Organic-inorganic System Research Articles

An artificial organic-inorganic Z-scheme photocatalyst WO3@Cu@PDI supramolecular with excellent visible light absorption and photocatalytic activity

Tungsten trioxide (WO3) has a wide application in environmental remediation due to its stability. Yet, the application of WO3 is severely limited by its wide band gap and weak electron reduction ability. In this work, we intend to enhance the visible light absorption and photocatalytic performance by constructing an organic-inorganic Z-scheme system WO3@Cu@PDI. Apparently, WO3@Cu@PDI has excellent visible light absorption and photocatalytic degradation ability in the degradation of tetracycline hydrochloride (TC). Under visible light irradiation, the degradation rate of composites is 40 times faster than that of sole WO3 and 5 times than PDI. The photocatalytic activity of WO3@Cu@PDI toward TC still kept 85% after three reuses. We revealed that this high photoactivity arisen from the efficient carriers separation and the formation of Z-scheme junction. Importantly, this Z-scheme electron transfer pathway was confirmed by thorough experimental study. This work demonstrated the significant potential of WO3-based inorganic-organic Z-scheme photocatalyst in environmental remediation.

New perylenebisimide decorated cyclotriphosphazene heavy atom free conjugate as singlet oxygen generator.

Perylenebisimide-cyclotriphosphazene based inorganic-organic system was synthesized by a multistep procedure. The substitution reaction of asymmetric perylenebisimide (PBI) derivative with the hexachloroyclotriphosphazene (trimer) resulted in the formation of fully PBI decorated cyclotriphosphazene (5). The identity of newly synthesized compound (5) was confirmed by using 31P, 1H and 13C NMR spectroscopies and mass spectrometry. The photophysical (UV- Vis absorption, fluorescence emission, fluorescence lifetime and fluorescence quantum yield) and photochemical (the singlet oxygen generation, and photostability) properties of this conjugate were investigated as novel heavy atom free triplet photosensitizer. The singlet oxygen quantum yield of the PBI-cyclotriphosphazene (5) was calculated to be 0.86 which is good for a heavy atom free triplet photosensitizer. These results will add to the development of cyclotriphosphazene based heavy atom free singlet oxygen triplet photosensitizer systems for applications in organic oxygenation reactions.

Enhanced photocatalytic performance of poly(3,4-ethylenedioxythiophene)-coated TiO2 nanotube electrodes

This study presents the design of a mixed organic–inorganic system to be utilized in solar-light chemical energy conversion applications, where the visible-light absorption properties of the conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), are combined with the enhanced charge transport properties of TiO2 nanotubes, thus creating an efficient photoelectrode. A dispersion of PEDOT doped with p-toluenesulfonate (tosylate) ions was synthesized using a simple solution-casting polymerization process, which was then spin-coated onto an ordered array of anodically fabricated TiO2 nanotubes to be used for solar energy conversion. Electron microscopy observation confirmed the presence of PEDOT in the hybrid (PEDOT–TiO2) and Fourier transform infrared spectroscopy verified the vibrational modes of the polymerized PEDOT. The ultraviolet-visible diffuse reflectance data indicated a change in the absorption edge of the pure TiO2 nanotubes to longer wavelengths after PEDOT coating. The developed photo-electrodes exhibited a significant increase in photocurrent response and lower charge transfer resistance with respect to the pure TiO2 nanotubes, as verified by electrochemical impedance spectroscopy.

Undoped and Eu3+ Doped Magnesium-Aluminium Layered Double Hydroxides: Peculiarities of Intercalation of Organic Anions and Investigation of Luminescence Properties.

The Mg3/Al and Mg3/Al0.99Eu0.01 layered double hydroxides (LDHs) were fabricated using a sol-gel chemistry approach and intercalated with different anions through ion exchange procedure. The influence of the origin of organic anion (oxalate, laurate, malonate, succinate, tartrate, benzoate, 1,3,5-benzentricarboxylate (BTC), 4-methylbenzoate (MB), 4-dimethylaminobenzoate (DMB) and 4-biphenylacetonate (BPhAc)) on the evolution of the chemical composition of the inorganic-organic LDHs system has been investigated. The obtained results indicated that the type and arrangement of organic guests between layers of the LDHs influence Eu3+ luminescence in the synthesized different hybrid inorganic–organic matrixes. For the characterization of synthesis products X-ray diffraction (XRD) analysis, infrared (FTIR) spectroscopy, fluorescence spectroscopy (FLS), and scanning electron microscopy (SEM), were used.

