crystal phase orientation and distribution, energy level matching, interfacial modification, etc. Finally, a summary is given, and the possible future research directions and methods to achieve high-efficiency and stable 2DRP perovskite solar cells are rationalized.

In Situ Construction of Morphologically Different Hydroxyapatite-Mineralized Structures on a Three-Dimensional Bionic Chitin Scaffold.

Slow healing at the tendon-bone interface is a prominent factor in the failure of tendon repair surgeries. The development of functional biomaterials with 3D gradient structures is urgently needed to improve tendon-bone integration. The crystalline form of hydroxyapatite (HAP) has a crucial impact on cell behavior, which directly influences protein adsorption, such as bone morphogenetic protein 2, the adhesion, proliferation, and osteogenic differentiation with cells. This work aimed to generate gradient mineral structures in situ by stabilizing calcium and phosphate ions using a polymer-induced liquid precursor process. To regulate the crystalline growth of HAP at the interface of β-chitin, this work made use of the surface properties of the organic matrix found in cuttlefish bone. These techniques allowed us to prepare an organic-inorganic composite gradient scaffold comprising plate-like HAP mineralized in situ on the surface of the scaffold and fibrous HAP in the scaffold's interior. Organic-inorganic composite gradient materials are anticipated for use in tendon-bone healing produced via the in situ construction of gradient-distributed HAP mineralization layers having varying crystalline morphologies on chitin scaffolds that possess a three-dimensional bionic structure.

Progress on Electron Transport Layers for Perovskite Solar Cells

The photovoltaic industry is very interested in designing and developing next-generation device architectures using organic-inorganic perovskite hybrid solar cell materials. In fact, perovskites represent one of the most promising materials for high efficiency, low-cost solar cells. This is most apparent in the power conversion efficiency of perovskite solar cells (PSCs) going from 3.8 to 24.2 % in recent years. One of the primary challenges of developing PSC’s however is the realization of an appropriate electron transport layer. As such, this review focuses on recent developments in the electron transport layer (ETL) of perovskite solar cells. It examines and summarises designs, electron transport layers and perovskite active layers for efficient perovskite solar cells. The performance and stability issues with organic-inorganic halide perovskite solar cells are also discussed with some recommendations for additional research on the ETL and perovskite active layer were offered.

From C4H7N2Ge0.4Sn0.6Br3 to C6H11N2Ge0.4Sn0.6Br3: Effective Modulation of the Second Harmonic Generation Effect and Optical Band Gap by Planar π-Conjugated Organic Cation Size.

In the search for nonlinear optical (NLO) materials with excellent overall performance, we have devoted ourselves to organic-inorganic hybrids consisting of anionic groups containing stereochemically active lone-pair (SCALP) electron cations and organic planar π-conjugated group cations. Accordingly, in this paper, two novel organic-inorganic hybrid metal halides, C4H7N2Ge0.4Sn0.6Br3 (I) and C6H11N2Ge0.4Sn0.6Br3 (II), have been synthesized. The powder second-harmonic technique shows that both C4H7N2Ge0.4Sn0.6Br3 and C6H11N2Ge0.4Sn0.6Br3 have moderately strong second-order nonlinear optical effects, which are about 2.03 (I) and 1.16 (II) times that of KH2PO4 (KDP), respectively. They also have different optical band gaps of 2.75 (I) and 2.88 eV (II) due to the different sizes of the organic cations, and their photoluminescent and thermal properties were also investigated. This work provides new structural insights for the design and modulation of organic-inorganic hybrid halide materials with multiple excellent optical properties.

Polarization manipulation on step-index composite polymer beam splitters for photonics circuitry

This paper presents composite beam splitters realized with polymer materials for developing photonic integrated circuits. We used organic-inorganic hybrid polymer materials to form this composite beam splitter realized with step-index (SI) core profiles. We used the alternating direction implicit technique of the Rsoft CAD BeamPROP solver to design and analyze these beam splitters. We successfully examined and manipulated the beam splitter’s polarization dependency to obtain a 99% output efficiency with a 50:50 splitting ratio. The SI beam splitter exhibits an excess loss of 0.014 dB. When we apply polarized light in this beam splitter, the excess loss increases to 2 dB, and this loss gradually decreases as the angle of incident light increases. The excess loss reduces to 0.05 dB at the 31-degree angles of the incident polarized light. We also investigated the crosstalk of this beam splitter by varying the wavelength, and it is evident that the lowest crosstalk is −19.77 dB at the polarized angle of 31°.

