Organic-inorganic Hybrid System Research Articles

Electrical response on the nickel-ion containing organic–inorganic hybrid system for the sensing of dopamine

A complexation mediated route has been applied for the synthesis of Ni(II)-HMDA (hexamethylenediamine) hybrid system and the synthesized complex material was tailored as a sensing platform of dopamine. The electric field induced polarization study exhibited the hysteresis loop for Ni(II)-HMDA and with the gradual addition of dopamine to the complex, a steady increase of maximum polarization value of the loop was noticed. The increment of the polarization hysteresis loops were associated with the ligand exchange mechanism between HMDA and dopamine. The dopamine sensing performance of Ni(II)-HMDA hybrid system was further studied using the dielectric capacitance, AC-conductivity measurement and impedimetric techniques.

Synthesis of Organic-Inorganic Hybrid Material with a Synergistic Interface as a Release Agent for Free Acid β-Hydroxy-β-Methyl Butyrate

We report the preparation and characterization of a new organic-inorganic hybrid system composed of type-I collagen and ZnAl layered double hydroxide (LDH) particles loaded with β-hydroxy-β-methyl butyrate (HMB) by coprecipitation reaction. X-ray diffraction (peaks well agree with those reported in the literature), infrared spectroscopy (stretching bonds for both organic-inorganic compounds), and X-ray photoelectron spectroscopy confirmed the hybrid system retained HMB in the carboxylate form, and a small fraction turned to the acid form. In both cases, the HMB molecules are assembled to the LDH surface. The hybrid compound results in improved thermal stability for HMB and collagen, as shown by thermal analysis. Scanning electron microscopy data reflects different arrangements from LDH sheets with interesting physicochemical properties since LDH and collagen protect free HMB and make it more bioavailable and functional. In vitro studies as part of high-throughput screening strategies indicated that LDH hybrids reduced cell viability around 75-90%, which is an acceptable viability value because of the L6 cell line susceptibility. However, all new nanomaterials must be carefully analyzed by different toxicity tests because a single test does not evaluate complete physiological compartments.

Highly Efficient Photocatalytic Cr(VI) Reduction by Lead Molybdate Wrapped with D-A Conjugated Polymer under Visible Light

Well-designed composite photocatalysts are of increasing concern due to their enhanced catalytic performance compared to a single component. Here, a photocatalyst composed of PbMoO4 (PMO) and poly-benzothiadiazole (BBT, a D-A-conjugated polymer) was successfully synthesized by BBT polymerization on the surface of the PMO. The resultant BBT-PMO with a heterojunction structure represented an enhanced ability to reduce highly toxic heavy metal Cr(VI) from water under visible light irradiation. The 16.7% BBT-PMO(N, nanoscale) showed the best performance. The corresponding kobs over the 16.7% BBT-PMO(N) was 26-fold (or 53-fold) of that over the pure BBT (or pristine PMO(N)), and this activity was maintained after four cycles. The reasons for its good performance are discussed in detail based on the experimental results. Moreover, the synthesis of the BBT in situ of the PMO also altered the morphology of the BBT component, increasing the specific surface area of the BBT-PMO(N) and endowing it with the ability to adsorb Cr(VI). Additionally, the photocatalyst was also environmentally friendly as such a wrapped structure could sustain the high stability of the PMO without dissociation. This work provides a good strategy for efficient photocatalytic Cr(VI) reduction by designing an organic–inorganic hybrid system with high redox capacity.