Optically Active Upconverting Nanoparticles with Induced Circularly Polarized Luminescence and Enantioselectively Triggered Photopolymerization.

In this work, lanthanide-doped upconversion nanoparticles (UCNPs) showing upconverted circularly polarized luminescence were demonstrated in an organic-inorganic co-assembled system. Achiral UCNPs (NaYF4:Yb/Er or NaYF4:Yb/Tm) can be encapsulated into chiral helical nanotubes through the procedure of co-gelation. These co-gel systems display intense upconverted circularly polarized luminescence (UC-CPL) ranging from ultraviolet (UV, 300 nm) to near-infrared (NIR, 850 nm) wavelength. In addition, the UV part of UC-CPL can be used to initiate the enantioselective polymerization of diacetylene.

Mesoporous silica nanobeans dual-functionalized with AIEgens and leaning pillar[6]arene-based supramolecular switches for imaging and stimuli-responsive drug release.

A bean-shaped and dual-functionalized organic-inorganic hybrid supramolecular system with a GSH-dependent turn-on fluorescence enhancement property and stimuli-responsive drug delivery function endowed with leaning towerarene-based switches has been constructed for simultaneous tumor inhibition and imaging.

Low dielectric constant silica-containing cross-linked organic-inorganic materials based on fluorinated poly(arylene ether)s

In this work, for the first time, we describe the design and synthesis of novel fluorinated poly(arylene ether)/silica cross-linked materials (FPAE/SiO1.5) through a sol-gel process by using the triethoxysilyl-containing fluorinated polyethers as precursors for both organic and inorganic networks formation. The polyether-based precursors with the sol-gel active species were synthesized via hydrosilylation reaction between triethoxysilane and the corresponding allyl-functionalized FPAE under Pt catalysis. Herein, we present two approaches of hydrolysis triethoxysilane groups to silanol ones within sol-gel chemistry: (1) hydrolysis with air moisture and (2) hydrolysis of the ethoxysilyl groups at the interface between two liquids. The mechanical and thermal properties of the FPAE/SiO1.5 materials were studied depending on the structure of macromolecular chains and synthetic route. Scanning electron and atomic force microscopies were employed to investigate the morphology of the resulting silica-containing cross-linked materials. The resulting FPAE/SiO1.5 films were flexible and tough with tensile strength above 25 МPа, and exhibited high thermal stability, having the initial decomposition temperature about 300°С. For more detailed explanation of the thermophysical behavior of the FPAE/SiO1.5 materials, the synthesis method of new silica-containing organic-inorganic system was developed by the direct hydrosilylation reaction between allyl-functionalized polyethers and 1,1,3,3-tetramethyldisiloxane. All films exhibited high hydrophobic properties (water contact angles above 102°), low dielectric constants and losses at room temperature. In particular, the FPAE/SiO1.5 film prepared from tetrafluorobenzene-based polyether showed the ultra-low dielectric constant of 1.86 at 10 kHz. This makes the obtained polymer FPAE/SiO1.5 materials attractive for microelectronics and many other emerging applications.

Analytical study on temperature effect on piezoelectric exciton dissociation rate (Onsager dissociation rate)

We discussed analytically the temperature effect on the piezoelectric exciton dissociation rate (Onsager dissociation rate, D on the p-n junction interface (hybrid inorganic-organic system). For high temperatures (\( T\gg 1\)), a power series expansion for D about a field parameter b (\( \ll 1\)) was used, resulting in \( D\cong\gamma/\frac{4}{3}\pi a^3 \cdot(1+b)\cdot 2\cdot n_e\). For low temperatures (\( T\ll 1\)), \( 1+b+ \frac{b^2}{3}+\ldots,\) resulted in an asymptotically complex value that approached zero, and allowed D to also approach zero. Therefore, it is suggested that high temperatures will be useful for verifying piezoelectric exciton dissociation theoretically.