DFT Study on the Spin States of Polyaniline-3d Transition-Metal (Sc-Zn) Composites and Their Sensing Application to Detect Chemical Warfare Agents.

Organic-inorganic composite materials, combining polymers with transition metal (TM) atoms based on PAni and 3d TMs, have been designed and investigated in various spin states by performing density functional calculations. These designed composites were analyzed for their stability in different spin states as well as for their calculated electronic properties, including binding energies, frontier molecular orbitals, and dipole moments. Additionally, 3D isosurfaces and 2D scattered plots of reduced density gradient as a function of (sign λ2)ρ provide insights into the noncovalent interactions between the composite units. The most stable Mn@PAni composite has been assessed as a sensing material for chemical warfare blood agents (HCN, NCCl, NCBr, NCCN, and AsH3) using density functional-based calculations. The reduced band gap and significant red/blue shift in the UV-vis spectra obtained through TDDFT calculations underline the selectivity and efficiency of the Mn@PAni composite toward different analytes.

Investigating the Structure-property Relationships of Two Cd-based Hybrid Multifunctional Compounds with High Tc, Bright Fluorescence and Wide Band-gap.

Organic-inorganic hybrid multifunctional materials have shown significant application in lighting and sensor fields, owing to their prominent performance and diversity structures. Herein, we synthesized two multifunctional compounds: (propyl-quinuclidone)2 CdBr4 (1) and (F-butyl-quinuclidone)2 CdBr4 (2). By introducing light-emitting organic cation with flexible long chain, 1 and 2 exhibit excellent transition properties and bright blue-white fluorescence. Then, combine fluorescence lifetime and first-principal calculation, providing evidence for the electron transfer emission. Subsequently, investigated the impact of substituent carbon chain length (methyl to butyl), structural rigidity (C-C to C-F) and halide framework (Cl to I) on the fluorescence properties. Results indicate that Cd⋅⋅⋅Cd distance and structural rigidity play an important role in fluorescence. Overall, our research provides valuable insight and example for chemical modifications enhance compound performance.

Study on improvement of copper sulfide acid soil properties and mechanism of metal ion fixation based on Fe-biochar composite

In this study, Fe modification of bamboo biochar (BC) with ferrate was used to construct a composite soil amendment based on K2FeO4-biochar (Fe-BC) system. Based on soil culture experiments, Fe-BC combined with organic–inorganic materials at the application levels of 3%, 5% and 10% to copper sulfide contaminated acid soil was studied. Adsorption kinetics experiment was used to investigate the adsorption capacity of Fe-modified biochar to heavy metal Cu. The results showed that the pH value of bamboo biochar could be increased by 1.12 units after K2FeO4 modification. Compared with the BC, the adsorption capacity of Cu2+ increased from 190.48 to 276.12 mg/g, which was mainly reflected in single-layer surface adsorption and chemisorption. Pore diffusion, electrostatic interaction and surface interaction are the possible mechanisms of Fe-BC interaction with Cu2+ ions. And the contents of Pb, Cu and Zn in soil leaching state decreased by 59.20%, 65.88% and 57.88%, respectively, at the 10% application level of Fe-BC. In general, the composite modifier based on ferrate and biochar has a positive effect on improving the characteristics of acidic soil in copper mining area.

Tunable Periodic Nanopillar Array for MAPbI3 Perovskite Photodetectors with Improved Light Absorption.

In the field of optoelectronic applications, the vigorous development of organic-inorganic hybrid perovskite materials, such as methylammonium lead triiodide (MAPbI3), has spurred continuous research on methods to enhance the photodetection performance. Periodic nanoarrays can effectively improve the light absorption of perovskite thin films. However, there are still challenges in fabricating tunable periodic patterned and large-area perovskite nanoarrays. In this study, we present a cost-effective and facile approach utilizing nanosphere lithography and dry etching techniques to create a large-area Si nanopillar array, which is employed for patterning MAPbI3 thin films. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) results reveal that the introduction of nanopillar structures did not have a significant adverse effect on the crystallinity of the MAPbI3 thin film. Light absorption tests and optical simulations indicate that the nanopillar array enhances the light intensity within the perovskite films, leading to photodetectors with a responsivity of 11.2 A/W and a detectivity of 7.3 × 1010 Jones at 450 nm in wavelength. Compared with photodetectors without nanostructures, these photodetectors exhibit better visible light absorption. Finally, we demonstrate the application of these photodetector arrays in a prototype image sensor.