Infliximab-based self-healing hydrogel composite scaffold enhances stem cell survival, engraftment, and function in rheumatoid arthritis treatment

Rheumatoid arthritis (RA) is a severe inflammatory autoimmune disease, but its treatment has been very difficult. Recently, stem cell-based therapies have opened up possibilities for the treatment of RA. However, the hostile RA pathological conditions impede the survival and differentiation of transplanted cells, and it remains challenging to fabricate a suitable biomaterial for the improvement of stem cells survival, engraftment, and function. Here we construct an optimal scaffold for RA management through the integration of 3D printed porous metal scaffolds (3DPMS) and infliximab-based hydrogels. The presence of rigid 3DPMS is appropriate for repairing large-scale bone defects caused by RA, while the designed infliximab-based hydrogels are introduced because of their self-healable, anti-inflammatory, biocompatible, and biodegradable properties. We demonstrate that the bioengineered composite scaffolds support adipose-derived mesenchymal stem cells (ADSCs) proliferation, differentiation, and extracellular matrix production in vitro. The composite scaffolds, along with ADSCs, are then implanted into the critical-sized bone defect in the RA rabbit model. In vivo results prove that the bioengineered composite scaffolds are able to down-regulate inflammatory cytokines, rebuild damaged cartilage, as well as improve subchondral bone repair. To the best of the authors’ knowledge, this is the first time that using the antirheumatic drug to construct hydrogels for stem cell-based therapies, and this inorganic-organic hybrid system has the potential to alter the landscape of RA study.

Electrochemical and electrical response of bismuth-aniline complex under the exposure of organic and inorganic environment

In this report, a simple complexation strategy has been adopted for the fabrication of bismuth-aniline based inorganic-organic hybrid system (BAC). The microscopic, optical and surface properties of the hybrid material were derived by using different analytical techniques. The synthesized material was applied as an electrocatalyst for the oxidation of iodide ion and also exhibited as a potential catalyst for the electrochemical recognition of dopamine. The device made with BAC displayed resistive switching behaviour under the exposure of iodine vapour and followed the Schottky, ohmic, space-charge and trapped-charge limited current mechanism at different voltage regions.

Aminobenzene stabilized bismuth halide nanoparticles with O-shaped hysteresis behaviour

A single pot synthesis method of aminobenzene stabilized bismuth iodide particles (ABBI) is reported for the nonvolatile random access memory application. The microscopic and surface property of the as-synthesized organic-inorganic hybrid system has been characterized using different techniques. The current-voltage characteristic of the device, made with ABBI, exhibited O-shaped hysteresis behaviour. For the random access memory application, the device was demonstrated the steady endurance and retention for 103 times and 2×103 sec, respectively. The charge transport property of the device was followed by space charge limited current and trapped assisted tunneling mechanism.

An insight into phenomenal optical non‐linearities arising from synergistic relationship between selected BODIPYs and noble metal nanoparticles

Materials with large and quick non‐linear optical response, excellent photo thermal stability, cost effectiveness and off resonant non‐linear absorption (NLA) are essential requirements for a good optical limiting (OL). Among them, organic systems and π‐conjugated polymers are getting special interest because of their flexibility in structural modification that leads to the tuning of optical and electronic properties that are suitable for working under large bandwidth. Here, we report a drastic enhancement of non‐linear optical activity and exceptional OL action of two organic–inorganic hybrid system based on BODIPY and Au and Ag nanoparticles (NPs). The organic system taken was certain set of BODIPYs with different substitution at the para and meta positions. All the compounds were found to be exhibiting good reverse saturable absorption (RSA) behaviour and negative non‐linear refraction property. An attempt was made to improve the non‐linear optical (NLO) property of the BODIPY by forming nanohybrids with Au and Ag NPs, and the best NLO active candidate among the studied system was chosen for it. A significant enhancement in NLO property was observed on hybrid system formation. The optical limiting (OL) threshold of the hybrid (1 J/cm2) was reduced almost 1/5 times than that of the parent compound (5.2 J/cm2), and this value is comparable with the benchmark OL materials like C60. The mechanism behind the NLA is found to be the combination of excited state absorption (ESA) and two‐photon absorption (TPA). The enhanced NLA and OL action of CAg/Au nanohybrids are attributed to the synergetic effect among the two parent components as well as the local field effects of NPs. Enhancement in non‐linear optical property is found to be stronger in hybrid system with Au NPs and is due to the resonant charge transfer and intense local field effect on exciting with 532‐nm pulse compared with that of Ag NPs. Both the parent compounds and the nanohybrids exhibit negative non‐linearity, and the non‐linear refraction is also found to be enhanced. The improved NLA and OL property of hybrid system guarantees successful usage of the strategy in OL applications.