Changes in Cementation of Reef Building Oysters Transitioning from Larvae to Adults.

Oysters construct extensive reef communities, providing food, protection from storms, and healthy coastlines. We still do not have a clear picture of how these animals attach to surfaces. Efforts described herein provide the first examination of adhesion at the transition from free swimming larvae to initial substrate attachment, through metamorphosis, and on to adulthood. Two different bonding systems were found to coexist. Larvae use an organic, hydrated glue that persists while the animal progresses into the juvenile phase, at which point a very different adhesive emerges. Juveniles bond with an organic-inorganic composite system, positioning the organic component for maximum adhesion by residing between the animal and substrate. Beyond understanding our marine environment, these insights may aid efforts in aquaculture, reef restoration, and adhesive design.

Antibiotic-anionic Clay Matrix Used for Drug Controlled Release

Anionic clay matrix acting as drug controlled release system have shown in last years a great potential for delivery of bioactive molecules and chemical therapeutics. This organic-inorganic nanohybrid system is high efficient offering an excellent protection of intercalated compounds from degradation. Compared to other nanoparticles used in medical area, anionic clays type layered double hydroxides have found to be biocompatible according to toxicological studies. Ampicillin containing MgAlLDHs and ZnAlLDH samples have been prepared following two routes: anion-exchange procedure and reconstruction from calcined layered double hydroxides. Solid samples have been characterized by FTIR and SEM-EDX highlighting the alteration of pristine LDHs structure when the antibiotic is introduced in the interlayer gallery.

Multi-wavelength optical data processing and recording based on azo-dyes doped organic-inorganic hybrid film.

While single wavelength all-optical information encoding through optically induced orientation of azobenzene dyes is being extensively pursued, we propose multi-wavelength optical data processing and recording based on disperse red 1 (DR1) and 4-(4-hydroxybutyloxy) azobenzene doped organic-inorganic hybrid films to increase the density of recording data. By investigating the change of absorbance spectrum of the doped film under different irradiations, results indicate a laser pulses around 470 nm would be suitable as the probe beam. In the measurement of optical data processing and recording, two cw lasers pulse at 532 nm and 355 nm induce trans-cis isomerization of the azo-dyes in the film, while the output of the probe beam record the processed data as {(-1), (0), (1)} according to different inputs of the pump beams. Since the light induced isomerization has a sensitive response in the as-prepared solid organic-inorganic matrix system, the films is promising as recording and monitoring element in all-optical devices over a wide range of repetition rates.

Structure and Gas Transport at the Polymer-Zeolite Interface: Insights from Molecular Dynamics Simulations.

We investigate the structure of polyimide (PI) at the surface of a silicalite zeolite (MFI), as part of a model hybrid organic-inorganic mixed matrix membrane system, through equilibrium molecular dynamics simulations. Furthermore, we report a comparison of the adsorption and transport characteristics of pure components CO2 and CH4 in PI, MFI, and PI-MFI composite membranes. It is seen that incorporation of MFI zeolite into PI results in the formation of densified polymer layers (rigidified region) near the surface, having thickness around 1.2 nm, before bulklike behavior of the polymer is attained, contrary to empirical fits suggesting the existence of an approximately 1 μm thick interface between the polymer and filler. This region offers an extra resistance to gas diffusion especially for the gas with a larger kinetic diameter, CH4, thus improving the CO2/CH4 kinetic selectivity in the PI-MFI composite membrane. Furthermore, we find that the kinetic selectivity of CO2 over CH4 in the rigidified region increases with temperature and that additivity of transport resistances in MFI, interfacial layer, and bulklike region of the polymer satisfactorily explains transport behavior in the composite sandwich investigated. The gas adsorption isotherms are extracted considering the dynamics and structural transitions in the PI and PI-MFI composite upon gas adsorption, and it is seen that the rigidified layer affects the gas adsorption in the polymer in the PI-MFI hybrid system. A significant increase in CO2/CH4 selectivity as well as gas permeability is observed in the PI-MFI composite membrane compared to that in the pure PI polymer membrane, which is correlated with the high selectivity of the rigidified interfacial layer in the polymer. Thus, while enhancing transport resistance, the rigidified layer is beneficial to membrane selectivity, leading to improved performance based on the Robeson upper bound plot for polymers.