Structural forming of soil composites using as a pavement subgrade strengthening

The article substantiates the possibility of obtaining composite materials with improved functional properties to strengthen the subgrade, containing technogenic soil stabilized by an additive based on a gelling polymer. The introduction of technogenic soils into composites will not only reduce the consumption of expensive materials, but also solve a complex of acute environmental problems. Composite materials can be used in the construction of structural layers of road pavements, foundations of buildings and structures, sites for various purposes, for the prevention and elimination of defects in the foundations of engineering structures during their construction, reconstruction and repair, including in permafrost areas. Stabilized technogenic soils are more durable, frost-resistant and waterproof, which makes them applicable for creating impervious curtains in hydraulic structures and sealing storage facilities for hazardous substances. The cryogenic effect on a composite material allows one to vary its properties within a wide range and modify its macroporous structure. Studying the process of structure formation of the resulting organic-inorganic materials, consisting of macromolecules of high-molecular substances and inorganic inclusions that have undergone cryogenic treatment, will make it possible to specifically regulate their performance characteristics. The best values of strength characteristics were obtained for samples with a stabilizing additive concentration of 100 g/l. The resulting composite materials are hydrophobic, frost-resistant, characterized by a compressive strength of 2.3–6.5 MPa and a thermal conductivity of 0.19–0.20 W/(m·K). Data from differential scanning calorimetry and thermogravimetry and IR spectroscopy revealed that the binding of mineral particles by a stabilizing additive occurs due to the formation of organomineral complexes with the participation of clay minerals and the restructuring of hydration shells. SEM data indicate that crystallinity zones formed due to hydrogen bonds of hydroxyl groups of neighboring polymer chains can participate in the formation of the composite structure. An increase in the number of cryogenic treatment cycles promotes additional structuring and strengthening of the polymer phase due to the formation of additional nodes of the supramolecular network, ordering of crystallinity zones and the appearance of compacted areas in the structure. Computed X-ray tomography revealed an increase in the density of the composite upon drying, which helps to increase its strength characteristics. The structure of the sample is characterized by heterogeneity of the pore space, which is characterized by the presence of both fine-porous and large-porous regions, which determines its thermophysical properties.

Catalytic applications of organic-inorganic hybrid porous materials.

Organic-inorganic hybrid porous materials (OIHMs) inherit the unique properties from both organic and inorganic components, and the flexibility in the incorporation of functional groups renders the OIHMs an ideal platform for the construction of catalytic materials with multiple active sites. The preparation of OIHMs with precise locations of organic-inorganic components and tunable structures is one of the important topics for the catalytic application of OIHMs, but it is still very challenging. In this feature article, we describe our work related to the preparation of OIHMs via confining active sites in the nanostructure and a layer-by-layer assembly method and their applications in acid-base catalysis, catalytic hydrogenation and photocatalysis with a focus on the elucidation of the synergistic effects of different active sites and the unique properties of OIHMs in catalysis.

An organic-inorganic hybrid perovskite material [Me3NCMe3]GaCl4 exhibits a two-step off-on-off SHG response with a large temperature interval.

Reaction of a quaternary ammonium salt with GaCl3 in concentrated HCl aqueous solution led to an organic-inorganic hybrid perovskite material [Me3NCMe3][GaCl4] (1), which shows a two-step off-on-off second harmonic generation (SHG) response with a rapid and large temperature interval.

Impact of inorganic/organic nanomaterials on the immune system for disease treatment.

The study of nanomaterials' nature, function, and biocompatibility highlights their potential in drug delivery, imaging, diagnostics, and therapeutics. Advancements in nanotechnology have fostered the development and application of diverse nanomaterials. These materials facilitate drug delivery and influence the immune system directly. Yet, understanding of their impact on the immune system is incomplete, underscoring the need to select materials to achieve desired outcomes carefully. In this review, we outline and summarize the distinctive characteristics and effector functions of inorganic nanomaterials and organic materials in inducing immune responses. We highlight the role and advantages of nanomaterial-induced immune responses in the treatment of immune-related diseases. Finally, we briefly discuss the current challenges and future opportunities for disease treatment and clinical translation of these nanomaterials.

Photoelectrochemical signal polarity transition mediated by quercetin for the detection of neuron-specific enolase.