The Infliximab-Based Self-Healing Hydrogel Composite Scaffold Enhances Stem Cells Survival, Engraftment, and Function in Aiding Rheumatoid Arthritis Management

Rheumatoid arthritis (RA) is a severe inflammatory autoimmune disease, but its treatment has been very difficult. Recently, stem cell-based therapies open new options for the treatment of RA. However, the hostile RA pathological conditions impede the survival and differentiation of transplanted cells, and it is still a great challenge to fabricate a new biomaterial for the improvement of stem cells survival, engraftment, and function. Here we construct a new scaffold for RA management through the integration of 3D printing porous metal scaffolds (3DPMS) and infliximab-based hydrogels. The presence of rigid 3DPMS is appropriate for large-scale bone defects caused by RA, while the designed infliximab-based hydrogels are introduced because of their self-healable, anti-inflammatory, biocompatible, and biodegradable properties. We demonstrate that the bioengineered composite scaffolds support adipose-derived mesenchymal stem cells (ADSCs) proliferation, differentiation, and extracellular matrix production in vitro. The composite scaffolds, along with ADSCs, are then implanted into the critical-sized bone defect in the RA rabbit model. In vivo results prove that the bioengineered composite scaffolds are able to depress inflammatory cytokines, rebuild damaged cartilage, as well as improve subchondral bone repair. To the best of the authors’ knowledge, this is the first time that using the antirheumatic drug to construct hydrogels for stem cell-based therapies, and this inorganic-organic hybrid system has the potential to alter the landscape for RA study.

Organic molecule stabilized bismuth iodide nanoparticles: a hybrid system with multifunctional physical properties.

An organic-inorganic hybrid system of aniline stabilized bismuth iodide nanoparticles (ABI) was synthesized and investigated for its dielectric properties, AC-conductivity, polarization hysteresis and non-volatile memory performances. The X-ray diffraction result indicates the single phase crystalline nature of the nanoparticles and a microscopic image shows the homogeneous distribution of the bismuth iodide nanoparticles within the organic matrix. The material has exhibited a moderate dielectric performance via an interfacial polarization mechanism. The decrease in dielectric constant with frequency is correlated with the carrier concentration and diffusion potential, and the behaviour revealed that the halide ion mediated polaron migration controls the overall relaxation and conductivity properties of the material. Octahedral distortion of bismuth iodide, through halide ion migration, induced a hysteresis loop in polarization-electric field (P-E) characteristics. The device fabricated with the aniline stabilized bismuth iodide nanoparticles exhibited a space-charge limited current and trap assisted tunneling mechanism for the charge transport process. The non-volatile property reveals that the device has the ability to store binary information and has potential for memory applications.

PW12/CN@Bi2WO6 composite photocatalyst prepared based on organic-inorganic hybrid system for removing pollutants in water

In the drive toward green and sustainable chemistry in wastewater treatment, it is necessary to explore more efficient and stable photocatalysts to achieve the degradation of antibiotic and reduction of heavy metal ions. To this end, an organic-inorganic hybrid PW12/CN@Bi2WO6 composite photocatalyst was prepared: PW12/CN composite was prepared by heating H3PW12O40, melamine and phytic acid; PW12/CN@Bi2WO6 was synthesized via PW12/CN and Bi2WO6 by hydrothermal method. The photocatalytic activity of as-prepared photocatalyst was evaluated by degrading tetracycline hydrochloride (TC) and reducing hexavalent chromium (Cr(VI)) under the simulated xenon light source. The results show the PW12/CN@Bi2WO6 composite always maintains high catalytic performance for TC and Cr6+ and has well cycle stability. After irradiation for 90 and 100 min, the most effective 10%-PW12/CN@Bi2WO6 achieved a removal rate of 98.7% for Cr(VI) and 97.5% for TC. Photoluminescence spectroscopy and photoelectrochemical results demonstrate that the charge separation is enhanced for the PW12/CN@Bi2WO6, attributed to the introduction of the organic-inorganic systems to enhance the absorbance of light energy, promote charge transfer and inhibit e− and h+ pair recombination. In addition, the free radical scavenging test and electron spin resonance analysis (ESR) test indicate that the main species of action are h+ and O2− in the photocatalytic oxidation reaction. Further, the mechanism of photocatalysis was proposed by Mott-Schottky. The strategy improving catalytic performance through organic-inorganic hybrid systems provides a new route for the development of photocatalysts.