Coupling of organic and inorganic aerosol systems and the effect on gas-particle partitioning in the southeastern US.

Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2× sulfate, RN/2S ≈ 0.8 to 0.9) with approximately 70% of total ammonia and ammonium (NHx) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H+]air (H+ in μgm−3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid–liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic–organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C≥0.6) compounds including several isoprene-derived tracers as well as levoglu-cosan but decrease particle-phase partitioning for low O: C, monoterpene-derived species.

Organic/inorganic hybrid composed of modified polyacrylamide grafted silica supported Pd nanoparticles using RAFT polymerization process: Controlled synthesis, characterization and catalytic activity

Reversible addition-fragmentation chain transfer (RAFT) polymerization was utilized for the preparation of polyacrylamide brushes grafted onto silica particles (SiO2-g-PAAm) via “grafting to” and “grafting from” approach in a controlled manner. Control of both the polymer's molecular weight and the density of grafted chains can be achieved by these methods. The polymer grafted silica was further modified to convert it to phosphinite ligand. Complexation of this ligand with Pd(OAc)2 was performed in order to obtain the Pd catalytic system. Various techniques such as FT-IR, TGA, XRD and electron microscopy systems such as SEM and TEM were conducted as characterization methods. Moreover, X-Ray photoelectron spectroscopy (XPS) of the catalyst disclosed the binding energy of Pd in zero oxidation state properly. This organic-inorganic hybrid catalytic system showed proper activity in Heck coupling reaction. The catalyst was successfully reused in repeating cycles with negligible change in its efficiency. Characteristic of the catalyst such as size and shape, chemicophysical stability and the structure of catalyst are retained almost unchanged even after successive reactions.

Enhanced thermal stability of RuO2/polyimide interface for flexible device applications

We have studied the thermal stability of RuO2/polyimide (Kapton) interface using experimental and theoretical methods. Based on calorimetric and spectroscopic analyses, this inorganic–organic system does not exhibit any enthalpic peaks as well as all bonds in RuO2 and Kapton are preserved up to 500 °C. In addition, large-scale density functional theory based molecular dynamics, carried out in the same temperature range, validates the electronic structure and points out that numerous Ru–C and a few Ru–O covalent/ionic bonds form across the RuO2/Kapton interface. This indicates strong adhesion, but there is no evidence of Kapton degradation upon thermal excitation. Furthermore, RuO2 does not exhibit any interfacial bonds with N and H in Kapton, providing additional evidence for the thermal stability notion. It is suggested that the RuO2/Kapton interface is stable due to aromatic architecture of Kapton. This enhanced thermal stability renders Kapton an appropriate polymeric substrate for RuO2 containing systems in various applications, especially for flexible microelectronic and energy devices.

Highly Networked Capsular Silica-Porphyrin Hybrid Nanostructures as Efficient Materials for Acetone Vapor Sensing.

The development of novel functional nanomaterials is critically important for the further evolution of advanced chemical sensor technology. For this purpose, metalloporphyrins offer unique binding properties as host molecules that can be tailored at the synthetic level and potentially improved by incorporation into inorganic materials. In this work, we present a novel hybrid nanosystem based on a highly networked silica nanoarchitecture conjugated through covalent bonding to an organic functional molecule, a tetraphenylporphyrin derivative, and its metal complexes. The sensing properties of the new hybrid materials were studied using a nanomechanical membrane-type surface stress sensor (MSS) with acetone and nitric oxide as model analytes. This hybrid inorganic-organic MSS-based system exhibited excellent performance for acetone sensing at low operating temperatures (37 °C), making it available for diagnostic monitoring. The hybridization of an inorganic substrate of large surface area with organic molecules of various functionalities results in sub-ppm detection of acetone vapors. Acetone is an important metabolite in lipid metabolism and can also be present in industrial environments at deleterious levels. Therefore, we believe that the analysis system presented by our work represents an excellent opportunity for the development of a portable, easy-to-use device for monitoring local acetone levels.