A photoelectrochemical (PEC) biosensor with a wide linear detection range was developed for the sensitive detection of neuron-specific enolase (NSE), which was achieved by applying a photocurrent polarity transition strategy mediated by quercetin. The coupling reaction between Cr(VI) and quercetin drives the signal polarity from anodic to cathodic. When only quercetin is present in the test solution, photogenerated electrons are transferred to the electrode to generate anodic photocurrent. However, in the presence of the target, the signal probe released Cr(VI), which interacted with quercetin, and the electron transfer direction was changed to achieve signal polarity conversion. Meanwhile, protoporphyrin-sensitized Bi:SrTiO3 nanocubes were used as matrix photoactive materials to provide basic photocurrent. The doping of Bi element would adjust the bandgap of SrTiO3, and the organic-inorganic composite material exhibits good photostability and chemical stability that can maintain stable photoelectric properties over a long period of time. Such a novel signal polarity transition strategy greatly broadened the sensor detection to the range of 0.00007-170 ng mL-1 and obtained a relatively low detection limit (25 fg mL-1), which greatly improved the detection sensitivity and accuracy of the biosensor.

High efficient and ultrahigh thermal stability in a rigid rare-earth hybrid molecular crystal: [(CH3CH2)4N]Tb[CH2(SO3)2

Organic-inorganic hybrid molecular fluorescent materials have attracted much attention due to their application potential in white LEDs and high-definition displays. However, achieving high thermal stability for the fields of lighting/displays remains greatly challenging based on the hybrid molecular materials. Herein, we reported a crystalline state 1D rigid rare-earth hybrid coordinate polymer molecular crystal [(CH3CH2)4N]Tb[CH2(SO3)2] (1) along with high quantum yield (QY) 75.2%. Interestingly, this hybrid molecular crystal remains stable up to 728 K (∼455 °C). Remarkably, it exhibits excellent fluorescence thermal stability at high temperatures (150 °C, >95% and 150–200 °C, >82%) and a high thermal activation energy of 568.7 meV. Besides, the fabricated n-UV chips based white-LED by 1, commercial red Y2O3:Eu3+ and blue BaMgAl10O17:Eu2+ phosphor emits white light with color coordinates (CIE, 0.33, 0.32), high color rendering index (CRI) of 91.2, and correlated color temperature (CCT) 5623 K. These results reveal that this ultrahigh thermal stability hybrid molecular crystal as a green phosphor has great potential applications for displays or WLEDs. Therefore, this study opens a new avenue to develop novel rare-earth phosphors and gives new visions for hybrid molecular fluorescent materials.

SYNTHESIS, CRYSTAL STRUCTURE, OPTICAL AND ANTIMICROBIAL PROPERTIES OF 2-NITROBENZYL TRIPHENYLPHOSPHONIUM TETRABROMOCOBALTATE(II)

A novel organic-inorganic hybrid multifunctional crystalline material, 2-nitrobenzyl triphenylphosphonium tetrabromocobaltate(II) [2-NO2BzTPP]2[CoBr4](1), has been synthesized using [2-NO2BzTPP]Br and CoBr2 in methanol solution acidified with hydrobromic acid and characterized using single-crystal X-ray diffraction and spectroscopic techniques. The single-crystal X-ray diffraction analysis showed that the hybrid [2-NO2BzTPP]2[CoBr4](1) belongs to the triclinic space group P–1 with a = 11.1815(17) Å, b = 12.954(2) Å, c = 19.426(3) Å, α = 99.312(5)°, β = 100.654(5)°, γ = 113.746(5)°, V = 2442.3(7) Å3, Z = 2, which consists of two [2-NO2BzTPP]+ cations and a [CoBr4]2– anion. The Co(II) ion in the [CoBr4]2– anion is coordinated to four Br– ions and has a tetrahedral geometry. The C–H···O hydrogen bonds, O···π and O···Br interactions in the crystal can favor crystal stacking and stabilization. The bulk phase purity, homogeneity, and morphology of the desired compound are checked using powder XRD, and SEM-EDX analysis. The hybrid crystal showed an emission peak near 468 nm at room temperature under the excitation of UV light at 241 nm. The low energy gap (2.85 eV) indicated that the crystal was a semiconductor suitable for optical applications. Furthermore, the compound exhibited good bactericidal activity against E. coli and S. aureus.

Synthesis of organic-inorganic composite materials by sol-gel method

Synthesis of organic-inorganic composite materials by sol-gel method

Formation of iminium ions during the processing of metal halide perovskites.

Ammonium ions are a key component of many organic-inorganic metal halide materials. We show that the hexagonal perovskite (Me2NH2)PbI3 is rapidly transformed to iminium-based perovskites (Me2CNMeR)PbI3 (R = Me, Et), simply by stirring the material in the respective ketone at room temperature, triggering clear changes in the materials' photophysical properties.