Fabrication of Robust Antibacterial Coatings Based on an Organic-Inorganic Hybrid System.

Antibacterial coatings have drawn much attention because of their high potential applications in medicine. However, the weak mechanical property, poor biosafety, and biocompatibility of most established antibacterial coatings restrict their applications. In this study, robust antibacterial coatings were fabricated via a simple organic-inorganic hybrid method. The polymer component provides an excellent antibacterial property to the coatings, and the hybrid silica sol improves the hardness of coatings. After cross-linking, network-structured coatings were formed. The coating surfaces exhibited high transmittance, excellent mechanical property, and good antibacterial effect against Escherichia coli (Gram-negative) and Streptococcus mutans (Gram-positive). Additionally, the robust coatings were noncytotoxic with satisfactory biocompatibility. Such results provide a theoretical basis for their applications in the biomedical field.

Strong Exciton-Plasmon Coupling and Hybridization of Organic-Inorganic Exciton-Polaritons in Plasmonic Nanocavity**Supported by the National Key Research and Development Program of China under Grant No 2016YFA0301300, the National Natural Science Foundation of China under Grant Nos 11574035 and 11374041, and the State Key Laboratory of Information Photonics and Optical Communications.

We investigate strong exciton-plasmon coupling and plasmon-mediated hybridization between the Frenkel (F) and Wannier–Mott (WM) excitons of an organic-inorganic hybrid system consisting of a silver ring separated from a monolayer WS2 by J-aggregates. The extinction spectra of the hybrid system calculated by employing the coupled oscillator model are consistent with the results simulated by the finite-difference time-domain method. The calculation results show that strong couplings among F excitons, WM excitons, and localized surface plasmon resonances (LSPRs) lead to the appearance of three plexciton branches in the extinction spectra. The weighting efficiencies of the F exciton, WM exciton and LSPR modes in three plexciton branches are used to analyze the exciton-polaritons in the system. Furthermore, the strong coupling between two different excitons and LSPRs is manipulated by tuning F or WM exciton resonances.

The dielectric and electrical properties of bismuth oxide nanoparticles within organic network: the effect of temperature and the role of polarons

In this communication, we report the dielectric property of organic molecule functionalized bismuth oxide nanoparticles under different temperature and frequency condition. A large value of dielectric constant and a non-Debye type of relaxation phenomena has been witnessed due to the polaron induced polarization of the system. The frequency dependent electrical modulus of the material is discussed in the light of localized and non-localized relaxation process of the polaron. The AC-conductivity behaviour is modeled based on two different mechanisms, (a) polaron tunneling (at lower frequency) and (b) polaron hopping (at higher frequency). The organic-inorganic hybrid system also exhibited a unipolar resistive switching performance with a stable ON/OFF current ratio (∼102) when used as an active material for a suitable device under a DC-bias.

Ultrafast fabrication of thermally stable protein-coated silver iodide nanoparticles for solid-state superionic conductors.