Nonequilibrium surface growth in a hybrid inorganic-organic system

Using kinetic Monte Carlo simulations, we show that molecular morphologies found in non-equilibrium growth can be strongly different from those at equilibrium. We study the prototypical hybrid inorganic-organic system 6P on ZnO(10-10) during thin film adsorption, and find a wealth of phenomena including re-entrant growth, a critical adsorption rate and observables that are non-monotonous with the adsorption rate. We identify the transition from lying to standing molecules with a critical cluster size and discuss the competition of time scales during growth in terms of a rate equation approach. Our results form a basis for understanding and predicting collective orientational ordering during growth in hybrid material systems.

Tunable Narrow Band Emissions from Dye-Sensitized Core/Shell/Shell Nanocrystals in the Second Near-Infrared Biological Window.

We introduce a hybrid organic-inorganic system consisting of epitaxial NaYF4:Yb3+/X3+@NaYbF4@NaYF4:Nd3+ (X = null, Er, Ho, Tm, or Pr) core/shell/shell (CSS) nanocrystal with organic dye, indocyanine green (ICG) on the nanocrystal surface. This system is able to produce a set of narrow band emissions with a large Stokes-shift (>200 nm) in the second biological window of optical transparency (NIR-II, 1000-1700 nm), by directional energy transfer from light-harvesting surface ICG, via lanthanide ions in the shells, to the emitter X3+ in the core. Surface ICG not only increases the NIR-II emission intensity of inorganic CSS nanocrystals by ∼4-fold but also provides a broadly excitable spectral range (700-860 nm) that facilitates their use in bioapplications. We show that the NIR-II emission from ICG-sensitized Er3+-doped CSS nanocrystals allows clear observation of a sharp image through 9 mm thick chicken breast tissue, and emission signal detection through 22 mm thick tissue yielding a better imaging profile than from typically used Yb/Tm-codoped upconverting nanocrystals imaged in the NIR-I region (700-950 nm). Our result on in vivo imaging suggests that these ICG-sensitized CSS nanocrystals are suitable for deep optical imaging in the NIR-II region.

Biomimicry Promotes the Efficiency of a 10‐Step Sequential Enzymatic Reaction on Nanoparticles, Converting Glucose to Lactate

AbstractFor nanobiotechnology to achieve its potential, complex organic–inorganic systems must grow to utilize the sequential functions of multiple biological components. Critical challenges exist: immobilizing enzymes can block substrate‐binding sites or prohibit conformational changes, substrate composition can interfere with activity, and multistep reactions risk diffusion of intermediates. As a result, the most complex tethered reaction reported involves only 3 enzymes. Inspired by the oriented immobilization of glycolytic enzymes on the fibrous sheath of mammalian sperm, here we show a complex reaction of 10 enzymes tethered to nanoparticles. Although individual enzyme efficiency was higher in solution, the efficacy of the 10‐step pathway measured by conversion of glucose to lactate was significantly higher when tethered. To our knowledge, this is the most complex organic–inorganic system described, and it shows that tethered, multi‐step biological pathways can be reconstituted in hybrid systems to carry out functions such as energy production or delivery of molecular cargo.

Biomimicry Promotes the Efficiency of a 10-Step Sequential Enzymatic Reaction on Nanoparticles, Converting Glucose to Lactate.

For nanobiotechnology to achieve its potential, complex organic-inorganic systems must grow to utilize the sequential functions of multiple biological components. Critical challenges exist: immobilizing enzymes can block substrate-binding sites or prohibit conformational changes, substrate composition can interfere with activity, and multistep reactions risk diffusion of intermediates. As a result, the most complex tethered reaction reported involves only 3 enzymes. Inspired by the oriented immobilization of glycolytic enzymes on the fibrous sheath of mammalian sperm, here we show a complex reaction of 10 enzymes tethered to nanoparticles. Although individual enzyme efficiency was higher in solution, the efficacy of the 10-step pathway measured by conversion of glucose to lactate was significantly higher when tethered. To our knowledge, this is the most complex organic-inorganic system described, and it shows that tethered, multi-step biological pathways can be reconstituted in hybrid systems to carry out functions such as energy production or delivery of molecular cargo.