Solid-state ionic conductor is an essential and critical part of electrochemical devices such as batteries and sensors. Nano-sized silver iodide (AgI) is the most promising ionic conductor due to its superionic conductivity at room temperature. In recent years, proteins have been used as organic templates to obtain high-performance solid-state ionic conductors as well as to extend their applications in a biosensor. Here, we report the unprecedented ultrafast synthesis of thermally stable protein-coated AgI nanoparticles (NPs) through the photo-irradiation method for solid-state electrolyte. The synthesis was performed using a hyperthermostable bacterial β-glucosidase. The protein-coated AgI NPs with an approximate diameter of 13 nm showed that the controllable transition from the α- to β-/γ-phase was drastically suppressed down to 41 °C in the cooling process. After drying, the product represents a thermally stable organic-inorganic hybrid system with superionic conductivity. It is noteworthy that the superionic conductivity (σ ˜ 0.14 S/cm at 170 °C) of thermally stable protein-coated AgI NPs is maintained during several thermal cycles (25-170 °C). To our knowledge, this is the first report showing the diffusion of mobile Ag+ ions on the surface of the AgI NPs through a protein matrix. The facile synthesis method and high performance of the protein-coated AgI NPs may provide a latent application in the mass production of nanobatteries and other technological applications.

Silver iodide nanowires grown within tubular J-aggregates

Silver iodide nanowires have been grown within tubular J-aggregates of the cyanine dye 3,3′-bis(2-sulfopropyl)-5,5′,6,6′-tetrachloro-1,1′-dioctylbenzimida-carbo-cyanine (C8S3) from aqueous AgNO3 solutions. Crystal structure analysis by selected area electron diffraction (SAED), high resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (EDXS) of single nanowires revealed that they are of silver iodide (AgI), while previously they were presumed to be of metallic silver. Iodine has not been added intentionally, but it is a remnant from the chemical synthesis of the dye and present in a dye:iodine ratio of almost 2:1, as revealed by inductively coupled plasma mass spectrometry (ICP-MS). The AgI wires grow as single crystals with lengths of several 10–100 nm and width of 6.5 ± 0.5 nm. The width and the orientation of the crystal relative to the aggregate axis are defined by the tubular structure of the templating dye aggregate. Caused by the nucleation at the tube wall the main growth is not along the usually preferred [0 0 0 1] direction but along the extension of the basal plane, which is furthermore tilted by an angle of 6° ± 2° against the main axis of the aggregate. This self-assembled system represents an organic-inorganic hybrid system with a well-defined semiconductor nanowire, AgI, that is strictly oriented with respect to the aggregated phase of conjugated molecules.

Construction of organic–inorganic cadmium sulfide/diethylenetriamine hybrids for efficient photocatalytic hydrogen production

The design and control of effective, sustainable, cheap, and reusable photocatalysts are crucial to the development of solar energy conversion to hydrogen (H2) for solving environmental problems. The cadmium sulfide/diethylenetriamine (CdS/DETA) hybrid in a single crystalline structure was achieved by a solvothermal approach. The organic–inorganic CdS/DETA hybrid shows high performance and satisfactory stability for H2 production under visible-light irradiation. The synergetic chemical coupling effect between CdS and DETA leads to a marked increase in the H2 generation rate and the apparent quantum yield. H2-production rate of CdS/DETA24 under visible light illumination are 31.7% and 8059.5μmolg−1h−1, respectively, which is 3.5 times more than CdS nanorods without DETA. Our findings may give a promising method to improve CdS for efficient electron-hole separation, electron transferring and anticorrosion in photocatalytic process, which reforms the conventional organic–inorganic hybrid system.

Bimetallic Au@Pt nanoparticles dispersed in conducting polymer—A catalyst of enhanced activity towards formic acid electrooxidation

Organic-inorganic hybrid system composed of bimetallic Au@Pt nanoparticles with diameter of a few nanometers uniformly dispersed in the conducting polymer matrix was synthesized by a simple electrochemical/chemical method on glassy carbon electrode. The elaborated catalyst demonstrates an enhanced specific catalytic activity (9.7Amg−1 Pt) in electrooxidation of formic acid. The reason of this improved performance is discussed in terms of the polymer structure used as the matrix for bimetallic catalyst and mechanism of formation of Au@Pt nanoparticles. Electrocatalytic activity of the hybrid systems obtained by means of two different procedures are compared to understand better the influence of the synthesis conditions on the properties of the catalyst. The composites are characterized by means HR-TEM, X-ray diffraction and X-ray fluorescence methods. Arrangement of nanoparticles in Au@Pt composite is determined by EDX elemental mapping. A new method of preparation of the samples embedded in thin polymer film for XRD and XRF measurements is proposed.

Unprecedented Ferroelectric-Antiferroelectric-Paraelectric Phase Transitions Discovered in an Organic-Inorganic Hybrid Perovskite.

As a promising candidate for energy storage capacitors, antiferroelectric (AFE) materials have attracted great concern due to their congenital advantages of large energy storage ability from double polarization versus electric field (P-E) hysteresis characteristics in contrast to ferroelectrics and linear dielectrics. However, antiferroelectricity has only been discovered in inorganic oxides and some hydrogen-bonded molecular systems. In view of the structural diversity and unique physical properties of organic-inorganic hybrid system, it remains a great opportunity to introduce antiferroelectricity into organic-inorganic hybrid perovskites. Here, we report that polarizable antiparallel dipole arrays can be realized in an organic-inorganic hybrid perovskite, (3-pyrrolinium)CdBr3, which not only exhibits an excellent ferroelectric property (with a high spontaneous polarization of 7.0 μC/cm2), but also presents a striking AFE characteristic revealed by clear double P-E hysteresis loops. To the best of our knowledge, it is the first time that such successive ferroelectric-antiferroelectric-paraelectric phase transitions have been discovered in organic-inorganic perovskites. Besides, a giant dielectric constant of 1600 even at high frequency of 1000 kHz and a bulk electrocaloric effect with entropy change of 1.18 J K-1 kg-1 under 7.41 kV/cm are also observed during the phase transition. Apparently, the combined striking AFE characteristic and giant dielectric constant make (3-pyrrolinium)CdBr3 a promising candidate for next generation high-energy-storage capacitors.

Design, Synthesis, and Characterization of Polyphosphazene Bearing Stable Nitroxide Radicals as Cathode-Active Materials in Li-Ion Batteries

A new synthetic strategy is developed for the synthesis of polyphosphazene bearing stable nitroxide radicals as a pendant group. The resulting material is investigated as a cathode-active material for rechargeable lithium–ion batteries that performs 80 mAh g−1 capacities at a C/2 current density over 50 cycles. Thus, the inorganic–organic hybrid system can be proposed as an alternative cathode-active material with improved performance.

Calcium phosphate-phosphorylated adenosine hybrid microspheres for anti-osteosarcoma drug delivery and osteogenic differentiation.

Biocompatibility, biodegradability and bioactivity are significantly important in practical applications of various biomaterials for bone tissue engineering. Herein, we develop a functional inorganic-organic hybrid system of calcium phosphate-phosphorylated adenosine (CPPA). Both calcium phosphate and phosphorylated adenosine molecules in CPPA are fundamental components in mammalians and play important roles in biological metabolism. In this work, we report our three leading research qualities: (1) CPPA hybrid microspheres with hollow and porous structure are synthesized by a facile one-step microwave-assisted solvothermal method; (2) CPPA hybrid microspheres show high doxorubicin loading capacity and pH-responsive drug release properties, and demonstrate positive therapeutic effects on six osteosarcoma cell lines invitro and a mouse model of 143B osteosarcoma subcutaneous tumor invivo; (3) CPPA hybrid microspheres are favorable to promote osteogenic differentiation of human bone mesenchymal stem cells (hBMSCs) by activating the AMPK pathway, with satisfactory evidences from cellular alkaline phosphatase staining, alizarin red staining, real time PCR and western analysis. The as-prepared CPPA hybrid microspheres are promising in anti-osteosarcoma and bone regeneration, which simultaneously display excellent properties on drug delivery and osteogenic differentiation of hBMSCs.